Rachu PDF

THESE
prsente
LINSTITUT NATIONAL DES SCIENCES APPLIQUEES DE TOULOUSE
pour lobtention du
DOCTORAT
SCIENCE DES PROCEDES
SPECIALITE : GENIE DES PROCEDES ET DE LENVIRONNEMENT
par
Srayut RACHU
Master of Environmental Engineering Chulalongkorn University, Bangkok, Thalande
CONTRIBUTION A LA MISE AU POINT DUN LOGICIEL DE

CALCUL DE PROCEDES ET FILIERES DE TRAITEMENT DEAUX
RESIDUAIRES HUILEUSES
Soutenance prvue le 16 Dcembre 2005 devant la commission dexamen:
M.
D. HADJIEV
Professeur, IUT, Lorient
Rapporteur
M.
J. ROLS
Professeur, UPS, Toulouse
Rapporteur
M.
Y. AURELLE
Professeur, INSA, Toulouse
Directeur de thse
M.
A. LINE
Directeur de LIPE
M.
R. BEN AIM
Professeur Emrite, INSA, Toulouse
M.
S. SAIPANICH
PDG, Progress Technology Consultants Co.,Ltd., Thalande
M.
H. ROQUE
Professeur Emrite, INSA, Toulouse
Invit
Executive summary
Sommaire
Sommaire
Le traitement des eaux rsiduaires huileuses est lun des sujets de recherche majeurs
dans le laboratoire GPI. Lhydrocarbure ou lhuile est lun des polluants de leau les plus
importants. Une petite quantit de lhuile peut produire le film vastement couvrant la surface
de leau, lequel affecte le transfert de loxygne et par consquence ruine lcosystme. Mme
sil est biodgradable, il contribue la demande biologique en oxygne (DBO) importante. En
plus, tant donn ses proprits, la haute concentration, il cause leffet nuisible dans le
procd de traitement biologique. Toutefois, lhydrocarbure ou lhuile peut avoir la valeur ou
tre rcupre ou recycle condition o il peut tre spar de leau. En cet effet, les
techniques de la sparation huile/eau sont parmi des recherches principales dans le laboratoire
GPI. Il y a plusieurs tudes sur les techniques, les procds et les innovations de la sparation
dhuile initie par le laboratoire GPI. Chaque tude peut tre approprie certaine condition
de lopration ou certain caractristique des eaux rsiduaires.
Ainsi, les buts de cette thse sont de rexaminer les recherches du laboratoire GPI,
ralises dans lEquipe du Professeur AURELLE, sur le procd de traitement des eaux
rsiduaires huileuses ; dtablir le design du procdure gnrale avec les prcautions de tels
procds ; et, ensuite, valoriser et maximiser lutilisation de ces connaissances tablies sous
forme du logiciel. Ainsi, les objectifs de la thse ont t dfinis pour raliser ces buts cidessus :
1. Rexaminer les technologies de traitement pour les eaux rsiduaires huileuses ou les
eaux rsiduaires pollues par lhydrocarbure, dans les recherches de doctorat ralises
dans lEquipe du Professeur Yves AURELLE, du commencement jusqu au prsent.
2. Gnraliser et proposer le modle de chaque procd relatif.
3. Composer le textbook sur les eaux rsiduaires hydrocarbure-pollues ou les procds
de traitement des eaux rsiduaires huileuses, bass sur le rsultat des 1er et 2me
objectifs.
4. Dvelopper le prototype du logiciel pour la recommandation de slection du procd,
le design des units procd et la simulation du plan de procd de traitement des eaux
rsiduaires huileuses.
Sommaire des procds de traitement des eaux rsiduaires huileuses

Les trois premiers objectifs sont accomplis dans la Partie 1 la Partie 3 de cette thse.
Tous les filires de procd de rcupration dhuile, tudies dans le laboratoire GPI, avaient
t rexamines ; et ses modles mathmatiques correspondantes aussi bien que la limitation
du design et les paramtres influents avaient t tablis. Ces procds qui sont rexamins
sous les buts et objectifs du travail de cette thse sont ;
1. Lcrmeur dshuileurs
Ce dispositif est dvelopp pour rcuprer slectivement la couche dhuile de la
surface de leau sans entranant de leau avec lui. On a trouv que le moyen pour raliser la
bonne slection dhuile dpend de lnergie de surface ou de la tension superficielle critique
du matriel crmeur. Le matriel avec la basse tension superficielle critique convient tre
utilis comme matriel crmeur.
[1]
Sommaire
Les modles mathmatiques de deux types dcrmeur : le tambour et le disque

dshuileurs sont vrifis ;
Pour le tambour dshuileur,
P=
0.486
3.035D1.541N1.541 o
L
m3/s
g 0.514
{1.1}
Pour le disque dshuileur,

P=
3.464N1.541 o
g 0.514
0.486
(0.5 D )2.54 (0.5 D I ) 2.54 m3/s
{1.2}
P = Productivit en huile du tambour ou du disque (relative une

surface) (m3/s)
D = Diamtre du tambour ou du disque (m)
N = Vitesse de rotation (rev/s)
2
o = Viscosit cinmatique de lhuile (m /s)
L = Largeur du tambour (m)
I = Hauteur dimmersion totale du disque dans le liquide (m), I
D/2.
g = Acclration de la pesanteur (m/s2)
o =
Tension superficielle tension de lhuile (kg/s2

dyne/cm)
or N/m = 1000
Tambour
Disque
Racleur
Moteur
Goulotte
de collecte
Vis dArchimede
Racleur
Nappe dhuile
Phase aqueuse
Fig. 1-1 Tambour dhuileur
Fig. 1-2 Disque dhuileur (Par: Abanaki)
Les modles sont valides dans ces hypothses ;

La tension superficielle de lhuile est dans lintervalle de 27 34 dynes/cm, ce qui
couvre pratiquement toute huile ordinaire.
Le nombre capillaire (Ca = o V/o) est de 0.04 3.6.
La densit de lhuile est denvirons 0.79 0.83 kg/m3. La viscosit dynamique dhuile
exprimente est entre 1.35x10-3 et 291x10-3 (N.s)/m2 (1.35-291 cp).
[2]
Sommaire
Pour le tambour dshuileur, la vitesse priphrique ne devrait pas tre suprieure de

0.8 m/s. En fin dviter lentranement deau, la vitesse de 0.44 m/s ou moins est
recommande.
Pour le disque dshuileur, la vitesse priphrique ne devrait pas tre suprieure de 1.13
m/s. En fin dviter lentranement deau, la vitesse de 0.5 m/s ou moins est
recommande.
Les modles se prouvent valides pour les crmeurs faites de SS, PP, PVC et PTFE.
2. Le Dcanteur
Sa thorie importante, savoir la loi de STOKE, est cite. Selon cette thorie, les
gouttelettes peuvent tre rcupres condition quelles entrent dans le dcanteur la
distance ascensionnelle ncessaire pour atteindre la surface de dcantation, comme la surface
de leau ou la surface de lintercepteurs dhuile intrieurs, avant dtre entranes hors du
rservoir par leau. Daprs ce concept, la relation typique de la taille de gouttelette et son
efficacit de sparation par classe de goutte (d) est comme celles montres dans la fig. 2-1.
L
ENTREE
SORTIE
Q
V
d > dc
API
PPI (n plaques)
H, D
U
d = dc
d < dc
L
H1
Zone 1
d < dc
Zone 2
H2
d = or > d c
d
La cellule Spiraloil
(section transversale)
Hauteures sont
differentes.
dc
Figure. 2-1 Schma et courbe caractristique de lefficacitdun dcanteur
Les modles mathmatiques gnrales pour les procd de 3 varits diffrentes, cest-dire le dcanteur classique (API), le dcanteur lamellaires (PPI), et le dcanteur compacte
(Spiraloil) sont proposes et vrifies :
Pour d diamtre coupure, dc
Pour d dc
d = 100 %
d =
Ud
100 %
U dc
La vitesse ascensionnelle dune

g d 2
Ud =
gouttelette (Ud)
18 c
{2.1}
{2.2}
{2.3}
La diamtre de coupure, cest--dire la plus petite taille de gouttelette dont lefficacit de

sparation est de 100%, est dtermine par les quations suivantes,
1/2
Le dcanteur simple,
{2.4}
18HQ c
(A = aire ecoulement, Q = debit d c =

gLA
deau)
[3]
Sommaire
Le PPI,
dc
Pour un dcanteur compact qui

hauteur de dcantation nest pas
bien connu.
dc
1/2
18Q c
=
gS (N + 1)
P
1/2
18Q
c
=
g S
d
{2.5}
{2.6}
Les modles sont valides condition que la loi de STOKE soit valide (Re = 10-4 1).
Pour le PPI, si les plaques sont inclines, le paramtre Sd dans lq. 2.5 sera remplac par
Sp cos (pour les plaques horizontales, = 0o). Le Sd , pour le dcanteur compacte, est
lespace totale de la surface de dcantation qui peut intercepter de lhuile, sans regardant aux
distances ascensionnelles des goulettes dhuile.
3. Le Coalesceur
Le coalesceur est le procd de sparation acclr, conu pour favoriser la
coalescence entre les gouttelettes dhuile en but de former les plus grosses gouttelettes
dhuile. Selon la loi de STOKE, la vitesse ascensionnelle est proportionnelle au carr de
diamtre de la gouttelette. Ainsi, en agrandissant la taille de la gouttelette, lefficacit de
sparation dhuile est augmente considrablement.
A partir du coalesceur de lit granulaire, AURELLE a propos que les mcanismes de
fonctionnement du coalesceur puissent tre diviss en 3 tapes ;
1re tape : La Transportation, qui se constitue de 3 phnomnes de transport

principaux : la sdimentation, linterception directe et la diffusion. Le modle
mathmatique de chaque phnomne est bas sur le modle de filtration. Ces modles
fournissent les ides claires concernant les paramtres influents sur la performance du
coalesceur.
2me tape : LAdhsion-Coalescence. Lefficacit de cette tape dpend

principalement de la mouillabilit du matriel coalesceur.
3me tape : La Relargage de la phase disperse. Cette tape dpend de 4

paramtres, i.e. la mouillabilit du matriel coalesceur la surface de relargage, la
vitesse dcoulement, la tension interfaciale, et la proportion de la phase disperse et
la phase continue dans lmulsion traite.
SORTIE:
Goutte grosse
Le diametre du collecteur
=dp,
Coefficient de vide =
H
ENTREE:
Gouttelette
Dia. = d
La surface de relargage
La grilles
Fig. 3-1 Schma dun coalesceur
[4]
Sommaire
Lignes de courant
Collecteur
Gouttelette
V U
V
U
U= Vitesse ascensionalle
V= Vitesse decoulment
a) Transport par interception
b) Sdimentation
c) Diffusion
Fig. 3-2 Schma des 3modes de transport de ltape 1

Les mcanismes 3-tapes peuvent tre utiliss galement pour dcrire la
performance dautres types du coalesceur, par exemple le coalesceur de lit fibreux et celui de
lit dynamique. Toutefois, pour la prdiction de lefficacit par classe de goutte, les modles
empiriques sont recommands car elles sont vrifies par un ensemble de donnes plus large.
Les modles empiriques, vrifies par le biais dune gamme de donnes relativement
large, sont proposes pour les coalesceurs de 4 varits : coalesceur de lit granulaire,
coalesceur fibreux type brosse, coalesceur fibreux dynamique (brosse tournante), et
coalesceur fibreux nonordonne (laine dacier). Veuillez noter que lefficacit calcule
suprieure de 100% sera compte pour 100%.
Pour le coalesceur de lit granulaire,
dpV 0.08 d 0.09 0.09
H
d
= (0.58( ) 0.2 ( ) 0.12 ( c
)
( )
( )
) 100%
d
c
c
dp
dp
o/w
{3.1}
La diemtre de collecteur (dp) = 0.36 - 0.94 mm.

Tension interfacielle (ow) = 11 - 42 dyne/cm.
Vitesse dcoulement (V) = 0.09 - 0.54 cm/s.
La diffrence de mass spcifique entre deux phases (huile/eau) () = 83 - 314 kg/m3.
Le lit est oleophile.
La concentration initiale de hydrocarbure < 1,000 mg/l.
Pure le coalesceur fibreux,
d
VD
d
0.35 H 0.694
= (104.5( c ) 0.77 ( ) 0.18 ( F ) 0.18 (1 )
( )
) 100 %
d
c
D
D
D
[5]
{3.2}
Sommaire
48 < Re < 1100. Re est le terme (cVD/c) dans lquation. 1 < H/D < 10.
La diamtre de coalesceur (D) est environ 5.0 cm. Pour le coalesceur de diamtre
important, il y a un risque de court-circuit par entrainant despassages prfrentiels le long
des parois du coalesceur.
Le modle est valide pour la diamtre de gouttelette (d) de 1 micron ou plus.
Vitesse dcoulement (V) est entre 0.5 et 2.0 cm/s (1.8 - 120 m/h).
Le diamtre de fibre (dF) = 100 - 200 microns.
Coefficienct de vide () est 0.845 - 0.96.
La concentration initiale de hydrocarbure < 1000 mg/l.
Les lits sont de type brosse et sont oleophiles.
Pour le coalesceur dynamique (ou brosse tournante),
=(
0.67d 0.58 (1 ) 0.35 H0.35 N0.53

) 100 %
D0.03 d 0.58 V0.74
F
{3.3}
Les modles sont valides dans ces hypothses,
52 < Re < 1164. Re est le terme (cVD/4c) dans lquation. 1 < H/D < 2.
Vitesse de rotation (N) = 0.167 - 3.33 rps (10 to 200 rpm).
Vitesse dcoulement (V) = 0.1 - 1.1 cm/s (3.6 to 39.6 m/h).
Diamtre de fibre (dF) = 100 - 300 microns.
Diameter de coalesceur (D) < 11.5 cm.
Le modle est valide pour la diamtre de gouttelette (d) de 10 microns ou plus.
Les lits sont de type brosse et sont oleophiles.
Pout le coalesceur fibreux non-ordonne (laine dacier),
d = ( 3 . 35 (
cVD 0.23 d 0.03 d F 0.. 03 H 0.36

)
( ) ( )
( ) ) 100 %
c
D
D
D
Les modles sont valides dans ces hypothses,
Re est entre 840 - 2470.

La diamtre de fibre (dF) = 40-75 microns.
Coefficient de vide () est environ 0.95.
La diamtre de coalesceur (D) = 5 cm.
La hauteur dintercepteur tournant (H) = 0.07 - 0.21 m.
Vitesse (V) = 1 - 2.5 cm/s (36 to 90 m/h).
Le modle est valide pour la diamtre de gouttelette (d) de 1 microns ou plus.
La concentration initiale de hydrocarbure est environ 1000 mg/l.
Le lit est oleophile.
[6]
{3.4}
Sommaire
Les modles des pertes de charge sont aussi proposes ;

Pour le coalesceur granulaire, lquation de Kozeny-Carmans est propose,
180 H cV (1 ) 2
m
g dp 2 3
= 0.13 0.23.
{3.5}
P=
Pour les coalesceurs fibreux, lquation de Hazen-William est utilise,

1.85
{3.6}
1.167
V 5L

m
P = 6.82
C HW D
CHW = 130. L = hauteur de lintercepteur.
Finalement, plusieurs ides initiatives pour amliorer la performance du coalesceur,

cest--dire lutilisation du guide pour augmenter la concentration dhuile entrante du
coalesceur et lutilisation du matriel de lit mlange dans le coalesceur de lit granulaire pour
traiter simultanment la mlange dmulsion directe/inverse, sont ralises.
4. La flottation air dissous
La flottation air dissous est le procd de sparation acclr, qui sopre par
laugmentation de la diffrence masse volumique entre la phase continue et la phase
disperse. Ceci est accompli moyennant la cration des bulles du gaz ou de lair dans les eaux
rsiduaires en fin de favoriser la formation des agglomrats air-solides ou air-huileux.
Le modle mathmatique bas sur le concept de filtration, propos par SIEM est
rexamin. Ce modle est utile pour comprendre les effets des paramtres influents sur la
performance de la DAF. Les quations de gnralisation du modle de SIEM, fondes sur la
thorie de lquilibre de population, sont tablies dans cette thse pour agrandir la gamme
valide du modle de SIEM et, donc couvrir la gamme des eaux rsiduaires huileuses
frquemment trouve. Les modles sont comme montrs ci-dessous ;
V
Concentration after
intercepted by bubbles
= C- dC
x
Ub
Hauteur de la colonne
=H
Vitesses decoulement = V Taille de bulle = db
Vitesse relative = Vr
Ud
dH
Bulle
Gouttelette
Concentration
=C
(en tenant compte
de la dilution)
Section de la
colonne = Ao
Fig. 4-1 Representation schmatique de vitesses at vitesse relative et schma de la

colonne flottation
[7]
Sommaire
Vr= vitesse relative decoulement

Ur= vitesse relative de decantation
Ur
Vr
Vr
Ur
Gouttelette
Bulle
Lignes de
courant
a) Interception directe
b) Sdimentation
c) Diffusion
Fig. 4-2 Schma des 3modes de transport
SIEMs model,
d , ref = (1 e
3
H
( exp )
)
2 AV
db
( exp ) = 0.009005( theo )
) 100 %
{4.2}
theo = sed + Int + diff
{4.3}
3 d
Int = ( ) 2
2 db
gd 2
sed = oil / water

18 cVr
KT
Diff = 0 . 9(
)2 / 3
dV r d b
{4.4}
{4.5}
{4.6}
air / water gd b2
Vr = U b =
18 c
{4.1}
0.5919
{4.7}
c =
K =
Viscosit de phase contenue (eau) (L2/T)

Constante de Boltzman (1.38*10-23)
T
db
d
Vr
Temprature absolue (Kelvin)

Taille de bulle (L)
Diamtre de gouttelette (L)
Vitesse relative enter des bulles et des gouttelettes (L/T)
=
=
=
=
Quant lquation de gnralisation du modle de SIEM, fonde sur le concept de

lquilibre de population, sa forme gnrale est comme montre ci-dessous. Le 2, ref est la
constante, calcule par d,ref dans le modle de SIEM. Mais, le point cl est le moyen
dadapter la valeur de et pour sapproprier la condition du design et contribue la
prdiction correcte de lefficacit, cest--dire, utiliser le de SIEM avec le design , ou viceversa, dans la calcul. La logique est assez complique pour rsumer en un paragraphe court, et
donc nest pas cite ici. Pour de plus ample information, veuillez consulter le rapport principal
de la thse (Chapitre 6, Partie 3). La logique est dailleurs disponible dans le logiciel.
[8]
Sommaire
d = (1 e
( 2 , ref )
{4.8}
) 100 %
Les quations pour le design du pressurisateur ou du systme de leau pressuris

sont aussi proposes et vrifies dans cette thse ;
La concentration du gaz dissous,
Conc .( gas ) = y P MW ( gas ) H '
mg/l
{4.9}
Le dbit du gas ou d air dgaz,

= y H 'R Q ( P P atm ) T ( 0 . 082 10
/( mol K ))
m3/s
{4.10}
o H = constante de Henry (molair/(m3water-atm)) et y = fraction molaire du gaz

dans lair. Pour lair, y = 1.
La consommation nergtique de la compresseur,
Power =
Q pw ( P Patm )
pump
Q pw P( gauge )
pump
Watt
{4.11}
La consommation nergtique du pressurisateur au dbit Qpw,

Power
comp
1 . 4 1
)
(
R air T P 1 . 4
Conc ( gas ) Q
1
pw
MW ( gas )
0 . 4 Patm
Watt
{4.12}
O Rair = Constante universal du gaz. T = temprature absolue

5. LHydrocyclone
Lhydrocyclone est le procd de sparation acclr. Son concept de travail principal
est de remplacer lacclration gravitationnelle qui dirige la vitesse de dcantation au moyen
de lacclration centrifuge suprieure. MA et AURELLE ont propos une approche nouvelle
de prvoir lefficacit hydrocyclone, appele le modle danalyse trajectoire pour
lhydrocyclone biphasique (liquide-liquide), fonde sur la loi de STOKE. En fait, ce modle
peut prvoir, par lquation thorique, lefficacit de sparation par classe des gouttelettes
dhuile de toute taille dans les eaux rsiduaires ; la diffrence des autres modles qui sont
bass sur les concepts du modle empirique et de la similarit. Ainsi, il est trs pratique de
comprendre leffet des paramtres relis la performance dhydrocyclone. Le modle est
constitu des quations qui dirigent 3 lments de vitesse des gouttelettes dhuile lintrieur
du cyclone, comme montr ci-dessous.
R
d dR L dZ
=
U 0W
R
zvv
d 2 V 2
U=
18 R
Q D n 0.65
V=(
)(
)
D 2 R
i
{5.1}
{5.2}
{5.3}
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
[9]
R
+ 1.19
Rz
{5.4}
Sommaire
Wz =
{5.5}
(0.5D n Z tan( / 2)) 2

D
R z = n Z tan( )
2
2
0.25( D n )
L=
tan(1.5 o / 2)
{5.6}
{5.7}
Pour le hydrocyclone de type THEW, quand Z = L:

{5.8}
RVZZ = 0.186( Dn / 2)
R
Paroi
s
0.5Dn
Rd
d > dc
d < dc
LZVV
d = dc
0.186Dn
d
100%
Zone 1
Zone 2
d = or > d c
d < dc
dc
Fig. 5-1 Trajectories of oil droplets and typical efficiency curve

from trajectory analysis model
Lefficacit par classes peut tre calcule par les relations:
Pour d diamtre de coupure,dc
Pour d < dc
d = 100 %
Dn 2
)
2
d =
100 %
D
D
( n ) 2 ( 0 . 186 n ) 2
2
2
Rd2 ( 0 . 186
{5.9}
{5.10}
Les modles sont valides dans ces conditions,
Veuillez noter que les quations sont fondes sur la gomtrie dhydrocyclone liquideliquide initie par Professeur THEW, en Angleterre. Pour les utiliser avec dautres
types dhydrocyclone, certaines constantes numriques (par exemple 0.63, 3.33, etc.)
dans les q. 5.3, 5.4 et 5.8 doivent tre rexamines pour sapproprier aux gomtries
nouvelles.
Le modle est valide pour la taille des gouttelettes (d) de 20 microns et plus.
Les quations sont valides pour lhydroclone ayant seulement 2 entres.
[10]
Sommaire
Le dbit de purge huile surverse (Qoveflow) est gnralement petite, pas plus de 10%.
Son effet sur les profils de vitesse et defficacit est petit, et donc, ngligeable. La
Qoveflow recommande est de 1.8 2 fois du dbit entrant de lhuile.
Le modle tend prvoir lefficacit plus basse quand d < d80%, et celle plus haute
quand d > d80%. Lerreur dans la prdiction de la diamtre de coupure est environs
10-20%, cest--dire, si la diamtre de coupure prvue est 50 microns, la diamtre de
coupure constate devrait tre environs 40-45 microns. Pour de plus ample
information, veuillez consulter la rfrence.
MA et AURELLE a galement invent une nouvelle type dhydrocyclone pour la

sparation simultane de lhuile, des matires en suspension (MES) et de leau, appele
lhydrocyclone triphasique. Le modle pour cet hydrocyclone est tabli nouvellement dans
cette thse et galement bas sur le concept danalyse trajectoire.
Solid-liquid
Liquid-liquid (de type Thew)

Di
Du
D Do
Dp
Ds
L4
L3
L1
L5
L3
Note: Di/D=0.25 pour 1- entre et 0.175 for 2- entre, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid :angle =12o, liquid-liquid angle =1.5o
Fig. 5-2 Hydrocyclone triphasique

Entree
Purge huile
Sortie eau
Purge MES
Entree
Fig. 5.-3 Trajectoires de lhuile (sphere) and MES (cube) dans le hydrocyclone triphasique
Solide-liquide
(RIETEMA)
Liquide-liquide
(THEW)
Fig. 5-4 Profils des vitesses axiales dans le hydrocyclone triphasique
[11]
Sommaire
Gnralement, les quations pour lhydrocyclone triphasique sont similaires celles

pour lhydrocyclone biphasique avec un peu de modifications, cest--dire ;
Remplacer lq. 5.3 par lq. 5.11.
(Q/2) D
( n ) 0.65
V = 0.676
D2 R
4 i
{5.11}
Remplacer, dans lq. 5.1, Dn par Do et L par L5 .
Pour lefficacit solide-liquide, elle peut tre calcule par le model de RIETEMA ou
dautres modles compatibles dont la partie solide-liquide de lhydrocyclone est conforme la
gomtrie de lhydrocyclone de RIETEMA.
Finalement, les quations de la fuite de pression ou la perte de charge pour
lhydrocyclone biphasique ou triphasique sont tablies dans cette thse :
Pour lhydrocyclone biphasique, la perte de charge dans lentre/surverse (Po) et
lentre/sousverse (Pu) peuvent tre calcule par les quations suivantes,
Q 2.3 2.6
Po = 16 4
Dn (1 R f )
Pu = 4 . 6
0.1611
bar (V : m/s et D : meter)
Q 2 . 2 bar
Dn 4
{5.12}
{5.13}
Pour lhydrocyclone triphasique, la perte de charge entre lentre et la sortie dhuile

(Poil), entre la sortie deau (Pw) et la sortie de MES (PSS) peuvent tre calcule par les
quations suivantes,
Pwater = 49.8
Pss = 21
Q 2.12 bar
D4
{5.14}
Q 2.34
bar
D4
{5.15}
Q 2.03 bar
D4
{5.16}
P = 55
oil
6. Les procds membranaires

Le principe de travail
Le procd membranaire est le procd de sparation qui est bas, principalement
mais non entirement, sur le concept de filtration. Physiquement, la membrane est le matriel
permable ou semi-permable qui restreindre la motion de certaines espces. Thoriquement,
on peut toujours sparer certains composants dmulsion condition que la membrane choisie
convient la diffrence dimensionnelle.
[12]
Sommaire
Fig. 6-1 Classification des techniques membranaires de filtration selon la taille des pores
(Par Osmonics)
Les applications des procds membranaires, cest--dire, la microfiltration (MF),
lultrafiltration (UF), le nanofiltration (NF) et losmose inverse (OI), au traitement deaux
rsiduaires huileuses dans le laboratoire GPI ont t rexamines. Plusieurs techniques utiles
manant de ces recherches sont raliss et les techniques de calcul sont tablies dans cette
thse :
Laugmentation du flux pour lUF dans le traitement dmulsion de lhuile de

coupe par la dstabilisation partielle. Laddition du sel, de moindre quantit
que celle pour la dstabilisation totale, dans lalimentation contribue
laugmentation du flux de permat, et donc conomiser la consommation
dnergie ainsi que la taille de la membrane. Linconvnient de ce technique,
inclus dans cette thse, est que lhuile dstabilise peut colmater la membrane
si elle nest pas correctement partitionne ou spare du courant dalimentation
recircul.
La rgnration de la membrane UF aprs le traitement de lhuile de coupe

par la micromulsion. Il peut efficacement laver de lhuile accumule ou les
foulants restant sur la membrane. Il peut tre rutilis pour plusieurs fois
jusqu ce quil est satur par lhuile.
Le technique pour gnraliser les donnes de la performance UF dans une

seule condition pour couvrir des autres conditions, bas sur la combinaison du
modle de la couche de gel et modle des rsistances en srie. Ce technique
est propos et vrifi dans cette thse. Il est utile quand les donnes limites sur
des eaux rsiduaires examines sont disponibles. Il nous permet destimer
lvolution du dbit ainsi que celle du volume de permat en fonction du
temps, lequel est utile pour le design du procd.
[13]
Sommaire
Le technique pour prvoir le dbit du mlange de 2 mulsions diffrentes. Ce

technique est galement propos et vrifi dan cette thse. Il est utile quand
lmulsion mlange peut tre prvue et sa proportion tend varier.
Retentat
Po
Reservoir
dalimentation
Membrane
Pp
Permeat
Pi
Alimentation
pompe Echangeur de chaleur
Fig. 6-2 Schma de lunit ultrafiltration tangentielle en batch
Quant au modle mathmatique des procds membranaires, on met laccent sur le
modle de lUF dans lopration batch car il joue un rle majeur dans le traitement deaux
rsiduaires huileuses. On a adopt deux modles largement utiliss : le modle de la couche
de gel et le modle des rsistances en srie. Les quations des deux modles sont comme
montres ci-dessous,
Le modle de la couche de gel
J = kV ln(
Cg
C
) l/(m -h)
{6.1}
Le modle de rsistance en srie,

J=
Pt
l/(m2-h)
R ' m + V Pt
{6.2}
Les valeurs de k, ,, , Rm, et Cg varient selon les caractristiques des eaux

rsiduaires et les types de la membrane.
7. Le procd thermique
Lintrt principal du procd de ce type est la distillation htroazotropique (DH).
Lapplication de la DH au traitement des slops de raffinerie ainsi que des retentats issus de
lUF de lhuile de coupe est ralise par LUCENA et AURELLE. Le procd est accompli par
laddition du produit chimique qui favorise la formation azotropique (appele extractant),
gnralement les hydrocarbures, dans leau rsiduaire. Ceci rduira la temprature dbullition
du systme, et donc conomisera lnergie. Ces applications apportent la possibilit de
revaloriser ces matriels rsiduaires potentiels. Son application inverse, savoir le stripping
(pour rcuprer la substance volatile de leau au moyen de laddition du vapeur), est
galement ralise.
Lhtroazotrope est lun des phnomnes lis au quilibre vapeur-liquide-liquide
(VLLE). Le diagramme isobare du mlange immiscible htroazotropique est dmontr dans
la figure 7-1. Il est constat que la courbe de bulle de ce diagramme est reprsente par une
ligne horizontale la temprature constante, appele la temprature azotropique . A
cette temprature, les deux liquides dans le mlange vaporent, quelle que soit la composition
du mlange. La composition de la vapeur est toujours yH jusqu ce que il reste seulement une
espce de liquide dans la phase liquide.
[14]
Sommaire
P = const.
T
A
Point debullition
de B
TH B
Vapeur (V)
Eau + V
Huile +V
Azeotrope (H)
Huile pur
yw,6
yw,5
xw,2
yw,1 to yw,4
= yH
xw,1
xw , yw
xw = 0
yw = 0
xw,6=1
xw,5=1
xw,3 xw,4=1
xw,1
Huile+eau
Point debullition
deau
D
xw = xH
yw = yH
Eau pur
xw = 1
yw = 1
Fig. 7-1Diagramme dquilibre isobar: temprature-concentration de leau residuaires

huileuses
Dans le cas des eaux rsiduaires huileuses, spcialement celles concentres comme le
slop ou le retentat de lUF drivant de lUF de lhuile de coupe, si lextractant est choisi
correctement, elles formeront une condition azotropique et, pendant son vaporation, extraira
le teneur en eau des eaux rsiduaires. Leau sera extraite jusqu ce que le rsidu devienne
lhydrocarbure sans eau. Le vapeur condensera pour former le distillat contenant deux
couches spares du extractant (la couche suprieure) et leau (la couche infrieure) de la
composition xH (= yH). Plus la valeur de yH est haute, mieux la capacit de lextraction deau
est. Les donnes thoriques de yH, bases sur la loi de Raoult et la loi de Dalton, sont
galement proposes comme montres dans la table 7-1.
Table 7-1 Heteroazeotropic temperature and composition des certaines hydrocarbures
Extractant
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
Molecular
weight
(g/mol)
56
100
114
128
142
156
170
184
198
212
226
TH
(deg. C)
yH
(by molar)
61.6
79.2
89.5
94.8
97.6
98.9
99.5
99.8
99.95
99.999
100
0.209
0.452
0.616
0.827
0.914
0.959
0.98
0.991
0.996
0.998
0.999
yH
y H observed
(by volume) (by volume)
0.0351
0.0922
0.188
0.3255
0.495
0.6663
0.7953
0.890
0.9542
0.9702
0.9840
0.468
0.767
Les quations utilises dans le calcul de lentraneur ou extractant, dans le cas des
eaux rsiduaires huileuses et la vapeur, dans le cas du stripping, sont comme montres cidessous,
[15]
Sommaire
(1 y H )
yH
yH
= Volume pollu tan ts
(1 y H )
Volume entrainer = Volume water
{7.1}
Volume
{7.2}
steam
8. Le procd chimique
Au cas o les eaux rsiduaires huileuses contiennent lmulsion stabilise, cest--dire
la macro/micromulsion, les tailles des gouttelettes sont si petites et stables quelles ne
peuvent pas tre spares par les procds bass sur la loi de STOKES, par exemple le
dcanteur, le coalesceur ou lhydrocyclone. A moins que les procds membranaires ou
thermiques soient appliqus, les gouttelettes doivent suivre un procd chimique qui dtruit
sa stabilit et favorise la coalescence de ces gouttelettes. Ainsi, le procd chimique dans ce
cas sappuie sur la dstabilisation chimique et la coagulation/floculation chimique. Selon ces
recherches, on peut conclut que la stabilit de lmulsion est fonde sur les facteurs suivants,
La barrire lectrique, laquelle peut tre dcrite par la thorie DLVO et la

thorie de la couche double, comme montre dans les figures 8-1 et 8-2.
La barrire strique, cause par la localisation des molcules tensioactives la

surface des gouttelettes dhuile. Elle sagira comme un film qui empche la
coalescence des gouttelettes.
En fin de dstabiliser lmulsion, les deux barrires doivent tre limines. Selon les
recherches du GPI, le mcanisme de dstabilisation (ou cassage) de lmulsion par laddition
de plusieurs produits chimiques, cest--dire du sel monovalent, des sels bivalents, les
polylectrolytes, lacide et les agents adsorbants, sont rexamines. Les mcanismes de
dstabilisation des ces produits chimiques, fonds sur lmulsion stabilise par les agents
tensioactifs anioniques, sont rsums comme ci-dessous,
Les produits chimiques monovalents : Le procd principal de

dstabilisation est fond sur la rduction de la couche diffuse au moyen de
laugmentation des ions chargs opposs. Linconvnient principal des
produits chimiques de ce groupe est la formation du saline ou des polluants
acides au terme de la dstabilisation. Les exemples de ces produits chimiques
sont NaCl, H2SO4.
Les produits chimiques bivalents : Le mcanisme principal de

dstabilisation est bas sur la prcipitation des tensioactifs ; lquilibre des
tensioactifs est donc modifi. Les tensioactifs focalisants la surface des
gouttelettes dhuile seront retransmis dans la phase deau. Ainsi, la
gouttelette est dstabilise. La performance est dirige par le produit de
solubilit des tensioactifs. Les exemples des produits chimiques sont CaCl2,
MgSO4 et MgCl2. Mme si la dose requise pour ce cas est infrieure celle
des produits chimiques monovalents, elle cause encore les polluants
rsiduaires de saline. Des sels organiques, comme le formiate de calcium
(Ca(COOH)2) seraient plus intressants car les polluants rsiduaires sont
(COOH)2 qui est organique et biodgradable.
[16]
Sommaire
+- - -+ - +
+
+
+
+ - Huile +
+
+-- tensioactif
+
+ + - -(TA)- - - +
+
+ + + +- - + +
+
Couche Stern
+
+
- +
- +
- +
-
+
-
- +
+
+
+
+
Couch de diffusion
+
Plan de cisaillement
+
+
Potentiel
+
+
+
- +
Huile avec
agents TA/COTA
+
+
-
Potentiel de Stern
Potentiel zeta
Couch de
diffusion
Distance
Couch Stern
+ Ion de charge positif avec

la solvation deau
Fig. 8-1 Diagramme de potentiel lectrique de gouttelette

Force repulsive
Repulsive electrostatique
+ Force attractive de
Force total
+
+- - -+ - + Van Der Waal
+- - -+ - +
+
+
+
-- +
++(court)
+
-+
+
-+
-+ + Gouttelette
+ + Gouttelette
--- +
+
+
+ Repulsive + + +- - + +
+
+ +
+
+ electrostatique +
(Long)
Force de
Val Der Waal
Distance
Force attractive prevaloir

Force attactive
Fig. 8-2 Interaction et bilan de forces entre gouttelette
Les lectrolytes multivalents : Les mcanismes principaux de dstabilisation

sont une combinaison de la prcipitation des agents tensioactifs et la
coagulation de type sweep. La concentration relle est donc moins que
celle calcule uniquement sur le produit de solubilit et est gnralement le
moins des trois premiers lectrolytes. Les exemples de produit chimique de
ce type sont le chlorure ferrique (FeCl3) et le sulfate daluminium.
Les agents tensioactifs de la charge oppose : Le mcanisme principal de

dstabilisation est ladsorption et la neutralisation de la charge. Le surdosage
doit tre vit pour prvenir la restabilisation de lmulsion par linversion
des charges lectriques. Les exemples des agents tensioactifs cationiques qui
peuvent tre utiliss dans la dstabilisation de lmulsion sont le chlorure Ncetylpyridinium et des sels de lhydroxyde dammonium quaternaire.
Dans le cas des mulsions stabilises par des tensioactifs nonioniques, le

mcanisme principal de dstabilisation doit se fonder sur la prcipitation des tensioactifs pour
former des composs insolubles. ZHU a propos la mthode classique de la dstabilisation
chimique de lmulsion stabilise par les tensioactifs nonioniques de lacide gras, base sur
laddition des tensioactifs anioniques (comme lakylsulfate des alcools gras) et les
lectrolytes trivalents cationiques (comme le sulfate daluminium, le chlorure ferrique).
[17]
Sommaire
Toutefois, il faut noter que il nexiste pas les produits chimiques et les doses
universels qui sont valides pour toute mulsion. Les types des produits chimiques efficaces,
de la concentration optimal et du niveau des polluants rsiduaires doivent tre valus dabord
dchelle de laboratoire avant le design du procd chimique complet.
En tout cas, lgard des design du racteur, ils sont identiques, quel que soit le
produit chimique appliqu. Ils sont pratiquement identiques au racteur utilis pour la
coagulation/floculation dans le traitement deau. Les quations utilises pour lvaluation du
racteur et de lagitateur, cest--dire 8.1 8.3, sont incluses dans le logiciel.
P
G =
V
P
V
0. 5
{8.1}
Gradient de vitisse (t-1, normalement en sec 1)

Viscosit deau,
Consommation nergtique dagitateur(ML2s-3,e.g. watt)
Volume de racteur (L3)
=
=
=
=
Pour les turbines,

P = N p n3 D5
{8.2}
Pour les pales tournantes ,

nAv 3 C d
G=
2V
Np
n
n
D
A
v
Cd
=
=
=
=
=
=
=
=
{8.3}
Nombre de puissance
Mass volumique de leau use (= celle de leau)
Vitesse de rotation (rev/s) (e.q. 8.2)
Nombre de pales (e.q. 8.3)
Impeller diameter (m)
Surface dune pale (m2)
vitesse priphrique (m2)
Coefficient de trane des pales (normalement = 0.6)
Produit
chemique
Emulsion
M
G = 50 s-1 G = 30 s-1
G = 20 s-1
Separateur
G = 100-300 s-1
Bassin de coagulation
Bassin de floculation
Fig. 8-3 Lexample de design de coagulation-floculation
[18]
Sommaire
9. Les procds de finition

Bien que lhuile soit rcupre de leau par les procds prcdents, il y a
normalement de lhuile laisse dans leau traite. En plus, les polluants dautres formes
gnralement prsents dans les eaux rsiduaires huileuses, surtout les agents tensioactifs/cotensioactifs, sont encore prsents dans leau traite, et contribue au haut niveau de la DOT.
Ainsi leau traite est normalement transmise au procd de finition avant de se dcharger au
corps deau recevant. Deux procds de finition largement utiliss, cest--dire le traitement
biologique et ladsorption sur le charbon actif, sont raliss.
Comme le procd biologique est lui-mme la science majeure, le calcul dtaill
nest pas inclus dans les buts et objectifs du travail de cette thse. Seulement les donnes
utiles sur le procd biologique, concernant le traitement des eaux rsiduaires huileuses, sont
rexamines et incluses dans le rapport principal de cette thse (Partie 3, Chapitre 11).
Les quations du design du filtre CAG, ainsi que la capacit dadsorption (q) de
certains co-tensioactifs, sont rexamines et incluses, cest--dire,
Le temps dopration totale avant le remplacement de lit (tT):
Quand lisotherme (q. VS.C relation) et les donnes du front dadsorption (Qa et Ha
comme les fonctions de C) sont disponible ;
tT =
HA b q Qa
Q (Co Ce )
tT
H
A
{9.1}
=
=
=
=
=
=
q
Qa
Q
Co,Ce
Temps dopration totale avant le remplacement de lit

Hauteur de lit
Section de la colonne
Mass volumique de charbon actif
Capacit dadsorption
Capacit dadsorption disponible dans la zone de
ladsorption
= Dbit
= Concentration initiale et concentration de la solution en
solut en quilibre avec ladsorbant
Quand les donnes mentionnes ci-dessus ne sont pas disponibles ;

E HA b q
{9.2}
tT =
Q (Co Ce )
E est la saturation efficace de lit. La valeur recommande est environs 50-95%.
[19]
Sommaire
ENTREE
Co
Ha
Lit fixe
de
charbon
actif
HT
Ce
Zone
Satured
dadsorption
zone
Ce
H SORTIE
Vitesse =V
Ha
t=0
Co
Regeneration
de lit est necessaire.
t = tT
Fig. 9-1 Evolution du front dadsorption

Temps de sjour ():
=
H
(Q / A)
{9.3}
Perte de charge (P):

La parte de charge peut tre calcule par lquation Kozeny-Carman.
P=
180 H cV (1 ) 2
m
g dp 2 3
{9.4}
10. La mthodologie gnrale pour la slection des procds

En fin de achever le premier objectif, la mthodologie sur la slection du procd
de traitement des eaux rsiduaires huileuses est propos, comme montr dans la table 10-1.
Les filires de procd recommands pour le traitement dmulsion de lhuile de coupe et
lmulsion secondaire, fonds sur les recherches GPI, sont galement proposs, comme
montrs dans les figures 10-1 et 10-2.
[20]
Table 10-1 La mthodologie gnrale pour la slection des procds
Sommaire
[21]
Sommaire
Retentat
Retentat
ENTREE
Po
Membrane
Pp
Po
Membrane
Pp
SORTIE
(Si possible)
Permeate
Buc
dalimentation
Pi
Pi
Pompe Echangeur
de chaleur
Ultrafiltration
TI Echangeur
de chaleur
Pompe Echangeur
de chaleur
Permeat
Retentat
Retentat
Alimentation
Osmose inverse
M
SORTIE
X
Extractant
boue
Recyclage
Chauffage
Distillat
Distillation heteroazeotropic
Bassin daerationClarificateur
Traitement biologique
Fig. 10-1 Schma dune filire de traitement des mulsions dhuile de coupe
huile
ENTREE
Charbon actif
(se necessaire)
SORTIE
huile
M
X
Recyclage
Bassin daerationClarificateur
API
Coalesceur/
hydrocyclone/
coalesceur
Traitement biologique
Fig. 10-2 Schma dune filire de traitement des mulsions non-stabilises
[22]
boue
Sommaire
Dveloppement du logiciel
Lobjectif final de cette thse est de dvelopper un logiciel de design et calcul dune
filire de traitement adopte lpuration des eaux rsiduaires huileuses. Ceci vise valoriser
et appliquer le savoir-faire ainsi que les rsultats importants de la recherche, en les prsentant
de faon conviviale. Pour russir ces objectifs, le logiciel, savoir le logiciel GPI, est divis
en 4 modes majeurs, cest--dire,
Le mode de documentation lectronique : fournit les connaissances de

fond ainsi que une base de donnes utile sur la pollution dhuile et les
procds de traitement. En fait, le textbook dans la Partie 3 est transform en
directoire e-book du logiciel.
Le mode de recommandation du procd : fournit les recommandations

pour restreindre la gamme des procds faisables pour tout influents dbits.
Le critre de slection est comme propos dans les mthodologies dans la
Partie 3, Chapitre 12.
Le mode de design (calcul) : est utilis pour valuer lunit procd. Les
modles utiliss dans le calcul sont comme rsums dans la Partie 3.
Le mode danalyse (simulation) : permet lutilisateurs dintgrer tout

procd de sparation qui est inclus dans la base de donnes du logiciel, en
but dtablir leur propre filires de procd de traitement. Et le logiciel va
simuler la filire de procd pour prvoir lefficacit de chaque unit.
Le logiciel est dvelopp pour tre upgradable . Son architecture compose de la

base de donnes sous forme de fichier texte ordinaire et les sub-programmes . Pour
upgrader le logiciel, il peut se faire facilement en ajoutant les donnes, comme le nom de
nouveau procd et son paramtre de lien ncessaire pour le calcul, la base de donnes. Le
logiciel liera automatiquement le nouveau procd linterface graphique dutilisateur. Quant
au calcul du sub-programme du nouveau procd, il peut tre dvelopp sparment en
utilisant la langue de programmation Visual Basic. Le moyen le plus facile est de copier le
code de source dun procd existant et modifier lquation pour convenir au nouveau
procd. Aprs la compilation dans un fichier excutable, il peut tre copi pour remplacer
lancien fichier de logiciel GPI sans rinstaller le logiciel. Ainsi le logiciel pourrait se
dvelopp davantage jusqu ce quil peut couvrir plus de recherches et procds dans
lavenir. Les interfaces du logiciel pour chaque mode sont comme montres dans les figures
suivantes.
Cette thse est accomplie par les supports considrables de Professeur AURELLE,
mon directeur de thse, et M. Surapol SAIPANICH, PD-G de la socit Progress Technology
Consultants Co.,Ltd. (Thailand). Je suis trs reconnaissant pour leur conseil et
encouragement.
[23]
Sommaire
Main menu
Tool bar
Project window
Main program
Fig 1 Linterface graphique dutilisateur du programme GPI
Fig. 2 Linterface graphique dutilisateur du mode de documentation lectronique
[24]
Sommaire
Fig. 3 Linterface graphique dutilisateur du mode de recommendation
Fig. 4 Resultat du mode de recommendation
[25]
Sommaire
tape 1 Wastewater data input
tape 2 Process selection
tape 3 Process data input
tape 4 Result
Fig. 5 Linterface graphique dutilisateur du mode de design

Calculation button
Basic drawing tool bar
Category selection
Input and result screen

(displayed when double clicking at the icon)
Process selection
Graphic editing area
Fig. 6 Linterface graphique dutilisateur du mode danalyse
[26]
Rsum
Nom : RACHU
Prnom : Srayut
CONTRIBUTION A LA MISE AU POINT DUN LOGICIEL DE CALCUL DE

PROCEDEDS ET FILIERES DE TRAITEMENT DEAUX RESIDUAIRES
HUILEUSE
562 pages
Thse de Doctorat : Science des procds
Spcialit :Gnie des Procds et de lEnvironnement
I.N.S.A. Toulouse, 2005, n
Rsum :
Lobjectif de cette thse est valorisation des diverses recherches dveloppes au sein du
Laboratoire dIngnierie des Procds de lEnvironnement de lINSA dans le domaine
spcifique du traitment des eaux rsiduaires huileuse. Cette thse rsume les diverse
recherchers rlises et permet dtablir une procdure gnrale de calcul associe un Know
-how pour chaque procd tudi qui permet lutilisation de ces connaissances dans la mise
au point dun logiciel spcifique de design et de calcul de fillires de traitemant des eaux
huileuse.
La premire partie du manuscript rsume les principaux rsultats obtenue dans chaque thse
relative au traitement des eaux huileuses ralises dans lEquipe du Professeur Y.AURELLE.
Le deuxime partie est relative la gnralisation des modles et procdures de calcul de
chaque type de procds. Dans cette partie, les modles de calucul proposs dans les diverse
thses sont compars aux autres donnes bibliographiques et gnralisas. Ainsi de nouveaux
modles de calcul sont proposs dans les cas o aucun modle nexist o dans les cas
spcifiques o les modles existants ont besoin dtre modifis.
La troisime partie permet dtablir un textbook qui intgre tous les rsultats significatifs de
chaque procd ainsi que leur procdure gnralise de dimensionnement et leurs limitations.
Ce textbook prend en compte les divers procds de deshuilage des eaux susceptibles dtre
intgrs dans une filire de traitement savoir : les deshuileurs de surface ou crmeurs de
type tambours et disques dhuileurs, les dcanteurs, les coalesceurs, les flottation air
dissous, les hydrocyclones, les procds membranaires, les procds thermique type
distillation htroazotropique, les procds biologiques ainsi que ladsorption sur charbon
actif. Enfin ce textbook propose une mthodologie gnrale permettant la slection des
procds selon le type deaux huileuses traiter.
La dernire partie de la thse propose le dveloppement dun logiciel spcifique et original de
design et calcul dune filire de traitement adapte lpuration des eaux rsiduaires huileuse
notamment de lindustrile ptrolire sappuyant sur le textbook prcdent.
Mots cls : Dshuiluer, Dcanteur, Coalesceur, Flottation, Hydrocyclone, Membrane,
Distillation, Dstabilisation, Traitement biologique, Absorption, Logiciel, Eaux huileuses
Jury et date de soutenance : 16 Dcembre 2005 l'I.N.S.A. de Toulouse
M. D. HADJIEV
Professeur, IUT, Lorient
Rapporteur
M. J. ROLS
Professeur, UPS, Toulouse
Rapporteur
M. Y. AURELLE
Directeur de thse
M. A. LINE
Directeur du LIPE
M. R. BEN AIM
Professeur Emrite, INSA Toulouse
M. S. SAIPANICH
PDG, Progress Technology Consultants Co., Ltd., Thalande
M. H. ROQUES
Professeur Emrite, INSA Toulouse
Invit
Dpt la Bibliothque Universitaire en 4 exemplaires.
Nom : RACHU
Prnom : Srayut
COMPUTER PROGRAM DEVELOPMENT FOR OILY WASTEWATER

TREATMENT PROCESS SELECTION, DESIGN AND SIMULATION
562 pages
Thse de Doctorat : Science des procds
Spcialit :Gnie des Procds et de lEnvironnement
I.N.S.A. Toulouse, 2005, n
Rsum :
The aims of this thesis is to summarize the researches of GPI lab on oily wastewater
treatment processes and establish general design procedure and consideration for such
processes, and then, value and maximize the use of these established knowledge in the form
of computer program.
The first part of the thesis contributes to reviewing the related researches in GPI lab,
directed by Prof. Y. AURELLE. Significant finding of each thesis is realized.
The second part of the thesis is generalization of models. In this part, models proposed
in the researches are cross-verified with other researches and generalised. New models are
also proposed when there is no existing model or the existing models need to be revised.
The third part of thesis contributes to composure of a textbook that includes all
significant finding from every research as well as the generalized models and their limitations
of every process found in the second part. The textbook includes these processes, i.e.
skimmer, decanter, coalescer, dissolved air flotation, hydrocyclone, membrane processes,
thermal process, chemical process, biological treatment and carbon adsorption, as well as
guideline for process selection.
The final part of the thesis is program development. The program developed in this
thesis consists of 4 main features, i.e. process recommendation for the wastewater being
considered, design of unit process, simulation of process train and provision of knowledge on
process design in the form of e-book, based on the text book in the third part.
The textbook, the program and its source code may be available upon request. For
more information, please contact Pr. Y. AURELLE or gpi_program@yahoo.com
Mots cls : Skimmer, Decanter, Coalescer, Dissolved air flotation, Hydrocyclone, Membrane,
Distillation, Destabilization, Biological treatment, Adsorption, Program, Oily wastewater
PRODUCTION SCIENTIFIQUE
Publications dans des actes de congrs avec comit de lecture, sur texte complet
S. Rachu, Y. Aurelle, S. Saipanich .
Simulation program on hydrocarbon polluted wastewater treatment processes
16th International Congress of Chemical and Process Engineering (CHISA 2004),
Prague, Czech Republic, 22-26 August 2004
A mes Parents
et toute ma famille
Remerciements
Je
m'avoir
remercie
accueilli
sincrement
dans
Monsieur
son
quipe,
le
professeur
pour
m'avoir
Yves
fait
AURELLE
pour
partager
ses
connaissances et ses ides innovantes et pour son assistance tout au long

de ce travail.
I would like to thank Dr. Surapol SAIPANICH for his overwhelming
support and encouragement. If not because of him, this work would never happen.
J'adresse galement tous mes remerciements :
Monsieur Dimitre HADJIEV , professeur l'USB de Lorient, , et
Monsieur Jean Luc ROLS, professeur l'UPS de Toulouse pour avoir accept
de juger ce travail en faisant partie du jury,
Monsieur BEN AIM, professeur mrite l'INSA et Monsieur Alain
LINE, professeur
l'INSA, pour avoir accept de participer au jury de
cette thse,
Monsieur Henry ROQUES professeur mrite l'INSA pour sa prsence
au jury de cette thse,

I
would
like
to
thank
my
colleagues
at
Progress
Technology
Consultants Co., Ltd (Thailand) for their support and their kindness. Many
thanks
to
gratitude
Krisana
to
KHWANPAE
Bowornsak
for
his
WANICHKUL,
great
support
Chaiyaporn
on
programming.
PUPRASERT
and
My
Pisut
PAINMANAKUL for their priceless advice. I owe you guys a boon.

Thank to the French Embassy in Thailand for their financial support
during the first two years of my studies. Thanks to the embassy personnels,
particularly,
Khun
Hataiporn,
Khun
Wanpen
for
their
assistance,
Khun
Chanida for her superb translation.

Mes remerciements s'adressent galement toutes les personnes qui
m'ont beaucoup aid tant Monsieur Louis LOPEZ, Monsieur Gilles HEBRARD,
Madame
Eugnie
BADORC,
Madame
Danile
CORRADI
et
Madame
AURELLE.
Je
remercie galement mes amis du labo, particulirement, Oliver LORAIN et

Eduardo LUCENA.
Enfin, je remercie mes amis Thalandais de Toulouse (PLek, PTou,
PAote, A, Pond, Por, Pew, Golf, Mon, Aey-Alexandre, 1, Fon, Chin, Chat,
Pat, Vee, Choke, Sith, Ju, Bomb, etc.) qui m'ont assur par leur humour,
une ambiance sympathique et permis deffectuer de grandes ftes pendant mon
sjour en France.
Table des matires
Contents
Contents
Page
Part I
Introduction and bibliography
Chapter
Introduction
Chapter
Objectives
Chapter
Bibliography
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
Categories of hydrocarbon-polluted wastewater and treatment

processes
STOKEs law
Decanting
Coalescer
3.4.1 Thesis of AURELLE [3]
3.4.2 Thesis of SANCHEZ MARTINEZ [6]
3.4.3 Thesis of DARME [7]
3.4.4 Thesis of TAPANEEYANGKUL [8]
3.4.5 Thesis of DAMAK [9]
3.4.6 Thesis of MA [16]
3.4.7 Thesis of SRIJAROONRAT [10]
3.4.8 Thesis of WANICHKUL [11]
Flotation
3.5.1 Thesis of SIEM [12]
3.5.1 Thesis of AOUDJEHANE [13]
3.5.1 Thesis of DUPRE [14]
3.5.1 Thesis of PONASSE [15]
Hydrocyclone
3.6.2 Thesis of CAZAL [17]
3.6.5 Thesis of PUPRASERT [25 ]
Ultrafiltration and other membrane processes
3.7.1 Thesis of BELKACEM [18]
3.7.2 Thesis of TOULGOAT [19]
3.7.3 Thesis of MATAMOROS [20]
Thermal treatment
3.8.1 Thesis of LUCENA[24]
3.8.2 Thesis of LORRAIN[23]
Chemical treatment
3.9.1 Thesis of ZHU[21]
3.9.2 Thesis of YANG[22]
Biological treatment
-i-
6
7
7
10
10
11
12
14
15
17
17
18
18
18
19
20
21
22
22
24
25
25
26
26
27
29
30
32
33
33
33
34
34
34
35
37
38
38
Contents
Contents (Cont)
Page
3.11
3.12
Chapter
Skimmer
Application researches
Conclusion
38
39
40
41
44
- ii -
Contents
Contents
Page
Part II
Generalization of models for oil-water separation process design
Chapter
Decanting
1.1
1.2
1.3
1.4
Chapter
Simple decanter or API tank

Lamella decanter or Parallel Plate Interceptor (PPI)
Model verification
Conclusion and generalized model of decanter
Skimmer
2.1 Drum skimmer
2.2 Disk skimmer
Chapter
3.2
4.2
4.3
4.4
5
Granular bed coalescer

3.1.1 Filtration-based model
3.1.2 Dimensional analysis-based model
3.1.3 Model verification
3.1.4 Conclusion and generalized model of granular bed
coalescer
3.1.5 Generalized model for guide coalescer
3.1.6 Generalized model for mixed bed coalescer
3.1.7 Generalized model for pressure drop of granular bed
coalescer and guided coalescer
Fibrous bed coalescer
3.2.1 Dynamic fibrous bed coalescer model
3.2.2 Simple fibrous bed coalescer model
3.2.4 Conclusion and generalized model of fibrous bed coalescer
3.2.5 Generalized model of random or disorderly fibrous bed
coalescer
3.2.6 Generalized model for pressure drop of fibrous bed
coalescer
55
55
56
57
58
59
60
60
62
62
62
62
65
67
68
Dissolved air flotation

4.1
Chapter
53
54
Coalescer
3.1
Chapter
48
49
50
51
Dissolved Air Flotation (DAF) model for oily wastewater

treatment
Model verification
4.2.1 Modification of filtration-based model
4.2.2 Population balance method
Generalized model for DAF
Generalized equations for pressurized water system calculation
69
70
70
72
74
79
Hydrocyclone
5.1
Two-phase hydrocyclone
5.1.1 Trajectory analysis-based model
5.1.2 Other models
- iii -
81
81
82
83
Contents
Contents (Cont)
Page
5.1.4
5.1.5
5.2
Chapter
6.2
7
84
85
Three-phase hydrocyclone
87
5.2.1 Model development and verification for liquid-liquid
87
section
5.2.2 Model development and verification for solid-liquid section89
5.2.3 Generalized Model for pressure drop of three-phase
90
hydrocyclone
Membrane process
6.1
Chapter
Conclusion and generalized model of two-phase

hydrocyclone
Generalized model for pressure drop of two-phase
hydrocyclone
Ultrafiltration
93
6.1.1 Resistance model
94
6.1.2 Film theory based model
96
97
6.1.4 Flux prediction for mixture of cutting oil microemulsion 102
and macroemulsion
6.1.5 Theoretical flux prediction for batch cross-flow UF process 104
6.1.6 UF efficiency
107
6.1.7 Minimum and maximum transmembrane pressure and
108
power required
6.1.8 Conclusion and generalized model of UF
110
Nanofiltration and Reverse osmosis
110
Heteroazeotropic Distillation
7.1 Theoretical model
113
7.2 Model verification
116
7.3 Conclusion and generalized model of heteroazeotropic distillation 116
- iv -
Contents
Content
Page
Part III
Summary of researches: Oily wastewater treatment
Chapter
Oily or hydrocarbon-polluted wastewater

1.1
1.2
1.3
1.4
1.5
1.6
Chapter
Introduction
Hydrocarbons and oils
1.2.1
Hydrocarbons
1.2.2
Fats and oils
1.2.3
Petroleum and petroleum products
1.2.4
Oils in term of oily wastewater
Other compositions of oily wastewater
1.3.1
Surfactants
1.3.2
Soaps
1.3.3
Co-surfactants
1.3.4
Suspended solids
1.3.5
Other components
Categories of oily wastewater
1.4.1
Classification by the nature of the continuous phase
1.4.2
Classification by the stability of oily wastewater
1.4.3
Classification by the degree of dispersion
Characteristics of certain oily wastewaters
Standards, Laws, and Regulations
119
119
119
124
124
126
126
126
127
128
1281
128
128
128
128
129
132
133
Overview for oily wastewater treatment process design

2.1
2.2
2.3
2.4
Decantation velocity and STOKEs law

Application of surface chemistry for oily wastewater treatment
2.2.1
Liquid-gas and liquid-liquid interfaces
2.2.2
Liquid-solid and liquid-liquid-solid interfaces
2.2.3
Capillary pressure and LAPLACEs law
Important parameters in oily wastewater treatment and
their method of analysis
2.3.1
Oil concentration
2.3.2
Size distribution , spectrum or granulometry
2.3.3
Other parameters
Overview of oily wastewater treatment processes
2.4.1
Decanter
2.4.2
Coalescer
2.4.3
Hydrocyclone
2.4.4
Dissolved air flotation (DAF)
2.4.5
Skimmer
2.4.6
Membrane processes
2.4.7
Thermal processes
2.4.8
Chemical process
2.4.9
Finishing processes
-v-
138
139
139
142
146
147
147
149
155
155
156
156
156
157
157
157
157
158
158
Contents
Content (Cont)
Page
2.5
Chapter
Determination of degree of treatment

2.5.1
Overall degree of treatment
2.5.2
Degree of treatment of each process
Oil skimmer
3.1 General
3.2 Oil drum skimmer
3.2.1
Working principles
3.2.2
Design calculation and design consideration
3.3 Oil disc skimmer
3.3.1
Working principles
3.3.2
3.4 Productivity comparison between drum and disc skimmer
3.5 Advantage and disadvantage of drum and disc skimmer
Chapter
4.3
162
164
164
169
171
171
173
173
174
Decanting
4.1
4.2
Chapter
158
158
158
General
Simple Decanter or API tank
4.2.1
Working principles
4.2.2
Design calculation
4.2.3
Design considerations
4.2.4
Construction of simple decanters
Compact decanter
4.3.1
Working principles
4.3.2
Design calculation
4.3.3
4.3.4
Variations, advantage and disadvantage of compact
decanters
176
177
177
179
182
183
186
186
190
192
193
Coalescer
5.1 General
5.2 Granular bed coalescer
5.2.1
Working principles
5.2.2
Design calculation
5.2.3
Design consideration
5.2.4
Variations, advantage and disadvantage of granular
bed coalescer
5.3 Guide coalescer
5.3.1
Working principles
5.3.2
Design calculation
5.3.3
5.4 Fibrous Bed coalescer
5.4.1
Working principles
5.4.2
Design calculation
5.4.3
5.4.4
Variations, advantage and disadvantage of fibrous bed
coalescer
- vi -
195
195
195
209
211
212
213
213
215
215
216
216
226
227
229
Contents
Content (Cont)
Page
Chapter

6.1
6.2
6.3
6.4
6.5
6.6
Chapter
7.3
232
233
233
238
240
241
244
254
262
262
267
270
Hydrocyclone
7.1
7.2
Chapter
General
Working principles
6.2.1
Filter based model
6.2.2
Population balance model
6.2.3
Generalized model of DAF from combination of
filtration based model and population balance model
6.2.4
Influent parameters
Design calculation
Design consideration and construction of DAF reactor
Pressurized water system or saturator
6.5.1 Working principle and design calculation
6.5.2 Type of saturator and injection valve
Variations, advantage and disadvantage of DAF
General
7.2.1 Working principles
7.2.2 Design calculation
7.2.3 Design considerations
7.2.4 Variations, advantage and disadvantage of
hydrocy clone
7.3.1
Working principles
7.3.2
7.3.3
Advantage and disadvantage of three-phase
hydrocyclone
272
273
273
289
292
295
295
295
299
299
Membrane process
8.1
8.2
8.3
General
8.1.1
Classification of membrane processes
8.1.2
Mode of operation of membrane processes
8.1.3
Membrane structure
8.1.4
Membrane material
8.1.5
Membrane module type
Ultrafiltration (UF)
8.2.1
Basic knowledge and working principles
8.2.2
UF process design for oily wastewater treatment
8.2.3
Design consideration and significant findings from
GPIs researches
Microfiltration (MF)
8.3.1
8.3.2
Significant findings on MF for oily wastewater
treatment from GPI researches
- vii -
300
300
302
302
303
306
311
311
323
338
349
349
350
Contents
Content (Cont)
Page
8.4
Reverse osmosis (RO)

8.4.1
8.4.2
Significant findings on RO for oily wastewater
treatment from GPIs researches
8.5 Nanofiltration (NF)
8.5.1
8.5.2
Significant findings on NF for oily wastewater
8.6 Comparison of membrane processes on emulsion treatment
Chapter
356
356
356
359
Thermal processes
9.1
9.2
Chapter
352
352
353
General
Basic knowledge on distillation
9.2.1
Basic knowledge on vapor/liquid equilibrium of
mixtures
9.2.2
Equilibrium of various mixtures
9.3 Heteroazeotropic distillation of oily wastewater
9.3.1
Working principles
9.3.2
Raoults law and Daltons law
9.3.3
Calculation of azeotropic temperature and composition,
dew curve and bubble curve.
9.3.4
Application of heteroazeotropic distillation on
treatment of inverse emulsion or concentrated oily
wastewater
9.3.5
treatment of the wastes polluted by trace hydrocarbons:
Steam stripping
9.3.6
Design calculation and design considerations
9.4 Classical or conventional distillation of oily wastewater
9.4.1
Working principles
9.4.2
Significant findings on classical distillation for oily
wastewater treatment from GPIs researches
10 Chemical treatment processes
10.1 General
10.2 Basic knowledge
10.2.1 Stability of the emulsion
10.2.2 Surface-active agents
10.2.3 Important properties to obtain stable emulsion
10.2.4 Destabilization of emulsion
10.3 Process design
10.3.1 Rapid mixing
10.3.2 Flocculator
10.4
- viii -
362
362
362
365
367
367
368
369
371
374
374
376
376
376
380
381
381
381
383
385
391
392
393
395
Contents
Chapter 11
Finishing processes
11.1 General
11.2 Biological treatment
11.2.1 Basic knowledge
11.2.2 Design consideration and significant finding on
biological treatment for oily wastewater from GPIs
researches
11.3 Adsorption
11.3.1 Activated carbon (AC)
Chapter 12
397
397
397
404
405
406
407
412
Guideline for treatment process selection and examples of treatment

processes for certain oily wastewaters
12.1 Guideline for treatment process selection
12.1.1 Oil film
12.1.2 Primary emulsion
12.1.3 Secondary emulsion
12.1.4 Macroemulsion and microemulsion
12.1.5 Concentrated oily wastewater or refinery slops
12.2 Examples of treatment processes for certain oily wastewaters
12.2.1 Treatment of cutting oil emulsion
12.2.2 Treatment of non-stabilized secondary emulsion
- ix -
414
414
416
417
418
418
419
419
420
Contents
Contents
Page
Part IV
Computer program development
Chapter
Program overview
1.1 Introduction
1.2 Conceptual design of the program
1.2.1
E-book mode
1.2.2
Recommendation mode
1.2.3
Design mode
1.2.4
Analysis mode
1.3 Development tools
1.3.1
Main development software package
1.3.2
Special graphic user interface (GUI) component
1.3.3
The third party software
1.4 Program architecture
1.4.1
Forms
1.4.2
Modules
1.4.3
Modules
1.4.4
Class modules
1.4.5
Add-in project
1.5 Program development
Chapter
423
423
424
426
427
428
432
432
433
433
434
434
437
437
437
437
438
Program reference and user manual

2.1
2.2
2.3
2.4
2.5
2.6
Overview of the program

2.1.1
Main program
2.1.2
Project window
2.1.3
E-books worksheet
2.1.4
Recommend worksheet
2.1.5
Design worksheet
2.1.6
Analysis mode
2.1.7
Warning dialog box
Program capability
Program limitation
System requirement
User instruction
2.5.1
Program Installation
2.5.2
Starting the program
2.5.3
Using E-book mode
2.5.4
Using Recommend mode
2.5.5
Using Design mode
2.5.6
Using Analysis mode
2.5.7
Printing and file operation
Upgrading procedure and recommendation for further
development
2.6.1
Upgrading procedure
2.6.2
Recommendation for further development
-x-
439
439
441
441
442
444
445
447
447
447
449
449
449
450
450
450
452
454
457
458
458
460
Contents
Contents
Page
Chapter
Process references
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
20)
21)
22)
23)
24)
25)
26)
Drum skimmer
Disk skimmer
Simple decanter
Compact decanter
Customized decanter
Brush type bed coalescer
Dynamic fibrous bed coalescer
Metal wool bed coalescer
Ultrafiltration
Reverse osmosis
Heteroazeotropic distillation
Stripping
Chemical destabilization, coagulation-flocculation
GAC filter
Customized concentrator
Customized oil separator
Customized inline concentrator
Inlet
Outlet
Flow merge
Flow split
- xi -
463
465
467
470
473
476
480
484
488
492
498
502
506
510
513
515
517
520
522
526
528
530
532
533
534
536
Contents
Contents
Page
General conclusion
537
Reference
540
Annexe
546
- xii -
Nomenclatures
Nomenclature
Nomenclature
a
A
A
A
C
Cg
Ca
Cg
Co
Cod
Cod
Conc(Air)
Conc(O2)
Cy50
d
D
db
dc
dF
Di
Dn
dp
dxx% , dxx
e
f
g
G
H
Href
Hreq
I
Constant for population balance equation

Flow area (Cross sectional) area of decanter
Cross section area of flotation column
Flow area in membrane module (= HW)
Considered or required or design oil concentration
The 1st (or lower or pseudo) gel concentration in film model,
used at the lower range of concentration before inflection
point in flux vs. Log (Concentration) curve (in mass/ volume
or volume/volume)
Capillary number = o V/o
Gel concentration in film model (in mass/ volume or
volume/volume)
Initial oil concentration of feed or influent wastewater
Inlet concentration of the droplet diameter d
Inlet concentration of the droplet diameter d, dilution effect
from addition of pressurized water is not included.
Concentration of dissolved air in pressurized water
Concentration of dissolved oxygen in pressurized water
Cyclone number of d50%
Diameter of dispersed phase, in our case, oil
Water depth or
Diameter of the skimmer or
Diameter of coalescer bed, such as diameter of brush or
Nominal diameter of 3-phases hydrocyclone (the largest
diameter of the cyclone) or
Hydraulic diameter of flow channel in membrane module
(Channel between membrane surface and membrane module
wall)
Average diameter of air bubble
Cut size of the decanter or API tank
Diameter of fiber in fibrous-bed coalescer
Diameter of inlet port of hydrocyclone
Nominal diameter of hydrocyclone. ( = diameter of inlet of
lower conical part for Thew type hydrocyclone)
Diameter of collector or coalescer bed material, such as resin
Diameter of droplet corresponding to removal efficiency of
xx%, such as d75%, etc. d100% or dc stands for cut size
Surface roughness of flow channel
Friction factor of Darcy-Weisbachs equation
Gravitational acceleration
Turbulent intensity
Travelling or rising distance of oil drop, depending on
configuration of the decanter. Exp. For PPI, H = distance
between plates or
Height of bed, or bed depth of coalescer or
Height of flow channel in membrane module or
Height of contact (or effective) zone of flotation column. If
both pressurized water and wastewater are fed at the bottom
of the column, the contact zone is equal to column height.
H at reference operating condition of DAF reactor
H at design or required operating condition of DAF reactor
Immersion depth of the disk in liquid or
xiii
L2
L2
L2
ML-3
ML-3
ML-3
ML-3
M/L3
M/L3
M/L3
M/L3
L
L
L
L
L
L
L
L
L
L
L
L
M
L
L/T2
L
L
L
L
L
L
L
Nomenclature
J
K
k
L
L3
L4
MW
N
The number of bubbles attached to the agglomerate

Permeate flux of membrane
Boltzman constant (1.38*10-23)
Constant in film model
Length of inserted plates or interceptor surface or
Length of lower conical part for Thew type hydrocyclone or
Length of flow channel in membrane module
Total length of RIETEMA part in 3-phases hydrocyclone,
includes conical and straight section.
Length of lower straight section of RIETEMA part in 3-phases
hydrocyclone, which locate oil and solid outlet ports.
Molecular weight
Numbers of inserted plates or
Rotational speed or
Rotational speed of fibrous bed or
n0, n1
P
p
Pcap
Psat
Pt
Q
Qpw
Qt
R
r
R
Rm
Rd
rd
Re
Rf
Rf
Rg
Rm
Rz
S
Sp
t
T
U
Ub
Ud
Ud
V
Total number of bubbles

The number of oil droplet attached by 0, 1, air bubles
Oil productivity of the skimmer or
Absolute pressure of the pressurized water system or
Pressure drop or
Pressure
Partial pressure
Capillary pressure
Vapor pressure (some references use b)
Transmembrane pressure
Wastewater flowrate or
Inlet flow or
Recirculation flowrate of membrane
Pressurized water flowrate
total water flowrate (= Qpw + Qwastewater)
Universal gas constant (8.314 Pa. m3 / (mol.K))
Radius of membrane pore
Distance in radial axis of hydrocyclone
Modified membrane resistance (= Rm+Rf)
Distant from center line of hydrocyclone in radial axis to
particle d considered
Radius of oil droplet
Reynolds number (VD/)
Split ratio (= Qoverflow/Q)
Fouling resistance
Gel (or polarization) resistance
Membrane resistance
Distant from center line of hydrocyclone in radial axis to the
wall of hydrocyclone at the axial distance Z
Bottom projection area of the tank
Inserted plate area
Time
Absolute temperature
Radial velocity of particle or oil drop in hydrocyclone
Rising velocity of bubble
Rising velocity of the droplet diameter d
Rising velocity of oil droplet
Tangential velocity or tip speed of the skimmer
xiv
L/T
L
L
L
L
L
g/mol
T-1, such as rev/s
(not rad/s)
T-1, such as rev/s
(not rad/s)
L3/T
MT-2 L-1
LT-2M-1
LT-2M-1
LT-2M-1
LT-2M-1
LT-2M-1
LT-2M-1
L3/T
L3/T
L3T-1
L3/T
L3/T
L
L
MT-1 L-2
L
L
MT-1 L-2
MT-1 L-2
MT-1 L-2
L
L2
L2
T
L/T
L/T
L/T
L/T
L/T
Nomenclature
Vol
Vr
W
x
y
Z
P
Po
Poil
PSS
Pu
Pwater
Empty bed velocity or

Empty bed velocity of DAF (based on sum of pressurized water
and wastewater flow) or
Tangential velocity of particle or oil drop in hydrocyclone or
Recirculation velocity in cross-flow membrane process
Volume
Relative velocity between bubble and oil drop
Axial velocity of particle or oil drop in hydrocyclone or
Width of flow channel in membrane module
Molar fraction in liquid (water)
Molar fraction in vapor
Distance in axial axis of hydrocyclone
Pressure drop, (in m of water, for Kozeny-Carmans equation)
Or pressure drop in bar, for hydrocyclones
Pressure drop across inlet and overflow port
Pressure drop across inlet and oil outlet port
Pressure drop across inlet and suspended solids outlet port
Pressure drop across inlet and underflow port
Pressure drop across inlet and water outlet port
L/T
L/T
L/T
L/T
L3
L/T
L/T
L
Mol/mol
Mol/mol
L
Bar
Bar
Bar
Bar
Bar
Greek Letter
Air flowrate in flotation column

Vapor pressure (some references use Psat.)
Probability of collision or
Exponent of recirculation velocity in gel resistance equation
Corrected experimental removal efficiency factor of the tank
for the droplet diameter d
Correction factor for inlet velocity of hydrocyclone
Conical angle of lower part of hydrocyclone or
Exponent of recirculation velocity in film model of
membrane
Adhesion efficiency between bubbles and oil drop/ bubble
agglomerate for population balance equation
Porosity or void ratio
Constant in gel resistance equation
Superficial tension of oil
L3/T
o/w
Interfacial tension between oil and water
M/T2
o/w
overall

Overall efficiency of pump
Collision rate constant for population balance equation
Modified collision rate constant for population balance
equation ( = 2)
Modified collision rate constant at reference condition
Modified collision rate constant at design or required
condition
Dynamic viscosity
Dynamic viscosity of continuous phase, in our case, water
Dynamic viscosity of dispersed phase, in our case, oil
Dynamic viscosity of oil
Kinematic viscosity of oil
Contact angle between oil and water surface (180o means the
oil drop in perfectly sphere.)
MT-2
.exp
, 3, Thew
0, 1, , i
2,ref
2,req
C
d
o
o
o/w
xv
LT-2M-1
M/T2
T-1
T-2
T-2
T-2
ML-1T-1
L2/T
L2/T
M/(L.T)
L2/T
Nomenclature
air
c
m
d
d,ref
Diff
Int
Sed
Sed
t
theo
?A, ?B
?H
?mac
?mic
?mix
?o
?ref
?b
B
Density
Density of air at required operating condition
Density of continuous phases
Density of emulsion
Difference between density of dispersed and continuous
phases
Retention time
Removal efficiency of the tank for the droplet diameter d
Removal efficiency of DAF process for the droplet diameter
d at the reference retention time (25 minutes)
Efficiency factor from diffusion
Efficiency factor from direct interception
Efficiency factor from sedimentation
Efficiency factor from sedimentation
Total Removal efficiency
Theoretical removal efficiency factor of the tank for the
droplet diameter d
Subscript indicating component A and B respectively
Subscript indicating heteroazeotropic point
Subscript indicating macroemulsion
Subscript indicating microemulsion
Subscript indicating mixture
Subscript indicating initial condition
Subscript indicating reference condition
Superscript indicating boiling temperature
xvi
ML-3
M/L3
M/L3
M/L3
M/L3
T
%
%
Part I Introduction and bibliography
Contents
Page
Part I
Introduction and bibliography
Chapter
Introduction
I-2
Chapter
Objectives
I-4
Chapter
Bibliography
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10

processes
STOKES law
Decanting
Coalescer
3.4.1 Thesis of AURELLE [3]
3.4.2 Thesis of SANCHEZ MARTINEZ [6]
3.4.3 Thesis of DARME [7]
3.4.4 Thesis of TAPANEEYANGKUL [8]
3.4.5 Thesis of DAMAK [9]
Flotation
3.5.1 Thesis of SIEM [12]
3.5.1 Thesis of AOUDJEHANE [13]
3.5.1 Thesis of DUPRE [14]
3.5.1 Thesis of PONASSE [15]
Hydrocyclone
3.6.2 Thesis of CAZAL [17]
3.6.5 Thesis of PUPRASERT [25 ]
3.7.1 Thesis of BELKACEM [18]
3.7.2 Thesis of TOULGOAT [19]
3.7.3 Thesis of MATAMOROS [20]
Thermal treatment
3.8.1 Thesis of LUCENA[24]
3.8.2 Thesis of LORRAIN[23]
Chemical treatment
3.9.1 Thesis of ZHU[21]
3.9.2 Thesis of YANG[22]
I-6
I-7
I-7
I-10
I-10
I-11
I-12
I-14
I-15
I-17
I-17
I-18
I-18
I-18
I-19
I-20
I-21
I-22
I-22
I-24
I-25
I-25
I-26
I-26
I-27
I-29
I-30
I-32
I-33
I-33
I-33
I-34
I-34
I-34
I-35
I-37
I-38
I-38
I-i
Contents (Cont)
Page
3.11
3.12
Chapter 4
Skimmer
Application researches
Conclusion
I-38
I-39
I-40
I-41
I-44
I-ii
Table
Page
Table 3.1
Table 3.2
Table 3.3
Summary of characteristics of wastewaters and sludges for on site

experiment
Summary of characteristics of synthetic wastewaters
Membranes test by MATAMOROS
I-24
I-24
I-31
Figure
Page
Fig.
1-1
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
3.1
3.2
3.3
3.4
3.5
3.6
Summary of researches of Prof. AURELLE on hydrocarbon-polluted

wastewater treatment
Schematic of decante
Schematic of Phase inversion coalescer
Three- phase hydrocyclone
Hydrocyclone tested by WANICHKUL
Ultrafiltration models used by BELKACEM
Treatment processes for macro- and microemulsion, recommended
by MATAMORS
I-3
I-8
I-15
I-23
I-26
I-29
I-32
I-iii
I-1
Chapter 1 Introduction
Chapter 1 Introduction
Water pollution is one of the most important environmental problems. Wastewater
from agriculture and industrial processes, as well as domestic wastewater, is the main
pollutant source that causes water pollution problem. There are many substances that can
deteriorate water quality, thus classified as water pollutants, such as, organic matter from
domestic wastewater, chemicals from industrial wastewater. Some valuable substances, such
as sugar, flour, oil, will become major pollutants when discharged into water bodies.
Among various kinds of pollutants, hydrocarbon, or simply called oil, is one of the
most severe pollutants because of its intrinsic properties. Small amount of hydrocarbon can
spread over wide area of water surface and affect the oxygen transfer, so cause adverse effect
to marine or water ecology. Furthermore, the hydrocarbon contributes to very high
biochemical oxygen demand and is relatively difficult for biodegradation, which is the major
natural self-purification process. So it can last relatively long in the water and causes long term effect.
Our laboratory has researched for various treatment processes that cover various types
of wastewater polluted by hydrocarbons. In the few decades of researches, many theses had
been accomplished as shown in Fig. 1.1. Among these, many innovations had been created
and some had been patented and commercialized. Some researches are the key steps to
understand or improve the treatment efficiency and process design. However, because there
are many kinds of oily wastewater, as well as, there are many kinds of treatment processes.
Moreover, treatment efficiency of each treatment process will vary with characteristic of
wastewater. Then, it may cause some difficulties in selecting or designing appropriate process
train that can deal with the wastewater considered as well as predicting effluent quality
accurately.
According to the difficulty stated above, this thesis had been initiated to provide the
solution and tool about how to select and optimize the process or processes train to treat the
specified wastewater to meet required effluent standard, as well as providing details about
hydrocarbon polluted wastewater and each treatment process. It can be, also, applied for
designing the process to recover valuable hydrocarbons from hydrocarbon/water mixtures in
some industries, such as perfume or pharmaceutical industries.
I-2
Hydrocarbonpolluted or oily
wastewater
treatment
Drum skimmer &

disk skimmer
THANGTONGTAWI [5], 1988
Flotation for oil-water
separation
SIEM [12], 1983
Decanter
Skimmer
Flotation
Chemical
treatment
Destabilisation of emulsion
ZHU [21], 1990
Low-pollution emulsion
YANG [22], 1993
Membrane processes for cutting

oil emulsion treatment
MATAMOROS [20], 1997
Crystallization for oil-water

separation
LORRAIN [23], 2002
Thermal
treatment
LUCENA [24], 2004
Ultrafiltration for thermal

emulsion treatment
TOULGOAT [19], 1996
Hydrocyclone with grit pot &

Combination Coagulation
-DAF-Hydrocyclone separator
PUPRASERT [25], 2004
Ultrafiltration for cutting oil

emulsion treatment
BELKACEM [18], 1995
2-phase hydrocyclone
for stormwater treatment
CAZAL [17], 1996
Deep shaft DAF

PONASSE [15], 1997
Mathematics model of DAF

DUPRE [14], 1995
Application of flotation on oily

wastewater treatment
AOUJEHANE [13], 1986
Pulsed granular bed coalescer &

Phase inversion coalescer
DAMAK [9], 1992

TAPANEEYANGKUL [8], 1989
Granular bed coalescer for

stabilized emulsion
DARME [6], 1983
Guided & Mixed bed coalescer

SANCHEZ MARTINEZ [5], 1982
Ultrafiltration
& membrane
processes
Hydrocyclone
Spiraloil decanter
CHERID [4], 1986
Coalescer
2 & 3-phase hydrocyclone

MA [16], 1993

AURELLE [3], 1980
Application
Treatment of
stabilized emulsion
WANICHKUL [11]
, 2000
Treatment of nonstabilized emulsion

SRIJAROONRAT [10]
, 1998
Fig. 1-1 Summary of researches of Prof. AURELLE on hydrocarbon-polluted wastewater treatment
I-3
Chapter 2 Objectives
Chapter 2 Objectives
The objectives of this study are as described below;
1.
To review the treatment technologies for oily wastewater or wastewater polluted

by hydrocarbon from doctorate researches, directed by Professor Yves
AURELLE in LIPE-GPI, from the beginning to the present.
To design and select the suitable treatment process or processes, firstly, one has to
know of all applicable processes and understand their working mechanisms. So it becomes the
first objective of this study to review these data. However, as previously described in Chapter
1, there are many processes for hydrocarbon-polluted wastewater treatment. For example,
decanter can be subdivided into many types, such as simple API decanter, decanter with plate
settler, etc. So there are many researches all over the world that had been conducted to study
the mechanism or working principle of these processes and, then, to predict their efficiencies.
Among these researchers, Professor Yves Aurelle, with his team of researchers at GPI,
INSA Toulouse, has dedicated his studies to oily and hydrocarbon-polluted wastewater
treatment for a few decades. Through many years of study, the researches, conducted and led
by him, cover relatively the whole processes of hydrocarbon-polluted wastewater treatment.
So, to value and make ultimate use of these researches, the processes taken into account in
this thesis are exclusive based on the researches of Professor Yves Aurelle with additional
supports in some parts from related literatures for completeness of this study.
2.
To generalize or propose the model of each related process.
Each treatment process has its own variations, adapted to improve working efficiency
or to suit some certain circumstances. Thus results or models from the researches, which
intended to study in detail of these variations can not be used or extrapolated beyond their
experimental operating conditions. In order to provide the solution to the widest range, if not
the entire range, of hydrocarbon-polluted wastewater, we set the 2nd objective to generalize or,
if case arises, propose the model or models that allow the prediction of efficiency of each
treatment process over the determined range of hydrocarbon-polluted wastewater.
3.
To compose the textbook on hydrocarbon-polluted wastewater or oily wastewater

treatment process, based on the result from the 1st and 2nd objective.
As previously described that there are a lot of researches dedicated to specific aspects
of various treatment processes, it is very interesting to combine these researches together to
get the whole picture. After we had reviewed and generalized all related researches as
described in the 1st and 2nd objective, we set out to work on our 3rd objective of this thesis to
compose the textbook. This textbook will feature the following topics;
Background knowledge on oily and hydrocarbon-polluted wastewater
Treatment technology overview
Chapters devoted to details of each treatment process
Guidance for selection and combination of processes
If we could compose it well as we intended. This textbook would provide readers

sufficient practical data to understand properties oily wastewater, working mechanisms of
4
I-4
treatment processes and key parameters affected their designs and operations, that can lead to
proper design and selection of treatment processes or creating their own variation of process
that suit their own situation.
4.
To develop the prototype of program for the design, comparison and simulation
of hydrocarbon-polluted wastewater treatment processes.
At the present, computer comes to play major role in every field and become standard
equipment in almost every household, office and academic institute. Because of its powerful
logical and mathematical calculation, as well as its presentation and interaction capability, it is
very interesting to use computer in the field of hydrocarbon-polluted wastewater treatment.
Up till now, there are many commercial softwares on industrial and wastewater treatment
process calculation. Anyway, those programs are not specifically designed to deal with
hydrocarbon-polluted wastewater treatment. Furthermore, the commercial softwares are
normally developed for expert users, so they do not provide much basic data, thus, render it
difficult for non-expert users to use efficiently. Besides, they normally do not provide any
data for decision supporting, for example they can not compare the efficiency between various
processes or recommend the feasible processes for considered wastewater.
So for our 4th objective, we intend to develop the prototype of program for design,
comparison and simulation of hydrocarbon-polluted wastewater treatment processes. The
program will feature;
E-book: provides background knowledge and useful database about the oil
pollution and the treatment processes,
Process recommendation part: provides recommendation or narrows the range of

feasible processes for any input influent,
Design (or calculation) part: used for sizing the process unit,
Simulation part: allows users to integrate any separation processes, included in

the program database, to build their own treatment process train. And the program
will simulate the process train to forecast the efficiency of each unit.
The treatment processes, which can be calculated or simulated by the program built-in
database, will then be based mainly upon the researches reviewed in the 1st to 3rd objective.
However, the source code of the program will be available upon request to allow upgrading to
include more processes in the future.
I-5
Chapter 3 Bibliography
3.1

processes
As hydrocarbon or oil requires a great amount of oxygen or oxidizing agent to oxidize,

moreover, the hydrocarbon is relatively difficult to biodegrade, thus, it becomes clear that the
use of the biological treatment with high-concentration oily wastewater is not the economical
alternative. Besides there are possibilities to reuse or recover the hydrocarbons in the
wastewater. Then almost all of treatment processes that have been studied in our laboratory
are based on separation, both physical and physico-chemical, techniques in order to separate
oil from water.
Thus, it is more suitable to categorize the oily wastewater by its physical properties.
Among these properties, the degree of dispersion of oil phase in water or the size of oil
droplet is the key parameter that plays an important role in separation process selection. So we
will categorize the oily wastewater into 4 groups, in accordance with its droplet size, i.e.,
Hydrocarbon in form of film or layer on the surface of wastewater, or hydrocarbon

in form of big oil drops in the wastewater
Emulsion without surfactants, by the word emulsion, it can be easily described
as the water with very fine dispersed oil drops
Emulsion with surfactants
Dissolved hydrocarbon
For treatment processes, each process has its own characteristic or limitation so it can
be used to separate some certain ranges of oil droplet. So each group of the oily wastewater
may require certain process or train of processes to separate the oil from the water to the
accepted degree. The treatment processes, studied by Professor AURELLEs researchers,
covered the entire range of the oily wastewater stated above and can be summarized as
follow;
Decanting
Skimmer
Coaleser
Flotation
Hydrocyclone
Ultrafiltration
Distillation
Moreover, there are researches on chemical treatment, which relates to breaking the
emulsion to allow the micro droplet to coalesce and make it possible to separate by the
processes stated above. There, also, are some researches contributed to formulation of
environmental-friendly oil product, which can be easily treated and still have the same
essential working properties as the existing products.
Furthermore, some researches can be extensively used to solve the problems of some
special types of oily waste, such as slop (viscous mixture between crude oil and water) or
inverse emulsion (fine drops of water dispersed in oil)
I-6
Details of wastewater characteristics and treatment processes are thoroughly described

in Part 3. So, this part emphasizes on reviewing of related researches, categorized by process,
about their scope of work and significant finding, as described in next sections.
3.2
STOKES law
It is important to mention about STOKES law (eq. 3.1), because almost all of
separation processes considered here are based upon modification of parameters in this
equation. The STOKES equation is the relation between rising (or settling) velocity of
spherical object (in our case, droplet of dispersed phase) with very small Reynolds number
(10-4 to 1) and properties of dispersed phase and continuous phase.
V=
Where
dE
C
g d E2
18 c
{3.1}
= rising or settling velocity (based on density of the 2 phases)

= Difference between density of dispersed phase and continuous
phase
= Diameter of dispersed phase
= Dynamic viscosity of continuous phase
In case of oily wastewater, the dispersed phase is hydrocarbon or oil and the
continuous phase is water. Because the density of hydrocarbons in our wastewater is normally
lower than waters. It is prone to rise to surface of the water. Even though the STOKES
equation is valid only for certain flow regimes, the equation covers the range of flow
regime normally encountered in wastewater problem. It can be used to explain important
phenomena or applied to many types of processes, even a bit beyond its valid regime, with
satisfactory result. There are few modifications of STOKES law brought about by applying
some correction factors into basic STOKES law. But the core equation usually remains the
same as shown in eq. 3.1.
Form eq. 3.1, one can increase the rising velocity of the oil drop by modifying 4
variables properly. The separation processes, which are based on the results of STOKES law
or modification of the variables in STOKES law, are decanting, coalescer, flotation process
and hydrocyclone or various types of centrifugal process. The researches on each process can
be summarized as follows.
3.3
Decanting
Decanting (or sedimentation) is the simplest separation process. It makes use of

gravity force and density difference between oil and water to separate them. Rising velocity of
oil or hydrocarbon drop in wastewater depends on its size, density, viscosity of water and
gravity constant, as described by STOKES equation. As shown in fig. 3.1, when the
homogeneous oil/water mixture flows uniformly pass through a control volume, some big oil
drops will rise to the water surface and can be retained, then, separated from the water by
means of proper equipment, such as overflow weir or skimmer. The small oil drop that can
not reach the water surface will be entrained with the water and exit the control volume
without separation.
I-7
Q
V
d > cut size
Influent
Effluent
d = cut size
d < cut size
Fig. 3.1 Schematic of decanter
When the size of the decanter (or settling tank) and the distribution of oil droplets in
the wastewater are known, we can calculate the separation efficiency of the tank by
comparing the time required for each size of oil droplet to reach the surface of the tank within
hydraulic retention time of the tank. The time required for oil droplet to reach the surface can
be calculated from STOKES equation and vertical travelling distance of the droplet. If the
droplet can reach the surface before the wastewater will flow off the tank, we can say that the
droplet can be separated by that decanter. American Petroleum Institute had recommended the
geometry of the decanter, generally known as API tank. This type of decanter has been widely
used.
Because all variables in STOKES equation are practically unchanged during the
separation process by decanter. Then, the efficiency of decanter can be enhanced only by
reducing the vertical travelling distance of oil droplet to the decanting surface. This fact leads
to the modification of simple decanter by inserting submerged plates into the tank. These
plates will act as oil interceptor. Instead of rising up to the water surface, oil droplets that
reach the surfaces of these plates are intercepted, collected, and then separated from the tank.
It can be said that these insertions reduce the vertical travelling time of oil drop without the
reduction of hydraulic retention time.
Theoretical efficiency of plate-inserted decanter, known as lamella decanter, parallel
plate interceptor (PPI), etc., can be calculated using the same equation as for API tank with a
little modification on decanting area. However, the selection of the shape and installation of
these plates are the state-of-art processes. The spacing between the plates should be as small
as possible to minimize the size of decanter. However, the flow of water and the collected oil
between the plates shall be taken into account to minimize shear force, thus minimize the
effect of surface distortion or snap-off.
Thesis of CHERID [4] is contributed to study on the compact lamella decanter,
known as SPIRALOIL, that shows far greater efficiency compared to the simple decanter of
the same size.
The research consisted of,
Study of interaction between oil drop and surface of lamella plate, and influence of
wettability of lamella material, inclination of lamella plate and characteristic of
wastewater to decanter operation
Model development for lamella decanter
I-8
Experimental procedure
The experiment of phenomena in the lamella decanter was conducted in transparent
model. Interaction between oil and surface of the lamella plate, as well as the influence of
wettability of plate and inclination of plate, could be observed clearly in this model. The
experiment to test the operation and efficiency of lamella decanter was conducted with 2
models of SPIRALOIL, the first one with normal spiral hydrophobic plate insertion, the
other with the combination of corrugated hydrophilic plate and smooth hydrophobic plate
insertion, also in spiral form. Kerosene/ water mixture was used for the research, with the
addition of surfactant in some tests to vary the interfacial tension.
Result
The result of this study provides models for sizing and calculating the efficiency of
two lamella decanters SPIRALOIL. The microscopic observation clearly shows the
interaction between oil and surface of lamella plate and influence of wettability and
inclination of the plate. The result leads to optimum configuration of the SPIRALOIL.
Significant findings
1.
In this thesis, mathematical models for sizing and calculating efficiency of the
decanters are proposed. The models are based upon theoretical model of classical
decanters.
2.
The microscopic study shows that the operation of the decanters consists of 2
steps, i.e., decanting and coalescing.
3.
For hydrophobic plate, decanted oil will adhere to the surface of the plate, then
coalesce to form a film on the surface. However, the following decanted oil drop
will adhere and coalesce with the oil film with more difficulty than adhering to
the plate itself.
4.
For hydrophilic lamella plate, decanted oil will not form a film at the surface of
the plate, but will accumulate in the form of big drop. This oil drop will be
entrained with the water when it reaches sufficient size and, then, separated from
water at the ends of the plate.
5.
The inclination of the plate will affect the coalescing step. For hydrophobic
plate, there is a possibility that the decanted oil drop will not coalesce with the
film, but roll over the film until reaching the end of the plate. However, at the
end of plate will appear the big oil drop, because the point will play the role of
drip point or salting-out point. This big drop can intercept those non coalesced
drops and becomes one larger oil drop until it reaches sufficient size to be
snapped off by the water flow.
6.
For hydrophilic inclined plate, the decanted oil drop will move along, rather than
adhere to, the inclination of the plate. Anyway it can coalesce with other
decanted oil drop along its way to be a larger drop in the same manner as a
snowball.
7.
Presence of surfactant will decrease the oil droplet size, thus hinder good
decanting step. Furthermore, it will lower the interfacial tension, thus hinder
good coalescing step and cause decreasing in the efficiency of decanter.
I-9
8.
3.4
From the study, the optimum SPIRALOIL configuration is the one with
combination of corrugated hydrophilic and smooth hydrophobic plate insertion,
installed in horizontal position. This configuration will combine the advantage of
enlarging of the oil drop both at the end of the plate (drip point enlargement) and
within the plate (snowball enlargement). Furthermore, the horizontal installation
(inclination = 0) will favor coalescing step.
Coalescer
From STOKES law (eq. 3.1), rising velocity of the oil droplet is proportional with
square of droplet diameter. So increasing the droplet diameter will make rising velocity
increasing at greater rate than other parameters in the equation. To increase the diameter, we
need a process that can integrate small droplets into the big one. Coalescer is very effective
process that enables coalescing or integrating of a number of small oil droplets in the
wastewater into relatively big drops, which can be easily separated by ordinary decanter.
Because coalescer operation depends upon several parameters or mechanisms and each of
them can be optimized to obtain better efficiency or to fit some specific working conditions,
then there are several theses related to coalescer, in order to cover every aspect of the process.
Some researches are dedicated to detailed study of mechanism of the process. Some are
contributed to various type of coalescer bed or modes of operation. While some are devoted to
application on some specific wastewater or working condition. All of these related theses on
coalescer can be outlined as follow.
3.4.1
Thesis of AURELLE [3]
This research contributed to the study on fundamental mechanism of granular bed

coalescer, which was used as a basis and guideline for following researches.
Influence of essential parameters, i.e., geometry of bed, and operation parameters,

such as feed rate to efficiency of coalescer
Fundamental mechanisms or phenomena, take place with in coalescer during its
operation
Model development for granular bed coalescer
The experiment was carefully planned to cover every aspect of coalescer operation,
i.e.,
Wastewater characteristic : Hydrocarbons, used in the research, included gasoline,

kerosene at various concentrations, in form of both direct and inverse emulsion.
Collector material : Alternatives of collector or bed material included;
Type of material : glass beads, resin, sand, chamotte (porous dried clay)
Wettability : Oleophilic or Hydrophilic
Granulometry or size and size distribution of the collectors
Geometry of colaescer
Diameter or size of the coalescer tank
Bed height
Empty bed flow velocity
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Result
The result of this study indicate the important parameters which influent the efficiency
of coalescer. It also shows complex phenomena in coalescer operation by means of
visualization or photographic technique. Model for sizing the coalescer was proposed. The
study also provided significant criteria to select the material of bed and guideline for
optimization and for further development of coalescer
1.
The main parameters, which effect the efficiency of the coalescer, consist of :
2.
Wettability of bed material,

Bed height,
Empty bed velocity,
Granulometry of bed,
Ratio of hydrocarbon in the wastewater
The phenomena or mechanism occur in the coalescer can be divided into 3

fundamental steps as follow.
Step 1: Interception, which consists of 3 major transport phenomena, i.e.,

sedimentation, direct interception and diffusion. This step is normally the
efficiency-determining step of coalescer. The research makes it possible to
develop the model, based on model of filtration process, which governs all
phenomena in this step.
Step 2: Adhesion-Coalescence. The efficiency of this step depends mainly on
wettability of bed material. So, this step can be optimized by using oleophilic
material as coalescer bed.
Step 3: Salting out or enlargement of coalesced liquid. This step depends on
4 parameters, i.e. wettability of bed material at the discharge surface, empty
bed flow velocity, interfacial tension and ratio of dispersed phase and
continuous phase in emulsion treated. So, for any given wastewater and bed
material, one can optimize this step only by varying feed flowrate. However,
the research shows that installation of guide, such as woven fibrous metal,
attached to discharge surface of granular bed, can eliminate influences of the
4 parameters described above and allow the coalescer to operate at much
higher velocity. This guide suppresses the limiting step 3 by channeling
coalesced oil directly into decanted oil layer at the decanter surface.
This thesis provides very important concepts and mechanisms of coalescer that leads
to further studies on various types of coalescer.
3.4.2
Thesis of SANCHEZ MARTINEZ [6]
This research contributed to extensive study on granular bed coalescer, first researched
by AURELLE [3]. The research was emphasized on granular bed coalescer with guide, and
mixed bed coalescer.
11
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Influence of essential parameters, i.e., geometry of guide, and operation

parameters, such as feed rate and ratio of oil in wastewater to efficiency of
classical coalescer and guided coalescer
Study on mixed bed coalescer to treat direct and inverse emulsion simultaneously
Application on mixed bed coalescer with guide in phenol extraction
The experiment was conducted with transparent glass coalescer models. Coalescer bed
materials used during the experiment were sand and glass bead. Both materials were specially
coated to acquire oleophilic or hydrophilic property. 2 guides of different sizes of woven fiber
and different porosity were tested. The author intended to study the operation of coalescer for
liquid/liquid extraction. So he chose phenol extraction in this study. Phenol in wastewater can
be extracted by dissolving into appropriate hydrocarbon solvent. Solvent and wastewater will
be intensely agitated to maximize contact, thus, mass transfer. So, they normally become
emulsion, both direct and inverse. Hydrocarbons used as solvent in the experiment were
L.C.O, medium-cut petroleum, and gasoline.
3.4.3
1.
Installation of guide, porous material preferably wetted by dispersed phase, helps

optimizing the 3rd mechanism salting out or enlarging of dispersed phase, thus,
allow the granular bed coalescer to work at the flowrate of 1.5 - 6 times higher
than classical coalescer without guide. It helps preventing formation of mousse,
jet at the bed outlet. It also prevents formation of zone of non-coalesced drops
between decanted solvent and clarified water zone. The guided coalescer can be
operated at higher ratio of dispersed phase/ continuous phase than the classical
coalescer. The research confirms the advantage of guided coalescer proposed by
Prof. AURELLE.
2.
When both direct and inverse emulsion are simultaneously present in the
wastewater, two-stages process of hydrophilic bed and hydrophobic bed
coalescers, connected in series, may encounter a problem of re-dispersion or refragmentation, thus, lower the total efficiency.
3.
Mixed bed coalescer, using combination of both hydrophilic and hydrophobic

bed material, is proven to be the effective way to treat direct and inverse
emulsion simultaneously.
4.
Application of mixed bed coalescer with guide shows satisfactory result and is
proven to be a good alternative in the field of liquid-liquid extraction process.
Thesis of DARME [7]
This research contributed to the application of coalescer on treatment of stabilized

emulsion. This work was one of successions of the research of AURELLE [3] in order to
understand profoundly about working mechanism, limitation and application of granular bed
coalescer.
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Influence of surfactant on coalescer operation

Trials on optimization of each basic mechanisms of coalescer
Study on mixed bed electrocoalescer
The experiment was conducted with transparent glass coalescer models. Coalescer bed
materials used during the experiment were oleophilic resin and glass bead. To study about
influence of surfactant on wettability, glass, resin and steel were tested. For the study on
mixed bed electrocoalescer, mixed material of aluminium and resin was tested. Emulsion of
kerosene and water was used throughout the experiment, with various dosages of cationic,
anionic and non-ionic surfactants.
1.
Surfactants have important effects on emulsion and operation of coalescer as

follow;
2.
Decreasing average size of droplet in emulsion, then, results in limiting the

efficiency of the 1st mechanism Interception step of coalescer.
Decreasing interfacial tension, increasing electric charge at the surface of the
droplets and increasing viscosity of surface of the droplets, then, result in
poor adhesion between droplets and bed, as well as, ineffective collision
(collision without coalescence) between droplets. These leads to limiting the
efficiency of the 2nd mechanism Adhesion-coalescence step of coalescer.
Decreasing interfacial tension and adsorption of surfactant on enlargement
surface (or grill) results in limiting the efficiency of the 3rd mechanism
Enlargement step
Trials to optimize the 1st and 3rd mechanism were conducted by;
Optimization of the 1st mechanism: increasing bed depth

Optimization of the 3rd mechanism: installation of guide
The efficiency of the coalescer after these 2 modifications is not improved.

Hence, it shows that the 2nd mechanism Adhesion-Coalescence is the limiting
step in this case.
3.
The 2nd mechanism can be optimized by destabilizing the emulsion, chemically

or electrically. To apply only the coalescer to treat stabilized emulsion, without
additional chemical process to destabilize or break the emulsion, the author
propose to destabilize the emulsion by electrostatic effect. To achieve the
electrostatic effect required, the author proposes to use the combination of
oleophilic resin and metal (such as aluminium) as coalescer bed. With carefully
selected bed materials, the electrostatic effect, caused by electrical potential of
the 2 materials, will be sufficient to subdue the surface charge of droplets,
caused by surfactants. Then, it will improve adhesion and coalescence within the
coalescer.
4.
However, this mixed bed is effective only when the emulsion is stabilized by
ionic surfactant. In case of non-ionic surfactant, coalescence is hindered by
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mechanical, not electrical, barrier, caused by adsorption of the surfactant at the

surface of droplets. This barrier cannot be subdued by electrostatic effect.
3.4.4
Thesis of TAPANEEYANGKUL [8]
This research was intended to study on a variation of coalescer, i.e., Dynamic

fibrous bed coalescer. This type of coalescer has advantage in its anti-clogging property
which allows it to be used with oily wastewater with high suspended solids concentration.
Influence of essential parameters, i.e., geometry of fibrous bed, and operation

parameters, such as feed rate, rotating speed of fibrous bed to efficiency of
coalescer
Model development for fibrous bed coalescer
The experiment was conducted with transparent glass coalescer model. Coalescer bed
materials used during the experiment were of brush type, made of nylon (polyamine) and
polypropylene fiber with various fiber diameters, brush sizes, and void ratios. The brush was
mounted to a variable speed motor, so the rotation of the brush can be adjusted. Emulsion
used in the experiment was kerosene emulsion.
1.
The main parameters, which effect the efficiency of the coalescer, consist of;
2.
Granulometry of emulsion (sizes of droplets)

Bed height
Bed diameter
Void ratio or porosity of the bed
Diameter of fiber of the fibrous bed
Empty bed velocity
Rotating speed of bed
In this thesis, mathematical model for sizing and calculating efficiency of fibrous
bed coalescer was proposed, i.e.;
0.67d 0.58 (1 ) 0.35 H0.35 N0.53
E
=(
) 100 %
d
D0.03 d 0.58 V0.74
F
P
Where
d
dE
H
N
D
dF
Vp
=
=
=
=
=
=
=
=
Efficiency of coalescer
Diameter of dispersed phase
Void ratio or porosity of bed
Bed height
Rotating speed
Diameter of bed
Diameter of fiber
Empty bed velocity
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This model is valid when 52<Re<1164. However, scaling-up of the model will
be limited by bed construction itself because the fiber elements of the bed tend to
compact by their own weight. Moreover, if the bed is too large, void ratio at the
tips of fibers will be very different from centers. This may cause error in
calculation. So, it is recommended to use a number of small coalescers instead of
a single large one.
3.
This coalescer has several advantages as follow;
3.4.5
Anti-clogging. No regeneration or backwashing required

High void ratio, thus, head loss is very low
Very small size of fiber, compared to granular bed material, ensures good
interception of oil droplets
Treatment efficiency is adjustable by mean of adjusting rotating speed of bed
Thesis of DAMAK [9]
This research was intended to study another variation of coalescer, i.e., Pulsed
granular bed coalescer. This type of coalescer had been initiated to enable the granular bed
coalescer to treat oily wastewater with high suspended solids concentration without
regeneration or backwashing process. This coalescer, in fact, is a classical up-flow coalescer,
except it bottom end is equipped with rubber diaphragm, driven by pneumatic piston. The
diaphragm will be periodically driven up, then released to go back down. This action will
cause brief fluidization of bed and the trapped solids will be released from the bed.
The author also studied a new type of coalescer, called Phase inversion coalescer.
For its operation principle, the wasted emulsion will be forced downward through small tubes,
equipped at the top of coalscer column, to produce emulsion drops of required size. These
drops will flow through thick layer of hydrocarbon, which is of the same type as dispersed
phase in the emulsion. The drops play the role of micro decanter. Theoretically, hydrocarbon
droplets in the emulsion drops will float to the top of the drops, then, coalesce with
surrounding hydrocarbon layer. With appropriate depth of hydrocarbon layer and size of
emulsion drop, the dispersed phase in emulsion drop will be totally separated and become
only the drop of water phase when it flow out off the hydrocarbon layer into water phase
underneath. The schematic of phase inversion coalescer will be as shown in Fig 3.2.
Influent
emulsion
Hydrocarbon
layer
Orifice plate
Top of hydrocarbon
layer
Emulsion jet
from orifice
Hydrocarbon
droplets in emulsion
drop
Emulsion
drop
Bottom of hydrocarbon
layer
Water layer
Effluent
Decanting of droplets in
emulsion drop
Fig. 3.2 Schematic of Phase inversion coalescer

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Influence of essential parameters, i.e.,diameters of droplets, height of hydrocarbon,

etc. to efficiency of Phase inversion coalescer
Study on up-flow pulsed granular bed coalescer
Model development for granular bed coalescer, based on dimensional analysis
For the phase inversion coalescer, the experiment was conducted with transparent
glass coalescer model. Furthermore, to achieve a better visual study, a special tube equipped
with micro-syringe was used to study internal phenomena in droplet. The tube was fixed at the
tip of the syringe, to be within hydrocarbon stream. Emulsions, used in the experimental, were
kerosene/water emulsion, hexane/water emulsion and T.I.O.A./water emulsion. T.I.O.A/water
emulsion is the solution of kerosene, triisooctylamine (T.I.OA) and tributylphosphate. This
solution is normally used as extracting solvent in hydro-metallurgical industries.
For up-flow pulsed granular bed coalescer, the experiment was conducted with glass
coalescer with rubber diaphragm bottom. The diaphragm was connected to pneumatic piston
that can drive the diaphragm up and down at preset interval. Coalescer materials were
hydrophilic glass bead and stainless steel. Emulsion tested were kerosene/water emulsion and
T.I.O.A./water emulsion with an addition of fly ash as suspended solids.
For model development of granular bed coalescer, transparent glass coalescer was
used. Hydrophobic and hydrophilic glass beads were used as coalescer material.
Hydrocarbons used in the experiment were kerosene, T.I.O.A., heptane, anisole and toluene.
1.
The efficiency of phase inversion coalescer will increase with the modification
of these parameters, i.e.;
Increasing in height of hydrocarbon layer (until certain limiting height)

Decreasing in size or diameter of emulsion drop that will be forced through
the hydrocarbon layer (again, until lower limit)
Incresing in flowrate of treated emulsion
Increasing in height of emulsion-drop-accumulated or dense layer
The efficiency will also depend on characteristics of emulsion e.g. viscosity,

interfacial tension, granulometry of emulsion etc.
2.
While the emulsion drop travels pass through hydrocarbon layer, internal
turbulence or circulation flow will be induced within the emulsion drop, which
then disturbs good decanting of oil droplets, thus causes the decrease in the
efficiency.
3.
To avoid this turbulence, the flowrate should be increased to produce more

emulsion drops. The rate of production has to be greater than the rate of
coalescence of the drops, at the bottom of hydrocarbon layers. So, this results in
formation of emulsion-drop dense bed or layer at the bottom of hydrocarbon
layer. This layer will dampen the downward velocity of the drop, which results
in decreasing of internal turbulence. The efficiency, then, will be improved.
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3.4.6
4.
This coalescer is suitable for treatment of primary emulsion (dE 50 m). And
the study shows that the efficiency is better than that of the classic decanter.
5.
For pulsed coalescer, the study shows that brief pulsation, which causes the bed
to fluidize, can regenerate the bed and clean up the accumulated matters.
6.
In classical coalescer, coalescer bed material is usually lightweight resin, which

requires the top grill to keep the bed in place without carrying over with the
wastewater. However, in this study, it shows the possibility of using of relatively
high density coalescer bed, e.g., stainless steel, without the top grill can replace
the use of lightweight material. When the grill is not required, it allows us to use
pulsating motion to fluidize, thus, regenerate the bed.
7.
In this thesis, a mathematical model for sizing and calculating efficiency of

granular bed coalescer was proposed. Unlike the model of AURELLE, which
derived from theoretical mechanisms of coalescence, this model is based on
dimensional analysis. So physical properties of wastewater, which are not shown
in AURELLEs model, are taken into account. Hence, it covers wider range of
wastewater.
Thesis of MA [16]
This thesis was the main research on hydrocyclone for hydrocarbon/water separation.
So it will be described in detail in section 3.6. However, the author had tested, for the first
time, the efficiency of the combination process of hydrocyclone and coalescer, which worth
describing here.
1.
3.4.7
This study shows, for the first time, the possibility to use the combination
process of hydrocyclone/coalescer and coalescer/hydrocyclone to improve the
total efficiency of oil/water separation.
Thesis of SRIJAROONRAT [10]
This thesis is an application research on treatment of non-stabilized oil/water

emulsion. This type of thesis provides important data that can be applied in real life situation.
So we will devote one section to review these theses. However, as one part of her thesis,
SRIJAROONRAT had studied on comparison between fibrous bed coalescer of brush type
and random, disorderly type (like a steel wool). She also studied on combination of
coalescer/hydrocyclone to treat non-stabilized emulsion. The idea is to use coalescer to
increase droplet size, permitting a good separation by the following hydroclclone. Her study
on coalescer will be briefly mentioned here to complete the entire coalescer studies.
1.
At high empty bed velocity, the coalescer with random bed will coalesce and
enlarge the droplets into relatively large drop, while the coalescer with brush
type bed tends to produce stream of jet, containing small oil drop.
2.
However, the disorderly fibrous (steel wool) bed coalescer tends to be clogged
by suspended solids, usually presence in the oily wastewater. So the author
proposed new configuration of fibrous bed in form of combination of 2 brushes.
The internal one is of ordinary brush. The external one will look like coil spring
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with its fiber elements protruding inward and toward the center. This type of bed
is believed to provide good interception, as same as the disorderly bed, yet
remain its anti-clogging properties, like brush-type bed.
3.
3.4.8
Combination between coalescer/ hydrocyclone is proven to provide good

efficiency on the wider range of feed flowrate and size of oil droplet.
Thesis of WANICHKUL [11]
This thesis is an application research on treatment of stabilized oil/water emulsion.

Details of this thesis will be described in the section devoted to application thesis. However,
as one part of his thesis, WANICHKUL had studied on the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer to treat non-stabilized emulsion, as well
as the efficiency of multi stage fibrous bed coalescer.
3.5
1.
Testing of the 2 types of the combination in industrial pilot plants shows

satisfactory result. These combinations provide promising alternatives for
industrial wastewater treatment process. Furthermore advanced combination of
coalescer-hydrocyclone-coalescer is tested. It promisingly shows that 2
coalescers can be used, one before the hydrocyclone to increase droplet size
entering the cyclone, and another at downstream of the cyclone to coalesce the
concentrated oil/water mixture from the outlet of the hydrocyclone.
2.
Result from multi stage fibrous bed coalescer test shows that this modified
bottlebrush bed provides better efficiency than classic bottlebrush bed. This is
because the gaps between each stage cause turbulance, then promote coalecence
between droplets that, somehow, fail to coalesce in the previous stage of bed.
Flotation
Flotation is the separation process that makes use of increasing the density difference
to increase the rising velocity of droplets of dispersed phase. The density difference can be
increased by mean of integrating air or gas bubble with oil droplets. The bubble/droplet
agglomerate will have lower density than droplet alone, thus, result in increasing of the rising
velocity. Because flotation mechanisms are very complex, then there are several theses related
to flotation, in order to cover every aspect of the process. All of related theses on flotation can
be outlined as follow.
3.5.1
Thesis of SIEM [12]
This research contributed to the study on fundamental mechanism of Flotation for

hydrocarbon/water separation, which was used as a basis and guideline for other followed
researches.
Study on the interaction between hydrocarbon droplets and air bubble, and
overview of efficiency of dissolved air flotation and induced air flotation.
Influence of essential parameters, coagulant dosage, pH, etc. to efficiency of
flotation
Model development for dissolved air flotation, based on filtration model.
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I-18
Visual study of interaction between oil droplets and bubble had been conducted in
special transparent model, equipped with a microscope and a VDO camera. For the study on
flotation, transparent flotation model was used. Emulsion used during the experiment was gasoil/water emulsion.
3.5.2
1.
From visual study on interaction between oil droplet and air bubble, it shows that
the bubble will agglomerate within the inside of oil droplet or the oil will form a
thin skin, as a shell, around the air bubble.
2.
In this thesis, mathematical model for sizing and calculating efficiency of

dissolved air flotation is proposed. The model is based on filtration model by
assuming that the air bubble is collector (sand or filter media in case of filter).
Prediction results of the model fit well with experimental results. Anyway, the
author did not account for the quantity of pressurized water that used to generate
the bubbles. This amount of water can cause dilution effect, thus, contribute to
reducing in wastewater concentration. So, the model proposed in this research
should be reconsidered again to clarify the efficiency of interception of air
bubble and the efficiency from dilution effect of pressurized water. The revised
model will be described in Part 2 of this thesis.
Thesis of AOUDJEHANE [13]
This research contributed to application of flotation on treatment of hydrocarbonpolluted wastewater. This work was one of successions of the research of SIEM [12] in order
to understand profoundly about working mechanism, limitation and application of flotation.
Study on structure of bubble/droplet agglomerate and influence of additional of

flotation reagent in form of the transfer compound( compos transferable)
Influence of hardness and salinity of pressurized water on production of air bubble
Study on probability of collision and coalesce of air bubble and oil droplet
Visual study of the interaction between oil droplets and bubble had been conducted in
special transparent models, equipped with a microscope and a VDO camera. The models are
equipped with 2 syringes, located close to each other. These 2 syringes were used to supply
air (or gas) and oil to form immobilized bubble and oil droplet respectively. Bubble and oil
droplets were brought into contact to study the formation of the agglomerate. For study on
flotation, transparent flotation model was used. Hydrocarbon used in this study was kerosene.
For transfer compounds, ammonia gas, cationic surfactant and methanol were used as
promoter of mass transfer between phases.
1.
From visual study on interaction between oil droplet and air bubble, it confirms
the result of SIEM [12] that the bubble will agglomerate within the inside of oil
19
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droplet or the oil will form a thin skin, as a shell, around the air bubble. The
agglomerate in from of bubble and droplet locating side by side of each other,
which is exist in case of bubble/particle interaction, occurs only in unstable,
transition forms. It also shows that coalescence time between bubble and oil
droplet is less than that of the same species.
3.5.3
2.
From the study with static transparent model, it shows that addition of transfer
compound (as gas to bubble air or as transfer compound to water) affects, more
or less, probability of coalescence between bubble/droplet, bubble/bubble and
droplet/droplet. It can be described that mass transfer of these transfer compound
from one phase to another (for example, bubble gas from bubble toward water,
etc.) can cause disturbance in local surface tension and thinning of film, then,
help increasing coalescence. This effect is well known in liquid-liquid extraction
process as the Marangoni effect.
3.
From the study with flotation lab-scale model, it shows that the effect of
turbulence, caused by movement of air bubble, promotes the probability of
collision both inter-species and same species of bubbles and oil droplets.
However, this augmentation in collision increases flotation efficiency only
slightly because the number of bubble, somehow, decreases from the effect of
collision and coalescence, that leads to depletion of the number of bubble/droplet
agglomerate. Anyway, the author notes that, because coagulation-flocculation
process is not applied, the number of oil droplets is, then, always greater than the
number of bubbles. Then, it may be interesting to study further on coalescence
or coagulation of oil droplets.
Thesis of DUPRE [14]
This research contributed to the study on related mechanisms and mathematical

model development of dissolved air flotation. Even though the author intended to study on
solids/ liquid separation, some parts of the study on formation of air bubble and some general
ideas can be applied in the field of hydrocarbon/water separation.
Study on precipitation of dissolved gas to form bubbles

Study on formation of bubble/particle agglomerate
Model development for dissolved air flotation
To study the precipitation of dissolved gas, the author tested several pressure-reducing
venturi tubes (convergence-divergence nozzles) of various divergent angles. Tube materials
tested consisted of stainless steel (hydrophilic) and plastic (hydrophobic). Influence of
divergent angle, wettability of tube, length of pipe after the pressure reducing device and
addition of some chemicals were studied.
To study the formation of bubble/particle agglomerate and operation of flotation, the
experiment was conducted using 3 apparatuses. The 1st one was a glass container with
syringes and holders, for supplying bubbles and particles. Bubble can be fixed in place while
particles were brought to contact with it or vice versa. The 2nd apparatus was glass container
with sealed cover, connected to a vacuum pump. The container was filled with water and
20
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various particles were added. Then, the air was pumped out to create vacuum. This apparatus
was used to observe nucleation of bubble. The 3rd one was a transparent flotation model.
3.5.4
1.
The study result, which can be applied to hydrocarbon/water separation, is the

one about formation of bubble at pressure reducing valve. The study shows that
efficiency of flotation can be improved if the design of pressure reducing valve is
optimized to generate microbubble in majority.
2.
The use of hydrophobic venturi or pipe can cause the increase in size of the
largest bubble generated. These large bubbles, though small in the number,
consume almost all of the gas volume. So the number of generated
microbubbles, which plays an important role in flotation, is left but only in small
proportion.
3.
Addition of surfactant in pressurized water can cause augmentation in population

of microbubbles. On the contrary, addition of polyelectrolyte will cause a
decrease in electric charge, which is favorable for the coalescence of bubbles.
Thesis of PONASSE [15]
This research contributed to study and trial on improvement of flotation efficiency.

The author had tested several ways to improve formation of microbubble, such as addition of
chemicals, using ultrasound vibrator to create microbubble. She also performed a feasibility
study on Deep shaft flotation unit.
Study on the influence of pressure reducing valve on formation of bubble

Feasibility study on deep shaft flotation unit
Feasibility study on combination of pressure reducing valve and ultrasound
vibrator.
To study the influence of pressure reducing valve on formation of bubble, the author
tested several pressure-reducing venturi tubes (convergence-divergence nozzles) of various
divergent angles. Tube materials tested consisted of stainless steel (hydrophilic) and plastic
(hydrophobic). Influence of divergent angle, wettability of tube, length of pipe after the
pressure reducing device and addition of some chemicals were studied.
For study on deep well flotation unit, a 30-m depth deep well unit was tested. The unit
consisted of 2 concentric pipes. The external pipe diameter was 0.15 m. On the top of the
pipes placed settling tank of 1.2*1.2 m, water depth 0.7 m. The wastewater was charged with
various suspended solids, both hydrophobic and hydrophilic. The air was introduced into the
system by several methods, i.e.,
Direct injection into the wastewater at static mixer

Via porous plate, located inside the wastewater pipe before enter the deep shaft
reactor
Via injection chamber, air will forced through small orifice into the chamber
Via membrane
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Via ejector
Injection in form of pressurized water via pressure reducing valve to form bubble,
then mix with inlet wastewater at the top of deep well reactor
3.6
1.
We are interested only in the result that can be applied to hydrocarbon/water

separation, i.e., formation of bubble. From the study, it shows that precipitation
of dissolved gas appears firstly in form of big gas pocket within pressure
reducing valve. Then the pocket is broken or fragmented by hydrodynamic force
to form bubble.
2.
Geometry of pressure reducing valve, which determines hydraulic condition, is

the key parameter to obtain microbubbles.
3.
To obtain good efficiency, pressure reducing device should be placed as close as

possible to mixing zone between wastewater and pressurized water
Hydrocyclone
From STOKES law (eq. 3.1), rising velocity of the oil droplet is proportional to
gravitational acceleration. So if one increases the acceleration, the rising velocity will be
increased as well. To increase the acceleration, it can be achieved by replace gravitational
acceleration with centrifugal acceleration. This can be done mechanically, such as the use of
rotating machine like centrifuge, or by converting hydrodynamic force to centrifugal motion.
Hydrocyclone is the process that uses the latter principle to increase the acceleration.
In our lab, we emphasize on hydrocyclone, rather than the centrifugal machine,
because of its simplicity and economy. Furthermore, for most of oily wastewater we
encounter, the centrifugal acceleration induced by hydrodynamic force alone is sufficient to
provide satisfying separation. The hydrocyclone have no moving part. Its structure is
relatively much more simple than centrifugal machine. And it uses the driving force only from
its feed flowrate. So it is more economic than centrifuge both in investment cost and operating
cost. Now, there are various types of hydrocyclone, commercialized by many manufacturers.
Even so, basic concept of these products is identical. Understanding of the concept including
related mechanisms and limitation of the process will lead to appropriate design, selection and
operation, as well as improvement of the process. There are several theses related to
hydrocyclone, in order to cover various aspects of the process. All of related theses on
hydrocyclone can be outlined as follows.
3.6.1
Thesis of MA [16]
This thesis was the main research on hydrocyclone for hydrocarbon/water separation.
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Study on new approach for calculating two-phase hydrocyclone, used for

liquid/liquid separation application
Study on three-phase hydrocyclone, used for liquid/liquid/solid separation
Feasibility study on the combination process of three phase hydrocyclone and
coalescer
To study on a new approach for calculation on 2-phase hydrocyclone, the author based
his experiment on THEW type hydrocyclone, initiated by Professor Thew, UK. For 3-phase
hydrocyclone, he had initiated this hydrocyclone by integrating the liquid/liquid hydrocyclone
of THEW type and the solid/liquid hydrocyclone of RIETEMA type to one unit. For
coalescer tested, he used coalescers with various sizes of brush type beds. The emulsions
used in the experiment were based on petroleum from the Sud-Ouest french oil rig, with
various additions of very fine bentonite (3.7 m) and calcium carbonate powder (6.2 or 16
m). Average oil droplet in the emulsion tested was 15 to 50 m.
1.
In this thesis, a mathematical model for sizing and calculating efficiency of

THEW type hydrocyclone was proposed. This model, based on calculation of
decanter, can be used to calculate trajectories of oil droplets in the cyclone, as
well as the separation efficiency for each size of oil droplet. Difference between
model prediction and experimental result is around 10%.
2.
It is recommended that the optimum angle of conical section of THEW

hydrocyclone should be 8 to 12. And ratio Dn/D (nominal diameter of cyclone/
diameter of cylindrical part of the hydrocyclone) should be around 0.5.
3.
The author had designed the 3-phase hydrocyclone by integrating THEW type
hydrocyclone with RIETEMA type hydrocyclone. To do so, the vortex finder of
RIETEMA hydrocyclone is replaced by THEW hydrocyclone, as shown in fig.
3.3. Test results show that the hydrocyclone is capable to separate, efficiently
and simultaneously, lightweight hydrocarbon and heavy suspended solids from
water.
4.
The study shows that separation efficiency of hydrocyclone will drop rapidly if
the diameter of oil droplet is smaller than 20 m.
Solid-liquid part (Rietemas part)
Liquid-liquid part (Thews part)
Di
Du
D Do
Dp
Ds
L4
L3
L1
L5
L3
Fig. 3.3 Three- phase hydrocyclone

Note: Di/D=0.25, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034, L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3
23
I-23
3.6.2
Thesis of CAZAL [17]
This research contributed to the feasibility study of solid/liquid separation

hydrocyclone on treatment of storm water, domestic wastewater, and thickening of sludge. In
spite of the fact that this research is mainly related to solid/liquid separation process, it
provides useful details about model development and basic concepts of hydrocyclone.
Furthermore, oily wastewater always contains some amount of suspended solids. So, some
parts of this thesis can fulfil the study of hydrocyclone for oily wastewater treatment charged
with suspended solids.
Feasibility study on application of hydrocyclone for treatment of storm water,

domestic wastewater, thickening of primary sludge and biological sludge
Model development for solid/liquid separation hydrocyclone and study on
influence of shape of suspended solids to separation efficiency
Study and proposal on multi-hydrocyclone processes for treatment of storm water
For the feasibility study on hydrocyclone for wastewater treatment and sludge
thickening, the author had performed the experiment on site, using a pilot plant. The pilot
plant was equipped with storage tank, pumps and piping system that allow to test 2
hydrocyclones instantaneously, both in series and parallel. The hydrocyclones used in the
experiment were product of NEYRTEC, equipped with replaceable outlet. The sizes of
cyclones were tested, i.e., nominal diameter of 75 and 50 mm. Outlet ports of the cyclones can
be changed to study the influence of their sizes on cyclone operation. The wastewater and
sludges were provided by the wastewater treatment plant at Ginestous. Characteristics of
wastewater were as summarized in table 3.1. For study in laboratory, The same pilot plant was
used with synthetic wastewaters, summarized in table 3.2.
Table 3.1 Summary of characteristics of wastewaters and sludges for on site
experiment
SS (mg/l)
Median diameter, d50
(m)
Domestic
wastewater
Storm water
Primary sludge
Biological
sludge
150-490
41-700
22000-16000
4170-6660
24-37
10-28.8
160
36-96
Table 3.2 Summary of characteristics of synthetic wastewaters

Calcium
carbonate
Talc
Talc
Ion
exchange
resin 1
Ion
exchange
resin 2
CaCO3
A60
Steamas 29
IRP 69
OG 4B
Density (g/cm )
2.7
2.7
2.7
1.57
1.57
Median diameter,
(m)
10
25
32
78
56
Name
3
24
I-24
1.
In this thesis, it shows that the efficiency of hydrocyclone for wastewater

treatment and sludge thickening application are relatively low, compared to
classic decanter or gravity thickener. Main reasons for poor efficiency consist of;
3.6.3
Shear force from flow pattern in hydrocyclone, which causes deflocculation

effect or decreasing in size of biological floc
Nature of the wastewater, which normally contains high contents of fiber
agglomerates. These fibers hinder separation phenomena in hydrocyclone
2.
The author had tested the operation of hydrocyclones using the range of influent
SS concentrations from 10 mg/l to 20 g/l and maximum purge ratio of 2%. The
result shows that efficiency will increase if influent flowrate is increased.
3.
Shape of suspended solid affects the efficiency of hydrocyclone. This influence

is the function of particles size. The smaller the size is, the less the influence is.
4.
In this study, mathematics model of hydrocyclone is proposed and form

coefficient is introduced.
5.
The author proposed the combination of 3 hydrocyclones in series as the

recommended process for storm water treatment. She also proposed installation
of grit pot (the short cylindical chamber), connected to discharge port of the
hydrocyclone, to minimize the influence of particle shape.
This thesis is an application research on treatment of non-stabilized oil/water

emulsion. SRIJAROONRAT, as one part of her thesis, had studied on the combination of
coalescer/hydrocyclone to treat non-stabilized emulsion. The hydrocyclone used in this
research is the product of Dorr Oliver, model DOXIE 5, nominal diameter of 1 cm, 10 cm
long. Her study on hydrocyclone is briefly mentioned here to complete the entire
hydrocyclone studies.
1.
3.6.4

This thesis is an application research on treatment of stabilized oil/water emulsion.

Details of this thesis will be described in the section devoted to application thesis. However,
as one part of his thesis, WANICHKUL had studied on the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer to treat non-stabilized emulsion. It will be
briefly mentioned here. WANICHKUL had been tested the combination of
coalescer/hydrocyclone and hydrocyclone/coalescer. In his experiment, he used Plexiglas
hydrocyclone as shown in fig. 3.4. The influent will be fed through 2 tangential inlet ports,
located at the upper cylindrical section. The oil and treated water will be discharged at each
corresponding outlet port. Because the oil and treated water outlet port locates at the same end
of hydrocyclone, so this configuration of hydrocyclone is called co-current.
25
I-25
Fig. 3.4 Hydrocyclone tested by WANICHKUL

3.6.5
1.
The results shows that key parameters that govern the efficiency of co-current
hydrocyclone are influent flowrate, recovered oil draw-off rate and ratio between
outlet velocity of oil and outlet velocity of treated water, calculated at each
corresponding outlet port.
2.
The author recommended that the velocity ratio of oil/ treated water mentioned
above should be greater than 1.5, which can be precisely adjusted by using of oil
draw-off pump.
3.
Testing of the 2 types of the combination in industrial pilot plants showed

satisfactory result. These combinations provide promising alternatives for
industrial wastewater treatment process. Furthermore an advanced combination
of coalescer-hydrocyclone-coalescer is tested. It promisingly shows that 2
concentrated oil/water mixture from the outlet of the hydrocyclone. The oil in
this case is separated, not just concentrated, from the wastewater.
Thesis of PUPRASERT [25 ]
This thesis is contributed to study on the efficiency of hydrocyclone equipped with

grit pot, as recommended by CAZAL [17]. It is also related to the feasibility study of an
innovation on solid/liquid separation, which is a hybrid of 3 processes, i.e., coagulationflocculation, dissolved air flotation and centrifugal separation. However, it seems that this
thesis is not related directly to oily wastewater treatment. So we will not mention about the
result of this research here. Anyway, some information and ideas presented in PUPRASERTs
thesis will be integrated in the stage of textbook composing in Part 3 of this thesis.
3.7
Membrane process seems to be the future of separation technology. Main component

of every membrane process is the membrane, which can be briefly described as a porous
material that plays the role of selective barrier. Under appropriate transmembrane pressure,
the membrane of appropriate characteristic will allow only certain components in wastewater
26
I-26
or emulsion to pass. The rest will be retained by the membrane. Working principle of
membrane process can be approximately compared to that of filtration.
Membrane processes can be divided into several categories according to the pore size
of membrane, i.e., microfiltration, ultrafiltration, nanofiltration and reverse osmosis. Each
category has different permeability and can retain different size of components. So it is crucial
to select the most appropriate membrane process to achieve the required effluent quality. Then
several researches are contributed to membrane selection.
In membrane treatment system, wastewater will be circulated on one side of
membrane. The water and some components that can be passed through membrane pore will
flow to another side of membrane. This portion is called filtrate or permeate. The portion
that can not pass the membrane will have higher oil concentration because it losses its water
component. It is called concentrate or retentate. So, the membrane can be considered as a
concentrating process because the pollutant, in our case, oil, is not exactly separated, just
concentrated. Increasing in oil contents of concentrate will cause important phenomena called
polarization concentration. This can be described as oil rich layer that can obstruct flow of
permeate. Solid content or some components in wastewater can be trapped in membrane pore
and cause clogging. Concentration polarization and clogging of membrane are the main
problems of this process. So many researches are devoted to solve this problem. All of related
theses on membrane process can be outlined as follows.
3.7.1
Thesis of BELKACEM [18]
This research is contributed to the application of ultrafiltration on treatment of cutting

oil emulsion. This type of emulsion is one of important oily wastewater. In metal industries,
especially metal forming plants and mechanical workshops, machine tools and products needs
good lubrication and cooling to ensure good quality of products and prolonged working life of
the tools. Water, by its property, is very good cooling liquid and a cost-effective choice. As
well as oil is very good lubricant and anti-corrosion substance. So the combination of oil and
water in form of emulsion provides users with both properties required. To fulfil this purpose,
the emulsion is charged with surfactants and co-surfactants to increase its stabilization. From
user point of view, it yields satisfying result.
However, from environmental point of view, presence of these surfactants or
emulsifiers makes separation process very difficult. This is because the oil phase in the
emulsion is dispersed in form of very fine droplets, which impossible to be decanted naturally.
So it requires special treatment.
Feasibility study on the application of ultrafiltration on treatment of cutting oil

macroemulsion
Study on treatment methodology of the cutting oil emulsion by ultrafiltration
process
Study on membrane washing solution
Feasibility study on the application of ultrafiltration on treatment of cutting oil
microemulsion
27
I-27
The experiment was conducted with a batch model and a pilot-scale model. For batch
model, the author used AMICON membrane test module, (fig. 3.5). The batch model was
transparent container with pressure-tight cover. The membrane was placed at the bottom of
the container. Wastewater was added into the container, then the cover was locked in place
and compressed air line was connected to the inlet port at the cover. The wastewater was
forced through the membrane by mean of air pressure, then collected and examined. During
ultrafiltration process, the wastewater was continuously stirred by mean of magnetic stirrer.
For pilot-scale model, the author used commercialized cross flow ultrafiltration test
module, model PLEIADE UFP2 of Tech Sep co,.ltd. (fig. 3.5).Wastewater was circulated
through narrow gap between membrane and transparent wall of the model. In this manner,
wastewater flow was tangential, not perpendicular to, the membrane surface. Some
components would pass through the membrane and become permeate. The rest would be
returned to storage tank, then circulated pass membrane again until it reached some certain
concentration. After being circulated for many times, the concentrate would gain in
temperature, so heat exchanger was provided to cool down the flow before re-entered the
UFP2 module.
He also tested the porous fiber membrane in the same way as the plain membrane,
described before. For the membranes, he used plain and porous fiber membrane of various cut
sizes, ranged from 40 to 150 Kdalton.
For the emulsions, he used commercialized cutting oil emulsion of both
microemulsion and macroemulsion types. He also used cutting oil macroemulsion from
mechanical workshops.
1.
In this thesis, the author proposed a mathematical model for calculating

ultrafiltration flux of macroemulsion, as function of non-dimensional numbers.
2.
The study indicates interesting aspect in integrating ultrafiltration with partial

destabilization, using salt. From this methodology, the membrane will play the
roles of filter and coalescer, which help reducing the influence of polarization
layer and concentration factor. This leads to increasing in ultrafiltration flux for
treatment of macroemulsion.
3.
To solve the problem about clogging, the author proposed to use new formulated
microemulsion, which is not saturated by oil, to wash the membrane and slow
down clogging process. With a careful selection of surfactants in the
microemulsion, it can be easily treated by the combination process of
polyelectrolyte breaking and ultrafiltration. Because the author used cosurfactant with poor water solubility, residual pollutant concentration after
ultrafiltration, mainly in dissolved form, was relative low, compared to ordinary
microemulsion.
4.
From study on treatment of microemulsion by ultrafiltration, it shows that

ultrafiltration provides good separation between oil and water. However, the
filtrate is heavily polluted by dissolved pollutant, then additional treatment is
inevitably required. The author proposed to use reverse osmosis process to treat
28
I-28
the ultrafiltrate. The result shows that reverse osmosis can treat this wastewater
with very high efficiency (approx. 98%).
1
2
3
4
5
6
7
Air compressor
Pressure reducing valve
Pressure guage
AMICON test module
Agitator
Balance
Computer
7
6
Fig. 3.5 Ultrafiltration models used by BELKACEM

3.7.2
Thesis of TOULGOAT [19]
This research is contributed to the study on formation mechanisms of thermal

emulsion and feasibility study on treatment of the emulsion by ultrafiltration. This type of
milky emulsion is generally encountered in essential oil extraction process, such as in perfume
industry. Not only this study provides information about one of the application of
ultrafiltration. It also provides the general idea of formation of thermal emulsion, which leads
to precaution to avoid it formation. This idea can be applied to heteroazeotropic distillation,
which is one of treatment processes for oily wastewater.
Influence of essential parameters, such as temperature, condensing surface, etc., on

the formation and characteristic of thermal emulsion
Preventive approach to avoid formation of the emulsion or, if case arise, limit its
concentration
Feasibility study on treatment of thermal emulsion by ultrafiltration
29
I-29
To study on the entraining of volatile compounds with steam, the author used glass
distillation apparatus, equipped with microscope to observe the condensate. She had tested
several hydrocarbon compounds, such as alcanes with the number of C atoms from 5 to 12
(pentane to dodecane), toluene, benzaldehyde, isobutanol, series of primary alcohols, etc.
To study mechanisms of thermal emulsion formation, hydrodistillation apparatus was
used. It is, in fact, the same device as the first one, with an additional installation of a stirrer.
For the plants used for the experiment, she used several plants, i.e., cinnamon, aniseed, celery,
lavender, etc. Condensate was found in form of decanted essential oil, floating on the top, and
milky thermal emulsion.
For ultrafiltration, she used tubular ceramic membrane of 10 nm. pore size. The
experiment was conducted with membrane test module, model MEMBRALOX T1-70 of SCT
co., ltd. For the emulsion treated, she used synthetic emulsion of kerosene/water as well as
thermal emulsion from extraction of cinnamon, aniseed and celery with various doses of
surfactants.
1.
In this thesis, it shows that the most important parameter in thermal emulsion
formation is the variation of solubility of essential oil with changes in
temperature. She also proposed the minimum variation of solubility that can
cause the formation of thermal emulsion.
2.
Condensation time is the important parameter that governs the size distribution
of the emulsion. If the condensation is relatively slow, average diameter of
droplet in the emulsion will increase.
3.
The author shows that if the following compounds are present in the essential oil,
thermal emulsion will not be formed;
3.7.3
Hydrocarbon of high vapor tension

Hydrophobic hydrocarbon that solubility is not sensitive to temperature
change.
4.
To avoid formation of thermal emulsion, she proposed the process called

hydrodistillation under reduced pressure (sub-atmospheric pressure).
5.
The study shows that white water or milky thermal emulsion, in fact, contains
natural surfactants. So its properties are close to that of stabilized emulsion.
6.
Under carefully selected operating condition, ultrafiltration can provide good

separation efficiency between water and essential oil.
Thesis of MATAMOROS [20]
This research is contributed to the study on treatment of stabilized emulsion,

especially cutting oil emulsion, by various membrane processes. This research provides many
useful information and comparison data of several membrane processes.
30
I-30
Feasibility study on the application of various membrane processes for treatment

of cutting oil emulsion, of both macroemulsion and microemulsion types
Feasibility study on the application of combination processes between one of
membranes and chemical destabilizing process for treatment of cutting oil
macroemulsion and microemulsion
The experiment in laboratory scale was conducted with two batch test modules, one
was fabricated in GPI Lab, and another was AMICON test module. For pilot-scale
experiment, the author used cross flow membrane test module, model PLEIADE UFP2 from
Tech Sep co., ltd., for micro- and ultrafiltration process. For nanofiltration and reverse
osmosis, he used test module from OSMONICS.
The membranes used in the research were as tubulated in table 3.3. For emulsions, he
used various commercialized cutting oil of macro- and microemulsio typesn.
Table. 3.3 Membranes test by MATAMOROS
Cut size
Initial permeate flux

(m.s-1.pa-1)
Microfiltration
0.10 0.45 m
655 - 125786
Ultrafiltration
40-50 Kda
750*10-12
Nanofiltration
150 2000 Da
1.72*10-12 - 20*10-12
Membrane
Reverse osmosis
-12
150 Da
2.2*10
Material
Cellulose compounds,
Polyamide and PTFE
Polyacrylonitrile,
Acrylonitrile
Cellulose
Polyamide
1.
The results from this research show that the combination between chemical
destabilization process with micro- or ultrafiltration can increase working
permeate fluxes of the membranes and still obtain good efficiency.
2.
For the combination of chemical destabilization and microfiltration, the system

can operate at relatively high flux with moderate transmembrane pressure. This
leads to development of continuous treatment process of cutting oil because, in
the past, working pressure is always the limiting factor of the process. However,
it requires high amount of salt.
3.
For the combination of chemical destabilization and ultrafiltration, the result

conforms to BELKACEMs [18] that the salt added plays important role, by
double layer compression, and/or adsorption/partial neutralization, in the
reduction of repulsive force and promotion of coagulation and coalescence of
droplets to form a free oil layer. This oil layer can be entrained by recirculation
stream, and then removed at the concentrate storage tank.
31
I-31
4.
The permeates from the combination of two processes stated above contain high
concentration of TOD, which is the result of dissolved pollutants, especially cosurfactants.
5.
Combination between ultrafiltration and reverse osmosis shows good result both
in oil separation and dissolved pollutant elimination in permeate. However,
operating cost is relatively high.
6.
The use of nanofiltration shows good efficiency result in good oil separation, as
well as dissolved pollutant elimination, at lower energy consumption than
reverse osmosis.
7.
From experimental results, the author recommended 2 treatment process trains

for micro- and macroemulsion as shown in fig. 3.6
Surfactant +
CaCl2
Macroemulsion
Microfiltrtion
Microfiltrtion
++
CaCl
CaCl22
Recycle
Decanter
Decanter
Reverse
Reverseosmosis
osmosis
or
or
Nanofiltration
Nanofiltration
Granular
Granularactivated
activated
carbon
carbonor
or
Biological
Biologicaltreatment
treatment
Effluent
Decanted oil
Surfactant +
Oil
Microemulsion
Granular
Granularactivated
activated
carbon
carbonor
or
Biological
Biologicaltreatment
treatment
Nanofiltration
Nanofiltration
Effluent
Fig. 3.6 Treatment processes for macro- and microemulsion,

recommended by MATAMOROS
3.7.4
This thesis is an application research on the treatment of non-stabilized oil/water

emulsion. As one part of her thesis, SRIJAROONRAT had studied on the application of
ultrafiltration to treat non-stabilized emulsion. In her thesis, SRIJAROONRAT had tested
several types of ultrafiltration membranes, i.e., organic, inorganic and ceramic. Wastewater
used in the experiment consisted of synthetic emulsion of kerosene/water, cutting oil
emulsion, crude oil/water emulsion, and wastewater from textile plant. The result can be
summarized as follows.
1.
Ultrafiltration process can be used to treat non-stabilized emulsion with

remarkable efficiency (approx. 100%).
2.
Major problem of the ultrafiltration is the rapid decrease in permeate flux, caused
by;
Presence of suspended solids in wastewater, these solids will deposit on the

membrane surface and/or in the pores and cause clogging.
32
I-32
3.
3.7.5
Presence of surfactant, the surfactant will be adsorbed or form micelles

within the membrane pores, as well as membrane surface, thus cause
changing in wettability of membrane.
Influence of surfactant on permeate flux also depends on material of membrane.

Inorganic (mineral) based membrane is more sensitive to surfactants than other
membranes.
This thesis is an application research on the treatment of stabilized oil/water emulsion.

WANICHKUL had studied on the application of ultrafiltration on cutting oil emulsion
treatment. He also studied on the treatment of ultrafiltrate by reverse osmosis.
1.
2.
3.
4.
3.8
The result on the treatment of cutting oil emulsion by ultrafiltration confirms the
result of MATAMOROS that the process is feasible and efficiency of the process
is satisfying. The author recommended that operating condition should be in
permanent regime to avoid influence of concentration factor.
Using microemulsion with under-saturated oil concentration is an effective
method to regenerate the membrane.
The author had studied the efficiency of reverse osmosis on ultrafiltrate
treatment. The result shows that the process provides remarkable efficiency.
The result of the comparison on efficiency between ultrafiltration and distillation
on cutting oil emulsion treatment can be concluded that ultrafiltration is suitable
for macroemulsion treatment, while distillation is more efficient for
microemulsion treatment. However, from economic point of view, energy
consumption of ultrafiltration is always lower than distillations.
Thermal treatment
This treatment approach makes use of physical properties of hydrocarbon, water and
their mixture. Because hydrocarbon is only slightly soluble in water, we can say that the
hydrocarbon/water mixture is practically an immiscible binary system. From this fact, we can
apply the basic of phase equilibrium to develop thermal processes for hydrocarbon/water
separation. Such processes are distillation and crystallization. All related theses based on
thermal treatment can be outlined as follows.
3.8.1
Thesis of LUCENA[24]
This research is contributed to the heteroazeotropic distillation for treatment of slop,

the wasted viscous water-in-petroleum emulsion that is usually very difficult and costly to
treat. This process is very interesting innovation that allows hydrocarbon recovery by
separating from water from the slop. Certain type of hydrocarbons, considered as efficient
water extractant or entrainer, is added to the slop, then the slop undergoes distillation to
extract the water. After distillation, the distillate obtained is composed of 2 layers of clear
liquid, the entrainer in the upper layer and the water at the lower. The water can be disposed
or further treated and the entrainer can be reused for next cycle of distillation. The residue
obtained is relatively fluid, contains no water, and can be recycled to refinery unit as crude
oil.
33
I-33
The experiment in laboratory scale was conducted with a simple glass distillation
apparatus. The author also used the pilot-scale model for on-site treatment tests.
3.8.2
1.
The result on the treatment of slop shows that the water is totally separated from
the slop. The residue consists of relatively water-free hydrocarbon. Distillate
consists of 2 separate layers of entrainer and water.
2.
Observed quantity of entrainer is slightly different (5-8%) from theoretical value.

So the theoretical method for calculating entrainer quantity is accurate enough
for practical use.
3.
Kerosene and gasoline are proven to be good entrainer. Their water-extracting

capacities are almost identical to that of decane and dodecane, respectively.
Thesis of LORRAIN[23]
This research is contributed to crystallization. However, this process has just been
studied by GPI lab for the first time. So we will not include it in this research.
3.8.3
This thesis is an application research on the treatment of stabilized oil/water emulsion.

WANICHKUL had studied on the application of distillation for the treatment of cutting oil
emulsion and permeate from ultrafiltration. He also studied the possibility to treat concentrate
from ultrafiltration of cutting oil emulsion by heteroazeotropic distillation.
3.9
1.
Comparison on the efficiency between ultrafiltration and distillation on cutting

oil emulsion treatment, the author concluded that ultrafiltration is suitable for
macroemulsion treatment, while distillation is more efficient for microemulsion
treatment. However, from economic point of view, energy consumption of
ultrafiltration is always lower than distillations.
2.
Heteroazeotropic distillation is proven to be an effective way to treat

mayonnaise-like retentate from the ultrafiltration of cutting oil emulsion. The
residue of distillation process is clear liquid, composed of oil without water. The
distillate consists of 2 separate layers of the entrainer (in this case, decane) on the
top and the water at the bottom. However, TOD of the distillate is still high
(around 2,800 mg/l). So the additional treatment of the distillate (either by
biological treatment or RO) is required.
Chemical treatment
When we talk about chemical treatment in oil/water separation process, we normally

refer to chemical destabilization, coagulation and flocculation. The process, then, does not
destroy oil. Its major role is to transform the oil into the form that facilitates oil/water
separation. So, chemical treatment process usually follows by physical separation processes as
we discussed in previous sections. Normally, chemical treatment will be required when oil or
34
I-34
hydrocarbon is present in the form of very stable emulsion, which will not be naturally
coalesced. So it is impossible or very difficult to separate them by mean of physical process
alone. Example of oily wastewater that requires chemical treatment process is stabilized
emulsion, such as cutting oil emulsion.
All of related theses on chemical treatment can be outlined as follows.
3.9.1
Thesis of ZHU[21]
This research is contributed to the study on influence of cutting oil emulsion formula
on its physico-chemical treatment.
Study on chemical destabilization of various macroemulsions and microemulsions

Study on treatment of residual pollution in treated emulsions after physicochemical treatment
Feasibility study on formulation of cutting oil emulsion to minimize the residual
pollution
The author had performed the experiment using 2 commercial macroemulsions and 2
microemulsions. Some used emulsions, provided by mechanical workshops, were also tested.
For chemical reagents for destabilizing (so-called breaking) the emulsions, he had tested
several chemicals, i.e.,
Inorganic electrolytes: Sulfuric acid and several salts, such as NaCl, CaCl2, Alum,
FeCl3
Organic electrolyte: Ca(HCOO)2
Commercial adsorption reagents
Cationic polyelectrolytes
Anionic polyelectrolytes
Cationic surfactants
Each chemical reagent was added to the emulsions, stirred, and left to decant for 20
hours. Decanting results were carefully observed. If the oil in the emulsion was separated
easily within 1 hour, the author concluded that the reagent used for destabilization was
effective.
For the study on the elimination of residual pollution, the author proposed to use
adsorption treatment by activated carbon. The experiment had been conducted with batch and
continuous lab scale models.
1.
From the experiment on macroemulsion, it shows that destabilization mechanism

of electrolyte depends on the number of its valences, which can be described as
follows;
35
I-35
Mono-valence cationic electrolyte, main destabilization mechanisms are

based on Zeta potential reduction and promoting micelle formation of
surfactants.
Bi-valence cationic electrolyte, main destabilization mechanism is based on
precipitation of surfactant to insoluble form.
Tri-valence cationic electrolyte, main destabilization mechanisms are based
on the bridging of its cations and hydroxides and precipitation of surfactant
to insoluble form.
2.
The result shows that destabilization techniques of fresh macroemulsion can also
be effective for used macroemulsion.
3.
For breaking emulsion by acid, the study shows that destabilization mechanisms
for micro- and macroemulsion are different, based on type of surfactant used in
the emulsions.
For microemulsion- surfactant used is soap. So it is sensitive to pH change.

Then, addition of acid will disturb the equilibrium of ionization of fatty acid
and make it lose its surfactant property. This type of destabilization requires
relatively small amount of acid.
For macroemulsion- surfactant used is sulfonate type. Main destabilization
mechanisms are based on Zeta potential reduction and promoting micelle
formation of surfactants. So it requires high dosage of the acid.
4.
Ferric chloride is an effective destabilization chemical for breaking

macroemulsion. However, it cannot be used to breaking microemulsion because
it will react with surfactants and form complex, which is difficult to separate.
5.
High residual pollution which presents after breaking the emulsion is caused by
co-surfactant, which is fatty acid that dissolves very well in water.
6.
To destabilize the emulsion stabilized by non ionic surfactant, the author

recommended to use a mixture of anionic surfactant and tri-valence electrolyte
(Alum, FeCL3) as destabilization reagent. Main breaking mechanism is based on
selective reaction between non-ionic surfactant, anionic surfactant and
electrolyte, which form insoluble complexes.
7.
Breaking mechanisms of commercial adsorption reagents are based on their

components. So, their efficiencies will be known only by testing.
8.
Activated carbon adsorption is proven to be an effective treatment for residual

pollution which is left after breaking the emulsion. However, investment and
operating costs of this system, esp. cost for regeneration or replacement, are
relatively high.
9.
The author had proposed, for the first time, to replace fatty acid co-surfactant
with other surfactant with less water solubility to solve the problem about
residual pollutant after breaking the emulsion. In his case, he used decanol,
which is slightly soluble in water, as a co-surfactant. The new emulsion has
satisfying property. But vigorous mixing by ultrasound device is required to
disperse the oil into droplets to create the emulsion.
10.
He suggested that new formula of this low pollution emulsion should be further
studied to make it soluble instantly in water, which is the way the users prefer.
36
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3.9.2
Thesis of YANG[22]
This research is a succession of ZHUs thesis and contributed to development of low

pollution emulsion. This thesis was a new approach in pollution control because it was one of
the first researches on pollution reduction from the source, as it is presently called cleaner
product, CP research, which is the branch of pollution control that is well-known and widely
acceptable now.
Study on the formulation of low pollution cutting oil emulsion

Study on the treatment process of that new emulsion
The author had tried to formulate low pollution cutting oil emulsion, using carefully
selected base components, i.e.,
Base oil: commercial naphthene (cyclic aliphatic compound) based oils and
paraffin based oils,
Surfactants: various succinic and sulfonate surfactants,
Co-surfactants: alcohol-based, ester-based, and other co-surfactants with low water
solubility,
Corrosion inhibitors: fatty acid alcanolamide, oleylsarcosinic acid, and fatty acid
polydiethanolamide,
Anti-mousse reagents: polysiloxane and a commercial reagent,
Bactericides: 4-chloro-3methylphenol, isothiazolinone, and parahydroxybenzoic
ester with phenoxyethylic alcohol,
Each emulsion formula was subjected to these 5 tests, i.e.,
Droplet size distribution measurement: using particle analyzer (granulometer)

Emulsification test: new products were diluted by water to observe its solubility
and stability.
Anti-rust test: new emulsions of various concentrations were used to coat on steel
chip and rust forming was observed.
Anti-mousse test: new emulsions were manually and intensely agitated and
characteristic and stability of mousse were observed.
Determination of residual pollutant after chemical destabilization process or
ultrafiltration.
1.
The author proposed new formulae of low-residual-pollutant microemulsions

and macroemulsions.
2.
These new emulsions can be treated efficiently by breaking with calcium

chloride or ultrafiltration. Residual pollution after treatment is 2-57 times lower
than present commercial products.
3.
Concentration of emulsion and hardness of dilution water are important

parameters, which affect stability of emulsion.
37
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3.10 Biological treatment

Biological treatment is the most common wastewater treatment process. Because of its
versatile, efficiency and economic, biological treatment plants are widely used for both
domestic and industrial wastewater treatments. Its working principles depend mainly on
degradation and/or assimilation of pollutants by microorganisms, so called biomass, present
in the biological reactor. Key to obtain satisfying treatment efficiency is to optimize the
environment in the reactor to promote function of biomass. Even though oil or hydrocarbons
are biodegradable, presence of some hydrocarbons at some concentrations can cause adverse
effect on the biological treatment mechanisms by;
Obstructing oxygen transfer: Oxygen content is an important factor in aerobic

biodegradation. Oil layer that covers water surface will obstruct transfer of oxygen
between air and water. Oil may surround biomass floc and impede oxygen transfer
of the floc in biological reactor. This leads to the decrease in treatment efficiency.
Its high oxygen demand: Oil requires high amount of oxygen for biodegradation. It
will cause problem on insufficient aeration capability in some treatment plants that
did not account for this type of pollutant in the design procedure. It also increases
investment cost and operating cost for aeration system.
Its toxicity: In petroleum product or industrial oil-based product, they, sometime,

contain toxic substance, such as sulfide, heavy metals, which may be added to the
oil product in form of inhibitor or additive to provide desired product properties.
When these products are discharged to water and become wastewater, these
substance will become toxicity to living water organisms, includes biomass.
There are many studies, includes some from our lab, on the effect of oil contents in
wastewater to biological treatment process and possibility or optimum condition to use
biological treatment to treat oily wastewater. However, none of doctoral thesis, directed by
M.Aurelle, is fully devoted to biological treatment of oil wastewater. So we will work on this
process by reviewing the available data from our lab researches as well as outside data.
Anyway, only our lab researches will be summarized here. Synthesized result from reviewing
will be presented as a section of textbook in Part 3 of this thesis.
This all-purpose thesis is also contributed to biological treatment. The author had
performed biodegradability test of permeate from ultrafiltration of cutting oil emulsion.
1.
The study shows that ultrafiltrate of cutting oil emulsion can be treated by
aerobic biological process. The result from biodegradability test shows very high
TOC reduction efficiency (82 to 90% at the retention time of 2 to 5 hours).
3.11 Skimmer
When hydrocarbon is in the form of layer on water surface. It can be simply removed
from the surface by mean of overflow weir, overflow pipe or be scooped out manually. There
is one thesis on skimmer, which is the thesis of THANGTONGTAWI [5]. This research is
38
I-38
contributed to study on oil drum skimmer and disk skimmer, which are very effective to
recover film or layer of oil or hydrocarbon on the surface of water.
Influence of skimming materials, geometry of devices and characteristic of

wastewater to skimmer operation
Model development for oil drum and disc skimmer
Behavior of skimmers under interesting working conditions, which may affect its
efficiency
The experiment was conducted with various sizes of disc and drum skimmers to verify
effect of skimmer geometry. Various types of skimming material were tested, i.e., stainless
steel, PVC, polypropylene and fluorocarbon coated material. Kerosene and 2 types of
lubricant oil, as well as real wastewater from 4 refineries, were used in the experiment. Effect
on interfacial tension was also considered by varying concentration of a commercial
surfactant.
Result
The result of this study provides models for sizing and calculating oil quantity,
recovered by the skimmers. The study, also, provides significant criteria for skimmer material
selection to obtain selective property, which allow the devices to recover only oil, not water.
Design consideration, such as limitation of model, working condition to be avoided, etc. is
included in this study.
1.
In this thesis, mathematical models for sizing and calculating oil productivity of
the skimmer are proposed.
2.
Influence of skimming material is studied and can be summarized as follow,
Material of high surface energy, such as stainless steel, which is conditioned

by submerging in oil, will effectively recover or separate the oil from water.
However, when oil film on the surface of the tank is broken and the skimmer
is exposed to water, it will start recover the water immediately. Even after the
oil layer is present again, it will not resume its function of oil recovering.
Material of low surface energy, such as PVC and PP, can effectively recover
oil. But it will start recovering water after the oil film is broken and the
skimmer is allowed to expose to the water surface for some times. Anyway,
it will resume its function after the presence of oil layer.
From the study, fluorocarbon coated material, which is patented by ELF, is
the best oil-water selectivity. It always recovers only oil.
3.12 Application researches

To apply treatment processes previously described in real life situation, our lab had
performed some researches that devoted to compare the efficiency of various stand-alone
processes or combination of processes on treatment of certain type of oily wastewater. This
39
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kind of research provides very useful information for process selection or process design. All
of related theses on membrane process can be outlined as follows.
This thesis is an application research on the treatment of non-stabilized oil/water
emulsion, which is one of the most encountered wastewaters.
Study on treatment of non-stabilized emulsion by ultrafiltration

Influence of operating condition, presence of surfactant and type of membrane on
ultrafiltration process
Study on treatment of non-stabilized emulsion combination of coalescer/
hydrocyclone
The experiment on ultrafiltration was conducted with 3 models, i.e. commercial batch
test module (effective area 37 cm2), lab scale cross flow model (effective area 100 cm2) and
pilot scale cross flow model (effective area 1 m2). The non-stabilized emulsions tested
consisted of synthetic emulsion kerosene/water and crude oil/water emulsion. However, the
author also tested the emulsion with presence of surfactant to study the effect of surfactant on
ultrafiltration. These stabilized emulsions were cutting oil emulsion and wastewater from
textile factory, which contained oil, water, dye and some surfactant from cleansing chemical
in form of emulsion.
For ultrafiltration membrane, she had tested various membrane materials, i.e.,
inorganic, organic and ceramic. She also used 2 forms of membrane, i.e. plain and tubular.
For combination of coalescer/hydrocyclone, two types of coalescer bed were used,
bottle brush type and disorderly fibrous bed (like metal wool). For hydrocyclone, a
commercial hydrocyclone, model DOXIE 5 of Dorr-Oliver, was used.
Results of this thesis are described in previous sections, corresponding to each process
that had been studied in this thesis. However, to get the whole picture of this thesis, we will
summarize overall significant findings of this thesis again as follow;
1.
Ultrafiltration process can be use to treat non stabilized emulsion with

remarkable efficiency (approx. 100%).
2.
Major problem of the ultrafiltration is a rapid decrease in permeate flux, caused

by;
Presence of suspended solids in wastewater: these solids will lodge tightly in

membrane pores and cause clogging.
Presence of surfactant: the surfactant will be adsorbed or form micelles
within the membrane pores, as well as membrane surface, then cause
changing in wettability of membrane.
40
I-40
3.
Influence of surfactant on permeate flux, also, depends on material of membrane.

Inorganic (mineral) based membrane is more sensitive to surfactants than other
membranes.
4.
Backflushing the membrane with its permeate is proven to be an effective way to

increase the limiting flux. The result shows that duration of ultrafiltrating and
backflushing cycle should be optimized to obtain best efficiency. Normally, the 2
cycles is preferred to be short.
5.
At high empty bed velocity, the coalescer with random bed will coalesce and
enlarge the droplets into relatively large drop, while the coalescer with brush
type bed tends to produce stream of jet, containing small oil drop.
6.
However, the disorderly fibrous (steel wool) bed coalescer tends to be clogged
by suspended solids, usually presence in the oily wastewater. So the author
proposed new configuration of fibrous bed in form of the combination of 2
brushes. The internal one is of ordinary brush. The external one will look like
coil spring with its fiber elements protruding inward and toward the center. This
type of bed is believed to provide good interception, similar to the disorderly
bed, yet remain its anti-clogging properties, like brush-type bed.
7.


This thesis is an application research on the treatment of stabilized oil/water emulsion,
one of the most encountered oily wastewaters. The author also extended the research of
SRIJAROONRAT [10] on the combination of coalescer and hydrocyclone by studying the
influence of order of the 2 processes. So, WANICHKUL tested both combinations of
coalescer/hydrocyclone and hydrocyclone/coalescer as well as the combination on
coalescer/hydrocyclone/coalescer.
Study on treatment of stabilized emulsion by ultrafiltration and distillation

Study on treatment of permeate from ultrafiltration by reverse osmosis, biological
treatment and distillation
Study on treatment of retentate from ultrafiltration by heteroazotropic distillation
Study on treatment of non-stabilized emulsion combination of coalescer/
hydrocyclone and hydrocyclone/coalescer
Study on multi stage fibrous bed coalescer
The experiment on ultrafiltration was conducted with 3 models, i.e. commercial batch
test module (effective area 37 cm2), lab scale cross flow model (effective area 100 cm2) and
pilot scale cross flow model (effective area 1 m2). For reverse osmosis, he used commercial
test module from OSMONIC co., ltd.
The stabilized emulsions tested consisted of 2 commercial cutting oil emulsions, 1
macroemulsion and 1 microemulsion. For membrane regeneration, he used the microemulsion
41
I-41
used in the experiment as a cleansing reagent. He also used water to rinse the membrane after
each test.
For ultrafiltration membrane, he used the asymmetric type organic membrane from
ORELIS S.A., pore size 50 Kdaltons. For reverse osmosis, he used hydrophilic organic
membrane, cut size 150-200 Daltons.
For distillation, lab-scale glass distillation apparatus was used. For biodegradation, the
apparatus, custom-made by our lab, called Respirometer BIOS-R was used. This apparatus
can track reduction of organic material and convert to biodegradability.
For hydrocyclone/coalescer study, co-current transparent hydrocyclone and bottle
brush fibrous bed coalescer were used. He also tested a new type of fibrous bed, multi stage
fibrous bed. In fact, the new bed is modified version of bottlebrush type with the rings of
fibers not placed close to each other, but placed separately.
Results of this thesis are described in previous sections, corresponding to each process
that had been studied in this thesis. However, to perceive the whole picture of this thesis, we
have summarized overall significant findings of this thesis again as follows;
1.
The result on the treatment of cutting oil emulsion by ultrafiltration confirms the
result of MATAMOROS that the process is feasible and the efficiency of the
process is satisfying. The author recommended that operating condition should
be in permanent regime to avoid influence of factor of concentration.
2.
Using microemulsion with under-saturated oil concentration is an

method to regenerate the membrane.
3.
The author had studied the efficiency of reverse osmosis on ultrafiltrate

treatment. The result shows that the process provides remarkable efficiency.
4.
Comparison on efficiency between ultrafiltration and distillation on cutting oil

emulsion treatment, the author concluded that ultrafiltration is suitable for
macroemulsion treatment, while distillation is more efficient for microemulsion
treatment. However, from economic point of view, energy consumption of
ultrafiltration is always lower than distillations.
5.
Heteroazeotropic distillation is proven to be an effective way to treat

mayonnaise-like retentate from ultrafiltration of cutting oil emulsion. The
residue of distillation process is clear liquid, composed of oil without water.
6.
The research results shows that key parameters that governs the efficiency of cocurrent hydrocyclone are;
effective
Influent flowrate
Recovered oil draw-off rate
Ratio between outlet velocity of oil and outlet velocity of treated water,
calculated at each corresponding outlet port
7.
The author recommended that the velocity ratio mentioned above should be
greater than 1.5.
8.
Testing of the 2 types of the combination in industrial pilot plants shows

satisfying result. These combinations provide promising alternatives for
42
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industrial wastewater treatment process. Furthermore, advanced combination of

coalescer-hydrocyclone-coalescer is tested. It promisingly shows that 2
concentrated oil/water mixture from the outlet of the hydrocyclone
9.
Result from Multi stage fibrous bed coalescer test shows that this modified
bottlebrush bed provides better efficiency than the classic bottlebrush bed. This
is because the gaps between each stage can cause turbulence, then promote
coalescence between oil droplets that, somehow, fail to coalesce in the previous
stage of bed.
43
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Chapter 4 Conclusion
In this part, we have reviewed all of the researches in our lab, directed by Professor
AURELLE. We can see the attempts to study many aspects of treatment processes to cope
with various type of oily wastewater. The results of each thesis make us understand working
principles and limitation of the processes in many specific cases or frameworks. In the next
part, we will analyze these specific data from these theses. And then try to integrate and
generalize them to formulate design criteria or mathematical models that can be used with the
entire (or as wide as possible) range of oily wastewater.
44
I-44
Part II Generalization of models for

oil-water separation process design
Part II Generalization of models for oil-water separation process design
Contents
Page

Chapter 1
Decanting
1.1
1.2
1.3
1.4
Chapter 2
Simple decanter or API tank

Lamella decanter or Parallel Plate Interceptor (PPI)
Model verification
Conclusion and generalized model of decanter
Skimmer
2.1 Drum skimmer
2.2 Disk skimmer
Chapter 3
3.2

3.1.1 Filtration-based model
3.1.2 Dimensional analysis-based model
3.1.4 Conclusion and generalized model of granular bed
coalescer
3.1.5 Generalized model for guide coalescer
3.1.6 Generalized model for mixed bed coalescer
3.1.7 Generalized model for pressure drop of granular bed
coalescer and guided coalescer
3.2.1 Dynamic fibrous bed coalescer model
3.2.2 Simple fibrous bed coalescer model
3.2.4 Conclusion and generalized model of fibrous bed coalescer
3.2.5 Generalized model of random or disorderly fibrous bed
coalescer
3.2.6 Generalized model for pressure drop of fibrous bed
coalescer
II-11
II-11
II-12
II-13
II-14
II-15
II-16
II-16
II-18
II-18
II-18
II-18
II-21
II-23
II-24

4.1
4.2
4.3
4.4
Chapter 5
II-9
II-10
Coalescer
3.1
Chapter 4
II-2
II-3
II-4
II-7
Dissolved Air Flotation (DAF) model for oily wastewater

treatment
Model verification
4.2.1 Modification of filtration-based model
4.2.2 Population balance method
Generalized model for DAF
II-25
II-26
II-26
II-28
II-30
II-35
Hydrocyclone
5.1
5.1.1 Trajectory analysis-based model
5.1.2 Other models
II-37
II-37
II-38
II-39
II-i
Contents
Contents (Cont)
Page
5.1.4
5.1.5
5.2
Chapter 6
II-40
II-41
II-43
5.2.1 Model development and verification for liquid-liquid
II-43
section
5.2.2 Model development and verification for solid-liquid section II-45
5.2.3 Generalized Model for pressure drop of three-phase
II-46
hydrocyclone
Membrane process
6.1
6.2
Chapter 7
Conclusion and generalized model of two-phase

hydrocyclone
Generalized model for pressure drop of two-phase
hydrocyclone
Ultrafiltration
II-49
6.1.1 Resistance model
II-50
6.1.2 Film theory based model
II-52
II-53
6.1.4 Flux prediction for mixture of cutting oil microemulsion II-58
and macroemulsion
6.1.5 Theoretical flux prediction for batch cross-flow UF process II-60
6.1.6 UF efficiency
II-63
6.1.7 Minimum and maximum transmembrane pressure and
II-64
power required
6.1.8 Conclusion and generalized model of UF
II-66
II-66
Heteroazeotropic Distillation
7.1
7.2
7.3
Theoretical model
II-69
Model verification
II-72
Conclusion and generalized model of heteroazeotropic distillation II-72
II-ii
Table
Page
Table 1.1
Table 6.1
Table 6.2
Table 6.3a
Table 6.3b
Table 7.1
Summary of tested decanters and operating conditions

Summary of parameters of resistance model from UF researches on
oilywastewater treatment (reference temperature = 20O C)
Summary of parameters of film model from UF researches on oily
wastewater treatment (reference temperature = 20O C)
Summary of RO data on oily wastewater treatment
Summary of NF data on oily wastewater treatment
Heterotropic temperature and composition from various extractants
II-6
II-51
II-54
II-67
II-68
II-72
II-iii
Contents
Figure
Page
Fig.
Fig.
Fig.
Fig.
1.1
1.2
1.3
1.4a
Schematic and typical removal efficiency curve of simple decanter

Schematic of PPI decanter
Spiraloil decanter a) Simple spiral b) Mixed spiral
Comparison between observed efficiency (1',2',3') and predicted
efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
II-3
II-4
II-5
II-6
Fig.
1.4b
Comparison between observed efficiency (1',2') and predicted

efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
II-6
Fig. 2.1
Drum and disk skimmer
Fig. 3.1(a) Schematic diagram of granular bed coalescer, (b) photo of bed material
with coalesced oil on their surface and (c) coalesced oil drops at the
discharge surface of bed
Fig. 3.2a Relation between droplet diameter VS. model's error
Fig. 3.2b
Comparison between observed efficiency and predicted efficiency from
DAMAK's model
II-10
II-11
II-14
II-14
Fig.
3.3
Relation between observed pressure drop of granular bed coalescer and

predicted upper & lower limits from Kozeny-Carman's porosity
Fig.
3.4

SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data
Fig.
3.5
Comparison between observed efficiency and predicted efficiency by

20TAPANEEYANGKUL's model for simple fibrous bed
rpm)
Fig.
3.6

modified SRIJAROONRAT's model (eq. 3.8b)
II-21
Fig.
3.7
Relation between observed efficiency and predicted efficiency from random

disorderly) fibrous bed coalescer model and simple fibrous bed model
II-23(or
Schematic diagram of DAF

Relation between theoretical efficiency factor and observed efficiency
factor
Relation between obseved efficiency and predicted efficiency of DAF
from modified SIEM's model
II-25
II-27
Fig. 4.1
Fig. 4.2
Fig.
4.3
Fig.
4.4
II-17
= 0.13 and 0.23
II-19
II(Assume rotating speed = 450
II-27
Relation between absolute pressure in pressure tank and dissolved quantity

and released air volume
II-36
Fig. 5.1
Fig. 5.2
Schematic diagram and trajectories of droplets in two-phase hydrocyclone

Ma's and Thew-Colman's models
II-37
II-39
Fig.
Relation between observed pressure drop (inlet/overflow) of Thew cyclone

and predicted pressure drop
II-42
5.3a
II-iv
Fig.
5.3b
Fig. 5.4
Relation between observed pressure drop (inlet/underflow) of Thew cyclone

and predicted pressure drop
II-42
II-43
Figure (Cont)
Page
Fig.
5.5
Fig. 5.6a
Relation between observed efficiency and predicted efficiency of

liquid-liquid (Thew) part of three-phase hydrocyclone
II-44
Relation between observed pressure drop (bar) across inlet and water outlet II-47
and predicted value from 2 approaches
Relation between observed pressure drop (bar) across inlet and SS outlet
II-48
Fig.
5.6b
Fig.
5.6c
Relation between observed pressure drop (bar) across inlet and oil outlet
II-48
Fig.
Fig.
Fig.
Fig.
6.1
6.2
6.3a
6.3b
II-49
II-52
II-52
II-
Fig.
6.4
Typical schematic diagram of Cross-flow membrane process

Typical relation between flux and various parameters
Relation between flux and concentration at any recirculation velocity [38]
Typical characteristic curve of concentration VS. Flux
53(Log-Normal scale) [38]
Relation between UF permeate flux and Transmembrane pressure at
reference concentration (C) of = 4%, V = 1.4 m/s and Predicted relations
at C = 2 and 8%
Fig.
6.5
Relation between observed and predicted flux by resistance model for

ultrafiltration of macroemulsion 4% conc. and extend to cover other conc.
II-56
II-57
by film model
Fig.
6.6
Comparison between predicted flux and observed flux for UF of micro/

macroemulsion mixture (Conc. shown as % by volume of concentrate)
II-59
Fig.
6.7
Relation between observed and predicted flux of micro/macroemulsion

II-60
mixture from weighted average method between flux of whole micro and macroemulsion at the same total oil
concentration
Fig. 6.8a
Fig. 6.8b
Relation between Flux VS. theoretical and observed permeate volume

Relation between time VS. theoretical and observed permeate volume
II-62
II-62
Fig.
Relation between theoretical flux VS. concentration of oil in retentate
II-63
Relation between oil concentration VS. viscosity of emulsion

Isobar equilibrium diagram : Temperature-Concentration characteristic of
immiscible binary mixture
Graphical method to find heteroazeotropic temperature
Graphical method to find dew curves
II-65
II-70
6.8c
Fig. 6.9
Fig. 7.1
Fig. 7.2
Fig. 7.3
II-70
II-71
II-v
Part II Generalization of model for oil-water separation process design
Part 2 Generalization of model for oil-water separation process design

In this part, the models or researches collected and summarized in the part I are
analyzed and then generalized to obtain the model or models that governs the entire range (or
as wide as possible) of oily wastewater that we are interested in. Basic concept of each model
is briefly described here providing that it will be fully described in the next part. Then the
models and their limitations will be presented. After that, models will be tested using various
sets of data to cover the considered range of wastewater. Finally the generalized model will
then be proposed.
45
II-1
Chapter 1 Decanting
Chapter 1 Decanting
Decanting or sedimentation is a non-accelerated process, which every input
parameters in STOKES law are not modified. According to the researches reviewed in Part I,
there are several types of decanters studied in GPI laboratory, i.e.,
1.1
Simple decanter, which is made well known and standardized by American Petroleum
Institute (API), is the simplest oil-water separation process based on classical STOKES law.
Concept of operation of the process is to provide sufficient time for droplets to float to the
surface, where it will accumulate into oil layer, before it flows out with the water at the water
outlet.
The model that governs the operation of the process is derived from comparing the
time required for the droplet to reach the surface with retention time of the tank. Fig. 1.1
shows again the diagram of decanting process. From the figure, the longest path to reach the
surface is the path starts at the bottom of the tank. The smallest droplet size that can reach the
surface is called the cut size. The droplet of cut size or bigger is always separated from
wastewater stream with 100% removal efficiency.
The smaller droplet can be also separated providing that it enters the tank near the
water surface. When uniformly distributed influent flow is valid, which is true for almost all
of properly designed tank, the removal efficiency of the droplets smaller than cut size is
proportional to its corresponding rising velocity. From these concepts, the models of
decanting process are as shown in eq. 1.1 to 1.4.
U
dc
Q
=
S
{1.1}
From STOKES law

U =
d
Then
g d 2
18 c
{1.2}
1/2
18Q c
d c =
g S
{1.3}
For oil droplet size, d cut size,dc

{1.4a}
= 100%
d
t =
U
U
Q
Q
{1.4b}
d 100%
dc
out
Q out = Q
1 d max
d C od 100%
C
o d min
d max
{1.4c}
{1.4d}
C od
d min
46
II-2
Q
U
Influent
d > cut size
Effluent
d = cut size
d < cut size
Zone 1
Zone 2
d = or > d c
d
d < dc
dc
Fig. 1.1 Schematic and typical removal efficiency curve of simple decanter
Typical characteristic of the removal efficiency of decanter is as shown in fig. 1.1. The
equations are valid while these conditions are satisfied i.e.,
1.2
1.
Reynolds number, Re, of droplet is between 10-4 to 1, which is the range that
STOKES law is valid.
2.
The oil droplets are uniformly distributed across the cross section area of the
tank.
3.
The oil droplet is spherical, which is normally true.
Lamella Decanter or Parallel Plate Interceptor (PPI)
This type of decanter is the basic modification of the simple decanter. The concept is
to decrease the rising distance of droplet to intercepting surface without decreasing the
retention time. This can be achieved by inserting plates into the simple decanter to act as the
interceptors for the rising oil droplets. Rising or travelling distance (H) is the distance
between the plates, not the depth of water (D) as shown in fig. 1.2. Some times, the plates are
inclined with angle () as related to horizontal axis. In this case, rising distance will become
H / cos .
The model that governs the operation of the process is modified from the model of
simple decanter, as shown in eq. 1.5. From the equation and figure, it can be implied that the
simple tank is divided into (N+1) small decanters.
47
II-3
Chapter 1 Decanting
Separated oil floats

to surface
L
Q
H
Influent
Effluent
Inserted plates
(No. of plates = N)
Fig. 1.2 Schematic of PPI decanter

1/2
18Q
c
dc =
gS (N + 1)
P
Where
{1.5}
Inserted plate area

Numbers of inserted plates
Length of inserted plates
Rising distance of oil drop, in this case, distance between inserted
plates
= Inclination angle, related to horizontal axis
When incline plates are used, replace Sp with Sp cos .
Sp
N
L
H
=
=
=
=
Removal efficiency can be calculated using eq. 1.4. Typical characteristic of the
removal efficiency of decanter is identical to simple decanters, as shown in fig. 1.1.But the
cut size of PPI tank will be smaller than the simple decanters, providing that they are the
same size. The equations are valid while these conditions are satisfied i.e.,
1.3
1.
The tank is operated under laminar flow regime. Reynolds number, Re, is
between 10-4 to 1, which is the range that STOKES law is valid.
2.
The oil droplets are uniformly distributed across the cross section area of the
tank.
3.
4.
The plates are identical in size and are inserted evenly and in parallel.
Model verification
According to the concept of decanting model that derives from comparing detention
time with rising time of droplet to intercepting surface, we can formulate the general model to
calculate dc for any decanters as shown in eq. 1.9
General model for calculating the cut size, when H, L and A can be clearly defined.
1/2
18HQ c
d c =
gLA
{1.9a}
48
II-4
Where
Q
H
L
A
=
=
=
=
Wastewater flowrate
Rising distance of oil drop, depends on configuration of the decanter
Length of interceptor surface
Flow area (Cross sectional) area of decanter
Removal efficiency can be calculated using eq. 1.4. From the equations, we can see
that the models of simple decanters and PPI are modified forms of eq. 1.9 by simple relations
of flow velocity and tank geometry. However the models described before are derived from
basic rectangular tank and flat insertion plates.
But, in real life situation, decanters are designed or produced in various forms, such as
corrugated plate inserted tank, concentric annular insertion decanter, etc. So, sometimes, it is
very difficult to define H. Then, we propose to simplify the general model by neglecting
complicate analyzing to define H, and using concept of decanting area (Sd) instead. Sd is
calculated from the sum of every surface area within the decanter that can intercept oil
without considering whether the values H of these areas are identical or not. The other form
of general model is shown in eq. 1.9b.
18Q
c
dc =
g S
d
1/2
{1.9b}
To verify the theoretical model, we select the research of CHERID [4] on 2 sets of the
SPIRALOIL decanter, i.e.,
Simple Spiraloil; fabricated from concentric annular plates as shown in fig. 1.3a
Mixed-spiral Spiraloil; ; fabricated from concentric annular plates with
corrugated plates spacer as shown in fig. 1.3b
We will use these decanters to compare the removal efficiency calculated from model
to experimental result from the research. Geometry of the decanter and operating parameters
used in the experiment are summarized in Table 1.1 and Annex A1.
Annular plates
H
Solid core,
radius = r
e
R
a)
b)
Fig. 1.3 Spiraloil decanter a) Simple spiral b) Mixed spiral
49
II-5
Chapter 1 Decanting
Table 1.1 Summary of tested decanters and operating conditions

Description
Simple spiral Spiraloil
Mixed spiral Spiraloil
Nominal radius R (mm)
50
50
Core radius r (mm)
10
10
Length of decanter L (mm)
300
300
Total length of inserted plates (m)
3.88
N/A
Plate thickness (mm)
0.3
0.2 for annular plates

0.4 for corrugated plates
Interceptor (decanting) area (m2)
1.66
2.1
Horizontal
Horizontal
0.4-1.6
0.5-1.5
14.4-57.6
18-54
Kerosene-water mixture
Kerosene-water mixture
Geometry
Spacing between concentric annular plate (mm)
Inclination of decanter
Operating conditions
Flow velocity (cm/s)
(m/h)
Wastewater used
100.00%
Removal efficiency (%)
90.00%
80.00%
1'
3'
V = 0.4 cm/s (1, 1')
70.00%
V = 0.8 cm/s (2, 2')
60.00%
V = 1.6 cm/s (3, 3')
50.00%
40.00%
2'
30.00%
20.00%
10.00%
0.00%
0
10
20
30
40
50
60
Droplet diameter (micron)
Fig. 1.4a
Comparison between observed efficiency (1',2',3') and predicted efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
100.00%
90.00%
1'
80.00%
1 (V = 0.5 cm/s)
70.00%
60.00%
2'
50.00%
2 (V = 1.5 cm/s)
40.00%
30.00%
20.00%
10.00%
0.00%
0
10
20
30
40
50
60
Fig. 1.4b
Comparison between observed efficiency (1',2') and predicted efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
50
II-6
Comparison graphs between observed efficiency and predicted efficiency from model
for both Spiraloil decanters are shown in fig. 1.4. These graphs show that;
1.4
1.
Predicted values for cut size are relatively accurate.
2.
Predicted efficiencies of the droplets smaller than cut size are always lower than
observed value because, in our simplified model, coalescing between rising oil
drops is not accounted. Furthermore, in case that the plates are placed very close
to each other like in Spiraloil, oil film will accumulated at the surface of plate,
then helps reducing rising height oil droplet, thus increasing the efficiency.
3.
Correction factor for efficiency prediction of these small droplets may not be
established accurately. However, the predicted cut size can be used to design the
tank with relative high accuracy. So it is reasonable to select the cut size to cover
the majority of droplet size distribution. The predicted efficiency of smaller
droplets, which is the minority part, will cause no harm but slightly
underestimation on the total efficiency.
Conclusion and Generalized Model of decanter
From model verification result, we can conclude and propose the generalized model,
as well as, its limitation as follows,
1.
To solve oil or hydrocarbons removal efficiency of decanter, the cut size of the
decanter will be determined first. Then, graded efficiency (efficiency of each size
of droplet) and then total removal efficiency can be determined.
2.
The cut size of the decanter can be determined from eq. 1.9. When configuration
of decanter is not complicate and rising distance of oil drop to interceptor can be
clearly determined, Using eq. 1.9a will give very accurate prediction. However,
when configuration of the decanter is so complicate to determine the rising
distance accurately, eq.1.9b provides relatively accurate result for the cut size.
For PPI tank, the cut size can be calculated from eq. 1.5, which is the modified
form of eq. 1.9a.
1/2
18HQ c
d c =
gLA
18Q
c
dc =
g S
d
{1.9a}
1/2
{1.9b}
1/2
18Q
c
dc =
gS (N + 1)
P
3.
{1.5}
To determine graded and total removal efficiency, use eq. 1.4.

For oil droplet size, d cut size, dc
{1.4a}
= 100%
d
51
II-7
Chapter 1 Decanting
U
U
{1.4b}
d 100%
dc
For total removal efficiency

t =
Q
Q
out
Q out = Q
4.
1 d max
C
100%
d
od
C
d
o
min
d max
{1.4c}
{1.4d}
C od
d min
To use the models described above, the following conditions need to be satisfied
and the assumptions and limitations would be noted.
1)
Reynolds number, Re, of oil droplet is between 10-4 to 1, which is the range
that STOKES law is valid.
2)
The oil droplets are uniformly distributed across the cross section area of
the tank, which can be achieved by proper design of inlet chamber. And the
oil droplet is spherical, which is normally true.
3)
For PPI or others forms of plate inserted decanter, the plates are identical in
size and are inserted evenly and horizontally. For PPI tank with incline
plates, Sp in eq. 1.5 will be replaced by Sp cos . is the inclination angle,
related to horizontal axis.
4)
If the decanter or the inserted plates are inclined, the rising distance will be
the spacing between plates, but will be measured in vertical direction. So
the shortest distance is obtained from the same spacing between plates,
when the plates are located horizontally.
5)
Prediction of cut size from eq.1.9b, even with its simplification, is

relatively accurate for the cut size larger than 20 microns.
6)
For droplets smaller than 20 microns, they are subject to Brownian motion
and cause error in the prediction of the efficiency. So it is recommended to
avoid using the decanter for the wastewater with majority part of oil
droplets smaller than 20 microns. However, if these small droplets are the
minority part of pollutants, the models can be used to predict the efficiency
without any harm because its prediction is usually lower than observed
value, thus make the prediction result on the safe side.
52
II-8
Chapter 2 Skimmer
Skimmer is the equipment designed to remove oil film or layer from water surface. It
is superior to basic hydraulic elements such as bell-mouth pipe or weir for its oil-water
selectivity. It will remove relatively water-free oil. According to the researches reviewed in
Part I, there are 2 types of skimmers studied in GPI laboratory, i.e., drum skimmer and disk
skimmer.
2.1
Drum skimmer
Drum skimmer is rotating drum or cylinder with specially selected surface material,
which can adhere to oil, not water. The oil will adhere to the drum as a film and, then, lift up
from water surface by The skimmers rotating movement. The skimmer will be equipped with
scrapper blade to scrape the oil film from drum surface into receiving trough or gutter. Fig.
2.1 shows the schematic of oil drum skimmer.
The generalized model of drum skimmer had been proposed by THANGTONGTAWI
[5]. His proposed model was developed by similarity analysis, using Buckingham Pi theory.
He had conducted his research thoroughly and covered every necessary aspect of drum
skimmer. So his model and its limitation will be quoted here again, as shown in eq.2.1,
without the need for further verification.
0.486
3.035D1.541N1.541 o
L
P=
0.514
g
{2.1}
t = 100%
{2.2}
The model will be valid when these conditions are satisfied, i.e.;
Superficial tension of oil is in the range of 27 34 dynes/cm, which practically

covers all common oil.
Capillary number (Ca = o V/o) is in the range of 0.2 1.0.
Oil density is around 0.8 g/cm3.
Peripheral or tip velocity should not be greater than 0.8 m/s. To avoid water
entraining, velocity of 0.44 m/s or less is recommended.
Recommended immersion depth is 1.0-2.0 cm.
Presence of surfactant has only little effect on skimmers operation.
Total removal efficiency of the equipment is always 100%, providing that above
conditions are satisfied, and then recovered oil is water-free.
53
II-9
Chapter 2 Skimmer
Scrapper
Scrapper
Oil layer
Water
Oil layer
Water
a)
b)
Fig. 2.1 Drum and disk skimmer
2.2
Disk skimmer
Disk skimmers operating principle is the same as drum skimmers. Major difference
is the replacement of the drum with thin circular disk. fig. 2.1 shows the schematic of oil disk
skimmer.
The generalized model of disk skimmer had been proposed, also, by
THANGTONGTAWI [5]. His proposed model, as shown in eq. 2.3, was developed by
similarity analysis, using Buckingham Pi theory.
P=
1.328D 1.258 N 1.212 o

g 0.332
0.452 1.17
I
{2.3}
{2.2}
t = 100%

Oil density is around 0.8 g/cm3.
Presence of surfactant has only little effect on skimmer operation.
Total removal efficiency of the equipment is always 100%, providing that above
conditions are satisfied, and then recovered oil is water-free.
54
II-10
Chapter 3 Coalescer
Coalescer is an accelerated separation process that is designed to promote coalescing
of oil droplets into bigger oil drop, which can be separated easily by relatively small decanter.
There are several types and modification of coalescer studied in GPI laboratory, i.e.,
3.1
This type of coalescer uses granular material as a bed to promote coalescing between
oil droplets, as shown in fig. 3.1. AURELLE [3] is the pioneer on coalescer study. He
established the 3-step working mechanisms of the coalescer, based on filtration model [35].
Then there are several follow up researches on coalescer, based on AURELLEs research.
However, for mathematics model of coalescer, there are only 2 major mathematical models
for coalescer. The first one is based on filtration concept and another is based on dimensional
analysis.
OUT:
Large drop
Collector
size =dp,
Void ratio =
H
IN:
Micro drop
Dia. = d
Discharge
screen
Inlet
screen/support
a)
b)
c)
Fig. 3.1 (a) Schematic diagram of granular bed coalescer, (b) photo of bed material
with coalesced oil on their surface and (c) coalesced oil drops at the
discharge surface of bed
3.1.1
Filtration-based model
The method is proposed by AURELLE [3]. In his study, AURELLE divided the
mechanisms taking place with in coalescer bed into 3 steps, i.e.;

sedimentation, direct interception and diffusion.

wettability of bed material.
Step 3: Salting out or enlargement of coalesced liquid. This step depends on 4

parameters, i.e., wettability of bed material at the discharge surface (or screen),
empty bed flow velocity, interfacial tension and ratio of dispersed phase and
continuous phase in emulsion treated.
AURELLE suggested that step 2 and step 3 can be optimized by using oleophilic and
hydrophilic material as coalescer bed and discharge screen, respectively, as well as keeping
the feed flowrate within optimum range. Then step 1 will become rate determining step of the
55
II-11
Chapter 3 Coalescer
coalescer. To calculate removal efficiency of step 1, he proposed the model, based on

filtration model, as shown in eq. 3.1 to 3.3.
3
H
(1 )
(
)
exp
2
dp
100 %
= 1 e
d
exp
= 0.5484(
theo
) 0.5143
{3.2}
KT
gd 2 3 d 2
=
+ ( ) + 0.9
theo 18 V 2 dp
c
c d dpV
t =
out
Q
Q
out
=Q
2/3
1 d max
C
%
d
od
C
d
o
min
d max
{3.1}
{3.3}
{3.4a}
{3.4b}
C od
d min
The model is valid when the shape of the collector is relatively spherical.
The collector shall be wetted by dispersed phase. In case of direct emulsion (oil in
water emulsion), the collector, then, shall be oleophilic. In this case, oleophilic
resin is recommended.
Range of empty bed velocity shall not be greater than 0.35 cm/s (12.6 m/h)
Density difference between dispersed phase and continuous phase shall be

approximately 200 kg/m3.
The model is developed for inlet oil concentration between 100-200 mg/l.
At velocity < 0.35 cm/s, efficiency of the coalescer is independent of velocity.

Beyond this range, The efficiency will decrease when the velocity increases. The
rate of the decreasing of efficiency varies with size and wettability and surface
roughness of collector.
The key assumption of this model is that mechanisms in steps 2 and 3 of the
coalescer are optimized.
This research has been studied thoroughly and covered every important parameter. But
the last assumption, related to mechanisms in steps 2 and 3, is difficult to verify. The evident
is clearly shown in eq.3.2 where the relation between exp and theo is not linear. This means
there are other factors, besides the 3 interception steps, which should be included in the theo.
However this filtration-based model is good for understanding the effect of various
parameters on coalescer efficiency.
3.1.2
Dimensional analysis-based model
The method is proposed by DAMAK [9]. The model is based on classic dimensional
analysis, which is the efficient tool when exact theory of the processes can not be established,
as described in the section 3.1.1. DAMAKs model is shown in eq.3.5.
56
II-12
dpV
d
d
H
= 0.58( ) 0.2 ( ) 0.12 ( c
) 0.08 ( ) 0.09 ( ) 0.09 100% {3.5}
d
dp
dp
o/w
c
t =
out
Q
Q
out
=Q
1 d max
C
%
d
od
C
o d min
d max
{3.4a}
{3.4b}
C od
d min
The model is verified under these conditions i.e.;
3.1.3
The model is tested at the range of dp from 0.36 to 0.94 mm. and interfacial tension
of dispersed phase (oil) 11 to 42 dyne/cm. (T.I.O.A, heptane, anisole, toluene and
kerosene)
The velocity tested is in the range of 0.09 to 0.54 cm/s.
Different density between dispersed phase (oil) and continuous phase (water) is
between 83 to 314 kg/m3.
The bed material used is spherical glass bead with silicon coated.
The inlet concentration of hydrocarbon tested is around 1,000 mg/l.
Model verification
Inspite of the fact that AURELLEs model is theoretical based and understandable,
from experimental conditions of the two models stated above, DAMAKs model covers wider
range of oil and accounts for every parameter that affects coalescer operation. So, from
application and design point of view, it is more reasonable here to use the second model as the
generalized model of coalescer.
However, DAMAKs model is tested at greater concentration of inlet oil (1,000 mg/l)
than AURELLEs (100-200 mg/l). In theory, the greater the concentration, the higher the
probability of coalescing between droplets. So it is interesting to verify DAMAKs model
using AURELLEs test data. The data used for model verification is tabulated in Annex A2.1.
However, firstly, difference between predicted and observed efficiency of both models
have been checked to eliminate inaccurate or error data. Fig. 3.2a shows that, at droplet size
smaller than 10 microns, the differences between predicted and observed efficiency of both
models are very high. This may be caused by the re-fragmentation of coalesced oil by shear
force, which both models can not predict. The error may also come from inaccurate
measurement of these tiny droplets. Then, to be on the safe side, the droplet smaller than 10
microns will not be considered and assumed that their removal efficiencies are zero.
Comparison between AURELLEs observed data and predicted data from DAMAKs
model (after error data removal) is as shown in fig. 3.2. From the graph, it shows that the error
in prediction of DAMAKs model for the whole range of wastewater tested by AURELLE
and DAMAK is not greater than 10%. So DAMAKs model can be used as the generalized
model for granular bed coalescer.
57
II-13
Chapter 3 Coalescer
Error (%)
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
-10%
-20%
-30%
0.0E+00 5.0E-06 1.0E-05 1.5E-05 2.0E-05 2.5E-05 3.0E-05 3.5E-05 4.0E-05 4.5E-05
Droplet diameter (m)
DAMAK's model
AURELLE's model
Predicted efficiency %
Fig. 3.2a Relation between droplet diameter VS. model's error

d = 58 (dE/dp)
110%
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0.2
(H/dp)
0.12
(c dp V / o/w )
-0.08
(d/ c)
0.09
(/ c)
0.09
+10%
-10%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Observed efficiency %
Fig. 3.2b Comparison between observed efficiency and predicted efficiency from DAMAK's model
3.1.4
Conclusion and generalized model of granular bed coalescer
From model verification result, we can conclude and propose the generalized model as
well as its limitation as follow,
1.
To predict removal efficiency of coalescer, graded efficiency (d) can be

calculated by eq. 3.5. If the result from eq. 3.5 is greater than 100%, then it will
be rounded up to 100%. Total removal efficiency can be calculated by eq. 3.4.
dpV
d
H
d
= 58( ) 0.2 ( ) 0.12 ( c

) 0.08 ( ) 0.09 ( ) 0.09
d
dp
dp
c
o/w
58
100 %
{3.5}
II-14
t =
2.
3.1.5
out
Q
Q
out
=Q
1 d max
C
%
d
od
C
o d min
d max
{3.4a}
{3.4b}
C od
d min
and the assumptions and limitations would be noted;
1)
Coalescer bed shall be oleophilic and relatively spherical in shape.Tested

range of bed height is between 1 to 10 cm. However, bed height 1 cm is
not recommended. The greater the bed height, the safer coalescer
operation. However, it also results in higher pressure drop.
2)
The model is valid for inlet concentration between 100 - 1,000 mg/l.
3)
Tested size of bed media is between 0.35 0.9 mm. The larger the media
size, the lower the efficiency.
4)
The density difference between dispersed phase (oil) and continuous phase
(water) is between 80 to 315 kg/m3 (approx).
5)
The velocity shall be in the range of 0.09 to 0.54 cm/s.(3.2 to 19.4 m/h) for
coalescer without guide.
6)
It is recommended to use the model only for the droplet size of 10 microns
or greater. For smaller droplet, the model can also be applied, but for
comparison purpose only.
Generalized model for guide coalescer
For guide coalescer, high porosity oleophilic material, such as steel wool, will be
placed next to downstream end of the granular and extended up to water surface (actually, up
to oil/water interface of the decanter). Coalesced oil drop will channel along this material until
it combines with oil layer at the water surface. This material is called guide.
Installation of guide helps preventing formation of oil mousse or jet, which normally
occurs in classical coalescer at high velocity or high concentration of oil. Thus, the maximum
velocity before formation of mousse or jet will occur (so called critical velocity) of the guide
coalescer is, at least, 1.5 times greater than usual [6].
Unfortunately, we do not have sufficient recorded data to develop the model for guide
coalescer. However, it is proven that, at velocity range below critical value, the efficiency is
approximately velocity-independent [3], [6]. It, also, can be confirmed by eq. 3.5, which
shows that the exponent of V is very low (0.08). Then, at recommended range of velocity,
V-0.08 is approximately constant.
So, from this fact, we can estimate the efficiency of guide coalescer by using classical
model of coalescer (eq. 3.5) with additional precautions and assumptions as follow,
When V < 0.54 cm/s: Use eq. 3.4 and 3.5 directly.
When 0.54 < V < 0.8 cm/s (1.5 times of 0.54): Use eq. 3.4 and 3.5 by using V =
0.54 cm/s for calculation. Using the real velocity instead of 0.54 cm/s will result in
59
II-15
Chapter 3 Coalescer
higher efficiency. However, because of the lack of verifying data, we recommend

using low prediction value for safety.
3.1.6
Velocity 0.8 to 1.9 cm/s may still be applicable at low concentration of inlet oil
(phase ratio around 1-2).
For oil inlet concentration, guide coalescer has been tested in liquid-liquid
extraction application [6] with maximum phase ratio (oil/water) of 6, the result
shows that it can operate effectively. So, for oily wastewater treatment process,
which the concentration is much lower, installation of guide can assure that the
coalescer should operate efficiently.
Generalized model for mixed bed coalescer
Mixed bed coalescer is another modified form of granular bed coalescer, used for
mixed direct/inverse emulsion separation, which is usually found in liquid-liquid extraction
process. In mixed bed coalescer, the bed will consist of separate layers of oleophilic and
hydrophilic materials, placed in series in the same column. From research [6], ratio of
oleophilic and hydrophilic material and order or configuration of column (upper hydrophilic
layer/lower oleophilic layer or vice versa) depends on wastewater characteristic. So it is
difficult to determine the efficiency of the coalescer by fixed equation. In this case, it is
recommended to perform pilot test to find optimum design criteria.
3.1.7
Generalized model
coalescer
for pressure drop of granular bed coalescer and guided
Many GPI researches provide data of pressure drop of granular bed coalescers. But
there is no model proposed and, unfortunately, there is insufficient data to develop new
pressure drop model by dimensional analysis. So we have to develop the model based on
available theory. According to the structure of coalescer, its components are similar to that of
a deep bed filter. Then, we will use pressure drop models of deep bed filter as basis to develop
coalescers pressure drop model.
Two pressure drop models are considered, i.e.,
Kozeny Carmans model: pressure drop is calculated from bed porosity.
Darcys model: pressure drop is calculated from bed permeability.
From normal practice, porosity may be used more often to describe the bed. So we
will use Kozeny-Carmans equation (eq. 3.6) to predict coalescer pressure drop (P), in m of
water.
P =
180H c V(1 ) 2
m g dp 2 3
{3.6}
All variables except porosity () will be determined by designer. For the porosity of
coalescer bed, from our literature review, there is no data provided in any research. Then we
will use the pressure drop data from researches to calculate back to find corresponding
porosity. From many researches [3], [26], [27], it shows that bed porosity varies with bed
depth and can be divided into 2 zones, i.e.,
60
II-16
Lower zone or critical zone: This zone represents effective zone of coalescer bed.
The maximum height of this zone is called critical height (Hc). When bed height
is greater than critical height, the efficiency will increase only slowly (From eq.
3.5: H 0.12). In this zone, the bed will be soaked with oil so the porosity will be
low.
Upper zone: If the bed is higher than Hc, practically, all of oil will be trapped in
critical zone. Then in higher zone, there will be enough oil in lower zone to flow
continuously through the bed in form of flow channeling. So the porosity in this
zone will be lower than critical zone.
We use data from various researches [3], [26], [27] to verify the value of bed porosity.
The verification result is shown in Annex A2.2 and fig. 3.3. We can conclude that pressure
drop of granular bed can be calculated by Kozeny-Carmans equation (eq. 3.6), using the
following recommendations, i.e.,
When Hc is known (from literatures, etc.), pressure drop in the lower and upper
part of bed can be calculated separately, using eq. 3.6. Recommended porosity ()
for the lower (critical) part of bed (H<Hc) is between 0.14 to 0.19. Recommended
porosity for the upper part of bed (H>Hc) is between 0.23 to 0.30.
If it is certain that H design < Hc, use single step calculation with = 0.14 - 0.19.
However, Hc is usually unknown, then it is recommended to use single step

calculation with = 0.13 and 0.23 to estimate minimum and maximum pressure
drop respectively (as shown in fig. 3.3).
Because of the fact that guide of guided coalescer has relative high porosity (0.9
approx.), then, The pressure drop is very low, compared to granular bed, and can
be negligible. So eq. 3.6 can also be used for guided coalescer.
160
Observed data
Upper limit (porosity = 0.13)
Lower limit (porosity = 0.23)
140
Pressure drop (m)
120
100
80
60
40
20
0
1
11
13
15
17
19
21
23
25
27
29
31
Run number
Fig. 3.3
Relation between observed pressure drop of granular bed coalescer and predicted upper & lower limits from KozenyCarman's porosity = 0.13 and 0.23
61
II-17
Chapter 3 Coalescer
3.2
This type of coalescer uses relatively porous fibrous material as a bed to promote
coalescing between oil droplets, as shown in fig. 3.4. Due to its high porosity, this type of bed
is hardly clogged and can handle wastewater containing suspended solids efficiently. It also
causes much less pressure drop than granular bed coalescer. However, fibrous element, which
is normally very small, can be deflected, especially in large-scale unit, and causes unpredicted
channeling, then decreasing in efficiency. Three basic steps for granular bed coalescer,
proposed by AURELLE [3], can also be used to describe phenomena taking place within the
coalescer. However, mathematical models, derived from dimensional analysis, are proven to
be more accurate.
There are 2 main categories of fibrous bed coalescers, i.e., simple fibrous bed
coalescer and dynamic (or rotating) fibrous bed coalescer. The latter is the modified form of
the former, by the installation of driving unit to drive the bed.
3.2.1
Dynamic fibrous bed coalescer model
The method is proposed by TAPANEEYANGKUL [8]. The model is based on the

classic dimensional analysis, which is an efficient tool when exact theory of the processes can
not be established. The author had conducted his research thoroughly and covered every
necessary aspect of the equipment. So his model and its limitation will be quoted here again,
as shown in eq.3.7, without the need for further verification.
0.67d 0.58 (1 ) 0.35 H0.35 N0.53

=
d
D0.03 d 0.58 V0.74

F
100 %
{3.7}
3.2.2
52 < Re < 1164.
Rotating speed of the bed is between 10 to 200 rpm.
Empty bed velocity is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h).
Diameter of coalescer bed is around 11.5 cm.
Diameter of fiber is around 100 to 300 microns.
The beds, used in the experiment, are bottle brush types, made of polyamide or
polypropylene with stainless steel shaft.
Simple fibrous bed coalescer model
This coalescer is a predecessor of dynamic bed coalescer, described in the previous

section. However, the researches on this type of coalescer are based mainly on its application
and design consideration, rather than model development. So there is no model proposed by
GPI researchers for this equipment.
3.2.3
Model verification
After reviewing existing experimental data, it shows that each research presents only
some parameters related to its own objectives. However we have tried to develop a model,
62
II-18
using dimensional analysis method, from SRIJAROONRATs data [10], which provided more
details than others. And then we verified the model with the data from other researches [11],
[16]. The proposed model is shown in eq. 3.8a. In our research, we will call it
SRIJAROONRATs simple fibrous bed model.
VD
d
d
H
= 45.005( c
) 0.77 ( ) 0.18 ( F ) 0.18 ( ) 0.694 100 % {3.8a}
d
D
D
D
100.0%
90.0%
80.0%
Predicted efficiency (%)
70.0%
60.0%
+20 %
50.0%
40.0%
-20 %
30.0%
SRIJAROONRAT's data
MA's data
WANICHKUL's data
20.0%
10.0%
0.0%
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%
100.0%
Observed efficiency (%)
Fig. 3.4
Comparison between observed efficiency and predicted efficiency from SRIJAROONRAT's model, Verified by MA's
and WANICHKUL's data
Comparison between observed and predicted efficiency is shown in fig. 3.4. From the
graph, it shows that;
The proposed model is valid for empty bed velocity up to 2 cm/s (72 m/h) and
concentration of inlet oil up to 1000 mg/l.
For higher empty bed velocity, there is not any detailed data on graded efficiency
to verify the model. However, SRIJAROONRATs research shows that the total
(or average) efficiency, more or less, still conforms to eq. 3.8 at the velocity as
high as 5 cm/s and that the equation tends to underestimate the efficiency.
For high inlet oil concentration, for example in case of WANICHKULs research,
The model, again, tends to underestimate the efficiency.
Because of the fact that there is not enough data to find the effect of porosity,
porosity is omitted in the proposed model.
From the observations above, SRIJAROONRATs simple fibrous bed model does not
include effect of porosity. However, from TAPANEEYANGKUL [8] research, he shows that
the efficiency of dynamic coalescer, operating at low speed, is almost identical to the simple
coalescers and his model readily includes the effect of porosity. So it may be a matter of
interest to verify if the model of dynamic coalescer is possible to apply to simple coalescer by
assuming a low rotational speed into the model.
63
II-19
Chapter 3 Coalescer
For this, data from several researches [10], [11], [16] have been used to verify
TAPANNEYANGKULs model. The data, used to verify the model, has been limited to the
droplet size of 10 microns and greater. For smaller droplet, it is difficult to measure the
concentration of these droplets accurately. So observed data is not complete and seems
erroneous. Comparison between observed and predicted efficiency is shown in fig. 3.5.
From the graph, it shows that TAPANEEYANGKULs model can be adapted to
predict the efficiency of simple fibrous bed coalescer with acceptable degree of accuracy (
20% error) when using the rotating speed = 450 rpm. This speed is too high to be reasonable.
This may be due to the fact that TAPANEEYANGKULs model is verified from relatively
short bed (H/D < 2) while other researches operate at H/D up to 10. So the exponent of (H/D)
from both models is quite different. In this case, we can conclude that TAPANEEYANGKUL
may not be applied to simple fiber bed coalescer.
However, it is still interesting to assume that the effect of porosity in
SRIJAROONRATs model should be the same as TAPANEEYANGKULs. So we add the
term (1-)0.35 into eq. 3.8a and solve for a new constant to replace 45.005. The modified
model is shown in eq. 3.8b. Comparison between observed and predicted efficiency is shown
in fig. 3.6. The graph shows that MAs data are better predicted, using eq. 3.8b. The model
still cannot cover WANICHKULs data for it is tested at very high oil inlet concentration
(7950 mg/l). However, the predicted efficiency is still on the safe side to use as a guideline.
VD
d
d
H
= 104.5( c
) 0.77 ( ) 0.18 ( F ) 0.18 (1 )0.35 ( ) 0.694 100 %
d
D
D
D
{3.8b}
120.0%
100.0%
80.0%
+20%
60.0%
40.0%
-20%
20.0%
0.0%
0.0%
20.0%
40.0%
60.0%
80.0%
100.0%
120.0%
Fig 3.5
Comparison between observed efficiency and predicted efficiency by TAPANEEYANGKUL's model for simple
fibrous bed (Assume rotating speed = 450 rpm)
64
II-20

100.0%
90.0%
80.0%
70.0%
60.0%
+20 %
50.0%
40.0%
-20 %
30.0%
SRIJAROONRAT's data
MA's data
WANICHKUL's data
20.0%
10.0%
0.0%
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%
100.0%
Fig. 3.6
3.2.4
Comparison between observed efficiency and predicted efficiency from modified SRIJAROONRAT's model (eq.
3.8b)
Conclusion and generalized model of fibrous bed coalescer
well as its limitation as follows,
1.
To predict removal efficiency of coalescer, graded efficiency can be calculated

by eq. 3.7. If the result from eq. 3.7 is greater than 100%, then it will be rounded
up to 100%. Total removal efficiency can be calculated by eq. 3.4.
0.67d 0.58 (1 ) 0.35 H0.35 N0.53

=
d
D0.03 d 0.58 V0.74

F
t =
2.
out
Q
Q
out
=Q
100 %
1 d max
C
%
d
od
C
o d min
d max
{3.7}
{3.4a}
{3.4b}
C od
d min
54 < Re < 1164.
1 < H/D < 2. However, the maximum H/D shows in

TAPANEEYANGKULs research is 6. Using H/D > 2 in the model can be
also applied for comparison purpose only.
Rotating speed of the bed is between 10 to 200 rpm. However, recommended

minimum rotating speed is 75 rpm. Using lower speed may not provide any
additional benefit over simple fibrous bed coalescer.
Empty bed velocity is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h).
65
II-21
Chapter 3 Coalescer
3.
Diameter of fiber is around 100 to 300 microns and diameter of coalescer bed
is around 11.5 cm. Using bigger coalescer diameter may cause deflection at
the end of fibers from longer overhung length, which may cause error in
calculation.
The beds, used in the experiment, are bottle brush types, made of
polyamide or polypropylene with stainless steel shaft.
It is recommended to use the model only for the droplet size of 10 microns or
greater. For smaller droplet, the model can also be applied, but for
comparison purpose only.
Internal diameter of coalescer casing, which contains the bed, should be as close
to the diameter of the bed as possible to avoid channeling problem.
Simple fibrous bed coalescer

1.
To predict removal efficiency of coalescer, graded efficiency can be calculated

by eq. 3.8b. If the result from eq. 3.8b is greater than 100%, then it will be
rounded up to 100%. Total removal efficiency can be calculated by eq. 3.4.
VD
d
d
H
= 104.5( c
) 0.77 ( ) 0.18 ( F ) 0.18 (1 )0.35 ( ) 0.694
d
D
D
D
t =
2.
out
Q
Q
out
=Q
1 d max
C
%
d
od
C
o d min
d max
100 %
{3.8b}
{3.4a}
{3.4b}
C od
d min
48 < Re < 1100.
1 < H/D < 10.
Unlike other granular bed model, eq. 3.8b is valid for droplet size of 1
microns and greater. The new technology on granulometer make it possible
to measure these very tiny droplets with high accuracy.
Empty bed velocity used in the researches is between 0.5 to 5.0 cm/s (1.8 to
180 m/h). However detailed data used to verify the model is between 0.5 to
2.0 cm/s. Using velocity > 2.0 cm/s may cause unpredictable error on
calculated efficiency.
Fiber size used in the researches is between 40 to 200 microns. However

detailed data used to verify the model is between 100 to 200 microns. Using
fiber size < 100 microns may cause unpredictable error on calculated
efficiency.
The model is verified at inlet oil concentration up to 1000 mg/l. Using the
concentration > 1000 mg/l, again, will cause underestimation of predicted
efficiency.
66
II-22
3.
3.2.5
Diameter of coalescer bed tested is around 5.0 cm. Using larger coalescer
diameter may cause deflection at the end of fibers from longer overhung
length, which may cause error in calculation.
The beds used in these researches vary from bottle brush type, simple
spiral type and combination of internal bed of simple spiral and concentric
coil spring like external bed with the tip of the fibers pointed to center
line. However, they are all oleophilic. There is some difference in efficiency
between each type, but there is too few data to make a conclusion. However,
because of its rigidity, the simple spiral in coil springlike bed tends to
operate more stable without the decrease in efficiency with time, while others
tend to be deflected by weight of accumulated oil drops. In fact, this type of
bed is invented to take advantage of spiral bed for its non-clogging and
disorderly bed for its rigidity.
Generalized model of random or disorderly fibrous bed coalescer
There is another special case of simple fibrous bed coalescer that uses random or
disorderly fibrous material (such as metal wool, etc.) as coalescer bed. SRIJAROONRAT also
studies this type of coalescer. In her research, she shows that the removal efficiency of this
coalescer is higher than that of coalescer that uses brush type bed. For this, it can be
concluded that tortuosity of bed also affects the removal efficiency. We use her data to
develop the model, based on dimensional analysis, as shown in eq. 3.9. So we will call it
SRIJAROONRATs random fibrous bed model. However, this model is developed from
rather small set of data. So we have tried to apply the generalized model in eq. 3.8b to this
type of coalescer. Comparison between eq. 3.9, 3.8b and observed value is shown in fig. 3.7.
VD
d
d
H
= 3.35( c
) 0.23 ( ) 0.03 ( F ) 0.03 ( ) 0.36 100 %
d
D
D
D
{3.9}
110.0%
100.0%
90.0%
80.0%
70.0%
SRIJAROONRAT's disorderly
bed model
SRIJAROONRAT's simple bed
model
60.0%
+10%
50.0%
-10%
40.0%
30.0%
20.0%
10.0%
0.0%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Fig. 3.7
Relation between observed efficiency and predicted efficiency from random (or disorderly) fibrous bed coalescer
model and simple fibrous bed model
67
II-23
Chapter 3 Coalescer
From the graph, it shows that SRIJAROONRATs random fibrous bed model (eq. 3.9)
can accurately predict the efficiency of the coalescer. SRIJAROONRATs simple fibrous bed,
(eq. 3.8b) is used to calculate the efficiency of the coalescer for comparison. However, from
the graph, it shows that the result from eq. 3.8b tends to underestimate the efficiency from 2 to
6 times. From this, we recommend the following procedure to calculate the efficiency of
metal wool bed coalescer.
1.
Apply SRIJAROONRATs random fibrous bed model (eq. 3.9) if these

conditions are satisfied, i.e.,
3.2.6
Velocity is between 1 to 2.5 cm/s or 36 to 90 m/h.

Inlet concentration is around 1000 mg/l.
The model is developed from metal wool bed coalescer, diameter = 5 cm.,
fiber diameter = 40 microns, and porosity = 0.95.
The wool is coated with silicone, so it becomes oleophilic.
2.
Even though eq. 3.9 is developed from small set of data and tortuosity can not be
established in the form of numerical factor. But, from graph 3.6, it can be
estimated that the disorderly bed coalescer is 2 to 6 times more efficient that
simple bed. However, it will be clogged easily if suspended solids are present in
the wastewater.
3.
Generalized model for pressure drop of fibrous bed coalescer
Many researcher [8], [10], [11], [16] observed pressure drop of fibrous bed coalescers
and reported that these coalescer causes very low pressure drop due to very high porosity of
their beds. There is no proposed model on pressure drop.
In order to calculate the pressure drop, we recommend to use any general piping loss
equations, such as Darcys, Colebrook-Whites or Hazen-Williams equation with the safety
factor of 2 to 5, multiplied to the actual length of the bed. However, the pressure drop of
fibrous bed coalescer is normally low (< 104 N/m2), compared to piping system pressure drop.
68
II-24
Chapter 4 Dissolved air flotation

Flotation is an accelerated separation process by increasing density difference between
continuous phase and dispersed phase. This is accomplished by mean of adding gas or air into
the wastewater to promote formation of air-solids or air-oil agglomerates. There are several
researches on flotation, its modification and applications, studied in GPI laboratory, such as
mechanical flotation, diffused air flotation, dissolved air flotation, etc. Here, we will consider
only the application of dissolved air flotation (DAF) on oily wastewater treatment.
4.1
Dissolved Air Flotation (DAF) model for oily wastewater treatment
For Dissolved Air Flotation, air bubbles are generated from pressurized (or air
saturated) water. At GPI laboratory, the model of DAF for oily wastewater treatment is
proposed by SIEM [12]. In his study, SIEM applies filtration-based model for granular bed
coalescer, proposed by AURELLE [3], by assuming the air bubble as collector (or filter
media), as shown in eq. 4.1. However, in this case, the media is also moving. Schematic
diagram of DAF is shown in fig. 4.1.
Clarified
water
Separated
Droplet
/ bubble
agglomerate
Air
bubble
Oil droplet
Pressurized
water system
Oily
wastewater
Fig. 4.1 Schematic diagram of DAF

Removal efficiency (or probability) factor of DAF is calculated from summation of
theoretical efficiency factors of 3 transport phenomena, i.e. sedimentation, direct interception,
and diffusion, as shown in eq. 4.2, and adjusted to fit with observed data, as shown in eq. 4.3.
3
H
(
(
)
)
exp
2
AV
d
b 100 %
= 1 e
theo
sed
sed
+ Int +
{4.1}
{4.2a}
diff
gd 2
188 r
{4.2b}
69
II-25
3 d
Int = ( ) 2
2 d
b
Diff
= 0.9(
{4.2c}
KT 2/3
)
dVr d
b
{4.2d}
Vr = |V-Ub|
( exp ) = 0.0074(
{4.2e}
theo
) 0.507
{4.3a}
4.2
Model verification
4.2.1
Modification of filtration-based model
From the model in section 4.1, air or gas flowrate () and the term AV can be
written in form of Qt as shown in eq. 4.4.
Q pw Conc(air)
AV
Qt
air
=(
Qpw
Qt
{4.4a}
{4.4b}
)x
Normally, under certain design condition, Qpw/Qt is constant. Solubility of air in water
(Conc(air)) and air density are intrinsic (internal) property, depends on pressure, and
temperature of pressurized water, which are constant for any given pressurized water system.
Then, from eq. 4.4, it shows that the term /(AV) is flow-independent.
From, eq. 4.2, it shows that the effciency factors vary with flowrate via relative
velocity between air bubble and oil droplet. Rising velocity of bubble (Ub) is calculated by
STOKEs law, so it does not depend on wastewater flowrate. However, if we consider eq.
4.2d, it can be implied that if we lower the flowrate until V = Ub, Vr is, therefore, equal to 0.
Or when V >> U, it will seem to some one that happen to be on an oil droplet, which will be
carried along with the flow, that he run pass very slow bubble, or bubble will stay in the
reactor longer than oil drop. This cannot be true because the bubble will be carried along with
the flow as well. Furthermore, from its lower density and its bigger size, the bubble will
usually rise up faster than oil drop at the same diameter.
In fact, relative velocity (Vr) is equal to difference between absolute velocity of bubble
(V+Ub) and flow velocity of water (V) (eq. 4.2f). If we replace Vr with Ub, it will cause some
changes in eq. 4.3a. We have already recalculated the eq. 4.3a (see fig. 4.1) and found that it
can be rewritten as shown in eq. 4.3b (modified SIEMs model). Fig. 4.2 shows comparison
between observed efficiency and predicted efficiency calculated from eq. 4.1, 4.2a to 4.2d,
4.2f and 4.3b. From the graph, prediction error is about 20%.
Vr = V+Ub-V = Ub
( exp ) = 0.009005(
{4.2f}
theo
) 0.5919
{4.3b}
70
II-26
-9.0E+00
-8.0E+00
ln (Observed efficiency)
-7.0E+00
-6.0E+00
y = 0.5919x - 4.71
R2 = 0.9821
-5.0E+00
-4.0E+00
-3.0E+00
-2.0E+00
-1.0E+00
0.0E+00
0.0E+00
-1.0E+00
-2.0E+00
-3.0E+00
-4.0E+00
-5.0E+00
-6.0E+00
-7.0E+00
ln(Theoritical efficiency)
Fig. 4.2 Relation between theoretical efficiency factor and observed efficiency factor
120.0%
110.0%
100.0%
Predicted efficiency
90.0%
80.0%
70.0%
60.0%
50.0%
+ 20%
40.0%
30.0%
20.0%
- 20%
10.0%
0.0%
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%
100.0%
Observed efficiency
Fig. 4.3
Relation between obseved efficiency and predicted efficiency of DAF from modified SIEM's model
However, since we replace Vr with Ub, it is interesting to note that the proposed model
(eq. 4.1 to 4.2a to d) is mathematically flow-independent. In fact, the effect of wastewater
flowrate, sometimes described in form of velocity or retention time, is studied by many
researchers. It is widely accepted that DAF efficiency varies with retention time. So,
considering SIEMs research, it can be interpreted that the effect of retention time is already
included in eq. 4.3. Since eq. 4.3 is evaluated from one set of operating condition and
retention time (approx. 25 minutes), it may be valid only for that condition.
To expand valid range of model, we need to verify or adjust the model by other sets of
data. However, from literature review, we cannot find enough data to do so. Then we have to
find theoretical criteria or equation that allow us to estimate the effect of retention time on
removal efficiency.
4.2.2
Population balance method

71
II-27
Population balance method is one of popular concepts, used by many researchers, to

develop DAF model. In our lab, DUPRE [14] uses this method in her research on application
of DAF for liquid-solid separation. Concept of this method is that rate of change in the
number of oil droplets which are free or attached by 1, 2 or more air bubbles is the function of
the number of air bubble and oil droplet, as shown in eq. 4.5. Oil droplet that is attached by at
least 1 bubble, so-called oil-bubble agglomerate, will be separated. So the rate of change in
number of oil droplets represents removal efficiency.
Main assumption of population balance method is that the number of bubble is
assumed to be constant. From many researches [14], [34], It is proven that, for liquid-solid
separation, the number of bubble (N) can be safely assumed as constant without serious error,
because there are a lot more bubbles than pollutant if normal range of (Qpw/Qt) is applied.
However, in case of oily wastewater, many researches [12], [13] show that bubble-oil
agglomerates are in form of oil shell with air inside and these agglomerates are still able to
intercept more oil droplets. Those researches also show that coalescence of oil and bubble is
more effective than that of the same species. So it should be safely assumed that the number
of bubble in this case is more or less constant and the population balance method is, then,
applicable.
dn 0
dt
{4.5a}
= k 0 n 0 N
dn
i = k n N k n N
i1 i1
i i
dt
{4.5b}
i = 0 to imax
N=
{4.5c}
3
d
6 b
no and ni represent the number of oil droplet which is free and attached by i bubbles
respectively. represents collision rate constant, from Saffman and Turners (1956)
coagulation theory, and represents adhesion efficiency or probability that the collision
between oil drop and bubble will be successful. Removal efficiency can be written as (ni/n0),
which can be achieved by integrating eq. 4.5.
To integrate eq. 4.5, complex numerical method is required. MATSUI and LEPPINEN
[34], [37] solve the equation by Laplace transforms and suggest the solution as shown in eq.
4.6.

2
2
d
/d
n
b 1
i = x : i e ( ) e
{4.6a}
i = 0 to imax 1
x :i =
x(x 1)...(x (i 1))

i(i 1)...(2)(1)
{4.6b}
x = d 2 /d 2
b
{4.6c}
72
II-28
When i = 0, the above function will be equal to 1.

=
6
aG(1 + (d/d )) 3 0
b
{4.6d}
G is a measure of turbulence intensity, which is normally proportional to V but we do

not know the exact relation. For i = 0, ni will become n0, which represents the number of free
oil drop remaining from contacting with air bubble. So 1-(n0/N) represents removal efficiency
of the process. Using i > 0 will result in greater value of efficiency. So, to be on the safe side,
we will use i = 0. Then eq. 4.6, when i = 0, can be rewritten as shown in eq. 4.7. Removal
efficiency of DAF is, then, can be written in form of eq. 4.8.
n0
N
=e
( )
{4.7}
n
( )
= 1 0 = 1 e
N
{4.8}
It should be noted that eq. 4.8 is about the same form as eq. 4.1, but the value of ,
represented by eq. 4.6d, clearly represents effect of every interesting parameter, including
retention time. The collision rate can be compared to the exponent term in eq. 4.1, as shown
in eq. 4.9a and 4.9b.
=
6
3
H
aG(1 + (d/d )) 3 =
( exp )
0
b
2 AV
d
b
{4.9a}
At constant d and db, eq. 4.9a can be rewritten as;

{4.9b}
= Const G =
2
(
)
( )
2
= 1 e
=1 e
{4.9c}
If x represents the variable or that we want to vary from SIEMs while another
variable still conforms to SIEMs condition, eq. 4.9c can be rewritten as show below.
= 1 e Ax
{4.9d}
Where A= constant
If
x = B.x ref
{4.10a}
Where B = Constant
Xref = x at SIEMs condition
Then
( Ax)
1 e
( Ax )
ref
ref 1 e
( ABx )
ref
1 e
=
( Ax )
ref
ref
1 e
{4.10b}
{4.10c}
73
II-29
= 1 (1
ref
)B
{4.10d}
However, changing of or will also cause some parameter in eq. 4.6d change. For
example, increasing of retention time from SIEMs condition will make V decrease. Then G
will decrease. So the constant A at design condition is not equal to A at SIEMs
condition. In this case, eq. 4.10 is not valid. And it is not possible to know the value of A at
design condition. So, the best estimation in this case is to use the value of A at some condition
that we are sure that will underestimate efficiency at design condition. Design reactor in this
case will be larger than it should be. Then it can be considered as safety factor.
Criteria to predict the efficiency from combination of SIEMs model and population
balance model will be described again in details in section 4.3.
In case of inlet oil concentration, SIEMs model is verified at inlet oil concentration of
800 mg/l before adding pressurized water or around 400 mg/l after adding pressurized water,
which is moderate value. If inlet oil concentration increases, the collision rate would
increase since probability of bubble collision (a) will be increased. However, DUPREs study
[14] shows that inlet concentration less than 600 mg/l does not have significant effect on the
efficiency. So, to be on the safe side, we can imply that modified SIEMs model is still valid
when inlet concentration is not greater that 600 mg/l (dilution included) or 1,200 mg/l
(dilution not included). Using the model for higher oil concentration will result in
underestimating of efficiency.
4.3
Generalized Model for DAF
From 2 models stated above, we can conclude and propose the generalized model as
1.
To predict removal efficiency of DAF, reference graded efficiency (based on Qt)

can be calculated by eq. 4.1, 4.2 and 4.3. If the result from the equations is
greater than 100%, then it will be rounded up to 100%. The values of (/AV)
have to be the same as SIEMs condition (see 2.) or its staightforward scale up.
3
H
(
(
)
)
exp d
2 AV
b 100 %
= 1 e
d, ref
{4.1a}
or
Q
H
3 pw Conc(air)
(
)
(
exp d
2 Q
b 100 % {4.1b}
t
air
= 1e
d, ref
theo
sed
+ Int +
diff
74
{4.2a}
II-30
sed
oil/water
188 r
Int =
3 d 2
( )
2 d
b
= 0.9(
Diff
gd 2
2.
{4.2d}
theo
air/water
18 c
) 0.5919
gd 2
b
{4.3b}
{4.2f}
To use the models described above, the following conditions need to be satisfied;
1)
Inlet oil concentration should not be greater than 1,200 mg/l (before
dilution) or 435 mg/l (after dilution). Using the model with higher oil
concentration will result in underestimating the efficiency.
2)
The model is tested at the following operating conditions;
3.
{4.2c}
KT 2/3
)
dVr d
b
( exp ) = 0.009005(
Vr = U =
b
{4.2b}
/AV = 0.0516. Only this value must be used in the equations. As

long as this value is fixed, SIEMs operating condition still holds and
the model is still valid.
Retention time (), based on Qt, is around 25 minutes.
Droplet diameter (d) tested is between 2 to 40 microns.
Diameter of air bubbles (db) varies from 15 to 130 microns. Tested
average diameter is 70 microns, which is used to verify the model, and
standard deviation of bubble diameters is 34.5 microns. The range of
bubble sizes is common for commercial pressurized water system or
saturator. The pressure of the test system is 4 atm (absolute).
Tested air flowrate () is 0.42 cm3/s (4.2e-7 m3/s).
Tested wastewater flowrate (Q) is 3.9 cm3/s (3.9e-6 m3/s)
Tested effective water depth (H) is 0.70 m. The value of H can be
freely changed as long as (/AV) is fixed. However, H between 1.8 to
2.7 is recommended by API [45].
Diameter of flotation column is 0.15 m Cross section area of column
(A) is 0.01767 m2.
Ratio of pressurized water to wastewater (Qpw/Q) is 1.76.
Air to pollutants ratio used is around 0.12 kg. air/ kg. oil.
Ratio of number of bubble/ oil droplet tested is around 1.4 oil droplet/ 1
air bubble.
Hydraulic loading rate or flow velocity (V), based on Qt, is 1.6 m/h
Because of the limitation of the pilot model, tested ratio of pressurized water to
wastewater is quite high (around 92%), compared to that of general DAF for
solid/liquid separation (less than 50%) [13]. However, API [45] recommended
air/wastewater ratio of 0.35 std. ft3/ 100 gal of total flow for full-flow DAF
process. This value is equivalent to 84% of 4-atm (abs) pressurized water/
75
II-31
wastewater. Anyway, it is interesting to adapt the model to calculate the

efficiency at lower ratio of pressurized water.
4.
Tested hydraulic loading rate or overflow rate (based on Qt) is 1.6 m/h, which is
relatively low, compared to normal rate of 3-15 m/h for domestic wastewater
treatment. The value recommended by the American Petroleum Institute (API)
[45] is between 4.8-6.1 m/h. So it is also interesting to adapt the model to
calculate the efficiency at higher overflow rate.
5.
To calculate graded removal efficiency at other operating condition, esp. at

higher overflow rate or lower ratio of pressurized water/wastewater, the
following procedure is recommended.
1)
Calculate the reference efficiency of the model (d,ref) at our required

height (Hreq), average bubble diameter (db) and droplet sizes (d) using eq.
4.1 to eq.4.3. Use /AV = 0.0516 in order that the operating condition of
SIEM still holds.
2)
Scale up the area from 0.01767 m2 to required area (Areq), which may be
calculated from general design criteria. Other operating condition from 1)
still holds. So efficiency from 1) remains the same.
3)
Find ref, corresponding to the area Areq, by the following equation,
4)
model
model
4.2 10 7 A req
0.01767
m3/s
{4.11}
Find ref, corresponding to the area Areq, by the following equation,
5)
ref
A req
ref
25H req
Hreq
1 hour
model
0.00046 3600
H
model
{4.12}
Find 2,ref, corresponding to Areq, Hreq, ref and ref from the reference
efficiency (from 1)) by the following equations. Please note that, at this
point, SIEMs constraint still holds.
2,ref
ln(1
d,ref
ref ref
{4.13}
Or
6)
d,ref
= 1 e
)
2,ref ref ref
{4.14}
To change or from SIEMs condition, the following procedure is

recommended and precaution should be noted.
To decrease (req < ref) and increase (req > ref):

This will cause decreasing of V, so G will decrease. Then 2 (see eq.
4.9) will be lower. However we do not know how much exactly. So, to
be on the safe side, we will assume that only decrease but = ref. In
this case, 2 will remain the same and be equal to 2,ref. The efficiency
can be calculated by eq. 4.15a.
76
II-32
= 1 e
d
)
2,ref req ref
{4.15a}
Because we use ref, instead of req, the calculated efficiency will be

lower than the real value.
To decrease (req < ref), as well as, (req < ref):

This will cause increasing of V, so G will increase. Then 2 (see eq.
4.9) will be higher. Again, we do not know how much exactly. So, to
be on the safe side, we will assume that 2 = 2,ref. The efficiency can
be calculated by eq. 4.15b. And again, the calculated efficiency will be
= 1 e
d
)
2,ref req req
{4.15b}
To increase (req > ref) and decrease (req < ref):

This can be done by increasing pressurized water flowrate. However,
the ratio of pressurized water/ wastewater is already high (176%). Thus,
this case is unlikely to heppen. In this case, 2(see eq. 4.9) will be
higher. Like the former case, the efficiency can be calculated by eq.
4.15b.
To increase (req > ref), as well as, (req > ref):

This case does not exist because it means that we have to decrease
wastewater flowrate. As stated above, the ratio of pressurized water/
wastewater is already high (92%). If we decrease wastewater flow,
quantity of pressurized water flow will exceed that of wastewater,
which is not feasible because we have to recycle effluent at 100% plus
additional makeup water to feed the pressurized water system.
There is no obvious limit for the 4 adaptations, shown above. However
we recommend using the values within general range, shown in item 2. to
4.
7)
Outlet concentration can be calculated from eq. 4.16a. If DAF effluent is

recycled to pressurized system, Cod,dil will be calculated as shown in item
8. If pressurized water comes from additional clean water, Outlet
concentration can be calculated by eq. 4.16b. In this case, effluent
quantity is equal to Qt, not Q. The subscript dil represents the condition
after dilution with pressurized water.
C
Q
Q
out
(1 )C
d
od, dil
Q
(1 )C
(
)
d
od Q
t
out
Q
Q out = Q
d max
C od
{4.16a}
{4.16b}
{4.16c}
d min
DAF efficiency (DAF), which is the efficiency based on flotation effect

alone, can be calculated by the following equation.
77
II-33

d max
(1 - d ) C od, dil
d
DAF = min
100%
C
o, dil
{4.16d}
In case that, additional clean water is used as pressurized water, eq. 4.16d
can be rewritten as follow.
d max
d
min
DAF =
Q
(1 - ) C
(
d
od Q
Q
Co (
)
Qt
d max
(1 - d ) C od
d
min
=
100%
Co
{4.16e}
Total removal efficiency, which is the efficiency calculated from ratio
mass between oil removed and initial mass of oil, can be calculated by
eq. 4.16e.
t =
Co C
Co
{4.16f}
100%
In case that, additional clean water is used as pressurized water, eq. 4.16e
and be rewritten as follow.
t =
8)
Co Q C Q t
Co Q
C o C(
Qt
Q
Co
100%
{4.16g}
If the effluent from flotation is recycled to use in pressurized water

system, some oil left in the effluent will be returned to the system. In this
case, mass balance of oil has to take into account. Thus, Cod will be
modified by adding this returned oil repeatedly, as shown in eq. 4.17.
Theoretically, rmax in eq.4.17 should be infinity. The value of Cod will
eventually convert to an asymptote. Anyway, for d greater than 50%,
using rmax between 5 to 10 will practically give the result sufficient
accuracy, esp. when d > 20%.
rmax
C
=
od, dil
r =1
pw
(1
)
Q
d
t
r 1
C od Q
Qt
{4.17a}
Where Qpw = RQ, Qt = Q + RQ. Then, eq. 4.17a can be simplified as

follows,
C
9)
od, dil
((
r
1
R
(1 d )) max
1) C Q
1+R
od
R
Qt
(1 d ) - 1
1+R
{4.17b}
It must be noted that there are many other parameters that can affect
efficiency of DAF, such as reactor hydraulic design, contact zone
configuration, design of pressurized water system (or saturator) and
pressure regulating device, etc. These parameters can cause some
discrepancies in efficiency prediction. However, the model will be a
useful tool for preliminary evaluation of the efficiency of DAF reactor.
78
II-34
Batch experiment, such as Flota-test, will provide valuable result, if not

exact, for design propose and can be used to compare with model result.
4.4
An important system that plays very significant role in DAF process is pressurized
water system, since, as shown in previous section, it is the source of air bubble and ratio of
air/oil droplet is one of the key parameters in DAF process. It is still the component that
consumes almost all of the energy required in DAF process. The other required energy is
pressure drop of the process caused by hydraulic elements of the reactor, such as pipeline,
outlet weir, etc., which can be calculated by familiar pressure drop equations. This pressure
drop is substantially lower than required energy of the pressurized water system.
The power for pressurized water pump can be calculated by normal pump equation
(Power =gQpwH/pump). Head of pump (H) can be assumed to equal the absolute pressure of
the pressurized water system. For the power required for an air compressor as well as the
quantity of air released by the pressurized water will be as show below.
To calculate quantity of pressurized water that can supplied the required amount of air
bubbles, our researches show that theoretical equations based on Henrys and Daltons law
give relatively accurate result. The equations can be summarized as follows,
1.
To predict molar fraction of dissolved gas in the water (x), Henrys law (eq.
4.18) will be applied. Normally, we use the molar fraction of air (yair), which
equals to 1 , to calculate. Anyway, if we need to know the quantity of some
certain gases, i.e., oxygen or nitrogen, etc. It can also be calculated by Henrys
law, using molar fraction of oxygen gas and nitrogen gas in air (yO2 and yN) of
0.11 and 0.89 respectively (in permanent regime). For the absolute pressure of
the saturator or pressurized water system (P), it is recommended to use pressure
within the standard of commercial equipment range (around 4 atm(abs)). The
higher the pressure, the more the amount of bubble generated and the greater the
energy required. Henrys constant (H) of air, oxygen, and nitrogen are 4.04 x104,
8.04 x104, 6.64 x104 atm/mole respectively
x=
2.
yP
H
{4.18}
When we know the molar fraction of dissolved air or gas (x) in water, we can
convert it to mg/l of dissolved air or gas or volume of air or gas per unit volume
of water by general conversion factor. The equation for calculating mg/l of
dissolved oxygen or air in pressurized water is shown in eq. 4.19a and 4.19b
respectively (using P in atm). Ratio of air flow to pressurized water flow at 20 o
C, assuming %saturation of air or gas in water is equal to 95%, are as shown in
eq. 4.20 (using P in atm).
Conc.(O 2 ) = 4.5893P
{4.19a}
Conc.(air) = 22.965P
{4.19b}
Q pw
{4.19c}
) = 0.0191P .0191
79
II-35
180.0
0.14
160.0
0.12
140.0
0.10
120.0
y = 22.965x
R2 = 1
100.0
y = 0.0191x - 0.0191
R2 = 1
0.08
80.0
0.06
60.0
y = 4.5893x
R2 = 1
40.0
0.04
0.02
20.0
Released air volume per

volume of pressurized water
(l gas/ l water)
mg of gas /l of water
0.00
0.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Absolute pressure (atm)

Dissolved oxygen
Fig. 4.4
3.
Dissolved air
Released air per volume of pressurized water
Relation between absolute pressure in pressure tank and dissolved quantity and released air volume
To estimate power required for the air compressor, SIEM shows that theoretical
equation (eq. 4.20a), based on adiabatic process (PV1.4 = const.), can be applied
with acceptable accuracy. Please note that the equation does not include the
overall efficiency (overall) of the system, which can be safely assumed to be
around 60-70%. So the overall power required can be calculated by eq. 4.20b.
Power
theo
Power =
1.4 1
Conc(air)
RT P 2 ( 1.4 )
(
)
1
Q pw
MW(air)
0.4 Patm
Power
{4.20a}
{4.20b}
theo
overall
Using R = 8.314 Pa.m3/(mol. K), Conc(air) in g/l and Qpw in m3/s will result in
Power theo in Watt. Molecular weight (MW) of air is 28.95 g/mol. For power
consumption of pressurized water pump, it can be calculated by the following
equation (P as atm).
Power =
Q pw ( P Patm )
3600 pump
R Q c g ( P Patm ) 10
3600 pump
80
watt {4.20c}
II-36
Chapter 5 Hydrocyclone
Hydrocyclone is an accelerated separation process by replacing gravitational
acceleration with higher centrifugal acceleration. Hydrocyclones are widely used in many
processes, i.e., classification and separation between solid-liquid and liquid-liquid. In our
scope of work, we will consider mainly on the mathematical model of liquid-liquid
hydrocyclone. There are 2 main types of hydrocyclones studied in GPI laboratory, i.e., twophase hydrocyclone and three-phase hydrocyclone.
5.1
5.1.1
Trajectory analysis-based model
Every commercial hydrocyclone has its own shape and ratio between each component.
So it is difficult to develop the model to cover every type of them. In our lab, main research
on hydrocyclone is based upon MAs study [16] on two-phase hydrocyclone for oil/water
separation. In his research, he bases his experiment on THEW type hydrocyclone, which is
initiated by Prof. THEW, UK. So, in our research, we will emphasize only on this type of
hydrocyclone.
MA develops hydrocyclone model, based upon trajectory analysis, which is normally
used in decanter calculation. The concept of the model is that oil droplet in the hydrocyclone
is subjected to 3 velocity components, i.e., radial velocity (U), tangential velocity (V) and
axial or vertical velocity (W), as shown in fig. 5.1. For the tangential velocity, he assumed
that the oil droplet has the same tangential velocity as the liquid, which follows the free vortex
pattern (VRn = const.). In the case of THEWs hydrocyclone, n is equal to 0.65. The equation
of V for THEWs hydrocyclone is a sshown in eq. 5.1c. He also assumed that vertical velocity
(W) of the droplet is similar to that of the liquid. Vertical velocity profile can be devided into
2 regions. The external region, near to the wall of the hydrocyclone, has downward flow,
while the internal region has upward flow. The equation of W is in 3rd order polynomial form
as shown in eq. 5.1d and 5.1e. For the radial velocity of the droplet, he assumed that it is
governed by STOKEs law. His assumption is that if the droplet can reach certain radial
distance where the vertical velocity starts changing from downward to upward direction (R =
RZVV, ZVV means zero vertical velocity), it will be carried upward to the overflow port,
then separated from the main stream, which will flow out at the bottom (underflow) outlet.
Do
Di
d < dc
Rd
D
R
d > dc
R
Dn
U
d = dc
W
Ds
a) Schematic diagram
= 100 %
= 100 %
b) Trajectory of each size of oil droplets
Note: Dn/D=0.5, Ds/D=0.25, Do/D<0.05, Di/D=0.25, =1.5 deg
Fig. 5.1 Schematic diagram and trajectories of droplets in two-phase hydrocyclone

81
II-37
MAs model is presented in eq. 5.1 to 5.2. Steps of calculation of the model will be
identical to decanters, beginning with cut size calculation. After finding the cut size, graded
and total removal efficiency, then, can be calculated.
R
d dR L dZ
=
U 0W
R
zvv
U=
{5.1a}
d 2 V 2
18
R
{5.1b}
(Q/2) D
( n ) 0.65
V = 0.5
D2 R
4 i
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
Wz =
{5.1c}
R
+ 1.19
Rz
{5.1d}
{5.1e}
(0.5D n Z tan( /2)) 2
Cut size (dc) is the smallest oil droplet diameter that moves from Rd = Dn/2 (eq.5.1a)
and can reach the central core of cyclone at Z = L. When d dc, removal efficiency will be
100%. For THEWs hydrocyclone, RZVV = 0.186 (Dn/2) at Z = L.
{5.2a}
= 100%
d
For d < dc, the oil drops that enter the hydrocyclone at relatively short distance from
the center line can also be separated, while those that enters at further distance will be carried
over with wastewater through the underflow outlet. The efficiency in this case can be
calculated by ratio of the area corresponding to the entering distance Rd to the whole cross
section area, as shown in eq. 5.2b. We can assume d (50%, 75%, etc.) and calculate the
corresponding Rd, then use eq. 5.1 to calculate corresponding d (d50%, d75%, etc.) from the Rd.
Dn 2
) )
d
2
=
100 %
d
Dn 2
Dn 2
((
) (0.186
) )
2
2
(R
(0.186
{5.2b}
Advantage of the concept of trajectory is that the concept can be applied to other shape
of hydrocyclone, if the equation of tangential velocity V and W are known, since the
equations of U is assumed to conform to STOKEs law. For the equation of V, the general
form is normally as shown in eq. 5.1c except the exponent (for THEW type, = 0.65) that will
vary with the shape of the hydrocyclone.
5.1.2
Other models
There are several researches that suggests the model to predict the efficiency of
hydrocyclone, both theoretical and empirical based, such as Bradleys, Rietemas,
Dahlstroms, Chebelins, Plitts, Lynchs, etc. [16],[28]- [34]. However, most of models are
developed from solid-liquid hydrocyclone. Some models are developed for specific
82
II-38
commercial liquid-liquid hydrocyclone, such as Vertoil. So it should be applied only with that
specific hydrocyclone. Extrapolation of model is normally not guaranteed.
For THEW hydrocyclone, used by MA in his research, Prof. THEW, himself, and his
colleague, COLMAN, have proposed the model for the hydrocyclone (eq. 5.3a). However, it
is an empirical model, which seems to be obtained from curve fitting. CHEBELIN [29]
quoted THEW-COLMANs correlation for solving d75% in his research, as shown in eq.
5.3b.
= (1 e
( 1.8(
d
0.19))
d 75%
{5.3a}
) 100 %
0.00001 (0.001D ) 3
n
d 75% = 10 6
Q
5.1.3
0.5
{5.3b}
Model verification
To verify the models, we will compare predicted efficiency, calculated from MAs
model, with observed data. Moreover, since MAs model is developed from THEW
hydrocyclone. So it will be interesting to compare the MAs model with THEWs model. We
use the data from MAs study, based on THEW hydrocyclone, nominal diameter 2 cm.
Operating condition used is tabulated in table 5.1. For COLMANs model, we used observed
value of d75% in eq. 5.3.Comparison between result from the 2 models and observed data is
shown in fig. 5.2.
110%
100%
90%
Efficiency (%)
80%
70%
60%
50%
40%
30%
Colman's model
Observed data
Ma's trajectory analysis
20%
10%
0%
0.00
10.00
20.00
30.00
40.00
50.00
60.00
Fig. 5.2
Comparison between observed efficiency and predicted efficiency from Ma's and Thew-Colman's models
From the graph, it shows that, at droplet size > 20 microns, MAs and COLMANs
models give relatively accurate result ( 10% error). However, at d > d 80%, COLMANs
model seems to cause higher degree of error and predict too high value of cut size. This may
because the researchers used different assumptions or operating condition to develop their
models. In effect, it is very difficult to point out that which model is more accurate.
83
II-39
However, Mas model is developed from theoretical assumption and does include
many parameters, such as viscosity, feed flowrate, and size of the hydrocyclone, etc., which
can be used to explain or verify the effect of these parameters to the efficiency. So, in this
research, we will base our model on MAs.
5.1.4
Conclusion and Generalized model of two-phase hydrocyclone
1.
To predict removal efficiency of the hydrocyclone, graded efficiency can be

calculated by eq. 5.1 and 5.2. If Rd in eq. 5.1a is equal to Dn/2, the corresponding
d will be equal to dc.
R
d dR L dZ
=
U 0W
R
zvv
U=
{5.1a}
d 2 V 2
R
18
V=(
Q
D 2
i
{5.1b}
D
)( n ) 0.65
R
{5.1c}
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
Wz =
R
+ 1.19
Rz
Q
(0.5D n Z tan( /2)) 2
{5.1d}
{5.1e}
For THEWs type hydrocyclone, when Z = L:

{5.1f}
RVZZ = 0.186( Dn / 2)
If Rd in eq. 5.1a is equal to Dn/2, the corresponding d will be equal to dc.

For d dc
= 100 %
{5.2a}
For d < dc,

Dn 2
)
2
=
100 %
d
Dn 2
Dn 2
((
) (0.186
)
2
2
(R
(0.186
{5.2b}
The equations are, somehow, very complex and require complicate numerical
method, such as Range-Kutta, to solve. However, our computer program,
developed in scope of work of this thesis, will be able to calculate these
equations.
84
II-40
2.
To design the hydrocyclone by MAs model, it is recommended to select the cut

size that covers majority of oil droplet in the wastewater and provide a safety
factor around 10% to 20%, because the model is apt to predict too small cut size.
For example, if the desired cut size is 50 microns, it is recommended to select
50(1-0.20) = 40 microns for eq. 5.1 and 5.2.
3.
1)
The model is valid for THEW hydrocyclone or other cyclones with relative
identical geometry.
2)
It is recommended to use the model only for droplet diameter of 20

microns or greater. For smaller droplet, it can also be applied, but for
comparison only.
3)
Eq. 5.2c is valid for the hydrocyclone with 2 inlet ports only. If the
hydrocyclone has only 1 inlet port, Q in eq. 5.1c will be modified as shown
in eq. 5.1c. However, using 2 inlet ports is recommended for its hydraulics
stability. Please note that the size of 2 inlet ports will be smaller than a
single inlet port to keep the inlet area constant.
V = 2(
4)
5.1.5
Q
D 2
i
D
)( n ) 0.65
R
{5.1c}
Overflow quantity is usually small, not greater than 10%. Its effect on
velocity profiles and efficiency is small, thus, negligible.
Generalized Model for Pressure drop of two-phase hydrocyclone
Many literatures [16], [28] [34] have studied pressure drop of hydrocyclone. Some
researchers also proposed models of pressure drop, obtained from their experimental data, i.e.,
Bradleys, Hottas, Rietemas. From these models, we find that, even derived from different
assumptions, the general form of pressure drop equation is as shown in eq. 5.4
4
P = f(Q 2.xx /D n )
{5.4}
We use the data from MA [16] and THEW [28] to find the constant in eq. 5.2. The
model, developed from these data, is as shown in eq. 5.5 (Q in m3/s and Dn in meter).
Comparison between observed data and predicted data is shown in fig. 5.3.
For pressure drop (bar) across inlet and overflow port (oil outlet);
Po = 16
Q 2.3
4
Dn
{5.5a}
For pressure drop (bar) across inlet and underflow port (water oultet);
Pu = 4.6
Q 2.2
4
Dn
{5.5b}
85
II-41
p o (bar) = 16 Q
6.0
2.3
/Dn
Predicted pressure drop (bar)
5.0
4.0
3.0
+10%
2.0
-10%
1.0
0.0
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
5.00
Observed pressure drop (bar)
Fig. 5.3a
Relation between observed pressure drop (inlet/overflow) of Thew cyclone and predicted pressure drop
p u (bar) = 4.6 Q
2.2
/Dn
7.0
6.0
5.0
4.0
+10%
3.0
2.0
-10%
1.0
0.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
Fig 5.3b
Relation between observed pressure drop (inlet/underflow) of Thew cyclone and predicted pressure drop
From THEWs research [28], Split ratio (Rf) or ratio between overflow and inlet flow
has some effect on pressure drop. However the effect of this parameter on under flow pressure
drop is very small, thus, negligible. There is more effect on overflow pressure drop. From
THEWs and MAs data, we can find the empirical correlation between split ratio and then
can transform eq. 5.5a to account for the split ratio. The modified equation is as follow;
Q 2.3
p o = 16
4
Dn
2.6
(1 R )
f
0.1611
{5.5c}
However, the correlation is developed from relatively small set of data. Furthermore,
range of split ratio, generally used, is around 1 to 10%. Within this range, eq. 5.5a alone can
predict the efficiency with an error of only 10-20%. So we recommend using eq. 5.5a and
86
II-42
5.5b to predict the pressure drop of the hydrocyclone. Anyway, to allow for prediction error,
safety factor of 1.2 should be applied.
5.2
Prof. AURELLE and MA develop the three-phase hydrocyclone in order to create a

new type of hydrocyclone that can separate both oil and suspended solids simultaneously in
the same unit. From this concept, MA proposed the new hydrocyclone, which is the
combination between THEW liquid-liquid hydrocyclone and RIETEMA solid-liquid
hydrocyclone, as shown in fig. 5.4. Geometry of this hydrocyclone is nearly identical to the 2
originals with slight adaptation.
Solid-liquid part

Di
Du
D Do
Dp
Ds
L4
L2
L1
L5
L3
Note: Di/D=0.25 for 1- inlet and 0.175 for 2- inlet, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid part cone angle=12o, for liquid-liquid part=1.5o
Fig. 5.4 Three-phase hydrocyclone

MA testd the performance of the prototype of this hydrocyclone. It showed very good
efficiency, which relatively conforms to the efficiency obtaining from separate solid-liquid
and liquid-liquid hydrocyclone. He also studied the influence of important parameters to
efficiency of this new hydrocyclone. However he did not propose the model. So we have to
develop new model for three-phase hydrocyclone. Model development detail will be
described in section 5.2.1.
5.2.1
Model development and verification for liquid-liquid section
From the fact that three-phase cyclone is the combination between THEW and
RIETEMA hydrocyclone. New model for liquid-liquid and solid-liquid part should conform
to that of each separate hydrocyclone.
For liquid-liquid hydrocyclone, we will apply the model of MAs, as stated in section
5.1, to three-phase hydrocyclone. The problem is how to adapt MAs model to this new
hydrocyclone. From MAs research, he observed that the phenomena in three-phase
hydrocyclone, such as oil central core formation, etc., are relatively identical to THEW
hydrocyclone. From this, we assume that the driving force of oil part in the hydrocyclone
should be identical to normal THEW hydrocyclone at the same flowrate and nominal diameter
(Dn in fig.5.1 = Do in fig. 5.4 = ND.). The driving force in hydrocyclone is generated by
energy of feed flowrate. From geometry in fig. 5.1 and 5.4, we get the following equations.
3 V
=
V
Thew i(Thew)
i(3 )
87
II-43
4Q
3
)2
(D
i(3 )
4Q
= 0.5
2
(D i(Thew) )
4Q
3
ND 2
))
(0.25(
0.43
4Q
= 0.5
ND 2
))
(0.25(
0.5
2
0.5
3 = 0.5
= 0.676
0.43
{5.6}
We use 3 in eq. 5.6 with the model in eq. 5.1 and 5.2 to predict the efficiency of the
oil part of three-phase hydrocyclone and compare the result with observed value from MAs
data [16]. Comparison result in fig. 5.5 shows that the error from prediction is 20%, which
is acceptable. We have tried to select the value of 3 arbitrarily and found that;
If the value of 3 is lower, the model will predict too low efficiency.
For higher value of 3, it may provide better curve fitting but we do not have any
data to support the use of it. The value of 0.676 seems more appropriate.
120.0%
100.0%
80.0%
+20%
60.0%
40.0%
-20%
20.0%
0.0%
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%
100.0%
Fig. 5.5
Relation between observed efficiency and predicted efficiency of liquid-liquid (Thew) part of three-phase
hydrocyclone
From model verification result, we can conclude and propose the model of liquidliquid part of three-phase hydrocyclone as well as its limitation as follows,
1.
To predict removal efficiency of three-phase hydrocyclone, graded efficiency

can be calculated by eq. 5.7 and 5.8.Dn in this case is equal to Dc. And L in this
case is equal to L5.
R
d dR L dZ
=
U 0W
R
vzz
{5.7a}
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II-44
U=
d 2 V 2
18
R
{5.7b}
(Q/2) D
( n ) 0.65
V = 0.676
D2 R
4 i
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
Wz =
{5.7c}
R
+ 1.19
Rz
Q
(0.5D n Z tan( / 2)) 2
{5.7d}
{5.7e}
For d dc,
{5.8a}
= 100%
d
For d < dc,

Dn 2
) )
2
=
100 %
d
Dn 2
Dn 2
((
) (0.186
) )
2
2
(R
(0.186
{5.8b}
2.
To design the hydrocyclone by the model, it is recommended to select the cut

size that covers majority of oil droplet in the wastewater and provide a safety
factor around 10% to 25%, because the model is apt to predict too small cut size.
For example, if the desired cut size is 50 microns, it is recommended to select
50(1-0.25) = 37.5 microns for eq. 5.7 and 5.8.
3.
1)
2)
3)
5.2.2
The model is valid for three phase hydrocyclone with geometry of the oil
part conforms to that of THEW.
microns or greater. For smaller droplet, the model can also be applied, but
for comparison purpose only.
Eq. 5.7c is valid for the hydrocyclone with 2 inlet ports only. If the
hydrocyclone has only 1 inlet port, replace Q/2 with Q. However, using 2
inlet ports is recommended for its hydraulics stability. Please note that the
size of 2 inlet ports will be smaller than single inlet port to keep the inlet
area constant.
Model development and verification for solid-liquid section
From the same reason as oil-part model development, we will base our model for
solid-liquid separation on RIETEMA hydrocyclones model. In MAs research, he used only
2 sizes of suspended solids. So the data is not sufficient to develop the model. However,
geometry of this part of three-phase hydrocyclone is identical to RIETEMAs. So RITEMAs
model should be applied without any modification.
89
II-45
RIETEMA [30] defined the performance of the hydrocyclone in form of d50% and the
dimensionless number Cy50, as shown in eq. 5.9. To find graded efficiency besides d50%,
correlation of YOSHIOKA and HOTTA [30], for 2% < d <98%, may be applied (eq. 5.10).
2
d 50 ( ss c )(L 2 L 4 ) p
= Cy 50
c c Q
(
= (1 e
d 0.115) 3
d
50%
) 100 %
{5.9}
{5.10}
The value of Cy50 of MAs hydrocyclone can not be calculated due to lacking of data.
However, RIETEMA recommended the value of Cy50 around 3.5 for RIETEMA type
hydrocyclone, which MA used in his hydrocyclone. So we recommend to use Cy50 =3.5 to
calculate the efficiency of solid part of three-phase hydrocyclone.
5.2.3
Generalized Model for pressure drop of three-phase hydrocyclone
MA proposed the model for pressure drop calculation for his prototype hydrocyclone.
For the prototype, he used Do = 14 mm and D = 32 mm. Pressure drops across various ports of
the prototype (in bar, m3/s) can be calculated from the following equations,
Pwater = 1.364Q 2.11
{5.11a}
Pss = 0.951Q 2.34
{5.11b}
Poil = 3.140Q 2.03
{5.11c}
The equations are valid only for 14/32-mm. three-phase hydrocyclone. Thus, to extend
the valid range of the equations or to develop generalized model. We consider 2 approaches,
i.e.,
Similarity approach
From TRAWINSKY [33], he suggested that hydrocyclone, like other centrifugal

machines, is subject to concept of similarity or affinity law.
P D 1d 50%
{5.12}
So combination of eq. 5.11 and 5.12 can be used to predict the pressure drops of
any size of three-phase hydrocyclone by calculating the pressure drops of 14/32-mm.
hydrocyclone at given flowrate by eq. 5.11 first, then use eq. 5.12 to find the flowrate at given
hydrocyclone diameter and given characteristic of wastewater.
Empirical approach
Similarity approach is theoretical based. In practice, many factors may cause some
discrepancies from theoretical value. To account for these factors, empirical approach is
introduced. We base our model on eq. 5.4 that we successfully applied for two-phase
hydrocyclone.
90
II-46
To develop and verify empirical model, we use the data from MAs and THEWs
research [16], [18]. The empirical models are as shown in eq. 5.13 (P in Bar, Q in m3/s, D in
m.).
Pwater = 49.8
Pss = 21
Q 2.12
D4
{5.13a}
Q 2.34
D4
{5.13b}
Q 2.03
D4
{5.13c}
P = 55
oil
Comparisons between the predicted pressure drops of the 2 approaches are shown
in fig. 5.6. The graphs show that the two approaches give very accurate results. However,
using eq. 5.11 and 5.12 may cause some difficulty because it requires calculation for d50%
first. So using eq. 5.13 may be more convenient.
(Empirical approach: p D 4 /Q2.12 = 49.8 )
4.500
4.000
3.500
3.000
2.500
2.000
1.500
1.000
0.500
0.000
0.00
Method 2- Similarlity approach

Method 1- Empirical approach
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
Fig. 5.6a
Relation between observed pressure drop (bar) across inlet and water outlet and predicted value from 2 approaches
91
II-47
(Empirical approach: p D4/Q2.34= 21.0 )
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0.00
Method 2- Similarity approach

0.50
1.00
1.50
2.00
2.50
3.00
3.50
Fig. 5.6b
Relation between observed pressure drop (bar) across inlet and SS outlet and predicted value from 2 approaches
(Empirical approach: p D4/Q2.03= 55 )
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
Method 2- Similarity approach
1.00
0.00
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
Fig. 5.6c
Relation between observed pressure drop (bar) across inlet and oil outlet and predicted value from 2 approaches
92
II-48
Chapter 6 Membrane process

Membrane process is a separation process based, mainly but not entirely, on filtration
concept. It can be said that the membrane is a very fine screen or filter. Theoretically, we can
always separate one or more components from fluid stream providing that the filter chosen is
suitable for size difference. Membranes can be categorized by their separation characteristics,
i.e., microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO).
MF and UF have relatively large pore sizes, so they work rather like screens or sieve filters.
While separation by NF and RO, which have very tiny pore sizes, is not simply by size alone
but involves more complex factors, such as osmotic pressure. So we can group the membranes
processes into 2 categories, i.e., 1) MF and UF, 2) NF and RO.
Membrane process design depends mainly on wastewater characteristics. So, the best
way to design the membrane process is to perform feasible study in lab scale or pilot scale.
However, our lab has several researches on UF. From these researches, we have gained some
understanding of phenomena taking place in the process. Then we can use our result to set a
guideline for conceptual design or preliminary evaluation of membrane process.
6.1
Ultrafiltration
Because of their pore sizes, MF and UF are suitable for finely dispersed emulsion,
such as, secondary emulsion, macroemulsion and microemulsion. However, there is only one
research on MF of oily wastewater treatment in Prof. AURELLEs team. Then, despite of its
feasibility on cutting oil emulsion treatment, which is one of the important applications of
membrane processes on oily wastewater treatment, we will not include MF in our thesis for
there is insufficient data. So we will emphasize on UF.
There are 2 main types of UF, as well as other, membrane processes, based on flow
pattern, i.e., dead-end and cross-flow. In dead end reactor, wastewater will be fed in
perpendicular direction to membrane surface. So this mode of operation is rather like cake
filtration. Dead-end process is normally used in bench scale experiment. For cross-flow,
wastewater will be fed in tangential direction, parallel to membrane surface. It is this mode of
operation that is widely used in real life situation. So our researches are related to this process.
For wastewater treatment, our aim is to reduce the quantity of the wastewater as much
as possible while the effluent quality still meets effluent standard. So wastewater will be
recycled repeatedly until its volume reaches required limit. In this case, UF system is
normally designed as batch processes, as shown in fig. 6.1.
Retentate
Permeate
Storage
tank
Membrane
Feed pump
Fig. 6.1 Typical schematic diagram of Cross-flow membrane process

93
II-49
From fig. 6.1, we have to apply enough pressure to force components that can pass
through the membrane pores to the other side. The components of influent that can pass
through the membrane is called permeate. The rest that can not pass is called retentate. The
pressure difference between retentate side and permeate is called transmembrane pressure (Pt).
The retained components will accumulate at the surface of membrane and its concentration
will be increased. This accumalation and high concentratio, called concentration polarization
or gel polarization, will hinder the permeate flow. Some components may lodge in the pores.
These phenomena will make the membrane clog and rate of permeate passing through the
membrane or permeate flux will decrease. In cross-flow process, we can alter the superficial
(or recirculation) velocity at the membrane surface (V) by changing recirculation flowrate to
reduce the effect of polarization. From this brief operating principle, we can see that there are
several parameters, relates to membrane process design. So models of membrane will be
developed to describe the relation between these parameters.
There are several researches in our lab [10], [11], [18]-[22] on membrane processes.
However, they were based mainly on application. Only some of them provided models.
Furthermore those models are limited by their scopes of the experiment, then they are not in
general forms to apply to general case. In this thesis, we will try to develop the generalized
models, based on well-accepted theoretical models, i.e. resistance model and film model.
6.1.1
Resistance model
General form of resistance model [38], [54], [18], [11] is similar to the equation for
electrical calculation as shown in eq. 6.1.
J=
Pt
Rm + R + Rg
f
{6.1a}
Membrane resistance (Rm) and fouling resistance (Rf) are property of membrane and
relatively unaffected by operating condition [38]. So it is normally be summed together and
called intrinsic membrane resistance (Rm). Eq. 6.1a , then, will become,
J=
Pt
R 'm + R g
{6.1b}
Gel resistance (Rg) is the function of Pt and V as shown in eq. 6.2. and are
numerical constants.
R g = V Pt
{6.2}
This model can give the accurate evolution of flux with Pt, starting from pressure
controlled region, which the flux varies with Pt, to mass transfer controlled region, which the
flux is relatively constant, as shown in fig. 6.2.
From researches in our lab, we can summarize the value of Rm, and for many
operating conditions, as tabulated in table 6.1. and are dependent of wastewater inlet
concentration so it can be applied only to their corresponding concentration only.
94
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Table 6.1 Summary of parameters of resistance model from UF researches on oily wastewater treatment (reference temperature = 20O C)
95
II-51
Pressure controlled
region
r flux
Higher recirculation flow

Higer temperature
Lower concentration
Wate
Flux
Mass transfer
controlled region
Transmembrane pressure (Pt)
Fig. 6.2 Typical relation between flux and various parameters

6.1.2
Film theory based model
This model is developed under the assumption that the process is in the mass transfer
controlled region. So flux is assumed to be controlled by mass transfer phenomena and
independent of Pt. Operating UF in this region will maximize the flux, thus minimize the size
of membrane. The general form of film theory based model [38], [54] is shown in eq. 6.3.
Cg
J = kV ln(
)
Co
{6.3}
From the equation, k is mass transfer coefficient. Cg is gel concentration, which

depends on type of wastewater. V is recirculation velocity. Two typical characteristic curves
of flux VS. retentate concentration are shown in fig. 6.3b. (Other curves also exist, but they
are very rare cases)
For the first type, the curve is flat without inflection point. This type of curve will
cross the horizontal axis at Cg. This Cg remains constant for the whole range of retentate
concentration.
For the second type, The curve presents an inflection point. In this case, we can say
that there are two Cg. The first one is obtained from extending the steeper part of the graph to
cross the X-axis. But it is not the real Cg and used only for flux calculation at lower range of
retentate concentration. The real Cg is obtained from the graph after inflection point. UF of
cutting oil emulsion will be in this category. In this case, the real Cg normally crosses the Xaxis at approximately 100% concentration. This can imply that, theoretically, we can use UF
to filter the oily wastewater until the retentate become water-free oil. However, the flux will
become very low and the operation may become unacceptable from economic point of view.
Flux
V2>V1
V1
Cg
Log (Concentration)
Fig. 6.3a Relation between flux and concentration at any recirculation velocity [38]
96
II-52
Flux
1
Cg
Cg
case 1 case 2
Cg
case 2
Log (Concentration)
Fig. 6.3b Typical characteristic curve of concentration VS. Flux (Log-Normal scale) [38]
From researches in our lab, we can summarize the value of k, Cg and for various
kinds of membranes for many types and inlet concentration of wastewater, as tabulated in
table 6.2.
6.1.3
Model verification
From section 6.1.1, it shows that the resistance model can predict flux at any pressure.
However, the constants in eq. 6.2 are valid for only their own specific operating conditions,
esp. the influent oil concentration. On the other hand, eq. 6.3, even though it is supposed to be
valid only in mass transfer region, can be used to predict flux at any influent oil concentration,
providing that the Cg is known. So, it is interesting to combine eq. 6.2 and 6.3 to see if they
can be used to predict flux at any influent concentration and pressure or not. The procedures
used to combine film theory and resistance theory, which are divided into 2 cases, are as
shown below.
Case 1: Know k, and Cg
1.
Find JC,Vref
If we know the value of k and at one known velocity (called reference velocity,
Vref), we can calculate limiting flux at any required concentration (called C) by the film
theory.
J
Cg
= kV
ln(
)
C,Vref
ref
C
{6.4a}
However, even the film theory is supposed to be pressure-independent, it should

be noted that k and are obtained from experimental data, which are conducted at certain
value of pressure. At that reference pressure (Pref), the flux may not yet fully reach the mass
transfer controlled region. In fact, we frequently find that flux/concentration curve never the
reach really flat part within the recommended operating range of pressure (generally 0 to 4
bar), especially when velocity is high.
In this case, we have tried to verify if the film theory is still valid. We studied the
flux/concentration relation of cutting oil macroemulsion (Elf SeraftA) at P = 2 and 3.5 bar, V
from 0.7 to 2.8 m/s from Belkacems data [18]. We found that eq. 6.3 is valid at P = 3.5 bar,
where is in the mass transfer controlled region. And we also found that the form of eq.6.3 still
holds at P = 2, where flux does not yet reach fully mass transfer controlled region at low C
and/or high V. But there are some little differences in the values of k, and Cg.
97
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Table 6.2 Summary of parameters of film model from UF researches on oily wastewater treatment (reference temperature = 20O C)
98
II-54
So we conclude that eq. 6.3 is valid even when the mass transfer controlled
region is not fully reached in some condition at the reference pressure. However, it is
recommended to select the reference pressure as high as possible, at the very least, more than
50% of recommended operating range of the membrane. It should be noted that, in this case,
JC,Vref from eq. 6.4a may not exactly be limiting flux but it represents the flux at required
concentration at the reference velocity and pressure. The equation may be rewritten as
J
2.
Cg
= kV
ln(
)
C,Vref,Pref
ref
C
{6.4b}
Find JC,V
Again from the film theory, we can find flux at required concentration and
velocity and at reference pressure by eq. 6.5.
J
3.
Cg
= kV ln(
)
C,V,Pref
C
{6.5}
Find C and C
From the resistance theory, if we know at least 2 fluxs at the same concentration
but at different velocity, we can find and at that concentration (C and C) by the
following equations.
J
C,V R m Pref K J
ln
J C,V R m P
ref
C =
V
ln( ref )
V
KJ =
J
J
C,V,Pref
C,Vref,Pref
=(
{6.6a}
V
)
V
ref
{6.6b}
So eq. 6.6a can be rewritten as,
J
V
C,V R m Pref ( V )
ref
ln
J C,V R m P
ref
C =
V
ln( ref )
V
C =
P
J
R
ref
C,V,Pref m
V c P J
ref C,V,Pref
{6.6c}
{6.6d}
Membrane resistance (Rm) (or modified resistance Rm) depends on type of

membrane and emulsion treated. Then it is usually constant for any given membrane and
emulsion. In case of cutting oil emulsion, we found that there is, more or less, no fouling
occurred. So we can safely replace Rm by Rm, as shown in eq. 6.6.
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II-55
Besides using the reference velocity and required velocity, other dummy velocities
can also be used to cross-check the value of c and c. Calculated values of the two
parameters may not be exactly the same as those calculated from Vref and V, since there is
normally some calculation error. Using average values of these c and c is recommended.
From c and c, we can calculate flux at any transmembrane pressure and at the required
concentration by the resistance theory (eq. 6.7).
J C,V,Pt =
Pt
{6.7}
R m + C V c Pt
To verify the procedure from eq. 6.4 to eq. 6.6, we use data from many researches
[10], [11], [18], [20], which , Cg, and of corresponding cases are available. Example of
verification data is provided in Annex A5. In this case, we use , Cg, and obtained from UF
test of cutting oil macroemulsion (Elf SeraftA) at influent concentration (Cref) of 4% V/V, Pref
= 2 bar, Vref = 1.4 m/s as a reference condition to predict flux/ pressure relation at C = 2 and 8
% V/V. Predicted relations and comparison between observed flux and predicted flux are as
in fig. 6.4 and 6.5. From the graphs, it shows that eq. 6.4 to 6.6 can be effectively used to
extend the range of eq. 6.1, 6.2 and 6.3 to cover any influent concentration.
180
Predicted Flux (l/ (h.m ))
160
140
120
100
80
60
40
20
0
0
0.5
1.5
2.5
Transmembrane Pressure (Bar)

Observed, C = 2%
Fig. 6.4
Predicted, C = 2%
Observed, C = 8%
Predicted, C = 8%
Reference, C = 4%
Relation between UF permeate flux and Transmembrane pressure at reference concentration (C) of = 4%, V = 1.4 m/s
and Predicted relations at C = 2 and 8%
100
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180.00
160.00
140.00
2
120.00
+10%
100.00
80.00
-10%
60.00
40.00
20.00
0.00
0
20
40
60
80
100
120
140
160
180
Observed flux (l/ (h.m ))
Fig. 6.5
Relation between observed and predicted flux by resistance model for ultrafiltration of macroemulsion 4% conc. and
extend to cover other conc. by film model
Case 2: Know , and Cg

1.
Find JCref,V
From resistance theory, we can find JCref,V, when Cref and Cref are known, by the
following equation.
J
Cref,V
R 'm +
P
ref
V Cref P
Cref
ref
{6.8}
Again, we recommend selecting the reference pressure as high as possible to

make sure that the calculated flux is in the mass transfer controlled region.
2.
Find JC,V
From film theory, we can write that;
ln(
J C,V = J
3.
Cref,V
ln(
Cg
C
Cg
{6.9}
)
ref
Find JC,Vref
In the same way as 1 and 2, we can find JC,Vref, when Cref and Cref are known,
by the following equation.
101
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C
ln( g )
P
C
ref
=
J
C,Vref
Cref
Cg
R 'm +

V
P
)
Cref
ref
ref ln(
C
ref
4.
{6.10}
Find C and C
c and c can be calculated by the same method as shown in case 1, no. 3.
6.1.4
Flux prediction for mixture of cutting oil microemulsion and macroemulsion
Wasted cutting oil emulsion is one of the most difficult-to-treat oily wastewater,
mainly because its stability and its very tiny oil droplet. From the researches stated above, we
could see that treatment of this wastewater is the main application of UF on oily wastewater
treatment. From table 6.1 and 6.2, we have some information on UF of microemulsion and
macroemulsion, summarized from many researches. However, in real life situation, some
mechanical workshops or factories may use more than 1 type of cutting oil, to meet individual
process requirement. So it will be interesting to predict the flux of the mixture of them.
To do this, we start with components of the cutting oil emulsion. Two main
components of cutting oil concentrate are base oil and surfactants/co-surfactants. Other
additives are also present but their quantities are usually very low. For macroemulsion, the
ratio of oil in cutting oil concentrate is around 80%. For microemulsion, the ratio of oil is
around 30 to 40%. The surfactants and co-surfactants are the components that give the
emulsion its characteristic.
When 2 types of emulsion are mixed. The oil components will be summed up.
Concentration of oil in the mixture is, therefore, the summation of oil concentration in each
emulsion. Excess surfactants/co-surfactants in microemulsion part will reduce oil droplet size
of macroemulsion, as they do in microemulsion. However, their quantities will not be
sufficient to convert all of macroemulsion into microemulsion. The resultant flux, then, will
be neither the same as the flux of pure microemulsion, nor that of pure macroemulsion. But it
will surely fall between these 2 extreme cases. Accurate prediction may require the
knowledge of the chemistry of surfactants/co-surfactants.
However, since the excess amount of surfactants/co-surfactants in the mixture is
directly proportional to the ratio of the microemulsion presenting in the mixture, we may
estimate that flux of the mixture is the weighted average of the two emulsions.
To formulate the equations, consider the mixture of Cmac % by V of macroemulsion
concentrate and Cmic % by V of microemulsion concentrate. Ratios of oil in the
macroemulsion and microemulsion concentrate are Rmac and Rmic %, respectively. Total oil
concentration in mixture can be written as follows.
C
oil,mix
= C mac R mac + C
R
mic mic
{6.10a}
However, if the concentrations are presented in %V of oil (not concentrate), total oil in
the mixture is a simple summation of the two concentrations (eq. 6.10b).
102
II-58
oil,mix
=C
oil,mac
+C
{6.10b}
oil,mic
Flux of macroemulsion and microemulsion at the total oil concentration (Jmac:Coil,mix

and Jmic:Coil, mix) can be calculated by the procedure described in the previous section.
Therefore, the flux of the mixture can be calculated by the following equation.
J
mix
J
J
+C
oil,mac mac:Coil,mix
oil,mic mic,Coil,mix
C
oil,mix
{6.11}
To verify this idea, we used reference data of flux of pure macroemulsion and
microemulsion, as used in section 6.1.3, to predict flux of various ratios of
micro/macroemulsion mixture. Relations between predicted values and observed data are
presented in fig. 6.6 and 6.7. Even though, the error from prediction is around 20%, this
procedure will be a useful tool for the preliminary estimation of mixture flux, especially when
UF test data on the wastewater is not available
o
(Module: UFP2, Membrane: IRIS 3042, T = 20C., data from [11]. The lines show predicted value.)
180.00
4% Macro
1% Micro
V = 2.8 m/s
160.00
Flux (l/(sq.m.h))
140.00
120.00
100.00
4% Macro
4% Micro
V = 2.0 m/s
80.00
60.00
4% Macro
2% Micro
V = 1.0 m/s
40.00
20.00
0.00
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
Pressure (bar)
Fig 6.6
Comparison between predicted flux and observed flux for UF of micro/ macroemulsion mixture (Conc. shown as
% by volume of concentrate)
103
II-59
180.00
Predicted flux (l/(sq.m.h)
160.00
+20%
140.00
120.00
100.00
80.00
60.00
40.00
20.00
0.00
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
160.00
180.00
Observed flux (l/(sq.m.h)

Macro 4%, Micro 1%
Fig 6.7
6.1.5
Macro 4%, Micro 2%
Macro4%, Micro 4%
Relation between observed and predicted flux of micro/macroemulsion mixture from weighted average method
between flux of whole micro and macroemulsion at the same total oil concentration
Theoretical flux prediction for batch cross-flowUF process
Models in section 6.1.1 and 6.1.2 are developed under the condition that permeate is
recycled back to feed storage tank, so the inlet concentration is kept constant. For real
situation, the process may be designed as batch process, continuous process, single stage
process or multi stage process. In these cases, mass balance will be taken into account.
However, for wastewater treatment process, UF is normally designed as batch system,
as shown in fig. 6.1. In batch process, the concentration of retentate will be increased up to
required limit or as much as possible. From film theory, flux will decrease when the
concentration increases. And from our procedure to predict flux in section 6.1.3, it will be
interesting to predict evolution of retentate volume, permeate volume, and flux with time.
These data is important to design UF process to meet the required operating time. However, it
must be noted that these evolutions are based on the assumption of fresh (not used) emulsion
thus there is no fouling from any other foreign materials, which, in practice, hardly exists.
Anyway, these data will provide the idea about the approximate size of membrane required.
To find permeate volume, we consider that a small volume of permeate (dVol),
passing through a UF membrane of area A at a small time (dt), will be defined by the
following equation.
{6.12}
dVol = J(c) Adt
If the system is operated in the mass transfer controlled region, the film theory can be
applied. Eq. 6.12 can be rewritten as follows,
Cg
dVol = kV ln
C
Adt
{6.13}
If we start with initial wastewater volume Volo and concentration Co and the rejection
of oil is totally completed, which is true from our every test, the concentration C will be the
function of the permeate volume at that moment V.
104
II-60
C=
C o Vol o
(Vol o Vol)
{6.14}
Eq. 6.9 can be rewritten as,

dVol = kV ln
(Vol o Vol)C g
Adt
C o Vol o
Vo
l
final
dVol
(Volo Vol)Cg
Volo
ln
Co Volo
t
= kV Adt
0
{6.15a}
{6.15b}
However, the system may not be operated in the mass transfer controlled region for the
whole time. In this case, the function J(c) in eq. 6.12 can be calculated by eq 6.7. Eq. 6.12 and
6.15b are in the form of integration of [1/ln (x)], so they can not be written in general form
since the equation will be infinity at x =1. However, a definite integration is possible, using
numerical method that can be calculated by computer.
In this thesis, we have compared the theoretical result, using reference data stated in
section 6.1.3, with observed results from UF test on used cutting oil macroemulsion (3% V of
concentrate or 2.4%V of oil, from Willamette SAS factory) from WANICHKULs research
[11], as shown in fig. 6.8a. The x-marked circles indicate the observed flux of fresh emulsion.
From the graph, it shows that the model can accurately predict flux of fresh (unused) emulsion
as the circles are closed to the theoretical flux curve.
Comparing with observed flux of the used emulsion, the graph shows that, at low
concentration, theoretical flux is greater than observed value. This simply because additional
fouling from foreign material in the emulsion. However, at high concentration, theoretical
flux is, somehow, lower than observed value. This can be explained by partial degradation of
the used emulsion. During its working lifetime, cutting oil emulsion will subject to many
foreign material, such as coated oil on specimen surface, small scraps of specimen, leaked
lubricant, and heat. So its quality, as well as its stability, will gradually deteriorate. This is
proven by milky appearance of used emulsion, compared with the translucent or transparent
characteristic of fresh emulsion. When partial oil is destabilized to be free oil, this means the
concentration of oil in emulsion form may be lower than its initial value. At lower
concentration, the effect of fouling overwhelms the effect of reduced concentration, so the
theoretical flux is higher than the observed value. However, at higher concentration where the
concentration effect is stronger, the theoretical flux shows lower value.
Fig. 6.8b shows evolution of permeate volume with time, the result from integration of
eq. 6.12. From the observed data, it confirms that the macroemulsion can be ultrafitrated until
the retentate is relatively pure oil. In this case, initial volume of 1643 l of 2.4%V of oil is
ultrafiltrated to the final volume of 40 l. The theoretical time required to do so is 45 hours,
compared to observed value of 34 hours. However, the theoretical volume of permeate is
higher until almost at the end of the operation. Fig.6.8c shows evolution of theoretical flux
with concentration. It must be noted that eq 6.12 to 6.15 are based on the assumption that no
additional emulsion is added to the storage tank. If the emulsion is added, eq. 6.12 must be
modified to account for it.
105
II-61
(Used cutting oil macroemulsion :initial volume 1643 l, final volume 40 l,

initial concentration 2.4% by volume of oil (not concentrate): Module UFP10: membrane IRIS 3042)
70.00
P = 1.0 bar, v = 1.17 m/s
P = 1.5 bar, v = 1.40 m/s
60.00
flux (l/(sq.m.h))
50.00
40.00
30.00
20.00
10.00
0.00
0
200
400
600
800
1000
1200
Theoretical data at P = 1.0 Bar, v = 1.17 m/s)
Observed data
1400
1600
1800
= Observed data from UF test ofnew

cutting oil at the same condition
Permeate volume (l)
Fig. 6.8a Relation between Flux VS. theoretical and observed permeate volume

initial concentration 2.4% by volume as oil (not as concentrate): Module UFP10: membrane IRIS 3042)
1800
1600
Permeate volume (l)
1400
P = 1.0 bar, v = 1.17 m/s
P = 1.5 bar, v = 1.40 m/s
1200
1000
800
600
400
200
0
0.000
5.000
10.000
15.000
20.000
25.000
30.000
35.000
40.000
45.000
50.000
Time (h)
Observed data
Fig 6.8b Relation between time VS. theoretical and observed permeate volume
106
II-62
(Elf SeralfABS cutiing oil macroemulsion: Membrane IRIS 3042, 20

C)
80.00
Permeate flux (l/m .h)
70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
1
10
100
Retentate concentration (% V of oil)

P = 1 bar, V = 1.17 m/s
P = 1.5 bar, V = 1.4 m/s
Fig. 6.8c Relation between theoretical flux VS. concentration of oil in retentate
6.1.6
UF efficiency
From many researches, with appropriate UF membrane pore size, it clearly shows that
oil, even in form of very tiny droplets in macroemulsion and microemulsion, cannot pass the
membrane. We can say that the removal efficiency of UF is 100%. Selection of membrane
involves many parameters. However, AURELLE [quoted by [18]] have grouped these
parameters and proposed 3 brief criteria, i.e.,
Pore size of membrane: To prevent oil droplets to pass through the membrane
pore, the size of the pore, firstly, must be smaller than the droplets. From
researches in our lab, we recommend that minimum pore size should be 1/4 to 1/3
of average droplet size.
Characteristic of membrane: for oil/water separation, membrane should be

hydrophilic. Membrane material should not react with the wastewater, which can
cause pour clogging. Hydrophilic material, such as polyacrylic, cellulose acetate,
zirconium oxide, etc., is recommended. Naturally without special treatment or
coating, polysulfonate tends to be fouled by oil, resulting in low flux and frequent
washing.
Operating condition: Operating pressure should be less than capillary pressure

required to force the oil droplets through the membrane pores. Capillary pressure
increases with the hydrophilicity of membrane and decreasing of pore size.
However, if pore size and hydrophilicity are carefully selected, the capillary
pressure is normally higher than recommended maximum pressure of the
membrane.
107
II-63
However, other soluble pollutants, especially surfactants and co-surfactants, can pass
through the membrane. So, after UF, these chemicals are still present in permeate, resulting in
high TOD, and require further treatment.
6.1.7
Minimum and maximum transmembrane pressure and power required
Transmembrane pressure and recirculation velocity are important factors in UF

process. In case of the pressure, many researches [11], [18] recommended that using moderate
pressure would reduce fouling, thus increasing operating time before cleaning. Increasing in
velocity will reduce polarization effect and lead to increasing of flux. However, using high
recirculation velocity inevitably cause high pressure drop, then the transmembrane pressure
will be increased accordingly.
Thus, the minimum transmembrane pressure required for any recirculation velocity
will be equal to pressure drop caused by that velocity. The pressure drop can be calculated, as
a friction loss of retentate flowing through narrow channel between membrane surface and UF
module wall, by general pressure drop formula, such as Darcy-Weisbachs equation. It must
be noted that the friction factor (f) depends on Reynolds number, which, in turn, depends on
viscosity of liquid. For oily wastewater, the viscosity varies with concentration of oil. Fig. 6.9
shows relation of viscosity and oil concentration (as % V of concentrate) of the cutting oil
macroemulsion (Elf Seraft ABS). So the pressure drop will be calculated using the highest
viscosity in the selected operating range of concentration.
L V2
P
=f
min
D 2
{6.16a}
For laminar flow,

f=
64
Re
{6.16b}
For turbulent flow (Colebrooks equation),

1
e/D
2.51
= 2 log(
+
)
0.5
3.7
f
Re f 0.5
{6.16c}
e/D is ratio of roughness to diameter. For plate membrane, the flow channel is usually
rectangular. D of this channel can be calculated as hydraulic diameter, as shown in eq. 6.16d.
H and W are height and width of the rectangular channel respectively.
D=
4HW
2(H + W)
{6.16d}
However, since L of the UF module is small, even though the velocity is as high as 3
m/s and D is as low as 1.0 mm., Pmin is still well below 0.5 bar.
The maximum transmembrane pressure will be controlled by the lower pressure
among 1) capillary pressure of oil droplet , 2) the maximum operating pressure, recommended
by membrane manufacturer. Capillary pressure of oil droplet of diameter rd and membrane
pore of diameter r can be calculated by the following equation [10].
108
II-64
cos
o/w
Pcap = 2
o/w
r
rd
4
r
1/3
3
3cos
cos
2
o/w
o/w
1
cos
+ (2 sin
+ sin 3
)
o/w
o/w
o/w
{6.17}
Normally, the value of the capillary pressure is higher than the maximum operating
pressure. For example, for UF of macroemulsion, o/w= 135o, o/w = 0.033 N/m, rd = 150 nm
and r = 100 nm, the capillary pressure is 11.45 bar while the maximum pressure
recommended by the manufacturer is only 4 bar.
o
(Elf SeralfABS cutiing oil macroemulsion, 20
C, 100% = pure cutting oil concentrate = 80% V(approx) oil )
350.00
300.00
Viscosity (cp)
250.00
200.00
150.00
100.00
50.00
0.00
0
10
20
30
40
50
60
70
80
90
100
Oil concentration (% V of cutting oil concentrate in water)
Fig. 6.9 Relation between oil concentration VS. viscosity of emulsion

For the power requirement of UF system, main power consumption is the power
required to maintain transmembrane pressure at require flowrate (or recirculation velocity).
This power can be calculated straightforwardly by the basic equation
Power =
PQ
overall
PVA
overall
{6.19}
Q in this case means recirculation flowrate, not the permeate flowrate. V is the
recirculation velocity and A is the flow area of liquid in UF module (the channel between the
membrane surface and the UF module wall). P in the equation is pump discharge pressure,
which is the summation of transmembrane pressure and other headloss from pipe and values
system. It should be noted that transmembrane pressure is average value of the pressure at
the inlet and outlet of UF module. Overall efficiency of pump depends on pump type. For
progressive cavity pump or progressive screw pump, the efficiency should be around 50-70%.
109
II-65
6.1.8
Conclusion and generalized model of UF
Both resistance and film theory based models can give accurate result if the numerical
constants from table 6.1 and 6.2 are chosen correctly. So both models can be used as
generalized models for UF process. It should be noted before using any parameters from any
UF researches that every parameter varies with type of emulsion and membrane. Experimental
procedure (such as recycling of permeate, preparation of emulsion by tap water or
demineralised water, reporting concentration of oil concentration as %V of concentrate or %
V of oil, etc.), as well as the difference from lot-to-lot of membrane manufacturing, also
affects the result. So, if possible, we strongly recommend performing a feasibility test in
bench scale or pilot scale, using real wastewater.
In this thesis, the combination of resistance and film models (section 6.1.3) is
proposed and verified. Advantage of this combine model is that, if we know k, and Cg and
the flux at one influent concentration (Co), we can find flux at any concentration. This fact is
very useful to extend the resistance model (section 6.1.1) at specific concentration to any
concentration. The constant in table 6.1 and 6.2 can be used to preliminarily calculate UF
process of cutting oil emulsion.
Estimation of flux of mixed micro/macroemulsion is verified in section 6.1.4.
Furthermore, prediction of permeate flux of batch UF process is proven to be useful tool for
process design for it can provide general idea of evolution of permeate flux with time (section
6.1.5). The oil removal efficiency of UF is considered to be 100% providing that the pore size
is suitably chosen. Minimum transmembrane pressure is controlled by required pressure drop
across UF module at the design recirculation velocity, which is usually lower than 0.5 bar.
Maximum theoretical pressure is controlled by the lower value among capillary pressure and
manufacturer recommended maximum pressure. Normally the former is much higher than the
latter.
6.2
NF and RO are the membrane processes that use very fine pore membranes. So it can
be retain almost all of components in the fluid stream and let only the water pass through.
Despite of their separation capability, they are normally costly and consume very high energy.
Thus, they are not economical choices for wastewater treatment. However, it is proven by our
lab [11], [18], [20] that it is useful for the post treatment of permeate from UF and MF for it
can retain dissolved pollutants such as surfactant and co-surfactant.
The phenomena, taking place in NF and RO, are more complex than those of MF and
UF. They involve osmotic pressure. So the model of RO and NF will be relatively complicate.
However, because we use them only as post treatment, which the characteristic of influent is
quite typical, so the process can be safely designed using simple criteria, such as aerial
loading rate. From researches of our lab, we can summarize such criteria, as tabulated in table
6.3.
110
II-66
Table 6.3a Summary of RO data on oily wastewater treatment
111
II-67
Table 6.3b Summary of NF data on oily wastewater treatment
112
II-68
Chapter 7 Heteroazeotropic Distillation

Heteroazeotropic distillation is a thermal treatment process that makes use of
vapor/liquid/liquid equilibrium (VLLE) to separate oil from water. Concepts of VLLE and
heteroazeotropic distillation are classical concepts for process engineers. However, the
application on oily wastewater treatment is not realized, or if any, very few.
Heteroazeoptropic distillation phenomena normally take place in a distillation column.
But, after condensation, evaporated water and hydrocarbons are condensed together and form
distillate mixture of hydrocarbons and water again.
Our lab studies find that it is feasible to apply heteroazeotropic distillation process on
treatment of oil/water emulsion by adding proper entrainer or extractant, which is relatively
volatile hydrocarbons, into the mixture. The distillate in this case will consist of 2 separate
layers, one of extractant on the top, and another of water at the bottom. The residue from
distillation is water-free hydrocarbons (efficiency = 100%), which can be reused or recycled.
Anyway, due to its relatively high-energy consumption, its application should be considered,
also, from economic point of view, especially for relatively dilute wastewater.
Our lab emphasizes on its application for highly viscous emulsion treatment, like
wasted slop from refineries and retentate left from emulsion treatment by membrane
processes. These applications are feasible because it provides a chance to valorize these
suppose-to-be-wasted materials.
Another application of heteroazeotropic distillation is the steam stripping, in which
steam is supplied into mixture of relatively non-volatile and volatile components to strip the
volatile components from the mixture. The steam is this case will act as the entrainer to
extract the volatile components. This process can be viewed as the inverse process of
heteroazeotropic distillation. If the mixture is a hydrocarbon/water mixture, the water will act
as an entrainer. So it is called a self-entraining mixture.
Researches in our lab are based mainly on the study on types of entrainers and influent
parameters, rather than developing distillation column. Main researches on heteroazeotropic
distillation in our lab are thesis of LUCENA [24] on slop treatment and thesis of
WANICHKUL [11] on retentate treatment. However, the concept of calculation, based on
classical theory, can be applied to other oil/water mixtures.
7.1
Theoretical model
Models or procedure for heteroazeotropic distillation, in our case, are based on nonmiscible mixture, like oil and water. For non-miscible binary mixture of water and
hydrocarbon, typical isobar diagram of VLLE is as shown in fig. 7.1.
113
II-69
Temperature
2 ph.vapor
Boiling point
of hydrocarbon
TH
Dew curves
Boiling point
of water
1 ph.vapor +
1 ph. liquid
Bubble curve
Azeotrope (H)
Pure 2 ph. liquid

hydrocarbon
x,y Pure H2O
yH
Fig. 7.1 Isobar equilibrium diagram : Temperature-Concentration characteristic of

immiscible binary mixture
From the figure, we can set the steps of calculation to create isobar diagram as
follows,
1)
Find bubble curve

For binary mixture
b
b
sat
sat
P = b
A + B = A + B = PA + PB
{7.1}
Relations between vapor pressures (b or Psat) and boiling temperature of A and

B, in our case, water and hydrocarbons, can be found in any standard property tables, such as
PERRYs [2]. Then, we obtain the relation between vapor pressure and boiling temperature of
the mixture from the summation of the vapor pressure of A and B, as shown in eq. 7.1. This
can be done easily by a graphical method, as shown in fig. 7.2. When we select our design
pressure (normally 1 atm), we can obtain heteroazeotropic temperature (TH) from the graph.
Pressure
A+B
Pdesign
Pure A
Pure B
TH
Temperature
Fig. 7.2 Graphical method to find heteroazeotropic temperature
114
II-70
2)
Find dew curves

From DALTONs law
And
pA = yA P
{7.2a}
pB = yB P
{7.2b}
On the dew curves, partial pressure is equal to vapor pressure, then For
condensation of A
d
d
pA = yA P = A yA = A
P
{7.3a}
For condensation of B
d
B
p B = y B P = d
y
=
B
B
P
{7.3b}
At any temperature between boiling points of pure substances and

heteroazotropic temperature (TH), we can find their corresponding vapor pressures () from
fig. 7.3a. Then, from eq. 7.3, we can obtain yA and yB. This can be done easily, again, by the
graphical method as shown in fig. 7.3
Calculate yA and yB from A,B
Temperature by eq. 7.3, then, plot T,y and T,y
A+B
Pressure
to obtain dew curves
Pure A
A 1
B 1
A 2
B 2
T1
T2
Pure B
T2
Pure
hydrocarbon
T1 Temperature
TH
yB 1 yH yA 1x,y Pure H2O
yB 2 y A 2
Fig. 7.3 Graphical method to find dew curves

3)
Find heteroazeotropic composition
Heteroazeotropic composition (yH) can be calculated, based on eq. 7.1 and 7.3,
as shown in eq. 7.4,
yH = yA =
b
A
{7.3a}
From eq. 7.1,

b
A
yH =
b
b
+
A B
{7.4}
115
II-71
Vapor pressures of A and B (water and hydrocarbons) can be obtained from any
standard property tables [2]. yH indicates capability of extractant to extract water from
wastewater. For example, if yH = 0.5 mole/mole, it means 1 mole of extractant can extract 1
mole of water. The higher the yH , the better the extractant.
7.2
Model verification
From section 7.1, we can find yH of pure hydrocarbon that can be used as an
extractant, i.e., alkane with the number of carbon from 6 atoms (n-Hexane) to 16 (nHexadecane). Theoretical values of yH of each alkane are tabulated in table 7.1. To compare
the theoretical value to experimental result, we use data from LUCENAs thesis on slop
treatment, using decane and dodecane. Comparison result in table 7.1 shows that the
theoretical values are slightly higher (3.5-5.5%) than observed values.
Table 7.1 Heterotropic temperature and composition from various extractants
7.3
Extractant
Molecular
weight
(g/mol)
TH
(deg. C)
yH
(by molar)
y H observed
yH
(by volume)
(by volume)
[24]
C6H14
56
61.6
0.209
0.0351
C7H16
100
79.2
0.452
0.0922
C8H18
114
89.5
0.616
0.188
C9H20
128
94.8
0.827
0.3255
C10H22
142
97.6
0.914
0.495
C11H24
156
98.9
0.959
0.6663
C12H26
170
99.5
0.98
0.7953
C13H28
184
99.8
0.991
0.890
C14H30
198
99.95
0.996
0.9542
C15H32
212
99.999
0.998
0.9702
C16H34
226
100
0.999
0.9840
0.468
0.767
Conclusion and generalized model of heteroazeotropic distillation
From data verification result, we can conclude that the theoretical model, stated in
section 7.1, provides very good prediction of heteroazotropic composition (yH). However, the
safety factor (S.F) of 1.05 or 1.1 is recommended. When we know the water volume in our
treated wastewater and determine the type of extractant, we can find quantity of extractant
required for extracting the water from the following equation. yH in eq. 7.5 will be by volume
basis, determined by the model in section 7.1. Heteroazeotropic distillation is suitable to treat
or recover valuable residue, such as slop or retentate from UF of cutting oil emulsion, which
is contaminated by relatively small amount of water.
Volumeextractant = S.F Volume water
116
(1 y H )
yH
{7.5}
II-72
On the other hand, for stripping, we can find the theoretical quantity of steam or water
required for extracting the design volume of volatile hydrocarbons from the following
equations. Please note that the calculated volume of steam is the quantity required for
heteroazeotropic distillation only. Additional heat may be required to raise the temperature up
to the design point. Stripping is suitable to treat the waste polluted by small amount of volatile
substance. The concept is also applied to essential-oil extraction from herbs or flowers in
perfume or chemical industries.
Volumesteam = S.F Volume
yH
{7.6a}
hydrocarbon (1 y )
H
Or
Volumesteam = S.F Concentration
hydrocarbon
117
Volume wastewater
yH
(1 y H )
{7.6b}
II-73
Part III Summary of researches :

Oily wastewater treatment
Part III Summary of researches: Oily wastewater treatment
Content
Page
Part III
Summary of researches: Oily wastewater treatment
Chapter
Oily or hydrocarbon-polluted wastewater

1.1
1.2
1.3
1.4
1.5
1.6
Chapter
Introduction
1.2.1
Hydrocarbons
1.2.2
Fats and oils
1.2.3
1.2.4
1.3.1
Surfactants
1.3.2
Soaps
1.3.3
Co-surfactants
1.3.4
Suspended solids
1.3.5
Other components
1.4.1
1.4.2
1.4.3
III-2
III-2
III-2
III-7
III-7
III-9
III-9
III-9
III-10
III-11
III-11
III-11
III-11
III-11
III-11
III-12
III-15
III-16
Overview for oily wastewater treatment process design

2.1
2.2
2.3
2.4
Decantation velocity and STOKEs law

2.2.1
2.2.2
2.2.3
Important parameters in oily wastewater treatment and
their method of analysis
2.3.1
Oil concentration
2.3.2
2.3.3
Other parameters
2.4.1
Decanter
2.4.2
Coalescer
2.4.3
Hydrocyclone
2.4.4
2.4.5
Skimmer
2.4.6
Membrane processes
2.4.7
Thermal processes
2.4.8
Chemical process
2.4.9
Finishing processes
III-21
III-22
III-22
III-25
III-29
III-30
III-30
III-32
III-38
III-38
III-39
III-39
III-39
III-40
III-40
III-40
III-40
III-41
III-41
III-i
Chapter 1 Oily or hydrocarbon-polluted wastewater
Content (Cont)
Page
2.5
Chapter
3.2
3.3
3.4
4
General
Oil drum skimmer
3.1.1
Working principles
3.1.2
Oil disc skimmer
3.2.1
Working principles
3.2.2
Productivity comparison between drum and disc skimmer
Advantage and disadvantage of drum and disc skimmer
III-45
III-47
III-47
III-52
III-54
III-54
III-56
III-56
III-57
Decanting
4.1
4.2
4.3
Chapter 5
III-41
III-41
III-41
Oil skimmer
3.1
3.1
Chapter

2.5.1
2.5.2
General
4.2.1
Working principles
4.2.2
Design calculation
4.2.3
4.2.4
Compact decanter
4.3.1
Working principles
4.3.2
Design calculation
4.3.3
4.3.4
Variations, advantage and disadvantage of compact
decanters
III-59
III-60
III-60
III-62
III-65
III-66
III-69
III-69
III-73
III-75
III-76
Coalescer
5.1
5.2
5.3
General
5.2.1
Working principles
5.2.2
Design calculation
5.2.3
5.2.4
Variations, advantage and disadvantage of granular
bed coalescer
Guide coalescer
5.3.1
Working principles
5.3.2
Design calculation
5.3.3
III-78
III-78
III-78
III-92
III-94
III-95
III-96
III-96
III-98
III-98
III-ii
Content (Cont)
Page
5.4
Chapter
6.3
6.4
6.5
6.6
General
Working principles
6.2.1
Filter based model
6.2.2
6.2.3
Generalized model of DAF from combination of
filtration based model and population balance model
6.2.4
Influent parameters
Design calculation
Design consideration and construction of DAF reactor
6.5.1
Working principle and design calculation
6.5.2
Type of saturator and injection valve
III-115
III-116
III-116
III-121
III-123
III-124
III-127
III-137
III-145
III-145
III-150
III-153
Hydrocyclone
7.1
7.2
7.3
Chapter 8
III-99
III-99
III-109
III-110
III-112

6.1
6.2
Chapter 7
Fibrous Bed coalescer

5.4.1
Working principles
5.4.2
Design calculation
5.4.3
5.4.4
Variations, advantage and disadvantage of fibrous bed
coalescer
General
7.2.1
Working principles
7.2.2
Design calculation
7.2.3
7.2.4
Variations, advantage and disadvantage of
hydrocy clone
7.3.1
Working principles
7.3.2
7.3.3
Advantage and disadvantage of three-phase
hydrocyclone
III-155
III-156
III-156
III-172
III-175
III-178
III-178
III-178
III-182
III-182
Membrane process
8.1
General
8.1.1
8.1.2
8.1.3
8.1.4
8.1.5

Membrane structure
Membrane material
III-183
III-183
III-185
III-185
III-186
III-189
III-iii
Content (Cont)
Page
8.2
8.3
8.4
8.5
8.6
Chapter 9
8.2.1
8.2.2
8.2.3
Design consideration and significant findings from
GPIs researches
8.3.1
8.3.2
Significant findings on MF for oily wastewater
treatment from GPI researches
8.4.1
8.4.2
Significant findings on RO for oily wastewater
Nanofiltration (NF)
8.5.1
8.5.2
Significant findings on NF for oily wastewater
Comparison of membrane processes on emulsion treatment
III-194
III-194
III-206
III-221
III-232
III-232
III-233
III-235
III-235
III-236
III-239
III-239
III-239
III-242
Thermal processes
9.1
9.2
9.3
9.4
General
III-245
III-245
9.2.1
Basic knowledge on vapor/liquid equilibrium of
III-245
mixtures
9.2.2
III-248
Heteroazeotropic distillation of oily wastewater
III-250
9.3.1
Working principles
III-250
9.3.2
III-251
9.3.3
Calculation of azeotropic temperature and composition, III-252
dew curve and bubble curve.
9.3.4
III-254
treatment of inverse emulsion or concentrated oily
wastewater
9.3.5
III-257
treatment of the wastes polluted by trace hydrocarbons:
Steam stripping
9.3.6
III-257
Classical or conventional distillation of oily wastewater
III-259
9.4.1
Working principles
III-259
9.4.2
Significant findings on classical distillation for oily
III-259
wastewater treatment from GPIs researches
III-iv
Content (Cont)
Page
Chapter 10
Chemical treatment processes

10.1
10.2
10.3
10.4
Chapter 11
III-263
III-264
III-264
III-264
III-266
III-268
III-274
III-275
III-276
III-278
Finishing processes
11.1
11.2
11.3
Chapter 12
General
Basic knowledge
Process design
10.3.1 Rapid mixing
10.3.2 Flocculator
General
11.2.2 Design consideration and significant finding on
biological treatment for oily wastewater from GPIs
researches
Adsorption
11.3.1 Activated carbon (AC)
III-280
III-280
III-280
III-287
III-288
III-289
III-290
III-295
Guideline for treatment process selection and examples of treatment

processes for certain oily wastewaters
12.1
12.2
Guideline for treatment process selection

12.1.1 Oil film
12.1.2 Primary emulsion
12.1.3 Secondary emulsion
12.1.4 Macroemulsion and microemulsion
12.1.5 Concentrated oily wastewater or refinery slops
Examples of treatment processes for certain oily wastewaters
12.2.1 Treatment of cutting oil emulsion
12.2.2 Treatment of non-stabilized secondary emulsion
III-297
III-297
III-299
III-300
III-301
III-301
III-302
III-302
III-303
III-v
Table
Page
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
1.2.1-1
1.2.1-2
1.2.1-3
1.4.3-2
1.5-1a
1.6-1a
1.6-1b
1.6-1c
2.1-1
2.2.1-1a
2.2.2-1
Table 2.3.2-1a
Table 2.3.2-1b
Table
Table
Table
Table
Table
2.3.2-2
2.3.2-3
3.2.1-1
3.2.2-1
5.4.1-1
Table 5.4.1-2
Table 6.3-1
Table 6.4-1
Table 6.5-1
Table
Table
Table
Table
Table
Table
6.5-2
8.1.4-1
8.1.4-2
8.1.5-1
8.2.2-1
8.2.2-2
Table 8.2.2-3
Properties of some normal alkanes [1],[2]

III-3
Properties of some unsaturated aliphatic hydrocarbons [1],[2]
III-5
Properties of some benzene-series hydrocarbons [1],[2]
III-6
Summary of oily wastewater classification
III-14
Data of pollution from certain oils, oil products and serfactants.
III-15
Industrial effluent standard of Thailand
III-17
Industrial effluent standard of France (1998)
III-18
Industrial effluent standards of USA, categorized by pollutant sources III-19
Summary of equations for rising velocity calculation [41]
III-22
Data of surface and interfacial tension (N/m) for some liquids at 20C III-24
Relation between contact angle, work adhesion, interfacial tension
III-28
and spread coefficient of oil/water/solid system [42]
Example of the decanting test of oil/water emulsio
III-35
Example of the decanting test of oil/water emulsion: sorting of the
III-36
result from table 2.3.2-1a
Criteria for visual observation of size distribution [22]
III-37
Criteria for visual observation of surface oil film [45]
III-38
Work adhesion and contact angles of oil, water and various materials
III-48
Critical surface tensions of certain materials [42]
III-53
Coalesced kerosene droplet size at various velocities and bed heights
III-108
from oleophilic bottle brush coalescer (dF = 100 microns,
D = 0.05 m,Co = 1 g/l, 120oC) [10]
Comparison between the individual efficiency of oleophilic bottle
III-108
brush coalescer, hydrocyclone, theoretical and observed efficiency of the
coupling of coalescer/hydrocyclone [10]
General design criteria of DAF from various literatures and
III-130
manufactures (hydraulic loading rate us based on total flowrate)
Data on efficiency and coagulant concentration of various oily
III-141
wastewater treatments by DAF [51]
Constant for calculation of concentration and quantity of gas for
III-148
o
saturator design (Operating pressure of DAF = Patm, T = 20 C)
Air characteristic and solubility at Patm [51]
III-148
Advantages and disadvantages of inorganic membrane [38]
III-188
Summary on membrane polymeric materials [38], [54], [57]
III-189
General characteristic of various membrane module [38], [54], [57]
III-193
General design criteria of UF process from various literatures
III-208
Summary of parameters of film model from UF researches on oily
III-209
wastewater treatment (reference temperature = 20oC)
Summary of parameters of resistance model from UF researches on oily III-210
wastewater treatment (ref. temperature = 20oC)
III-vi
Table (Cont)
Page
Table 8.2.2-4 Procedure to predict flux/pressure relation for case 1: Know k,
, Cg and Rm
Table 8.2.2-5 Procedure to predict flux/pressure relation for case 2: Know , ,
Cg and Rm
Table 8.2.3-1 Composition of the special cleaning microemulsion concentrate [18]
Table 8.4.2-1 Summary of RO data on oily wastewater treatment
Table 8.5.2-1 Summary of NF data on oily wastewater treatment
Table 8.6-1
Comparison of membrane processes on cutting macroemulsion
treatments (based on Elf Seraft ABS at 4% by V of oil)
Table 9.3.3-1 Heterotropic temperature and composition from various
hydrocarbons [24]
Table 9.3.4-1 Water extracting performance of various commercial hydrocarbons [24]
Table 10.2.4-1 Results from ZHUs research on destabilization of various emulsions
Table 10.3.2-1 Recommended value of gradient and detention time
Table 11-2.1-1 Rate coefficient for selected wastewaters [51]
Table 11.2.1-2 Biodegradability and biotoxicity data [51]
Table 11.2.1-3 Concentration of certain metals affecting biological systems [45]
Table 11.2.2-1 Case studies on biological treatment of oily wastewater [66]
Table 11.3.1-1 Examples of PAC and GAC properties
Table 11.3.1-2 Adsorptive capacity of AC for some hydrocarbons [65]
Table 11.3.3-1 Adsorption isotherm and MTZ data of some co-surfactants [21]
Table 12.1-1 Guideline for oily wastewater process selection (based on
GPIs researches)
III-211
III-213
III-230
III-240
III-243
III-244
III-254
III-257
III-272
III-277
III-282
III-284
III-287
III-287
III-289
III-291
III-295
III-298
III-vii
Figure
Page
Fig. 1.2.1-1
Fig. 1.2.1-2
Fig. 1.4.3-1
Fig. 1.4.3-2
Fig. 2.1-1
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
2.2.1-1
2.2.1-2
2.2.1-3
2.2.2-1
2.2.2-2
2.2.2-3
2.2.3-1
2.2.3-2
2.3.2-1
Examples of normal alkanes and derivatives with equal number of

III-4
carbon atoms
Examples of benzene series
III-6
Relation between droplet sizes and rising velocity of primary and
III-13
secondary emulsion [11]
Classification of oily wastewater by degree of dispersion
III-14
Free body diagram of oil drop in water and relation between
III-21
Cd and Re [55]
Force diagram of oil drop in water
III-23
Model for visualization of [40][42]
III-24
Model for visualization of adhesion work
III-25
Diagram of Oil drop on solid surface in water
III-25
Model for visualization of cohesion work
III-26
Effect of surface roughness on contact angle
III-27
Section of air bubble in water
III-29
Diagram for visualizing the capillary pressure
III-30
Example of the size distribution of oil droplet in cutting oil
III-32
macroemulsion (Elf Seraft 4% V of concentrate), measured by
Coultronics nanosizer NDM4 [11]
Fig. 2.3.2-2
Fig. 2.3.2-3
Fig. 2.3.2-4
Granulometer (Source: above - Ankermid Techcross / below - CILAS) III-33

Decanting test column
III-33
Relation between accumulated C/Co (% of C/Co when the droplet size
III-36 is
equal or smaller than the given dE) and oil droplet size
Fig.
2.3.2-5
Example of estimated size distribution of oil droplets from

decanting test
III-37
Fig.
Fig.
Fig.
Fig.
2.5.2-1
2.2.5-2
3.1-1
3.2.1-1
Cut size determination

Economics of processes (least cost criteria)
Examples of oil skimming devices
Lab-scale drum skimmer: Major components are shown.
(Source: GPI lab)
Surface energy or superficial tension of materials, oil and water
Influent parameters on drum skimmer performance
Occurrence of eddy currents from drum operation and no oil zone
or non-productive zone that affects the productivity of the skimmer
(Source: Oil Spill Cleanup)
Application of the skimmers
III-43
III-44
III-46
III-47
Fig. 3.2.1-2
Fig. 3.2.1-3
Fig. 3.2.2-1
Fig. 3.5-1
III-48
III-52
III-54
III-58
III-viii
Fig. 4.1-1
Fig. 4.2.1-1
Fig. 4.2.2-1
Examples of decanters
Schematic and typical removal efficiency curve of simple decanter
Relation between rising velocity, hydraulic loading rate of simple
decanter and kerosene droplet size
III-59
III-61
III-64
Figure (Cont)
Page
Fig.
Fig.
Fig.
Fig.
Fig.
4.2.4-1
4.2.4-2
4.3.1-1
4.3.1-2
4.3.1-3a
Variations of simple decanters

Important components of simple decanter
Schematic of PPI decanter
Spiraloil decanter a) Simple spiral b) Mixed spiral
Comparison between observed efficiency (1',2',3') and predicted
efficiency (1,2,3) for Simple Spiral "Spiraloil" decanter
III-67
III-67
III-69
III-70
III-71
Fig.
4.3.1-3
Comparison between observed efficiency (1',2') and predicted

efficiency (1,2) for Mixed Spiral "Spiraloil" decanter
III-71
Fig.
Fig.
Fig.
Fig.
Fig.
4.3.1-4
4.3.1-5
4.3.4-1
5.1-1
5.2.1.1
Effect of wettability of inserted plates

III-72
Schematic of inclined and horizontal decanter
III-73
Examples of compact decanters
III-77
Examples of coalescer
III-79
Schematic diagram of granular bed coalescer Mechanisms taking place III-79
inside the coalescer bed
Schematic diagram of the 3 transport phenomena
III-80
Relation between oil droplet diameter and efficiency factors of each
III-82
transportation phenomena
Schematic of a single collector and the entire bed of coalescer
III-83
Phenomena in step 2: Adhesion-Coalescence
III-85
Phenomenon in step 3: Salting out or enlargemant of coalesced oil
III-86
Relation between experimental (or observed) efficiency factor and
III-88
theoretical efficiency factor
Typical relation between efficiency of granular bed coalescer and
III-90
various parameters
Relation between cut size and coalescer dimension
III-93
Guide coalescer
III-97
Fibrous bed coalescer (Source: GPI lab)
III-100
Comparison between observed efficiency and predicted efficiency from III-102
SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data.
Relation between observed efficiency and predicted efficiency from
III-104
random fibrous bed coalescer model and simple fibrous bed model
Random or disorderly fibrous bed, used in the research of
III-105
SRIJAROONRAT
Typical relation between efficiency of fibrous bed coalescer and various III-106
parameters
Fig. 5.2.1-2
Fig. 5.2.1-3
Fig.
Fig.
Fig.
Fig.
5.2.1-4
5.2.1-5
5.2.1-6
5.2.1-7
Fig. 5.2.1-8
Fig
Fig.
Fig.
Fig.
5.2.2-1
5.3.1-1
5.4.1-1
5.4.1-2
Fig. 5.4.1-3
Fig. 5.4.1-4
Fig 5.4.1-5
III-ix
Fig. 5.4.3-1
Fig. 5.4.3-2
Examples of fibrous bed coalescer casing

Various types of bed tested by WANICHKUL [11]: From left, a)
Simple spiral, b) Double spiral, c) Solid plastic spiral, d) A module of
multi-stage bed [No. of stage can be added by increase the number of
module into the same center shaft]
III-111
III-112
Figure (Cont)
Page
Fig. 5.4.3-3
Fig. 6.2-1
Fig. 6.2.1-1
Fig. 6.2.1-2
Fig. 6.2.1-3
Fig. 6.2.1-4
Fig.
Fig.
Fig.
Fig.
6.2.4-1
6.2.4-2
6.3-1
6.4-1
Fig. 6.4-2
Fig. 6.4-3
Fig. 6.5-1
Fig.
6.5-2
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
6.5-3
6.5-4
6.5-5
7.1-1
7.2.1-1
7.2.1-1
7.2.1-2
7.2.1-3
7.2.1-4
7.2.1-5
7.2.1-6
7.2.1-7
7.2.1-8
Characteristics of oil and water drops on silicon coated (oleophilic)

III-112
steel fibers and non-coated (hydrophilic) steel fibers
Example of schematic diagram of DAF (Source: Aquatec Maxcon)
III-115
Diagram for considering relative velocity of bubble and oil in flotation III-117
column
Schematic diagram of the 3 transport phenomena
III-117
Schematic of single bubble and entire height of flotation column
III-118
Relation between theoritical efficiency factor and observed efficiency III-120
factor
Typical relation between efficiency of DAF and various parameters
III-124
Solid-bubble agglomerate and formation of oil-bubble agglomerate [14] III-126
Pilot-scale DAF test and Flota-test
III-135
Example of necessary equipment and component details of DAF system III140(Source: Environ Treatment System)
Necessary equipment and reactor components of DAF system
III-141
Examples of characteristics of scum from DAF processes
III-145
Example of good bubble formation from pressurized water
III-146
(Source: Cornell DAF pump)
Relation between power required for pump, compressor and absolute
III-149
3
(assume %air saturation = 95%)
pressure of saturator for pressurized water flowrate of 10 m /h
Schematic diagrams of saturator systems (Source: Edur pump)
Examples of saturator system
Examples of injection valve
Basic flow pattern and examples of hydrocyclones
General flow pattern and features of hydrocyclones
General flow pattern and features of hydrocyclones
Velocity components in hydrocyclone
Tangential velocity profile in hydrocyclone and various typed of vortex
Examples of tangential velocity profile
Example of axial or vertical velocity profile
Example of radial velocity profile [30]
Forces on oil droplets or particles in hydrocyclone
Components of velocity of oil droplets or particles in hydrocyclone
III-151
III-152
III-153
III-155
III-158
III-159
III-159
III-160
III-161
III-162
III-163
III-163
III-163
III-x
Fig. 7.2.1-9
Fig. 7.2.1-10
Fig. 7.2.1-1
Trajectories of oil droplets and typical efficiency curvefrom trajectory III-166

analysis model
Comparison between observed efficiency and predicted efficiency
III-168
form MAs model and THEW-COLMANs model
Corresponding flowrate and velocities of various sizes of hydrocyclones III-173
at overflow pressure drop (Po) = 3 and 5 bars
Figure (Cont)
Page
Fig. 7.2.3-1
Fig. 7.2.4-1
Fig. 7.3.1-1
Fig. 7.3.1-2a
Fig. 7.3.1-2b
Fig. 7.3.1-3
Fig. 8.1.1-1
Fig. 8.1.1-2
Fig. 8.1.2-1
Fig. 8.1.3-1
Fig. 8.1.4-1
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
8.1.5-1
8.2.1-1
8.2.1-2
8.2.1-3
8.2.1-4
8.2.1-5a
8.2.1-5b
Fig. 8.2.1-6
Fig. 8.2.1-7
Fig. 8.2.1-8
An example of the coupling between solid-liquid and liquid

hydrocyclone for the treatment of oily wastewater containing suspended
solids (Source: Ultraspin)
Relation between oil and water outlet velocity in co-current
hydrocyclone
Oil drop (sphere) and particle (cube) trajectories in three-phase
hydrocyclone
Typical vertical velocity profiles in three-phase hydrocyclone
Comparison between observed pressure drop and predicted valued from
the 2 approaches (similarity and semi-empirical model)
Material sizes and corresponding membrane processes
184(Source: Osmonics)
Separation characteristic of membrane processes (Source:
Koch membrane system)
Mode of operation of membrane process [11]
Membrane structures (Source: SCT, Millipore)
Membrane materials (Structures depend on manufacturing processes.)
(Source: Millipore, Orelis, WWW.Scienceinafica.co.za)
Membrane modules
Relation between pore sizes and MWCO [59]
Typical characteristic curves of UF membrane
Oil drop at membrane pore
Typical schematic of cross-flow UF for wastwater treatment
Examples of pure water flux and solution flux characteristics
Typical characteristic curves of water and solution flux VS.
transmembrane pressure when feed conc. is constant
Characteristic curves of permeate flux and feed concentration
Typical characteristics of permeate flux VS. time for constant feed conc
system
An example of characteristic of flux VS. time for non-constant feed
conc. system
III-176
III-177
III-178
III-179
III-179
III-182
IIIIII-184
III-185
III-186
III-187
III-191
III-194
III-195
III-196
III-196
III-197
III-197
III-198
III-198
III-199
III-xi
Fig. 8.2.1-9
Fig. 8.2.1-10
Fig. 8.2.2-1
Fig. 8.2.2-2
Fig. 8.2.2-3
Diagram of polarization layer and effect of velocity on flux in film

theory
Various resistances in UF processes
Examples of flux VS. oil concentration in UF of macroemulsion
III-201
III-203
III-211
Case 1: find flux/pressure relation when k, , Cg and Rm are known

III-211
Relation between UF permeate flux and Transmembrane pressure
III-212 at
Cref = 4% by volume of oil , V = 1.4 m/s and Predicted relations
at C = 2 and 8% (Oil: Elf SeraftA
cutting oil macroemulsion,
Membrane: IRIS 3042 PAN )
Figure (Cont)
Page
Fig. 8.2.2-4
Fig 8.2.2-5
Relation between Flux VS. theoretical and observed permeate volume

Relation between time VS. theoretical and observed permeate volume
III-216
III-217
Fig. 8.2.2-6
III-218
Fig. 8.2.3-8
Fig. 8.3.1-1
Calculation of required storage volume of equalization tank by

graphical method
Relation between oil concentration VS. viscosity of emulsion
Flux of non-stabilized emulsion
Photographs of non-stabilized emulsion influent, retentate and permeate
222(from left) [10]
Typical relation between CaCl2 concentration and flux at low Pt
Partially destabilization by salt and coalesce of oil droplets
Magnified images (x100) of oil droplets from original (left) and
partially destabilized macroemulsion (right) [11]
Magnified images of new membrane surface (left) and the surface after
UF of macroemulsion at 3 bars without salt (middle) and with salt
addition (600 mg/l CaCl2) [11]
Relation between fluxes VS. pressure and calculated VS. observed oil
concentration in retentate for partially destabilized emulsion
Examples of feed emulsions and their corresponding UF permeates
Examples of flux enhance techniques [38]
Example of evolution of flux of macroemulsion UF with periodical
cleaning with macroemulsion (membrane IRIS 3042, P = 1 bar,
V=1.5 m/s. 25oC) and schematic of interaction between membrane/
surfactants [18]
Examples of UF test modules
Examples of MF membranes
Fig.
Fig.
Fig.
Fig.
Fig.
Evolution of flux from MF (with salt addition) of macroemulsion [20]

Examples of RO membranes
Working principles of reverse osmosis
Typical relation between flux and pressure of RO
Typical relation between flux and log of concentration
Fig. 8.2.2-7
Fig. 8.2.3-1a
Fig. 8.2.3-1b
Fig. 8.2.3-2
Fig. 8.2.3-3a
Fig. 8.2.3-3b
Fig. 8.2.3-3c
Fig. 8.2.3-4
Fig. 8.2.3-5
Fig. 8.2.3-6
Fig. 8.2.3-7
8.3.2-1
8.4-1
8.4.1-1
8.4.2-1a
8.4.2-1b
III-220
III-222
IIIIII-223
III-224
III-224
III-224
III-225
III-226
III-228
III-229
III-231
III-232
III-234
III-235
III-235
III-237
III-237
III-xii
Fig. 8.4.2-2
Fig. 8.4.2-3a
Fig. 8.4.2-3b
Fig. 8.4.2-2
Fig. 8.5.2-1
Examples of flux evolution from RO of the UF permeates of various

III-237
emulsions(the RO permeate are not recycled) [11]
Relation between rejection, TOD of permeate and concentration factor III-238
Relation between rejection and transmembrane pressure
III-238
Examples of permeate TOD evolution from RO of the UF permeates
III-238
of various emulsions (the RO permeate are not recycled) [11]
Relation of flux and transmembrane pressure of NF for macroemulsion III241(Elf Seraft ABS) and microemulsion treatment (Elf Emulself G3 EAB),
using desal5 membrane at 20oC [20]
Figure (Cont)
Page
Fig. 8.5.2-2
Fig.
Fig.
Fig.
Fig
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
9.2.1-1
9.2.1-2
9.2.1-3
9.2.1-4
9.2.1-5
9.2.1-6
9.2.2-2
9.2.2-1
9.3.1-1
9.3.3-1
9.3.3-2
9.3.4-1
Fig. 9.3.4-2
Fig. 9.3.4-3
Fig. 9.4.2-1
Fig. 9.4.2-2
Fig. 9.4.2-3
Fig. 9.4.2-4
Fig. 9.4.2-5
Relation of flux and theoretical feed concentration of NF for macroIII-242

and microemulsion treatment [20]
Diagram of a binary mixture system
III-246
Evolution of temperature of a binary mixture at a constant P
III-246
Examples of P-T diagram
III-246
Examples of T-x-y and P-x-y diagrams
III-247
An example of P-T-x-y diagram
III-247
An example of T-x-y diagram
III-247
Examples of evolution of VLE and VLLE with pressure
III-248
Examples of various types of vapor/liquid equilibrium
III-249
Typical isobar diagram oily wastewater
III-250
Graphical method to find heteroazeotropic temperature
III-252
Graphical method to find dew curve
III-253
Examples of lab-scale apparatus for heteroazeotropic
III-255
distillation [11], [24]
Example of evolution of temperature with time from the treatment of UF III-255
permeate of cutting oil emulsion, using decane as entrainer [11]
Pictures of feed, residue and retentate of slop and UF retentate of used III-256
macroemulsion (30% by volume of oil) [24], [11]
Evolution of temperature, volume of distillate, TOD of mixed distillate III-260
and TOD of water part of the distillate (Based on Elf Seraft ABS, 4%
by volume of concentrate) [11]
The feed, residue and distillate from distillation of the
III-260
macroemulsion [11]
Evolution of temperature, volume of distillate , TOD of mixed distillate III-261
and TOD of water part of the distillate (Based on Elf G3 EAB, 4% by
volume of concentrate) [11]
The feed, residue and distillate from distillation of the
III-261
microemulsion [11]
Evolution of temperature, volume of distillate, and TOD of distillate
III262(Based on UF of used macroemulsion, TOD of feed =4400 mg/l) [11]
III-xiii
Fig. 10.2.2-1
Fig. 0.2.2-2
Fig. 10.2.3-1
Fig. 10.2.3-2
Fig. 10.2.3-3
Fig. 10.2.4-1
Symbols of surface active agent and its localization at oil/water

interfaces
Diagram of the electrical double layer
Interfacial of oil and water with the presence of surfactants
Coalescence and redistribution of droplets in thermodynamiclly
stabilized emulsion
Diagram of the electrical double layer
Force diagram of oil droplets and relation of repulsive, attractive and
resulting force with the distance between oil droplets
III-264
III-266
III-266
III-266
III-267
III-268
Figure (Cont)
Page
Fig. 10.3-1
Fig. 10.3.1-1
Fig.
Fig.
Fig.
Fig.
10.3.1-2
10.3.2.1
10.4-1
10.4-2
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
11.2.1-1
11.3-1
11.3.2-1
11.3.2-2
11.3.2-3
11.3.3-1
12.2.1-1
12.2.2-1
12.2.2-2
Schematic diagram of chemical process for emulsion destabilization

Static mixer (leftmost) and impeller types (from left): flat turbine,
pitched blade turbine, propeller type (Source: Memko, Sharp mixers)
Relation between Np and Re [63]
Paddle type mixers (Source: Norfolk WTP, Aqua Pak)
Jar test equipment (Source: ECE engineering)
Example of stabilized emulsion before (right) and after chemical
treatment (left)
General schematic diagram of activated sludge
Schematic diagram of adsorption
Examples of adsorption isotherm diagrams
Evolution of pollutant concentration along the bed depth
C/V curve and C/H curve
Examples of AC and GAC filter
Schematic diagram of cutting oil emulsion treatment system
Schematic diagram of conventional oily wastewater treatment system
Schematic diagram of compact oily wastewater treatment system for
Non-stabilized secondary emulsion
III-274
III-275
III-276
III-277
III-278
III-279
III-281
III-289
III-291
III-292
III-292
III-296
III-303
III-304
III-304
III-xiv
Part 3 Summary of researches: Oily or hydrocarbon-polluted wastewater

treatment
In this part, we will use the data reviewed and verified in Part 1 and Part 2 to
summarize and compose the textbook that covers every research of Prof. AURELLE. The text
will consists of;
Types and characteristics of oily wastewater
Related theories on oily wastewater treatment
Oily wastewater treatment processes, based mainly on researches of Prof.

AURELLE with additional data from well-proven literatures
Special treatment process trains for some specific oily wastewater, based on
Professor AURELLE s researches
118
III-1

1.1
Introduction
Water pollution is one of the most important environmental problems. Wastewater

from agriculture and industrial processes, as well as domestic wastewater, is main pollutant
source that causes water pollution problem. There are many substances that can deteriorate
water quality and, then, can be counted as water pollutants, such as, organic matter from
domestic wastewater, chemicals from industrial wastewater. Some valuable substances, such
as sugar, flour, oil, will become major pollutants when discharged into water bodies.
Among various kinds of pollutants, hydrocarbon or oil is one of the most severe
pollutants because of its intrinsic properties. Examples of adverse effects of hydrocarbons or
oil when it is discharged into water bodies or environment can be summarized as follow;
Even the small amount of oil can cause unpleasant odor and taste, so the water can
not be used in potable water production system. Some hydrocarbons, such as
benzene series, are noted for their carcinogen property.
Presence of oil or hydrocarbons in visible form on the water surface is

objectionable from aesthetic and recreation point of view.
For ecosystem, floating oil layer is dangerous for it can directly harm aquatic
animals such as fishes and waterfowls. It may coat and destroy algae thereby
destroying food sources of aquatic animals.
Small amount of hydrocarbon can spread over wide area of water surface. API
reports that only 40 liters of oil can cover 1 km2 of water surface in form of visible
film. It can affect photosynthesis and oxygen transfer, so causes adverse effect to
marine or water ecology.
The hydrocarbon contributes to very high biochemical oxygen demand (BOD) and
is relatively difficult for biodegradation, which is main natural self-purification
process. So it can last relatively long in the water and cause long term effect.
Therefor, it is obligatory to separate or remove oil from wastewater before disposal. In

European countries, standard for hydrocarbons in effluent is normally 5 mg/l (see section 1.6).
The first step to proper oily wastewater treatment design is to have basic knowledge
on types and characteristics of oily wastewater, which are described in the following sections
1.2
This section will provide background knowledge on definitions and basic chemistry of
various from of hydrocarbons and oils, normally present in oily wastewater.
1.2.1
Hydrocarbons
Chemically, the hydrocarbons are compounds of carbon and hydrogen. They are also
in the family of organic compounds, thus can be divided into 3 types, according to formation
of characteristic groups i.e., aliphatic hydrocarbons, aromatic hydrocarbons and heterocyclic
hydrocarbons.
119
III-2
1.2.1.1 Aliphatic Hydrocarbons

The aliphatic hydrocarbons are the hydrocarbon compounds those in which the carbon
atoms are linked to a straight line. There can be subdivided into 2 groups i.e., saturated and
unsaturated aliphatic hydrocarbons.
1.
Saturated aliphatic hydrocarbons
The saturated aliphatic hydrocarbons are the compounds in form of CnH2n+2.The

compounds are also called Methane series, Alkanes or Paraffins. Principle source of these
compounds is petroleum.
Properties: These saturated hydrocarbons are normally colorless, relatively
odorless, and relatively insoluble, particularly those with five or more carbon atoms. They are
present in form of gas, liquid and solid. Alkanes with 1 to 5 carbon atoms are gases at
ambient, those from C6 to C17 are liquids, and those above C17 are solids. Saturated aliphatic
hydrocarbons are quite inert toward most chemical reagents. They are readily soluble in many
solvents. However, their water solubility is relatively low. Solubility decreases with
increasing size or molecular weight, while boiling and melting point increase with increasing
molecular weight. Like common chemicals, properties of these hydrocarbons are subject to
change with pressure and temperature.
Nomenclature: The hydrocarbons that form to a straight line are the basic form,
called normal alkanes or n-alkanes, such as n-butane. The names and properties of some
normal alkanes are shown in table 1.2.1-1. There are also another formations of hydrocarbons
with the same number of carbon atoms as shown in fig. 1.2.1-1. These hydrocarbons are
named differently from n-alkanes. To name such hydrocarbons, the IUPAC system is
commonly used, somehow, will not be presented here.
Table. 1.2.1-1 Properties of some normal alkanes [1],[2]
Name
Formula
Melting
Boiling point
point(C/ 1
(C/1 atm)
atm)
Specific
gravity
(20/4)
Solubility
(at 25
C)(mg/l)
Methane
CH4
-182.4
-161.5
0.423 -162C
Ethane
C2H6
-182.8
-88.6
0.545 -89C
Propane
C3H8
-187.6
-42.1
0.493 25C
Butane
C4H10
-138.2
-0.5
0.573 25C
n-Pentane
C5H12
-129.7
36
0.626
40
n-Hexane
C6H14
-95.3
68.7
0.655
10
Cyclohexane
C6H14
n-Heptane
C7H16
55
-90.6
98.5
-56.8
125.6
0.684
0.699
25C
n-Octane
C8H18
Isooctane
C8H18
Nonane
C9H20
-53.5
150.8
0.718
Decane
C10H22
-29.7
174.1
0.730
3
0.66
2
120
III-3
H CHC
C
a) n-Butane
b) Isobutane
Fig. 1.2.1-1 Examples of normal alkanes and derivatives with equal number of
carbon atoms
Basic chemical reactions: The hydrocarbons in this category are quite inert. In
ambient, they do not react with strong bases, acids or aqueous solutions of oxidizing agents.
However, at elevated temperature, strong oxidizing agents, such as concentrated sulfuric acid,
oxidize the compounds to CO2 and water. Other important reactions of the compounds are as
follow;
Oxidation with oxygen or air and heat:
Ex: CH4 + 2O2 CO2 + 2H2O
Substitution of hydrogen by halogens (scarcely occurs):
Ex: CH4 +Cl2 HCl + CH3Cl
Pyrolysis or cracking:
High-mol.-wt. Alkanes + Heat + Pressure Low-mol.-wt. Alkanes + alkenes +
hydrogen + naphthenes +carbon
Biological oxidation:
1st step: Alcohol forming (relatively slow)
Ex: 2CH3CH2CH3 + O2 +bact. 2CH3CH2CH2OH
2nd step:
Ex: 2CH3CH2CH2OH + 5O2 3CO2 + 4H2O
2.
Unsaturated aliphatic hydrocarbons
The unsaturated aliphatic hydrocarbons are can be divided into 4 groups,

catagorized by the number of double or triple bond in between carbon atoms, i.e., Alkenes,
Diolefins, Alkadienes, and Alkynes. Examples of these compounds and their properties are
shown in table 1.2.1-2. Solubility of these hydrocarbons is very low, normally less < 1.0
g/100g water.
Alkenes: The hydrocarbons in this category contain one double bond between
two adjacent carbon atoms. Their general formula is CnH2n, such as Ethylene (C2H4), Butene
(C4H8). They are also called Olefins. The compounds are produced in large number during
the cracking of petroleum.
Diolefins: The hydrocarbons in this category contain two double bonds, such as
1,3-butadiene (CH2=CHCH=CH2), which has been used to make polymers.
121
III-4
Table. 1.2.1-2 Properties of some unsaturated aliphatic hydrocarbons [1],[2]
Formula
Melting point
(C/ 1 atm)
Boiling point
(C/1 atm)
Specific
gravity
(20/4)
Ethene
CH2=CH2
-169
-103.7
0.568-104C
Propene
CH2=CHCH3
-185.2
-47.6
0.50525C
1-Butene
CH2=CHCH2CH3
-185.3
-6.2
0.58825C
1-Pentene
CH2=CH(CH2)2CH3
-165.2
29.9
0.640
1-Hexene
CH2=CH(CH2)3CH3
-139.7
63.4
0.673
1-Heptene
CH2=CH(CH2)4CH3
-119.7
93.6
0.697
1-Octene
CH2=CH(CH2)5CH3
-101.7
121.2
0.715
1-Nonene
CH2=CH(CH2)6CH3
-81.3
149.9
0.72525C
1-Decene
CH2=CH(CH2)7CH3
-66.3
170.5
0.741
Name
Solubility
(at 25
C)(mg/l)
50
2.7
Alkadienes: The hydrocarbons in this category contain more than two doubles,
such as the red coloring matter of tomatoes, lycopene. Example of presence of these
compounds in industrial wastes is wastewater from vegetable canneries. They require
extremely high demand of oxidant.
Alkynes: The hydrocarbons in this category contain one triple bond, for
example, H-CC-H. They are found to some extent in industrial wastes, such as synthetic
rubber industries. Solubility
Basic chemical reactions: These compounds have many properties in common,
regardless of the type of compound in which they exist. Their important reactions are as
follow;
Oxidation: Oxidizing agents, such as potassium permanganate, easily
oxidizes the compounds, in an aqueous solution, to glycol.
Reduction: Hydrogen may be added to double or triple bonds under proper
temperature and pressure.
Addition: Halohen acids, hypochlorous acids and halogens can be added at
double or triples bonds.
Polymerization: The compounds prone to combine with each other, by their
unsaturated link, to form polymers.
Biological oxidation: These compounds are easier to be biodegraded by
bacteria than saturated compounds.
3.
Cyclic aliphatic compounds (Naphthenes)
These compounds are the special cases of aliphatic hydrocarbons. They are also
called Naphthenes and can be count as saturated hydrocarbons. The compounds can be
easily described as a ring of CH2 molecules. They are found in petroleum product. Examples
122
III-5
of these compounds are cyclopropane, cyclopentane, cyclohexane, etc. At the same number of
carbon atoms, naphthenes have higher density and lower melting point than paraffins.
1.2.1.2 Aromatic hydrocarbons
The aromatic hydrocarbons are the hydrocarbon compounds that contain ring
structure. The difference between these compounds and the cyclic aliphatic compounds is that
a carbon atom has one single bond and one double bond to the adjacent carbon atoms (see fig.
1.2.1-2). For the cyclic aliphatic compounds, they do not have double bond. There are 2 major
series of the aromatic hydrocarbons, i.e., Benzene and Polyring series.
1.
Benzene series
Benzene (C6H6) ring is the simplest aromatic ring, containing 6 carbon atoms.
Benzene ring is knows as the parent compound of the aromatic series. The formula of benzene
is shown in fig. 1.2.1-2. The compounds in benzene series are made up of alkyl (CnH2n+1)
substitution product of benzene. Examples of the compounds in benzene series are as shown
in table 1.2.1-3 and fig .1.2.1-2.
These compounds are widely used as solvents and in chemical synthesis. They
are commonly found in petroleum products, such as gasoline. The compounds are hazardous
for human health. They are known to be carcinogenic and cause leukemia. Eventhough they
are relatively insoluble in water, there are limits of these compounds, such as xylene, toluene,
set in drinking water standards.
Table. 1.2.1-3 Properties of some benzene-series hydrocarbons [1],[2]
Name
Formula
Benzene
Toluene
o-Xylene
m-Xylene
p-Xylene
Ethybenzene
C6H6
C6H5CH3
C6H4(CH3)2
HC
H
C
C6H5C2H5
Melting
point(C)
Boiling
point(C/1
atm)
Specific
gravity
(20/4)
5.5
-94.9
-25.2
-47.8
13.2
-94.9
80.0
110.6
144.5
139.1
138.3
136.1
0.877
0.867
0.88
0.864
0.861
0.867
CH3
CH
Solubility
(at 20 C)
1,600
500
170
130
CH3
CH3
CH
HC
C
H
a) Benzene ring
b) simplified formula
of benzene
c) Toluene
d) o-Xylene
Fig. 1.2.1-2 Examples of benzene series
123
III-6
2.
Polyring series
The compounds contain more than 1 benzene ring. Some compounds are in
from of solids at ambient, such as Naphthalene (mothball). Other examples of the compounds
in this group are Anthracene and Phenanthrene (C14H10). They are known as carcinogen, thus
also hazardous to human health. Furthermore, the larger compounds (5 or more rings) are very
difficult to be biodegraded.
3.
Chlorinated aromatic hydrocarbons
The compounds are derivatives of aromatic hydrocarbons that are of interest

because of their industrial importance, as well as, their toxicity. Well-known example of these
compounds is the polychlorinated biphenyls (PCBs), which are widely used as coolants in
transformer, plasticizer, solvents and hydraulic fluid for they are very stable. The compounds
are known to be very hazardous to human health.
1.2.1.3 Heterocyclic hydrocarbons
The heterocyclic hydrocarbons are the hydrocarbon compounds that have one other
element in the ring in addition to carbon. An important hydrocarbon in this group is epoxides.
Epoxides are three-membered rings where oxygen is bonded with two carbons. They are very
reactive. Example of epoxides is ethylene oxide, which is in synthetic surfactant and pesticide.
1.2.2
Fats and oils
Chemically, fats and oils are esters (product formed by reaction between acid and
alcohol) of the trihydroxy alcohol, glycerol. They are also described as glycerides of fatty
acids. These glycerides that are liquid at room temperature are called oils and those that are
solids are called fats. The oils, here, are mainly vegetable or animal oil and normally edible.
Basic chemical reactions: Their important reactions are as follow;
Oxidation: For some oils, such as linseed oil, oxygen may be added to the double
bonds and forms resin-like material. These drying oils are major component in all
oil-based paints.
Hydrolysis: since they are esters, oils can be easily hydrolyzed into glycerol plus
fatty acids. If hydrolysis is accomplished by using of NaOH, it is called
saponification. The product from saponification is soap.
Addition: Oils containing unsaturated acids can add chlorine at the double bonds.
This process is normally slow. However, it may represent a significant part of
chlorine demand in some wastes. Oils that contains large amount of oleic and
linoleic acids may be converted to fats by the process of hydrogenation. Thus, lowpriced oils can be converted into magarine.
1.2.3
1.2.3.1 Petroleum or crude oils
Petroleum and petroleum products are one of the major sources of oil in oily
wastewater. Petroleum is the mixture of various hydrocarbons, as well as other chemicals. If
contains (by weight) about 80% of carbon, 10-15% of hydrogen, 1.55 of oxygen, 0.1-t% of
124
III-7
sulfur, 0.65 of nitrogen and also trace amount of iron, calcium, sodium, potassium, and other
elements [39]. The density of crude oils is around 650 to 1,200 kg/m3.
Crude oils normally consist of paraffins, olefins, naphthenes and aromatic
hydrocarbons. Oxygen, sulfur and nitrogen are present in the forms of compounds. Normally,
paraffins of 5 to 16 atoms of carbon are present in the form of liquid. They are important
components in gasoline and kerosene, as well as, desire components of diesel and lubricant
oil. Paraffins of 17 carbon atoms or more are solids.
Olefins are found relatively rarely and in significant amount. Because of their highly
reactive and easily polymerizing, they are relatively undesirable components in fuels and
lubricant oils.
Naphthenes are normally found in forms of cyclo-pentane and cyclo-hexane. They are
also important components of fuels and lubricant oils for their temperature resistance
property.
Aromatic hydrocarbons of 1 to 4 rings are also found in crude oils. These compounds
have the greatest density, compared to other hydrocarbons. They provide good viscositytemperature property to petroleum product. They are also good solvents
Solubility of crude oils is low. The solubility of petroleum fractions decreases in the
following order: aromatic compounds naphthenes paraffins. It also decreases with
increasing in molecular weight.
1.2.3.2 Petroleum products
Petroleum products are the product derived from crude oils through processes such as
catalytic cracking and fractional distillation. These products have physical and chemical
characteristics that differ according to the type of crude oils and subsequent refining
processes. Several examples of refined petroleum products and their physical properties are as
follow:
Gasoline: a lightweight product that flows easily, spreads quickly, and may evaporate
completely in a few hours under temperate conditions. It poses a risk of fire and explosion
because of its high volatility and flammability, and is more toxic than crude oil. Gasoline is
amenable to biodegradation, but the use of dispersants is not appropriate unless the vapors
pose a significant human health or safety hazard.
Kerosene: a lightweight product that flows easily, spreads rapidly, and evaporates
quickly. Kerosene is easily dispersed, but is also relatively persistent in the environment.
No. 2 Fuel Oil: a lightweight product that flows easily, spreads quickly, and is easily
dispersed. This fuel oil is neither volatile nor likely to form emulsions, and is relatively nonpersistent in the environment.
No. 4 Fuel Oil: a medium weight product that flows easily, and is easily dispersed if
treated promptly. This fuel oil has a low volatility and moderate flash point, and is fairly
persistent in the environment.
125
III-8
No. 5 Fuel Oil (Bunker B): a mediumweight to heavyweight product with a low
volatility and moderate flash point. Preheating may be necessary in cold climates, and this
fuel oil is difficult, if not impossible, to disperse.
No. 6 Fuel Oil (Bunker C): a heavyweight product that is difficult to pump and
requires preheating for use. This fuel oil may be heavier than water, is not likely to dissolve, is
difficult or impossible to disperse, and is likely to form tar balls, lumps, and emulsions. It has
a low volatility and moderate flash point.
Lubricating Oil, a medium weight product that flows easily and is easily dispersed if
treated promptly. This oil has a low volatility and moderate flash point, but is fairly persistent
in the environment
Because of the difference in their properties, as stated above, it is helpful to know

which type of oils is present in the oily wastewater considering.
1.2.4
From section 1.2.1 to 1.2.3, the definitions and properties of hydrocarbons and other
substances have been described. Those substances can be accounted as oil in oily
wastewater. Even though they are some discrepancies in their chemical formula, their source
of origin or some or their properties, they are some physical properties in common. Since the
treatment processes studied in GPI lab are based on separation process, which depends mainly
on these physical properties, it can be concluded that substances that have identical properties
can be accounted as oil by the meaning of this book. These properties include:
Liquidity: oils, in our case, must be liquids only. So some solids hydrocarbons and
fats will not be accounted as oil in our case.
Solubility: oils, in our case, must have very low solubility in water. So it can be
treated as non-miscible binary mixture, which is main assumption or condition that
governs operating principles of most separation processes. However, dissolved
pollutants in oily wastewater are considered in some treatment processes, even
though their major components come from other additives in oil, rather than the
dissolved portion of oil its self.
Specific gravity or density: oils, in our case, must have less density or specific
gravity than water.
So, after this section, the word oils found herein this book will normally refer to the
substances that conform to the above criteria.
1.3
Apart from oil and water, oily wastewater can contain other substances that may
affect its properties, as well as selection and design of its treatment processes. Important
components of oily wastewater include:
1.3.1
Surfactants
In many applications, such as in cleansing processes, it is necessary to change the level

of free surface energy. By the surface energy (or interfacial tension, in case of liquid/liquid
126
III-9
interfaces), it means the work required to form new surfaces. The substances that can decrease
the level of surface energy are called surface-active substances or surfactants. They are
also called by other names, such as, detergents (for solid/liquid interface, e.g. in washing or
cleaning process), emulsifier, or dispersant, etc. With proper amount of surfactants, surface
energy can be substantially decreased until almost to zero. This makes it possible to create a
lot of new surface.
In our interest, surfactants can help making a lot of new surfaces of oil in the water.
This means the oils can be divided into very small droplets, which contributes to many new
surfaces, in the water, called emulsion. Theory of surface energy will be described in chapter
2. Effect and some further details of surfactants and co-surfactants will be described again
in chapter 10 Chemical treatment processes.
All surfactants have rather large functional groups. One end of the molecule, which
normally is organic group, is particularly soluble in oil. The other (polar group) is soluble in
waters. There are 4 main types of surfactants i.e., cationic, anionic, non-ionic and ampholytic
surfactants
1.3.1.1 Cationic surfactants
These surfactants are generally salts of quaternary ammonium hydroxide. The surfaceactive properties are contained in the cations. Besides their surface-active properties, the
compounds are known for their disinfecting properties.
1.3.1.2 Anionic surfactants
These surfactants are generally sodium or potassium salts. The common ones are
sulfates and sulfonates. The surface-active properties are contained in the anions.
1.3.1.3 Non-ionic surfactants
These surfactants do not ionize and have to depend upon groups in the molecule to
render them soluble. All depend on polymers of ethylene oxide (C2H4O) to give them this
property.
1.3.1.4 Ampholytic (or amphoteric) surfactants
For these surfactants, they contain both cationic and anionic functional groups.
1.3.2
Soaps
Ordinary soaps are derived from fats and oils by saponification with sodium
hydroxide. Saponification is the special case of hydrolysis in which an alkaline agent is
present to neutralize the fatty acids as they are formed. The fats and oils are split into glycerol
and sodium soaps. The nature of the soap depends on the type of fat and oil used. Sodium and
potassium soaps are normally soluble. If the water contains hardness, calcium, magnesium
and other hardness-causing ions will precipitate soap to form metallic soap. Soap will
precipitate all hardness ions first, after that it becomes a surfactant.
127
III-10
1.3.3
Co-surfactants
In emulsions, especially microemulsion, they contain co-surfactants. These

compounds are normally alcohol, such as butyldiglycol, or benzylic alcohol. These
compounds are readily soluble in water thus provide good solubility to certain products, such
as cutting oil emulsion. They also increase the stability to the emulsion by promoting both
electrical stability and mechanical stability.
1.3.4
Suspended solids
Suspended solids are commonly found in oily wastewater, especially when combined
collection systems are used. Types and concentration of suspended solids, present in oily
wastewater, depends on the sources of the wastewater. Some oil separation processes, esp. the
ones that are based on filtration concept such as granular bed coalescer and membrames, are
sensitive to the suspended solids. Suspended solids can cause adverse effect on oil separation
processes, unless it has already accounted for and mitigation measure is provided.
1.3.5
Other components
Others components found in oily wastewater depend on their source. Normally they
are the additives of the oil product, such as anti-foaming agents, anti-mousse agents,
bactericides, dyes, or anti-corrosion agents, etc. Some can present adverse effect on treatment
processes. Some may be present as residual pollutants in the effluent after oil separation
processes. So it will be very helpful if we know in advance the components of the oily
wastewater considering.
1.4
Oil/water mixture systems can be categorized by many criteria. However, as stated

before that the treatment processes summarized in this book are based mainly on separation
processes, the criteria, used to categorize these oil/water mixtures, are based upon physical
properties. There are 3 main criteria, i.e., the nature of continuous phase, the stability of oily
wastewater, and the degree of dispersion.
1.4.1
In binary mixture systems of oil and water, their components can be divided into 2
main phases, i.e., continuous phase, which is the majority of the two, and dispersed phase.
Direct emulsion: If continuous phase is the water, the mixture will be called direct
emulsion, and can be written as o/w emulsion, which stands for emulsion of oil in water.
Inverse emulsion: On the other hand, if the continuous phase is oil, the mixture will
be called inverse emulsion or w/o emulsion.
The treatment processes described herein this book will emphasize on oily wastewater,
which is direct emulsion. However, some processes can also be applied to inverse emulsion.
1.4.2
By these criteria, oily wastewater can be divided into 2 groups:

128
III-11
1.
Non-stabilized emulsion
This type of wastewater mainly consists of 2 components, i.e., oil and water,
without presence of surfactants. So its stability is not enhanced by surfactants and depends
mainly on degree of dispersion (the size of oil droplets) in the wastewater. If the droplet size
is small, the oil drop will take long time to rise to the surface, so it stays relatively long within
the water phase. As long as there are oil dispersed in the water, the mixture is still called
emulsion. The longer the time that droplets stay in the water, the greater the stability of the
emulsion. Without surfactants, the degree of dispersion depends on energy added to the
system to disperse the oil phase. This energy is normally supplied by mechanical means, such
as agitation, pump, or hydraulic mixing, such as venturi.
2.
Stabilized emulsion
This type of wastewater contains oil, water and surface-active agent, which may
consists of only one surfactant or both surfactant and co-surfactant. Presence of these surfaceactive substances cause decrease in interfacial tension between oil and water, thus make the
oil disperse into very fine droplets, down to micron size. Furthermore, localization or
orientation of the surface-active agents causes electric barrier as well as mechanical barrier
that prevent collision and coalescence between droplets. So the droplets remain small (See
chapter 10). Their rising velocity is then very small and can be negligible, compared to
Brownian motion. So this type of emulsion is stable, as it is called, and not prone to decant
naturally.
1.4.3
This classification is based on rising velocity of oil droplet, which is controlled by

properties of the oil/water system and its size or its degree of dispersion. For common
treatment processes, this velocity is governed by STOKES law. Theory of rising velocity will
be described in chapter 2. By these criteria, oily wastewater can be divided into 5 groups:
1.
Film or layer of oil on water surface
This type of wastewater is relatively easy to treat for the oil and the water are
readily separated. However, extraction or removal of oil from the water surface should be
carefully performed to prevent entraining of water with oil.
2.
Primary emulsion
Oily wastewater will be categorized into this type if the oil droplets are greater
than 100 microns.
3.
Secondary emulsion
Oily wastewater will be categorized into this type if the oil droplets are smaller
than 20 microns.
Classification of primary and secondary emulsion can be summarized as shown
in fig. 1.4.3-1.
129
III-12
10-3
Primary
emulsion
Rising velocity (m/s)
10-4
Secondary
emulsion
10-5
10-6
10-7
Primary
emulsion
10-8
Secondary
emulsion
10-9
10-10
1
Oil
density
10
100
Droplet diameters (microns)
0.60
0.80
0.70
0.98
1000
0.75
0.90
Fig. 1.4.3-1 Relation between droplet sizes and rising velocity of primary
and secondary emulsion [11]
4.
Macroemulsion
This type of emulsion contains droplet size between 0.06 to 1.0 microns. It
usually contains surfactant (and co-surfactant). This type of emulsion has a milky appearance.
A common example of this emulsion is cutting oil macroemulsion.
5.
Microemulsion
This type of emulsion contains droplet size between 10 to 60 nm. It contains

extensive amount of surfactants and cosurfactants. Since the droplets is very small, this type
of emulsion is usually transparent (sometimes, translucent if dyes are present or amount of osurfactants is low). A common example of this emulsion is cutting oil microemulsion.
Details of microemulsion amd macroemulsion will be described in details in the
chapter 10, related to emulsion destabilization.
From the three criteria stated above, some classes of oily wastewater from
different criteria might be overlapped. So, to summarize all of three criteria, oily wastewater
can be categorized as shown in fig. 1.4.3-1 and table 1.4.3-2.
130
III-13
Solubility
Forms of oil Continuous phase
Stability
Dispersion
Type of emulsion
Soluble
Soluble
Oil
Oil
Non
Non
soluble
soluble
Non
Non
stabilized
stabilized
Film
Film
> 100
Emulsion
Emulsion
Inverse
Inverse
Stabilized
Stabilized
Direct
Direct
Non
Non
stabilized
stabilized
Primary
Primary
emulsion
emulsion
< 20
Secondary
Secondary
emulsion
emulsion
<1
MacroMacroemulsion
emulsion
Stabilized
Stabilized
< 60 nm
MicroMicroemulsion
emulsion
Fig. 1.4.3-2 Classification of oily wastewater by degree of dispersion

Table. 1.4.3-2 Summary of oily wastewater classification
Continuous
phase
Direct
emulsion
(o/w)
1.5
Degree of dispersion
Stability
Primary
emulsion
Secondary
emulsion
Macroemulsion
Microemulsion
Non-stabilized
emulsion
Exist
Exist
Exist
Not exist
Stabilized
emulsion
Exist
Exist
Exist
Exist
From the previous sections, it can be concluded that the characteristics of oily
wastewater can greatly very from wide varieties of oils and compositions of oily wastewater,
as well as degree of dispersion. So, the best solution to characterize the oily wastewater is to
have it analyzed by standard methods to get important data necessary for treatment process
consideration. Important parameters and their method of analysis will be present in chapter 2.
However, in this section, data of oily wastewater from many literatures, include GPIs
researches, will be presented as shown in table 1.5-1. These data can be used as guideline for
treatment process consideration, when the real data is not available.
131
III-14
Table 1.5-1a Data of pollution from certain oils, oil products and serfactants.
132
III-15
1.6
To study or design wastewater treatment process, it is necessary to determine the

quality of the effluent after the treatment. In case that the effluent will be recycled or reused,
the treatment process will be designed to meet the requirement for reuse or recycle. However,
in general case, the effluent will be discharged to public collection system or receiving water
bodies. To do so, The effluent quality will have to meet the requirement of that receiving
water bodies, set by local laws, standards, or related regulations. For oily wastewater
treatment process, apart from oil concentration, other parameters that usually relate to oil or
come with oil product, e.g. BOD and COD (from surfactants in cutting oil), phenol (from
petroleum product), should be considered.
Table 1.6-1 shows effluent standards data from various sources. It must be noted that,
Applicable effluent standards or laws for individual site usually depend on type of
pollutant source and receiving water body as well as location of the source. The
same type of industries locating at different towns may subject to different effluent
standards.
Summary of standards that should be considered for each site generally consists of,
National standards (e.g. Normes franaises pour les eaux use in France,
Notification of the Ministry of Science, Technology and Environment in
Thailand, or Code of Federal Regulations on Environment in the USA)
Regional and specific industrial standard (e.g. standards of Toulouse, Bangkok
metropolitan administration standard, standards for petroleum industries, etc.)
Receiving water body standards (e.g. standards for coastal aquaculture, etc.)
Generally, there are many conditions and exceptions in the laws. In some
countries, such as the USA, the standards are meticulous categorized based on
treatment technology, e.g. the best available technology (BAT) and the best
practicable technology (BPT), which makes it more complicate to select the right
applicable standard. Thus, conditions of the laws shall be studied carefully.
133
III-16
Table 1.6-1a Industrial effluent standard of Thailand

Parameters
1. pH value
Standard Values
4. Temperature
5. Color and Odor
6. Sulphide as H2S
5.5-9.0
not more than 3,000 mg/l depending on receiving
water or type of industry under consideration of
PCC but not exceed 5,000 mg/l
not more than 5,000 mg/l exceed TDS of receiving
water having salinity of more than 2,000 mg/l or
TDS of sea if discharge to sea
not more than 50 mg/l depending on receiving
water or type of industry or wastewater treatment
system under consideration of PCC but not exceed
150 mg/l
not more than 40C
not objectionable
not more than 1.0 mg/l
7. Cyanide as HCN
2. Total Dissolved
Solids (TDS)
3. Suspended solids
(SS)
9. Formaldehyde
not more than 5.0 mg/l depending of receiving

PCC but not exceed 15.0 mg/l
10.Phenols
8. Fat, Oil & Grease

(FOG)
11.Free Chlorine
12.Pesticides
13.Biochemical
Oxygen Demand
(BOD)

not detectable
PCC but not exceed 60 mg/l
14.Total Kjedahl
Nitrogen (TKN)
15.Chemical Oxygen
water of type of industry under consideration of
Demand (COD)
16.Heavy metals
1. Zinc (Zn)
2. Chromium (6)
3. Chromium (3)
4. Copper (Cu)
5. Cadmium (Cd)
6. Barium (Ba)
7. Lead (Pb)
8. Nickel (Ni)
9. Manganese (Mn)

10. Arsenic (As)
11. Selenium (Se)

12. Mercury (Hg)

Method for Examination

pH Meter
Dry Evaporation 103-105

C, 1 hour
Glass Fiber Filter Disc

Thermometer on-site
Not specified
Titrate
Distillation and Pyridine
Barbituric Acid Method
Solvent Extraction by
Weight
Spectrophotometry
Distillation and 4Aminoantipyrine Method
lodometric Method
Gas-Chromatography
-Azide Modification at 20
C , 5 days
Kjeldahl
Potassium Dichromate
Digestion
Atomic Absorption
Spectro Photometry; Direct
Aspiration or Plasma
Emission Spectroscopy ;
Inductively Coupled Plama
: ICP
Atomic Absorption
(AA)Spectrophotometry;
Hydride Generation, or
Plasma Emission
Spectroscopy; Inductively
Coupled Plasma : ICP
AA Cold Vapour
134
III-17
Table 1.6-1b Industrial effluent standard of France (1998)

Parameters
1. pH value
2. Total Dissolved
Solids (TDS)
3. Total suspended
solids (TSS)
4. Temperature
5. Color and Odor
6. Sulphide as H2S
7. Cyanide as HCN
8. Fat, Oil & Grease
(FOG)
9. Formaldehyde
10.Phenols
11.Organic
halogenated
compounds
12.Pesticides
13.Biochemical
Oxygen Demand
(BOD)
Standard Values
5.5-9.5, 9.5 if there is alkaline neutralization
Depend on receiving water or type of industry
100 mg/l for maximum daily rate not more than 15
kg/d, 35 mg/l for those that exceed, 150 mg/l for
lagoon treatment system
Not more than 30C
Not specified
Not specified
Method for Examination

pH Meter
Dry Evaporation 103-105
C, 1 hour
Glass Fiber Filter Disc
Thermometer on-site
Not specified
Not specified
Not specified
Depend of receiving water or type of industry
Not specified
Not specified
Not specified
Not specified
not more than 1.0 mg/l if discharge > 30 g/d
As AOX or EOX
Not specified
Depend on receiving water or type of industry,
Level A to D: 30-100 mg/l, Level E: not more than
30 mg/l, Level F: not more than 15 mg/l
TKN and ammonia N not more than 10-40 mg/l for
14.Nitrogen (N)
level NK1 to NK3,
TKN+AmmoniaN+Nitrite+Nitrate not more than 20
mg/l for level NGL1 and NGL2.
15.Chemical Oxygen
Level A to D: 125-150 mg/l, Level E: not more than
Demand (COD)
50 mg/l, Level F: not more than 90 mg/l
Not specified
At 20 C , 5 days
Kjeldahl
Potassium permanganate
Digestion
16.Heavy metals
1. Zinc (Zn)
2. Chromium (6}
3. Chromium (total)
4. Copper (Cu)
5. Cadmium (Cd)
6. Barium (Ba)
7. Lead (Pb)
8. Nickel (Ni)
9. Manganese (Mn)
10. Tin
11. Iron, aluminium
12. Mercury (Hg)

Not specified
Not specified
Not specified
Note:
Not specified
Extracted form Les normes de rejet des eaux uses et d'effluents (normes guides) (Source:
Web site of Grenoble eau pure)
2. The standards may be amended and some special remarks for each type of receiving water
and type of industry, which refers to other notification or decree, are not completely
included.
135
III-18
Table 1.6-1c Industrial effluent standards of USA, categorized by pollutant sources

(1)
CFR 40 part 419Petroleum refining point source category

Kg / 1000 m3 of feed stock
Effluent characteristics
BOD5
COD
TSS
Oil and grease
Phenolic compound
Ammonia as N
Sulfide
Total chromium
Chromium (hexavalent)
pH
Note:
(2)
Maximum for any 1 day
Average of daily values for 30

consecutive days shall not exceed
34.6
210.0
23.4
11.1
0.25
23.4
0.22
0.52
0.046
6.0-9.0
18.4
109.0
14.8
5.9
0.120
10.6
0.099
0.30
0.020
6.0-9.0
The limits shown in the table are to be multiplied by the process factors and size factor
to calculate the maximum for any one day and maximum average of daily values for
thirty consecutive days
CFR 40 part 437The centralized waste treatment point source category

Maximum daily (mg/l)
Maximum monthly average (mg/l)
Oil and grease

pH
TSS
Metals
Arsenic
Cadmium
Chromium
Cobalt
Copper
Lead
Mercury
Tin
Zinc
Organic parameters
Bis(2-ethylhexyl) phthalate
127.0
6.0-9.0
74.1
38.0
6.0-9.0
30.6
2.95
0.0172
0.746
56.4
0.500
0.350
0.0172
0.335
8.26
1.33
0.0102
0.323
18.8
0.242
0.160
0.00647
0.165
4.50
0.215
0.101
Butylbenzyl phthalate
Carbazole
0.188
0.598
0.0887
0.276
n-Decane
Fluoranthene
n-Octadecane
0.948
0.0537
0.589
0.437
0.0268
0.302
Note:
The limits shown in the table arebased on best practicable control technology currently
available (BPT)
General note: The standards may be amended and some special remarks for each type of receiving
water and type of industry, which refers to other notification or decree, are not
completely included in this chapter.
136
III-19
Table 1.6-1c Industrial effluent standards of USA, categorized by pollutant sources (Cont.)
(3)
CFR 40 part 417Soap and detergent manufacturing point source category

Kg / 1000 kg of anhydrous product
Maximum for any 1 day
Average of daily values for 30

consecutive days shall not exceed
BOD5
0.90
0.30
COD
4.05
1.35
TSS
0.09
0.03
Surfactants
0.90
0.30
Oil and grease
0.15
0.05
6.0-9.0
6.0-9.0
pH
(4)
CFR 40 part 438Metal products and machinery point source category

Maximum daily (mg/l)
TSS
62.0
Oil and grease (as HEM)
46.0
General note: 1
The standards may be amended and some special remarks for each type of
receiving water and type of industry, which refers to other notification or decree,
are not completely included in this chapter.
137
III-20
Chapter 2 Overview for oily wastewater treatment process design

This chapter provides basic theories, which are important to understand the
phenomena, taking place in oily wastewater, and to understand operating principle of oily
wastewater treatment processes. The analysis methods of some important parameters and
overview of oily wastewater treatment processes are also described.
2.1
Decantation velocity and STOKES law
Oily wastewater can be considered as an immiscible binary mixture system of oil and
water, with the oil as a dispersed phase, because the solubility of oil in water is very low (<
1g/ 100 g of water). So the oil will be present in the water in form of oil droplets, which is the
result of surface tension, which will be described in the next section. Because of its low
specific gravity, these droplets will try to separate themselves from the water by floating or
rising to the water surface. Consider a single oil drop, when the oil drop is rising, it will be
subject to 2 forces as shown in fig. 2.1-1. The first one (F1) is the gravitational force,
calculated from oil drop size and density difference of oil and water (eq. 2.1.1). The second
force is called drag force, which is the resultant of the resistance inertia force and viscous
force (eq. 2.1.2).
F1
V
Oil drop,
dia. = d
F2
F1 =
F2 =
d 3
6
( c )g
1
C d c AV 2
2
Water
{2.1.1}
{2.1.2}
Fig. 2.1-1 Free body diagram of oil drop in water and relation between Cd and Re [55]
Cd is a numerical constant, called drag coefficient, which depends on the flow region,
represented by Reynolds number (Re) as shown in fig. 2.1-1. A is the projection area of oil
drop. In this case, the oil drop is spherical, then A is the cross sectional area of the sphere.
The oil drop will start to rise from a stationary position (V = 0 m/s, F2 = 0). After
some time, it will reach the terminal velocity or rising velocity, which will remain constant
along its course. At this velocity, F1 = F2. So, from this condition, the rising velocity (V) can
be written as follows.
4 d
V =
(
1) g
3 cd c
1/ 2
{2.1.3}
138
III-21
Chapter 2 Basic theory for oily wastewater treatment process design
By substituting the relation between Cd and Re at various ranges of Re into eq. 2.1.3
[41], The rising velocity can be calculated by the equations, summarized in table 2.1-1. In
most of oil separation processes described hereafter, they normally operate in laminar flow
regime. So rising velocity are governed by STOKES law (Table 2.1-1, eq. 2.1.4).
From STOKES law, one can increase the rising velocity by modifying related
parameters in eq. 2.1.4. To increase the rising velocity is to increase the oil separation
efficiency. Several treatment processes in this book are based upon this idea of modification.
And because some parameters in STOKES law have been modified from natural condition,
these processes will be called accelerated separation process. Examples of these processes
include coalescer, flotation and hydrocycloning.
Table. 2.1-1 Summary of equations for rising velocity calculation [41]
Equation
STOKES law
2.1.4}
Flow Regime
Laminar
Re
Cd
10-4 - 1
24
Re
( c ) gd 2
or
18 c
0.545(
ALLENs law
2.1.5a,b,c}
Intermediate
NEWTONs law Tubulent

(Eddy flow)
{2.1.6}
Turbulent
1) 1 d 2
c
1 - 10
26
Re 0.77
0.57(
1) 0.814 0.625 d 1.439

c
10 100
20
Re 0.65
0.73(
1) 0.741 0.481 d 1.222

c
100 1000
4.92
Re 0.316
1.81(
1) 0.604 0.209 d 0.813

c
103 - 2*105
0.44
> 2*105
5.40(
1) 0.5 d 0.5
c
Newtons law is applicable
2.2
2.2.1
In liquid, there are short-length attraction forces (Van de waal and polar forces)
reacting between adjacent liquid molecules. The molecules located inside the bulk of liquid
are subject to equal force in all direction, as shown in Fig 2.2.1-1. However, the molecules
located at the surface of air/liquid are subject to unbalanced force, resulting in net inward pull
(R) (see fig. 2.2.1-1). From this force, the molecules will try to move from the surface into
bulk liquid. The surface of liquid, thus, tends to contract spontaneously. That is the reason
why the oil or air present in the water tends to form a sphere shape, as oil drop or bubble
(Laplaces law).
This phenomenon is identical for the surface between 2 liquids. To avoid confusion,
when talking about the surface between 2 substances, not the surface between one substance
and air, this surface will be called interface
139
III-22
Fig. 2.2.1-1 Force diagram of oil drop in water

Surface tension (between liquid-air) or interfacial tension (between liquid-liquid or
liquid-solid) [40] is defined as the work required to increase, isothermally and reversibly, the
surface or interface area by 1 unit. Sometimes, it is also called surface free energy or
surface energy (esp. in case of solid surface). It is measured in unit of work per unit area
(ex. Nm/m2) or unit of force per unit length (ex. N/m or dyne/cm).
From this definition, interfacial tension between oil and water (ow) and between oil
and air can be written in form of the following equations. Interfacial tension of liquid
normally decreases with increasing temperature in a nearly linear fashion [40]. Data of surface
tension and interfacial tension for some liquids are presented in table 2.2.1-1
ow =
W
Aow
{2.2.1a}
o =
W
Ao
{2.2.1b}
W represents effective work required to increase the interfacial area between oil and
air or water by Ao or Aow (or Ao/w) m2 respectively. For emulsion, Aow is the total area of every
oil droplet. This effective work will be used to calculate mechanical work of the mixer to
create the emulsion providing that the efficiency of the mixer is known. This concept will be
used to create the emulsion of required degree of dispersion.
140
III-23
Tip To visualize the surface tension [42], we will consider a tank that one side
wall can be moved as shown in fig. 2.2.1-2. If we try to move the wall to extend the
surface of liquid, we have to apply the force F. Then, the wall move by the distance dl.
From this, the work done or effective work can be written as:
W = F dl
{2.2.2a}
When the wall is moved, we increase the surface area of the liquid, which can
be written as shown in eq. 2.2.2b.The increasing in energy of the system is as shown in
eq. 2.2.2c.
A = L dl
G = A
{2.2.2b}
{2.2.2c}
We assume the process is isothermal and

reversible, so there is no heat loss. Then,
work done will be equal to energy (eq.
2.2.2d). From this, we will see that the
surface tension can be derived as shown in
eq. 2.2.2e and eq. 2.2.1
Section
dl
F dl = L dl
F
=
{2.2.2d}
F dl W
F
= or =
L dl
A
L
{2.2.2e}
Plan
Fig. 2.2.1-2 Model for Visualization of

Table. 2.2.1-1a Data of surface and interfacial tension (N/m) for some liquids at 20C
[40][42]
Name
Surface
tension
Water
72.8
Benzene
28.9
Acetic acid
Interfacial
tension
(/water)
Name
Surface
tension
Interfacial
tension
(/water)
Ethanol
22.3
n-Octanol
27.5
8.5
27.6
n-Hexane
18.4
51.1
Acetone
23.7
n-Octane
21.8
5038
CCl4
26.8
Mercury
485
375
Polar organic
compounds
22-50
Aqueous
detergent
solutions
24-40
Hydrocarbon
18-30
Fluorocarbon
8-15
35
45.1
141
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Adhesion work: Interfacial tension between oil and water (or any two liquids) can
relate to surface tension of each liquid by DUPREs equation (eq. 2.2.3a). This equation can
be also applied to solid-liquid interface, as shown in eq. 2.2.3b. s represents surface energy of
solid.
ow = o + w Wadh (ow)
{2.2.3a}
so = s + o Wadh ( so )
{2.2.3b}
Tip To visualize the concept of adhesion work [42], we will consider a tank that
one side wall can be moved, filled with 2 liquids (oil and water). When we move the
wall, from eq. 2.2.2, it can be described that:
Water
Oil
o/w
o
F
We increase the surface of oil and water

by o and w, respectively.
Then we attach the oil and water surface
together. For this, we recover an amount
of energy, called adhesion work
Fig. 2.2.1-3 Model for visualization of

adhesion work
2.2.2
2.2.2.1 Wetting, Contact angles, Adhesion work, and YOUNGs equation

Wetting is the displacement from a surface of one fluid by another [40]. Therefore, it
involves three phases and, at least two phases must be fluid. To understand this, we will
consider the oil drop on a solid surface in water, as shown in fig. 2.2.2-1.
Water
ow
Oil droplet
sw
so
so
Solid
Fig. 2.2.2-1 Diagram of Oil drop on solid surface in water

Contact angle: The angle between tangential line of oil drops surface and the surface
of solid is called contact angle. In case that the oil remains as a drop, it means the system is
in equilibrium. We will have definite contact angle so. Equilibrium of force on the droplet
can be written as shown in eq. 2.2.4, known as YOUNGs equation.
142
III-25
For oil/water/solid system

sw = so + ow cos so
{2.2.4a}
For oil/air/solid system

s = so + o cos so
{2.2.4b}
If we combine DUPREs equation (eq. 2.2.3) with YOUNGs equation, we will get an
equation, called YOUNG-DUPRE equation, as shown in eq. 2.2.5. This equation allows us
to calculate the adhesion work of the system.
For oil/water/solid system
Wadh ( so ) w = ow (1 + cos so )
{2.2.5a}
For oil/air/solid system

Wadh ( so) = o (1 + cos so )
{2.2.5b}
To define the degree of wetting or wettablity, we use the simple criteria as follow:
If the contact angle is equal or less than 90, it can be said that the solid is wetted
by oil. So it has oleophilic property.
If the contact angle is greater than 90, it can be said that the solid is not wetted by
oil. So it has hydrophilic property. The shape of oil drop is almost spherical in
this case.
2.2.2.2 Cohesion work and Spreading
Cohesion work: If we have a tank of
oil and we want to separate the oil to create
air-oil surface of 1 unit area within the oil
bulk, we can apply eq. 2.2.1 to find the
work required. In this case, we will have 2
surface of oil. Each surface has the area of
1 unit (see fig. 2.2.2-2).
From eq. 2.2.1, the required work
will be calculated as shown in eq. 2.2.6a,
which we call Cohesion work.
Fig. 2.2.2-2 Model for visualization of

cohesion work
W c (o ) = 2
{2.2.6a}
When applied to oil/water system, cohesion work, in order to separate oil in presence
of water, can be written as follows:
Wc (o) w = 2 ow
{2.2.6b}
143
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Spreading: From YOUNG-DUPREs equation, if contact angle is zero, it means that

the oil surface is parallel to solid surface. In this case, we call that the oil spreads over the
solid surface. In this case, adhesion work can be calculated as follows:
W adh ( so ) w = ow (1 + cos(0)) = 2 ow
{2.2.7}
From eq. 2.2.7, it shows that adhesion work, in this case, is equal to cohesion work.
From this fact, HARKINS [quoted by AURELLE [42]] sets the criteria to consider if the
liquid will spread over the solid or not, by a constant called spreading coefficient().
= Wadh ( so ) w Wc ( o ) w
{2.2.8}
If 0, or Wadh(so)w Wc(o)w, then the oil will spread over the solid.
If < 0, or Wadh(so)w < Wc(o)w, then the oil will not spread over the solid.
Concept of spreading is very useful for oil/water separation process. When we bring
the emulsion to contact with the solid, if the solid is olephilic or the oil prefer to spread over
the solid, the oil that collides with the solid will attach to solid surface, thus, be separated
from the emulsion. From this concept, we can define the relation between contact angle,
adhesion work, interfacial tension, and spread coefficient as shown in table 2.2.2-1.
Critical surface tension (or critical surface energy): Zisman [quoted by AURELLE
[42]] studies that if the oil drop is placed on the solid surface, the contact angle will decrease
linearly with decreasing surface tension of oil. When the surface tension of the oil is low
enough, the contact angle will be zero, then that oil will spread over the surface. That surface
tension will be called Critical surface tension of the solid. The value can be interpreted that
any oil will spread over the solid surface when surface tension of that oil is equal or lower
than critical surface tension of the solid, as shown in eq. 2.2.9. This concept is very useful for
material selection in several separation processes, such as skimmer (chapter 3).
If o c , the oil can spread over the solid surface. {2.2.9}
Effect of roughness of solid surface: Surface roughness of solid can effect its
wettability. If the surface is not smooth, the contact angle will increase as described by
WENZELs equation (eq. 2.2.10, fig 2.2.2-3). r represents the roughness coefficient and is
equal to ratio between actual surface area to geometrical surface area . The value of r is equal
to 1, when the surface is smooth. Otherwise, r will always be greater than 1. The effect of
roughness should be considered when design the oil/water separation process.
cos( ' so ) = r cos( so )
Smooth
Rough
{2.2.10}
Smooth
Rough
Fig. 2.2.2-3 Effect of surface roughness on contact angle
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Table 2.2.2-1 Relation between contact angle, work adhesion, interfacial tension and spread
coefficient of oil/water/solid system [42]
Contact angle
so
Wadh(so)w
Relation beween
interfacial tension
= 0
> 2ow
>0
sw > so + ow
= 0
0<so<90o
= 2ow
ow <W< 2ow
=0
<0
sw = so + ow
Characteristic of oil drop
ow
so
sw
so
sw
ow
sw > so
ow
sw
so
= 90o
W = ow
<0
sw = so
ow
sw
so
ow
90<so<180o
0<W < ow
<0
sw < so
so
=180o
W=0
<0
sw
so = sw+ow
ow
so
145
sw
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2.2.3
2.2.3.1 LAPLACEs law

LAPLACEs law is the relation of pressure difference across the surface of liquid of
surface tension . If we consider the air bubble in water, at one fraction of the bubble with the
radius of curvature R1, and R2 on 2 perpendicular plains (fig. 2.2.3-1), the pressure
difference, by LAPLACEs law, will be as shown in eq. 2.2.11:
P = P P ' = (
P (Outside pressure)
P
(Inside pressure)
R
Section of 1
surface of air
bubble in water
R2
1
1
+
)
R1 R 2
{2.2.11}
From the equation, we can calculate the

pressure difference of the following
systems, i.e.,
A soap bubble of radius R in air
P = 4
Because there are 2 interfaces of air/soap.

An air bubble of radius R in water
P = 2
A cylindrical jet of water in air

P =
Fig. 2.2.3-1 Section of air bubble in water
Because R2 is infinity.
2.2.3.2 Capillary pressure

Capillary effect is an important phenomenon for oil/water separation process when we
consider flowing through porous media, such as ultrafiltration membrane. This phenomenon
will be described by fig. 2.2.3-2. When the tube with very small diameter (capillary tube) is
plunged into liquid surface. Because of surface tension of liquid, the liquid will rise into the
tube to the height h. From equilibrium, we can calculate the capillary pressure (Pc) as follow:
Pb Patm = gh = Pc
{2.2.12}
From LAPLACEs law,

Pb Patm =
2 2 cos
=
R
r
{2.2.13}
From eq. 2.2.12 and 2.2.13,

Pc =
2 cos
r
{2.2.14a}
And
h=
2 cos
gr
{2.2.14b}
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From eq. 2.2.14, it shows that the value of Pc or h will vary with the size of capillary
tube. In case that the contact angle is greater than 90o, the surface of the liquid in the tube will
be lower than that outside of the tube. So if we want to force the liquid through the tube, the
applied force must be greater than capillary pressure plus the resistance of tube. This concept
is very useful to understand membrane process.
a)
b)
Fig. 2.2.3-2 Diagram for visualizing the capillary pressure
2.3
Important parameters in oily wastewater treatment and their method

of analysis
From chapter 1, it shows that characteristics of oily wastewater can greatly vary,
depending on their sources, degree of dispersion and compositions. However, to design the
oily wastewater treatment process, it is, somehow, necessary to know its characteristic. In
case that characteristic data is not available, we have to have it analyzed by an acceptable
method. This chapter will suggest the important parameters necessary to consider or design
the treatment processes, esp. those that are included in this book.
For the methods of analysis, if the result will be used to report to authorities, such as
effluent quality report, method of analysis used has to be those that are approved by
authorities or related standards. However, if the result is used for preliminary consideration, or
standard method is not available, this section will provide simple technique that can be
performed by basic or commonly available apparatus.
2.3.1
Oil concentration
Oil concentration is one of important parameters for oily wastewater treatment

consideration or design. Effluent standard is set by oil concentration. Inlet oil concentration
and effluent standard are the parameters that determine the degree of treatment required.
Furthermore, some separation processes are limited by oil concentration. Normally, the oil
concentration is reported in the form of mg/l. However, for inlet oil concentration, it may be
measured in the form of % by volume.
147
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Method of analysis
1.
Solvent extraction [1]
This method is the standard method of examination of oil and grease. They are at
least 4 variations. However, they all involve an initial extraction of oil and grease by hexane
or CFC-113. The 4 variations include,
2.
Partition-gravimetric method: Hexane will be used to extract the oil. Then

it will be separated from water and then evaporated. The residue will be used
as an inditator of oil and grease content.
Partition-infrared method: CFC-113 will be used as extractant. Then it will

be measured with infrared scanning. This method is faster than gravimetric
method. The accuracy depends on selection of oil standards for calibration.
The oil used for calibration should be the same type as oil in the wastewater.
Soxhlet extraction: It involves the initial step of acidification and then

hexane extraction. This method tends to retain more volatile hydrocarbons.
However, it is time consuming.
Hydrocarbon analysis: Silica gel is added to hexane to remove fatty

materials. And then the hexane will be analyzed by the first method.
Turbidity measurement
Oil concentration can be measured by light loss (turbidity) or light scatter from
oil droplets in the wastewater [43]. The main advantage of this method is its simplicity and
fast response. However, it will be difficult to distinguish between oil droplets and other
particles. Some manufacturer claim that this effect can be minimized by the selection of the
angle of scatter and detector. In GPI lab, some researchers use this method to measure the oil
concentration. It is suitable to use for relatively clear wastewater, such as condensate.
However, in most situations, oily wastewaters are usually contaminated by color materials and
suspended solids. This method, thus, may not provide accurate result on oil concentration.
3.
TOD measurement
If total oxygen demand (TOD) measuring instrument is available, oil

concentration can also be measured as TOD. Again, the main advantage of this method is its
fast response. However, it will be difficult to distinguish between TOD of oil and other
substances, especially surfactants and co-surfactants. So this fact should be taken into
account. In GPI lab, some researchers use this method to measure the oil concentration. The
data from the researches are presented in chapter 1. It must be noted that TOD includes
oxygen demand from non-organic factors, such as ammonia, sulfide. Thus its value is usually
higher than BOD.
4.
Other methods
Total organic carbon (TOC) is also widely used to measure pollutant

concentration. Its working principle bases on oxidizing of the sample, usually at high
temperature, to convert carbons to carbondioxide, which will be measured by IR, UV probe.
TOC machine can cover from ppm to ppt range. It is very useful for online control. But it does
not account for nitrogen compounds, which have much higher oxygen demand than carbons.
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There are also others techniques to measure the oil concentration. However, some techniques
are developed for specific application. Some are not widely used or not suitable for
wastewater analysis. So they will not be described in detail here. Such techniques include
direct infrared absorption, ultraviolet absorption, optical fiber sensor, gas chromatography,
etc.
2.3.2
The size distribution, spectrum or granulometry is the data on the number of each size
of oil drop, air bubbles, particles or other dispersed material in continuos phase. Normally, it
is reported in the form of percent of total number of dispersed material or percent by volume
or percent by weight. Example of the size distribution of oil droplet in cutting oil
macroemulsion is shown in fig. 2.3.2-1.
45.0
40.0
Percent by weight (%)
35.0
30.0
25.0
20.0
15.0
10.0
5.0
0.0
10.0
17.8
31.6
56.2
100.0
178.0
316.0
562.0
1,000.0
1,780.0
Droplet diameter (nm)
Fig. 2.3.2-1
Example of the size distribution of oil droplet in cutting oil macroemulsion (Elf Seraft 4% V of
concentrate), measured by Coultronics nanosizer NDM4 [11]
Oil drop or particles diameter is one of the parameters in the STOKES equation.
Since treatment efficiency of several separation processes, which will be described in the
following chapters, are based on the rising velocity that is governed by STOKES law. So the
diameter is one of the key parameters to calculate the efficiency of the process. Furthermore,
each process can provide acceptable or competitive efficiency in only a certain range of
droplet size. So the size distribution is an important data to select feasible treatment process.
Method of analysis
1.
Particle size analyzer or Granulometer
Particle size analyzer or granulometer or nanosizer is the specific

equipment designed for measuring size and quantity of particle in liquid. There are many
generations of granulometer with different operating principles. However, present
granulometers are based on laser detection technology. This equipment can be used to
measure size distribution of oil droplet or particle down to the range of submicron size
(depend on manufacturers). It can report the result in the form of table or graph of size
149
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distribution, both by number and by volume or weight. An example in fig. 2.3.2-1 was also
measured by the granulometer. Fig. 2.3.2-2 shows the picture of granulometer.
Fig. 2.3.2-2 Granulometer (Source: above - Ankermid Techcross / below - CILAS)

2.
Decanting test
When the use of granulometer is not available, there is a simple method to

measure the size distribution, which is called decanting test. This method requires a simple
equipment as shown in fig. 2.3.2-3.
h4
h3
h2
h1
0 min
5 min
10 min . t min
Fig. 2.3.2-3 Decanting test column
150
III-33
Analytical procedure
1)
Pour the wastewater into the decanting test column and stir. Make sure it is
homogeneous.
2)
Leave the wastewater to decant, taking the water samples from various
heights of the column at preset interval.
3)
Analyze the samples to find the oil concentration or other parameters that
are directly proportional to the oil concentration, such as TOD, turbidity,
etc.
4)
From the collected data, we can calculate the granulometry, using this
procedure:
At t = 0, the wastewater is homogeneous, then the oil concentration is

Co throughout the column.
At t = t1 and height (from the bottom of the column) = h1, the

corresponding rising velocity Vh1t1 = h1/t1.
So at this point, the oil drop that have rising velocity greater than Vh1t1
will rise past the height h1 then will not be found in the sample taken
from h1. From Vh1t1, we can calculate the corresponding droplet
diameter dh1t1 by STOKES law.
If the oil concentration at this point is Ch1t1, and the calculated droplet
diameter is dh1t1, we can conclude that:
The fraction of d < dh1t1 = Ch1t1/Co
5)
Repeat step 4), at other t and h. then, use the fraction of d < dhx tx to plot the
size distribution curve.
6)
Concentration of each droplet size can be roughly represented by the

differences between value of adjacent % of accumulated C/Co. Please note
that the size and %C/Co are estimated values only. But it can provide an
idea of how the sizes of droplet are distributed.
An example of the analysis of decanting test data is shown in tab. 2.3.2-1 and fig.
2.3.2-4 and 2.3.2-5.
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Table 2.3.2-1a Example of the decanting test of oil/water emulsion
Time
At sampling height
(from the bottom
of column)
% accumulated C/Co Corresponding droplet

Corresponding rising Oil concentration of
when
d < size (from STOKES
velocity
the sample
dEht
law)
Vh,t
Ch,t
% Ch,t/Co
dEh,t
sec
m/s
mg/l
micron
0.5
86
100
900
0.5
5.56E-04
57
66.28
72.8
1800
0.5
2.78E-04
25
29.07
51.4
2700
0.5
1.85E-04
9.30
42.0
3600
0.5
1.39E-04
3.49
36.4
5400
0.5
9.26E-05
1.16
29.7
7200
0.5
6.94E-05
0.00
25.7
1.25
86
100
900
1.25
1.39E-03
83
96.51
115.0
1800
1.25
6.94E-04
63
73.26
81.3
2700
1.25
4.63E-04
49
56.98
66.4
3600
1.25
3.47E-04
37
43.02
57.5
5400
1.25
2.31E-04
16
18.60
47.0
7200
1.25
1.74E-04
6.98
40.7
7200
1.25
2.06E-03
80
93.02
140.0
Note:
Assume the oil is kerosene so the density (20o C) = 790 kg/m3. Water dynamic
viscosity = 1.08E-3 (N.S)/m2.
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Table. 2.3.2-1b Example of the decanting test of oil/water emulsion: sorting of the result
from table 2.3.2-1a
% accumulated
Corresponding droplet size Corresponding rising velocity when
< dEht
C/Co
Estimated C/Co
d
each droplet
dE
Vh,t
% Ch,t/Co
%C/Co
micron
m/s
25.72
6.94E-05
29.70
9.26E-05
1.16
1.16
36.38
1.39E-04
3.49
2.33
40.67
1.74E-04
6.98
3.49
42.00
1.85E-04
9.30
2.33
46.96
2.31E-04
18.60
9.30
51.44
2.78E-04
29.07
10.47
57.52
3.47E-04
43.02
13.95
66.41
4.63E-04
56.98
13.95
72.75
5.56E-04
66.28
9.30
81.34
6.94E-04
73.26
6.98
115.03
1.39E-03
96.51
23.26
for
size
100
90
% Accumuleted C/Co
80
70
60
50
40
30
20
10
0
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
Oil droplet size (dE) (micron)

Accumulated conc. curve
Fig. 2.3.2-4
h = 0.5 m
h = 1.25 m
Relation between accumulated C/Co (% of C/Co when the droplet size is equal or smaller than the
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given dE) and oil droplet size

25
% by weight
20
15
10
0
26
30
36
41
42
47
51
58
66
73
81
115
Droplet size (micron)
Fig. 2.3.2-5 Example of estimated size distribution of oil droplets from decanting test
3.
Visual observation
To roughly estimate the granulometry of oily wastewater, there are simple

criteria for visual observation as shown in table 2.3.2-2. However, these criteria may be used
only when the wastewater is not polluted by suspended solids or other substances that makes
it opaque. In case of surface oil layer, API [45] recommended useful guide to evaluate oil
thickness as shown in table 2.3.2-3.
Table 2.3.2-2 Criteria for visual observation of size distribution [22]
Visual aspect
Average particle size
Example
Particles visible by eye
500 micron
Very fine sand
Not clearly visible by eye
100 micron
Starch
Opaque milky
10 micron
Milk
Whitish milky
1 micron
Homogenized milk
Bluish milky
0.1 micron
Macroemulsion
Semitransparent
50 nm
Microemulsion
Transparent
10 nm
Microemulsion
Transparent
2-6 nm
Micelles
Transparent
1 nm
Molecules
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Table 2.3.2-3 Criteria for visual observation of surface oil film [45]
Film thickness
(micron)
2.3.3
Appearance
Approximate volume of oil

for film 1 km2 in area (l)
38.1
Barely visible under most

favorable light conditions
37
76.2
Visible as silvery sheen on

surface of water
74
152.4
First trace of color may be

observed
148
304.8
Bright bands of color are visible
296
1016 (1 mm)
Colors begin to turn dull
985
2032 (2 mm)
Colors are much darker
1970
Other parameters
Each treatment process may require some special data for its calculation. However,
common data required by several processes include:
Interfacial tension
Viscosity of oil
These data can be analyzed by specialized laboratories. However, if we know the

source of the oily wastewater, we can estimate these parameters. Even when we can not
specify the exact source of oil, we still can estimate them, using the general data of oil or from
references, without too much error. These data can also be found in chapter 1 and this chapter.
2.4
As hydrocarbon or oil requires a great amount of oxygen or oxidizing agent to oxidize,

moreover, the hydrocarbon is relatively difficult to biodegrade, thus, it becomes clear that the
use of biological treatment with high-concentration oily wastewater may not be the
economical alternative. Besides there are possibilities to reuse or recover the hydrocarbons
in the wastewater. Then, if possible, it is reasonable to separate oil from the wastewater,
rather than destroy or change them into other forms.
Thus almost all of treatment processes that have been studied in GPI laboratory are
based on separation process, both physical and physico-chemical, techniques in order to
separate oil from water. From chapter 1, it shows that oily wastewaters can be divided into
several categories, mainly depending on their stability and degree of dispersion. And in the
previous sections on this chapter, it shows that physical separation of oil from water depends
on STOKES law.
Thus, to enhance separation between water and oil, it can be archived by modification
of parameters in STOKES law in the manner that make the rising velocity of oil droplets
increase. Actually, almost all of oil/water separation processes covered by Prof. AURELLEs
research team are STOKES law-based processes, i.e. decanter, coalescer, hydrocyclone, and
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dissolved air flotation (DAF). Thus each process will has its own limitation, bound by
assumptions of STOKES law as well as its unique working characteristic.
Apart from STOKES law-based processes, there are other oil/water separation
processes that based on other physical properties between oil and water. In GPI lab, Prof.
AURELLEs teams also studied these processes, i.e. skimmer (which is based on interfacial
tension concept), membrane process (which depend on mass transfer phenomena), thermal
process (which depends on thermodynamic properties), and chemical process (which depends
on chemical reaction).
Thus, to design an efficient oily wastewater treatment process, designer should
understand working principle and limitation of each process. The following chapters will
devote to each oily wastewater treatment processes studied and perfected by Prof.
AURELLEs team within 3 decades. However, in this section, description of each process will
be described briefly as follows,
STOKES law-based processes
2.4.1
Decanter
Decanter is an oil separation process that depends purely on STOKES law without
modification of their parameters. The oil droplets in wastewater will allow to decant (or rise)
naturally to the surface of water .It is very simple and proven to be very good process for
separation of free oil and primary emulsion. Rising velocity depends mainly on the droplet
size. In case of very small droplets, it may take too long time for the droplets to reach the
surface or it may need so large tank to become economical. However, performance of
decanter can be enhanced by reducing of rising distance of droplets, such as by lamella-plate
insertion. Actually, GPI lab had initiated a very compact decanter by this concept, called
Spiraloil, which is commercialized by Elf Total Fina. Decanter is described in details in
chapter 4.
2.4.2
Coalescer
Coalescer is a modified or accelerated STOKES law-based separation process by

increasing the size of oil droplet. Since rising velocity is proportional to square of droplet
size, theoretically, coalescer can enhance oil separation efficiency more rapidly than other
process that work on other parameters. AURELLE is one of the pioneers on granular bed
coalescer, which was patented and, later, commercialized by Elf Total Fina. He also initiated
other type of coalescer, i.e, granular bed coalscer with guide to handle wastewater with high
oil concentration, fibrouse bed coalescer that can handle wastewater with SS. Coalescer can
handle secondary emulsion effectively. However, its performance with stabilized emulsion is
not so good since the droplets are very table and unlikely to coalesce with each other.
Coalescer is described in details in chapter 5.
2.4.3
Hydrocyclone
Hydrocyclone is a modified or accelerated STOKES law-based separation process by

increasing the acceleration of the system. Hydrocyclone replaces gravity acceleration (g)
with centrifugal acceleration, which can reach several hundreds times of g. Thus it is very
compact separation process. AURELLE and MA had initiated three-phase hydrocyclone that
can separate oil, solids and water simulteneously. Hydrocyclone use its inlet flow energy to
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operate. So it is noted for its increase in efficiency with the increase of inlet flow, which is
unique advantage of the system. It can handle secondary emulsion effectively. However, its
operation has high shear characteristic. Furthermore, it driving force come only from its inlet
flow so the centrifugal force is limited. So it can not separate very small droplets (<10
microns). It must also be noted that hydrocyclone is actually a concentrator. It can not
separate water-free oil. Separated oil usually contains some water. Thus it need to be further
treated by other process. Hydrocyclone is described in details in chapter 6.
2.4.4
DAF is a modified or accelerated STOKES law-based separation process by

decreasing density difference between oil and water. It can be obtained by addition of gas
bubble or air bubble to wastewater to form agglomerates with oil droplets. Since air or gas has
low density the agglomerates, then, has lower density than oil drops, resulting in higher rising
velocity. DAF is noted for its versatility. It can separate both solids and oil. Its efficiency
depends on formation of oil-bubble agglomeration. Thus its performance is low if droplets are
very small, since collision between air bubble and oil drops is difficult. In practice, DAF will
be used after coagulation-flocculation process, which can increase the droplet sizes
chemically. DAF is described in details in chapter 7.
Other processes
2.4.5
Skimmer
Skimmer is the device designed to remove oil film from the water surface. GPI lab had
studied and perfected skimmers oil performance so it can selectively remove only oil without
drawing the water with it. Operating principle of the oleophilic oil skimmer is based on
surface tension concepts. The skimmer studied in GPI lab was also commercialized. Details
about skimmer are described in chapter 3.
2.4.6
Membrane processes
Membrane processes are the promising separation processes that gain popularity in
these recent years. The key part of the processes is the membrane, which is porous material
with various ranges of pore size to suit the sizes of material to be retained or separated. Its
working principle can be compared, but not exactly identical, to that of filtration process.
With properly selected pore size, membrane processes can separate target materials with
relatively high efficiency. GPI lab had studied application of various membrane processes,
i.e., microfiltration, ultrafiltration, nanofiltration and reverse osmosis on oily wastewater
treatment. The lab also initiated studies on capacity (or flux) enhancement of membrane
process for cutting oil emulsion treatment. Membrane processes are described in details in
chapter 8.
2.4.7
Thermal processes
Thermal process is the separation process based on thermodynamic properties of

oil/water mixture. GPI lab emphasizes on heteroazeotropic distillation, which can be carried
out at the temperature that is lower than those of pure water and pure hydrocarbons. It is
achieved by addition of proper hydrocarbons, called entrainer or extractant, into the
wastewater to azeotrope point, where oil, water and vapor co-exist, during distillation. The
process can be used to separate water from refinery slops and permeate from membrane
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process of oily wastewater treatment. Thus it provides opportunity to recover these supposedto-be-wasted oil and treat the most problematic waste. Thermal processes are described in
details in chapter 9.
2.4.8
Chemical process
Chemical process for oily wastewater treatment is mainly destabilization process for
destabilizing of stable emulsion. It consists of 2 main mechanisms, i.e. destabilization of oil
droplets and coalescence or flocculation of destabilized oils. This process is necessary when
the wastewater to be treated contains stable or stabilized emulsion, otherwise it can not be
treated by STOKES law-based processes. Destabilization chemicals includes salts, acids, and
polyelectrolytes. GPI lag had studied destabilization mechanisms of each chemical which
provide understanding and knowledge on chemical selection. The detail is discussed in
chapter 10.
2.4.9
Finishing processes
To meet the effluent standards, effluent from aforementioned processes may need
further treatment before discharge to receiving water body. The most widely used processes
for finishing propose are biological treatment and adsorption (by activated carbons). These
processes are not the main interest in Prof. AURELLEs team, which emphasize of physical
processes. However, to fulfil the whole oily wastewater treatment processes, biological
treatment and adsorption are briefly described in chapter 11.
The theories and details of each processes described in section 3 to 11 will, then, be
used to develop the software for design and simulation of oily wastewater process train,
which is the scope of work of this thesis.
2.5
2.5.1
Before designing oily wastewater process, required overall degree of treatment or

effluent quality of the treatment system must be set. In case that the effluent is discharged to
public receiving water body, such as sewage system or natural stream, the final effluent
quality must conform to every applicable law. Examples of effluent standards are shown in
chapter 1. In case that the water is recycled or reused, required water quality for those
purposes, such as standard of recycled water quality, standard of recycled cooling water, etc.,
will determine the overall degree of treatment.
2.5.2
Since the performance of every treatment process depends mainly on wastewater

characteristic, for existing facilities, wastewater must be thoroughly analyzed to obtain its
detailed characteristic. For new facilities, its characteristic must be carefully estimated. In
case of oily wastewater, performances of oil separation processes are based on degree of
dispersion and stability of the wastewater. When these data are available and limitation as
well as expected performance of each treatment process is thoroughly understand, it is
possible to select feasible process train that can treat the wastewater to meet the required
degree of treatment.
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Example A: consider wastewater from in-land refinery contains 230 mg/l of nonstabilized secondary emulsion and 10 mg/l of emulsified oil. If applicable effluent standard in
this case is 12.0 mg/l, in this case, the degree of treatment of the system is (10+23012)/(10+230)*100 = 95%. We can separate the secondary emulsion by compact decanter,
coalescer or DAF, which secondary emulsion removal efficiency is expected at 90%. So it
requires further treatment and the degree of treatment required in the next stage is at least 100((100-950)/(100-80)) = 50%. In this case, It can be archieved by sending to the water to mix
with domestic wastewater and treat by biological treatment. The concentration of 12.0 mg/l
may be met by dilution effect of domestic wastewater alone. Moreover the biological process
can be reduced the oil concentration at least 50%. Thus it can be certain that the effluent
concentration of 12 mg/l is guaranteed at all times.
2.5.2.1 Graded efficiency and total removal efficiency
As stated before that efficiency of most separation process depends on the size of oil
droplets, most of researches in GPI lab had common aim to establish the relation between
the efficiency and droplet size, which will be shown in the following chapters. If
granulometry data (see fig. 2.3.2-5) is available, it will provide clear data on percentage of
each size of oil droplets. So it is very useful for removal efficiency calculation of each droplet
size (graded removal efficiency) of each process. Summation of graded efficiency of each
process results in total removal efficiency of that process corresponding to that particular
wastewater, which is more accurate than the estimated value from literatures alone. In case
that the treatment system consists of several processes, overall efficiency can be determined
from summation of greaded effeciecny of ecah process, as shown in eq. 2.5.1.
d ,overall = (1 (1 d ,1 )(1 d .2 )....( 1 d ,i )) 100 % {2.5.1a}
d max
t ,i =
d ,i
C od
C o ,i
d max
overall =
Where
overall
d,overall
d,i
t,i
Co
Co,i
Cod,i
i
,i
)
100 %
d min
d , overall
d min
Co
C od
{2.5.1b}
)
100 %
{2.5.1b}
= Overall efficiency of the treatment process train

= Graded removal efficiency of the treatment process train
= Graded removal efficiency of the process i, calculated by
equation of each process shown in the following chapters
= Total removal efficiency of the process i
= Oil inlet concentration of the treatment process train
= Oil inlet concentration of the process i
= Graded oil inlet concentration of the process i
= the number of processes in the process train, i 1
To achieve the required effluent standard, overall efficiency of the system must be
equal of higher than the required degree of treatment, established in section 2.5.1.
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2.5.2.2 Cut size determination

Since the bigger oil drops are realtively easier to remove than the smaller ones, it is
recommended to select the treatment process to handle the range of oil drops from the biggest
to the smallest size that contributes to the required degree of treatment (in case that the
granulometry data is known). This smallest size in the range described above is called cut
size.
For example, if the granulometry of the wastewater is as shown in fig. 2.3.2-4, if the
required degree of treatment is 90%, from the curve, the cut size will be 90 microns.
The cut size is very useful in process design for it can be used as a representation of
the whole wastewater to calculation the required size of separation process. It can save
calculation time when many processes are to be compared. However, sizing of the process
calculated from this theoretical cut size may not be exactly equal to the degree of treatment
since the cut size is selected based on the assumption that the graded removal efficiency of
droplet equal to larger than cut size is 100% (see fig. 2.5.2-1). Thus some adjustments should
be made after detailed calculation of the efficiency by eq. 2.5.1.
Acc. %
(by weight)
overall
R = Required degree
of treatment
100%
100%
Required degree
of treatment
Theo. eff
Real eff.
Theo.
cut size
Real
cut size
Droplet size
Droplet diameter
Theo.
cut size
Fig. 2.5.2-1 Cut size determination

2.5.2.3 Economics of the processes
Performance of each separation process also depends on other parameters apart from
the droplet size. Change in these parameters will also make the performance of the process
change. Thus the process train can be optimized by changing influent parameters, usually the
geometry, of each process in the process train to make the overall efficiency as close to the
required degree of treatment as possible.
Treatment capability of processes may overlap in some range of droplet sizes, which
will be summarized again in chapter 12. For example, droplet size around 20 microns can be
treated by coalescer or compact decanter. This leads to several combinations of process trains.
For example, the process train in example A may be divided into 2 alternatives, i.e. (1)
Compact decanter+activated sludge (AS), (2) Coalescer+Activated sludge. In each alternative,
the sizes of equipment and reactors can be varied within its own valid range. Thus, to select
the best alternative and process sizes, economics of each alternative should be compared.
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Since the expected degree of treatment is identical, least cost criteria are usually adopted.
The most suitable process train is practically the system that can treat the water to meet the
required degree of treatment at the least capital cost and operating expense (see fig. 2.5.2-2).
Technical acceptable range
Required degree
of treatment
Overall eff.
Hydrocyclone
Coalescer
Most suitable
(economic) size
Size or cost
Fig. 2.2.5-2 Economics of processes (least cost criteria)

However, to select such a system, many alternatives must be calculated. This is the
reason that the computer program for oily wastewater treatment process calculation,
according to the scope of work of this thesis, is developed. The program will help perform
complex calculation and handle calculation of many alternatives within very short time. So
the results will lead to the effective oily wastewater treatment system design. Details of the
program is described in Part 4.
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Chapter 3 Oil skimmer

3.1
General
The most basic form of oily wastewater is the presence of oil film or layer on the
water surface. The most severe case of this form of oily wastewater is the large-scale oil spill,
caused by tanker or offshore platform accident. The oil will spread over wide area and cause
adverse effect on ecosystem. When the accident occurs, the oil confinement, such as booms, is
arranged to limit the spreading area. Then, the spilled oil is, sometimes, dispersed by chemical
dispersant to form tiny droplets, then left to biodegrade. Biological accelerating agents may
be added to promote biological degradation. Sometimes, specific adsorbents are added to the
oil to make it settleable or in more manageable form, such as floating agglomerate scum.
These methods may still cause adverse effect on the environment. Thus, if possible, the oil
layer is preferably removed in form of water-free oil for it can be reused.
In oily wastewater treatment process, the goal of almost all of the separation processes
is to separate the oil droplets and form an oil layer on the water surface. After that, it is also
crucial to remove this oil layer as water-free oil, otherwise it will become new oily
wastewater. In a small container, the oil layer can be removed manually or by simple devices,
such as weir, bell mouth pipe. Anyway, in case of oil spill at sea, or upscale tank, it is difficult
to remove only oil without getting water with it even though the oil film is visibly stratified
from the water. In these cases, specific devices that have good oil selectivity are required.
There are many variations of these devices as shown in fig. 3.1-1. However, they can be
generally divided into 2 concepts i.e.,
Pumping or hydraulic devices: The oil will be directly pumped out or intercepted
by controlled hydraulic devices, such as adjustable-weir. Important factor that
governs the performance is the oil layer thickness. So, some mechanisms are
provided to locally thicken the oil layer before removing it. Examples of the
devices include pump skimmer and weir skimmer.
The devices based on adsorption property: This group of devices makes use of
difference between oil and water adsorption property of material to remove the oil.
The oil selectivity of material is based on the concept of interfacial tension, as
described in chapter 2. When design properly, the device can remove virtually
water-free oil from the wastewater. Examples of the devices include drum
skimmer, disc skimmer, belt skimmer, etc.
This chapter emphasizes on the drum and disk skimmer, which are thoroughly
researched in GPI lab.
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a) Disc skimmer (source: Highland tank)
b) Belt skimmer (Source: Ultraspin)
c) Drum skimmer (source: ELF/GPI lab)
d) Mop skimmer (source: Ultraspin)
e) Weir skimmer (Source: Skimoil)
f) Pump skimmer (Source: Ro cleandesmi)
g) Dispersant spray (Source: Ro-cleandesmi)
h) Absorbent (Source: Ro-cleandesmi)
Fig. 3.1-1 Examples of oil skimming devices
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3.2
Oil drum skimmer
3.2.1
Working principles
Oil drum skimmer is the equipment that has a rotating drum which its surface acts as
an oil-skimming surface (fig. 3.2.1-1). The oil will adhere to the skimming surface, lift up
from the surface by the skimmers rotating movement, and then be scraped off by a scrapper
blade into a receiving channel or container.
Drum skimmer
Scrapper
Oil receiving
trough
Oil layer
Water
Fig. 3.2.1-1 Lab-scale drum skimmer: Major components are shown. (Source: GPI lab)
The working principle of oil drum skimmer, as well as other absorption based devices,
is based on surface energies of hydrocarbon, water and skimmer material. To obtain waterfree oil, the material must have good oil selectivity. THANGTONGTAWI [5] had studied the
effect of surface energies on oil selectivity and concluded that oil selectivity of the material
depends on the difference between its critical surface tension (see chapter 2) and the
superficial (surface) tensions of hydrocarbon and water.
Water normally has higher superficial tension (around 72 dyne/cm, depending on the
temperature) than oil (25 40 dyne/cm). The diagram in fig. 3.2.1-2 shows surface energy of
water, oil and various materials. Adhesion of oil or water at the material surface can be
explained in term of the adhesion work (see chapter 2, eq. 5.2.5) as shown in table 3.2.1-1. If
the adhesion work of oil on solid surface in presence of water (Wadh(so)w ) is greater than that
of water on the surface in presence of oil (Wadh(sw)o), the oil film will adhere to the skimmer
surface and not be replaced by water film when the skimmer is rotated until the oil film
submerges in water. Thus, it still adheres to the surface when it is lifted from the liquid and
then removed by the scraper.
From this concept, the oil selectivity of materials can be summarized as follows,
Material of high surface energy (or critical surface tension), such as stainless steel
( > 72 dyne/cm), tends to be adhered by water, rather than oil.
Material that have the surface tension in the vicinity of oils, such as
polyvinylchroride (PVC), polypropylene (PP), tends to adhered by oil, rather than
water. It can be adhered by water if the oil film is not present. However, it will
start recovering oil once the oil is present again.
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Material that has very low critical surface tension (lower than surface tension of
oil), such as PTFE and fluorocarbon variations, is proven to have very good oil
selectivity since its surface energy is so low that it is hardly adhered by water.
When used as a skimmer material, it recovers only oil and hardly or does not
recover water.
PTFE
(19)
Water Stainless steel

(72)
(> 72)
PP PVC
(30) (39)
oil
10
20
25
30
35
40
50
60
Surface energy
(dyne/cm)
70
Material of high
surface energy
Material of low
surface energy
Fig. 3.2.1-2 Surface energy or superficial tension of materials, oil and water
Table 3.2.1-1 Work adhesion and contact angles of oil, water and various materials
Material
Contact angle of oil

drop in water ()
Wadh(so)w =
(ow(1+cos ))
Wadh(sw)o =
(ow(1+cos (180))
Stainless steel (SS)
124o
0.01543 N/m
0.05457 N/m
PVC
26
0.06650 N/m
0.0035 N/m
PP
17o
0.0685 N/m
0.0015 N/m
PTFE
47o
0.0589 N/m
0.0111 N/m
Note: The oil used is kerosene. ow (at 20o C) = 35 dyne/cm.

It is interesting to note that the stainless steel, which is the most oleophilic material
(oil can spread over its surface), makes the worst oil selectivity. This, sometimes, causes
confusion since the device is, sometimes, called oleophilic oil drum skimmer. So, It should be
reminded that the device got its name from its oil selectivity, but the skimming material itself,
even though can considered as oleophilic (contact angle < 90o), is selected from its low
surface energy, rather than its oleophilicity.
3.2.1.1 Exposure history
Another important characteristic of material related to oil selectivity is the exposure
history or the order and duration of contact between solid and liquids. THANGTONGTAWI
study shows that,
Material of high critical surface tension
Even the high critical surface tension material can remove oil if it is exposed to
pure oil first. Performance from SS, PVC, PP and PTFE skimmers in this case are
about identical. In case of SS, this does not seem to conform to the adhesion work
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calculation result. This can be explained by the effect of masking. The oil film
covers overall surface of the skimmer so the water cannot contact directly to the
skimmer to form a water film.
However, if the oil is entirely recovered, or oil film locally raptures, the SS will be
immediately adhered by water and stop recovering oil. Then it will recover
substantial amount of water.
Even though the water film is removed by scrapper, there is always a thin film left
due to very high adhesion work of the film that causes by chemi-sorption or polar
bond to the solid surface. When the oil is present again, the oil cannot contact
directly to the solid surface, then cannot be recovered.
Material of medium critical surface tension (PVC, PP, etc.)
When oil film is present, PVC or PP skimmer will recover oil. After the oil is
totally removed, the skimmer is still not immediately adhered by water film. This
can be explained by the presence of residual oil film on the surface of the skimmer.
The residual oil film will gradually disappear. So, after some times (about 24
hours), the skimmer will be wetted by water and start recover water.
If the oil is present again, the skimmer will immediately resume oil recovery since,
from concept of work adhesion, it is preferably adhered by oil.
Material of very low critical surface tension (PTFE, etc.)
Because of its low critical surface tension, this type of material is not affected by
exposure history for it is hardly adhered by water. PTFE skimmer always recover
oil without water even when it is left to operate without the presence of oil layer
for a long period of time.
3.2.1.2 Mathematical model of drum skimmer

Mathematical model of oil drum skimmer, proposed by THANGTONGTAWI, was
derived from dimensional analysis approach, using Buckingham Pi theory under a wide range
of material and wastewater properties as well as operating parameters. The model is as shown
below.
P=
0.486
3.035D1.541N1.541 o
L
0.514
g
Where P
D
N
L
G
=
=
=
=
=
=
{3.2.1}
Oil productivity of the skimmer (m3/s)

Diameter of skimmer (m)
Rotational speed of the skimmer (rev/s)
Kinematics viscosity of oil (m2/s)
Length of the skimmer (m)
Gravitational acceleration (m/s2)

Superficial tension of oil (kg/s2 or N/m = 1000 dyne/cm)
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Oil density is around 0.79 0.83 kg/m3. Oil dynamic viscosity () tested is
between 1.35x10-3 to 291x10-3 (N.s)/m2 (1.35-291 cp).
Recommended minimum immersion depth is 1.0-2.0 cm.
Drum skimmer surface used for model development is polypropylene. But it is

proven to be valid for SS, PVC, and PTFE [5]. As shown in fig. 3.2.1-2.
Oil removal efficiency of the skimmer is usually 100%, if the conditions stated above
are satisfied.
{3.2.2}
t = 100%
3.2.1.3 Influent parameters

Parameters that affects the performance of drum skimmer are as summarized below.
Graphical presentation of effect of various parameters on the performance of the skimmer is
shown in fig. 3.2.1-3.
1.
Diameter of drum
The oil productivity is proportional to drum diameter because it directly relates

to the skimming surface area. The larger the diameter, the bigger the area, thus the
productivity. However, the study on the oil film thickness on the surface of the drum [5]
shows that the diameter has only little effect, thus negligible, on the film thickness, which
direct relates to the skimmer performance. So the diameter of the drum could be selected to
suit the tank freeboard.
2.
Length of drum
The oil productivity is proportional to drum length because, again, it directly

relates to the skimming surface area. The longer the drum, the bigger the area, thus the
productivity. It does not affect the oil film thickness on the surface of the drum. So there is no
effect on the performance. However, the rotation of the drum will cause eddy current at the 2
ends of the drum. This turbulence will propel the oil film and prevent it to contact with the
parts of drum surface. If the drum is long, the area of eddy zone, compared to the entire length
of drum, will be small. So the length of drum will help improving the skimmer performance in
this sense.
3.
Oil layer thickness
Oil layer thickness on the water surface will affect the oil productivity of the
skimmer when it is thinned out until it cannot supply the oil fast enough to the skimmer. Then
there will be some part of skimmer that does not contact with the oil layer and has no
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productivity. So the overall productivity will drop. The layer thickness of 0.4 0.5 cm is
considered thick enough to ensure continuous supply of oil to the skimmer.
4.
Immersion depth of drum
Immersion depth means the height of the part of the drum that is lower than
water surface, measured from the bottom of oil layer. At immersion depth of 1-2 cm.
THANGTONGTAWI reported that this parameters does not practically affect the
performance of the skimmer. The author has tested at the immersion depth around 5 - 7 cm.
The result still confirmed THANGTONGTAWIs conclusion.
5.
Immersion depth of drum
Immersion depth means the height of the part of the drum that is lower than
water surface, measured from the bottom of oil layer. At immersion depth of 1-2 cm.
THANGTONGTAWI reported that this parameters does not practically affect the
performance of the skimmer. The author has tested at the immersion depth around 5 - 7 cm.
The result still confirmed THANGTONGTAWIs conclusion.
6.
Roughness of drum surface
Surface roughness affects the contact angle, thus wettability, as described in

chapter 2. However, in case oil skimmer, this change is overshadow its affect on difficulty to
remove film from the drum surface. Concavity on the surface may cause some difficulty to
scrape the oil film off the drum surface even though the oil thickness may be increased by the
roughness. So it is recommended to use relatively smooth drum surface.
7.
Velocity of drum
Rotating velocity directly affects the oil productivity as shown in eq. 3.2.2. The
higher the velocity, the higher the productivity. However, the velocity also governs the
entraining of water by the dynamic force. If the velocity is too high, the rotation of the drum
will draw the water up too fast until it can reach the scrapper blade and entrain with the
skimmed oil. It is recommended to use peripheral velocity (or tip speed) of 0.44 m/s or less to
prevent water entraining.
8.
Viscosity of oil
Oil productivity, as well as the oil film thickness on the surface of the drum, will
increase if the viscosity of the oil increase, as clearly shown in eq. 3.2.1.
9.
Superficial tension of water and interfacial tension of oil/water
Surfactant is usually present in oily wastewater. The presence of the surfactants

lowers the superficial tension of water and interfacial tension of oil/water. Effect of surfactant
on the skimmer operation can be divided into 2 cases, i.e.,
When oil layer is present: The efficiency of the drum skimmer is proven to
be practically independent of the presence of the surfactant [5]. So change in
superficial tension of water and the interfacial tension of oil/water does not
affect the performance of the skimmer.
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When oil layer is absent: After the oil is removed and the skimming surface
is exposed to water. The surfactant will lower superficial tension of water
until it is close to naturally interfacial tension of oil/water. So there is no
difference between oil and the water. Thus the skimmer will lose its
selectivity, even in the case of PTFE, and start recovering the water.
Oil Productivity (P)
Increase D, L
Increase oil viscosity
0.44 m/s
0.8 m/s
(recommended) (max of
model)
a) Oil productivity of various drum materials

when the oil layer is not a limiting factor [5]
Tip speed
of drum
b) Effect of parameters on drum skimmer

performance
Fig. 3.2.1-3 Influent parameters on drum skimmer performance

3.2.2

1
Drum skimmer sizing
The size of the skimmer can be calculated by eq. 3.2.1. If oil concentration or
quantity of inlet oil is known, it could be used as required oil productivity of the skimmer.
Then, the oil productivity, geometry of tank (width, length), tank freeboard and available
installation space of the skimmer and oil outlet pipe should be taken into account in order to
select a suitable size of the skimmer.
Energy requirement of the skimmer is the energy for driving the skimmer. It can
be calculated by simple product of torque and speed. The torque required depends on the
structure, weight and size of the drum.
2
2.1
Limitations of the equation
The mathematical model of drum skimmer (eq 3.2.1) is valid only under its
limitations shown in section 3.2.1. Application of the model beyond its limitation may cause
unpredictable error.
2.2
Practical design consideration
Besides the limitations of models shown in section 3.2.1, there are some
assumptions or operating condition that affect the performance of the skimmer but cannot be
expressed in the form of equation. To design a skimmer, these assumption and precaution, as
described below, should be taken into account to ensure good performance of the skimmer.
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1)
The model is developed under the assumption that the scrapper can
totally remove or scrape the oil film from the drum surface. So in the
real situation, scrapper should be designed properly to make sure that
it will not be a limiting factor in the operation. Scrapper should be
made of flexible material to ensure its close contact to the entire
length of the drum. However it should have good abrasive resistance.
2)
The oil productivity in eq. 3.2.1 is valid under the condition that the
oil layer is not the limiting factor and the entire length of drum can
contact to the oil film. To ensure these condition, the following
precaution should be considered;
The drum should be properly sized to accommodate the inlet oil

quantity. So it can operate continuously without the problem
about lack of oil layer.
Automatic control should be provided to stop the skimmer when
the oil layer in the tank is too thin to avoid the recovery of water,
esp. when high or moderate critical surface tension is used as
skimming material, or when there is a risk of the presence of
surfactant in wastewater.
If possible, the skimming surface should be of low critical
surface tension material, such as variants of flouorocarbon, to
guarantee good oil selectivity and avoid exposure history
problem. Critical surface tensions of certain materials are listed in
table 3.2.2-1.
Table 3.2.2-1 Critical surface tensions of certain materials [42]

c (dyne/cm, 20 oC)
Material
Poly(1,1-dihydroperfluoroctyl methacrylate)
Polyhexafluoropropylene
Polytetrafluoropropylene
Polytrifluoretylene (PTFE)
Poly (vinylidene fluoride) (PVDF)
Poly(vinyl fluoride)
Polyethylene ({PE)
Polytrifluorchloroethylene
Polystyrene
Poly (vinyl alcohol)
Starch
Poly (methylmethacrylate)
Poly (vinyl chloride) (PVC)
Poly (vinylidene chloride)
Poly (ethylene terephthalate)
Cellulose
Poly (hexamethylene adipiamide)
10.6
16.2
18.5
22
25
28
31
31
33
37
39
39
39
40
43
45
46
Operation of the skimmer can cause eddy current around the ends
of the drum that causes the oil layer in this area vanished quicker
than other area. It results in non-productive zone of the skimmer
(see fig. 3.2.2-1). To avoid this, the oil layer should be kept at
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certain thickness to cope with this effect. The thickness of 1.0 cm

is considered safe.
If the length of the drum is smaller than the width of the tank to
be skimmed, guide walls should be installed to help guiding the
oil layer to the drum.
No oil zone
Eddy
a) Eddy currents
b) No oil zone or non-productive zone
Fig. 3.2.2-1 Occurrence of eddy currents from drum operation and no oil zone or nonproductive zone that affects the productivity of the skimmer (Source: Oil Spill Cleanup)
3.3
Oil disc skimmer
3.3.1
Working principles
Oil disc skimmer is the equipment that has a rotating disc or discs, instead of drum,
which surface act as oil-skimming surface (fig. 3.3.1-1). The oil will adhere to the skimming
surface, lift up from the surface by the skimmers rotating movement, and then be scraped off
by a scrapper blade into a receiving channel or container.
Working concept of the disc skimmer is identical to that of the drum skimmer except
the skimming surface. The concept of surface tension and exposure history described in the
previous is still valid. For the skimming surface area, in case of disc skimmer, it is circular
surface of the disc.
Drive unit
Disc
Oil trough
Eddy
Scrapper
Components of disc skimmer

(Source: Abanaki)
Eddy current from rotating of the disc

(see section 3.3.2)
Fig. 3.3.1-1 Disc skimmer

171
III-54
3.3.1.1 Mathematical model of disc skimmer

Mathematical model of oil disc skimmer, proposed by THANGTONGTAWI, was
derived from dimensional analysis approach, using Buckingham Pi theory under a wide range
of material and wastewater properties as well as operating parameters. The model is as shown
in eq. 3.3.1
P=
0.452 1.17
1.328D1.258 N1.212 o
I
g 0.332
Where P
D
N
I
g
=
=
=
=
=
=
{3.3.1}
Oil productivity of two sides of the skimmer (m3/s)

Diameter of skimmer (m)
Rotational speed of the skimmer (rev/s)
Kinematics viscosity of oil (m2/s)
Immersion depth of the skimmer (m), I D/2.
Gravitational acceleration (m/s2)

Superficial tension of oil (kg/s2 or N/m = 1000 dyne/cm)

Oil density is around 0.79 0.83 kg/m3. Oil dynamic viscosity () tested is
Disc skimmer surface used for model development is PVC. But it is proven to be
valid for SS, PP, and PTFE [5].
The major difference between drum and disc model is that the disc model is the
function of immersion depth while this parameter hardly affects the drum skimmer
performance.
Oil removal efficiency of the skimmer is usually 100%, if the conditions stated above
are satisfied.
{3.3.2}
t = 100%

Parameters that affect the performance of disc skimmer are identical to that of the
drum skimmer, as described in section 3.2.1.2, except the immersion depth. Graphical
presentation of effect of various parameters on the performance of the skimmer is shown in
fig. 3.2.1-2.
Immersion depth of disc skimmer, in this case, represents the depth of a part of the
disc that is under the liquid free surface. From eq. 3.3.1, it shows that oil productivity incerase
172
III-55
with increase in the immersion depth. However the immersion depth is limited by the
diameter of the disc (I D/2)
3.3.2

1
Disc skimmer sizing
The size of the skimmer can be calculated by eq. 3.3.1. If oil concentration or
quantity of inlet oil is known, it could be used as required oil productivity of the skimmer.
Then, the oil productivity, geometry of tank (width, length), tank freeboard and available
installation space of the skimmer and oil outlet pipe should be taken into account in order to
select a suitable size of the skimmer.
Like the drum skimmer, energy requirement of the skimmer is the energy for
driving the skimmer. It can be calculated by simple product of torque and speed. The torque
required depends on the structure, weight and size of the drum.
2
2.1
Limitations of the equation
The mathematical model of disc skimmer (eq 3.3.1) is valid only under its
limitations shown in section 3.3.1. Application of the model beyond its limitation may cause
unpredictable error.
It must be noted that the oil productivity from eq. 3.3.1 is for two sides of
the disc. If scrapper is installed at only one side of the disc, the productivity can be safely
assumed to be 50 % of the value from eq. 3.3.1. Productivity of several discs are the product
of the result from eq. 3.3.1 and the number of the disc n.
2.2
Practical design consideration
Like the case of drum skimmer, besides the limitations of models shown in
section 3.3.1, there are some assumptions or operating condition that affect the performance
of the skimmer but cannot be expressed in the form of equation. The precaution proposed for
the drum skimmer can also be applied for the disc skimmer. Like the drum skimmer,
operation of disc skimmer also results in non-productive zone of the skimmer, starting at the
axis of the skimmer (see fig. 3.3.1-1), when the oil layer is almost totally recovered. To avoid
this, the oil layer should be kept at certain thickness to cope with this effect. The thickness of
1.0 cm is considered safe [5].
3.4
Productivity comparison between drum and disc skimmer
To compare the productivity of drum disc skimmer, THANGTONGTAWI had

proposed the alternative model of the disc skimmer (eq. 3.4.1) that has the same exponents as
the drum skimmer except for that of geometric parameters (D, L, I).
P=
3.464N1.541 o
g 0.514
0.486
(0.5 D )2.54 (0.5 D I ) 2.54
173
{3.4.1}
III-56
From eq. 3.4.1 and 3.2.1, it the productivity of the two skimmers are assumed to be
equal, we can write the relation between the length of the drum and immersion depth of the
disc at the same diameter as shown in eq. 3.4.2. This equation is useful for comparison the
dimensions of the two devices. The dimension can be used for preliminary cost estimation,
which can help determining which type of skimmer is more suitable for the project.
L=
3.464 n
(0.5 D )2.54 (0.5 D I ) 2.54
3.035 D1.541
Where
3.5
{3.4.2}
the number of the disc (n 1)
Advantage and disadvantage of drum and disc skimmer
Advantages: Main advantage of drum skimmer and disc skimmer, as well as other
adsorption based skimming devices, is its oil selectivity. The devices require no additional
chemicals and the oil recovered from these devices will relatively water-free, which is more
suitable to recycle or reuse. Application on oil-spill recovery, developed by ELF-INSA
collaboration, is one of the outstanding achievements of the skimmer (fig 3.1-1). The device
helps solving the environmental problem by collect the oil out off water surface.
Disadvantages: An inconvenience of disk and drum skimmer may be due to its
geometry. The scrapper cannot to be placed higher than the top of the drum or disc. This
means the device cannot lift the oil higher than its diameter. So, in case that the tank freeboard
is large or in case of the tank with variable water level, it may cause an inconvenience on
installation of oil outlet pipe. However, this inconvenience can be solved if outlet pipe sleeve
through the wall is designed and installed in advance. In case of a variable-water level tank,
the skimmers can be installed on a pontoon and a small oil pump can be used to lift the oil to
the desire elevation. Otherwise a high-lift device of the same type, such as belt skimmer, can
be used. But, from its more complex structure, it is always more costly.
174
III-57
a) Drum skimmers and booms for oil spill

recovery (ELF/ GPI lab)
b) Installation of skimmer in variable water level

tank. An oil pump (below) is used to lift the
skimmed oil. (Source: SkimOil, Ro-clean Desmi
Fig. 3.5-1 Application of the skimmers
175
III-58
Chapter 4 Decanting
Chapter 4 Decanting
4.1
General
Decanting or sedimentation is the most basic separation process. Its working principle
bases only upon properties of oil and water, which tend to separate from each other naturally.
This process is widely used, even becomes legal standard for some industries, such as
refineries in USA. Because of its working principle, which bases on natural unadapted
properties, decanting is suitable for separating oil in form of big oil drop or primary emulsion.
There are many variations of decanting process, however they can be categorized into 2
groups, i.e.,
Simple decanter: This group of decanter is the most basic process. They may vary
in geometry and details of some components. But they all use the same working
principle of natural unadapted decanting. The well known example of this type of
decanter is API tank, as shown in fig. 4.1-1.
Compact decanter: This group of decanter is the modified version of the first
group, intended to upgrade the capacity of the existing simple decanter. Or it can
be newly designed equipment. The objective of compact decanter design is to
enhance the efficiency of decanter, making it handle more capacity, using smaller
footprint. This can be achieved by the modification of decanter geometry, such as
the insertion of lamella plates. However, the working principle is still identical to
that of the simple decanter as, theoretically, there is no modification of any natural
properties. Examples of this type of decanter are shown in fig. 4.1-1. Among these,
GPI lab has developed one of the most compact decanter, called Spiraloil. Its
special features and technical design consideration will be presented hereinafter.
a) API tank (Source: Pan American

Environmental)
b) Spiraloil compact decanter
c) Oil layer at the surface of API tank
Fig. 4.1-1 Examples of decanters

176
III-59
d) Example of up-scale API tank with tank enclosure (Source: USFilter)
e) Graphical image of lamella plate decanter

(Source: USFilter)
f) Corrugated plate module of corrugated plate

decanter (Source: Dewaterworks)
Fig. 4.1-1 Examples of decanters (Cond)
4.2
4.2.1
Working principles
Simple decanter, which is made well known and standardized by the American
Petroleum Institute (API), is the simplest oil-water separation process. Its working principle
bases on classical STOKES law (cf. Chapter 2). Concept of the operation of the process is to
provide sufficient time for oil droplets to float to the water surface and accumulate into oil
layer before they have a chance to flow out with the water at the water outlet. The equation
that governs the operation of the process is derived from comparing the time required for the
droplet to reach the surface with retention time of the tank (), as shown in eq. 4.2.1.
177
III-60
Chapter 4 Decanting
(Rising distance of droplets / Rising velocity of droplets)

L
Separated
oil layer
Q
Ud
Influent
d > cut size
{4.2.1}
H, D
Effluent
V
d = cut size
d < cut size
Oil droplets
Zone 1
Zone 2
d = or > d c
d
d < dc
dc
Figure. 4.2.1-1 Schematic and typical removal efficiency curve of simple decanter
Figure 4.2.1-1 shows the diagram of decanting process. From the figure, the longest
path to reach the surface is the path starts at the bottom of the tank. The smallest droplet size
that can reach the surface is called the cut size (dc). The droplets of cut size or bigger are
always separated from wastewater stream with 100% removal efficiency.
The smaller droplets can be also separated providing that it enters the tank near the
water surface. When uniformly distributed influent flow is valid, which is true for almost all
of properly designed tanks, the removal efficiency of the droplets smaller than cut size are
proportional to theirs corresponding rising velocity. From these concepts, the models of
decanting process are as shown in Eq. 4.2.2 to 4.2.5.
For the simple decanter of the length L, the width W and the water depth D,
from eq. 4.2.1, we have,
=
L
(Q
WD
=
)
H
U dc
{4.2.2a}
For the simple decanter, rising distance of the droplet (H) is equal to the water depth
(D), then
Q Q
U dc =
=
LW S
{4.2.2b}
In laminar flow regime (Re < 1), STOKES law is applicable. So, rising velocity of
droplet of diameter d (Ud) can be written as shown in eq. 4.2.3.
Ud =
g d 2
18 c
{4.2.3}
178
III-61
Then
18Q c
d c =
g S
1/2
{4.2.4}

d = 100 %
{4.2.5a}

d =
Ud
100 %
U dc
Where dc
D
S
Q
A
H
D
c
=
=
=
=
=
=
=
=
=
Ud
Udc
Co
d
=
=
=
=
{4.2.5b}
Cut size of the decanter

Diameter of dispersed phase, in this case, oil
Wastewater flowrate
Flow (Cross section) area
Travelling or rising distance of oil drop
Water depth
Density of continuous phase, which is water, for oily wastewater
Difference between density of dispersed phase and continuous
phase
Dynamic (or absolute) viscosity of continuous phase, which is
water, for oily wastewater
Rising velocity of the droplet at cut size dc
Total inlet concentration of oil
Removal efficiency of the tank for the droplet diameter d, or
graded efficiency
Typical characteristic of the removal efficiency of decanter is as shown in Figure.

4.2.1-1. Zone 1 in the graph represents the droplet sizes smaller than dc. Zone 2 represents
those, which are equal or bigger than dc.
4.2.2
Design calculation
Design procedure for simple decanter is based upon the equations, shown in the
previous section. To design the simple decanter, the required cut size will be determined first.
After that, the size of the tank can be calculated. Then, graded efficiency (efficiency of each
size of droplet) and then total removal efficiency can be determined. Calculation in each step
is described below.
1.
The cut size can be determined from the degree of treatment required as well as
from the limitation of the decanting processes. Cut size determination from the degree of
treatment is described in chapter 3. For the limitations of the decanting process, they come
from 2 main parts, i.e.,
179
III-62
Chapter 4 Decanting
Theoretical limitation: Since the decanters working principle is based on

STOKES law, it can be applied only when the droplet behavior conforms to
the law. Thus, it can not be used with very small droplet sizes for they are
subjected to Brownians motion and their rising velocity are not governed by
STOKES law. Commonly, the simple decanter is used for primary emulsion
treatment (d 100 microns).
Economic limitation: As stated before that the process is a non-accelerated

process, its required footprint or installation area may be unacceptable if too
small cut size is selected.
Thus, the suitable cut size will be considered by accounting for the 2 limitations
above. API recommends the cut size of 150 microns for API tank.
2.
Decanter sizing
The size of the decanter can be determined, based on the equation in section
4.2.1, as follow:
Bottom surface area (S): The decanter size is based mainly on its bottom
surface area. In general case, it is identical to the tank surface area. Presence of some
structures or components, such as effluent trough or gutter or tank cover (at the water
surface), may affect the efficiency of the decanter. However, if these structures are present in
the ways that make the rising distance of oil droplets decrease, they will help enhancing the
efficiency. However, their effects are normally small, thus, negligible, unless they
substantially reduce the rising distance of oil drops. In latter case, the tank will become a
compact decanter, which will be described in the next section. Bottom surface area of the
simple decanter can be calculated from the rising velocity of the cut size, as shown in eq.
4.2.6. The example of relation between kerosene droplet size and its corresponding rising
velocity as shown in fig. 4.2.2-1.
Q
S =
U dc
U dc =
{4.2.6a}
g d c2
18 c
{4.2.6b}
Flow velocity (V): Flow velocity means the velocity of total wastewater along
the tank, determined from wastewater flowrate and cross sectional area of the tank. Using
high flow velocity may cause turbulent or eddy current, especially when the wastewater
collides to the far end of the tank. Turbulence in the tank may interfere the decanting of
droplets, as well as suspended solids, which are usually present in the wastewater. This may
cause carry-over of oil drop and suspended solids with the effluent of the tank.
API recommends that V should not be greater than 0.15 m/s or greater than
15Vdc, whichever is smaller.
Water depth (D) and width (W): Theoretically, the efficiency of the tank does
not depend directly on these parameters. However, they have some effects on the tank
operation since they are ones of the parameters that govern the flow regime of the tank.
Furthermore, if they are not selected properly, they can cause adverse effect, such as eddy, or
short circuit.
180
III-63

200
Hydraulic loading rate ((m3/h)/m2)
160
0.04
140
120
0.03
100
80
0.02
60
40
Rising velocity of droplet (m/s)
0.05
180
0.01
20
0
0
0
100
200
300
400
500
600
700
800
Cut size (micron)
Fig. 4.2.2-1
Relation between rising velocity, hydraulic loading rate of simple decanter and kerosene droplet size
API recommends that the ratio D/W should not be smaller than 0.3. The value of
0.5 is recommended. The depth (D) should be in the range of 0.9 to 2.5 m.
3.
Removal efficiency
To determine the removal efficiency, the graded efficiency (d) will be

calculated first by eq. 4.2.7a and b. Then, the total removal efficiency (t) can be determined
from eq. 4.2.7e.
d = 100 %
{4.2.7a}

d =
Ud
100 %
U dc
{4.2.7b}
It must be noted that the graded efficiency described above is not yet accounted
for effect of flow splitting between water outlet flow and separated oil outlet flow. To
calculate graded outlet oil concentration, the effect must be taken into account, as shown in
eq. 4.2.7c.
Cd =
Q
(1 d ) C od
Q out
{4.2.7c}
Qout is outlet flow at treated water outlet port of the process. Qout is calculated
from difference between inlet flow and separated oil (in relatively pure condition) as shown
below.
d max
Q out = Q
Q ( d C od )
d min
181
{4.2.7d}
III-64
Chapter 4 Decanting

d max
t =
C od
d min
Co
)
{4.2.7e}
100 %
t = Total Removal efficiency of the tank

d = Density of dispersed phase, which is oil, for oily wastewater
Cod = Inlet concentration of the droplet diameter d
4.
Energy required
The simple decanter does not require extra energy to make it function. The
energy is required only to feed the water into the tank, then the water will flow, naturally,
through the tank by gravity. Pressure drop across the tank and piping system depend on tank
and piping design. This pressure drop can be calculated by general hydraulic equations, such
as Darcy-Weisbachs, Mannings, or Hazen-Williams equation, thus will not de described
here.
4.2.3
1.
Limitations of the equations
The equations described above are developed from the following assumptions.
Thus, it is necessary to ensure that these assumptions are valid when design your decanter.
1)
Reynolds number, Re, of droplet is between 10-4 to 1, which is the range

Re =
2.
c U d d
c
{4.2.8}
2)
the tank, which can be achieved by proper design of inlet chamber.
3)
4)
For droplets smaller than 20 microns, they are subjected to Brownian

motion and cause error in the prediction of the efficiency. So it is
recommended to avoid using the decanter for the wastewater with the
majority part of oil droplets smaller than 20 microns. However, if these
small droplets are the minority part of pollutants, the models can be used to
predict the efficiency without any harm because its prediction is usually
lower than observed value, thus make the prediction result on the safe side.
Safety factors
Since the design equations are simplified by many assumptions, it is

recommended to provide some safety factors to the sizing, calculated from the equations, to
cover some unexpected effects such as short circuit flow or local turbulent flow.
API recommends the safety factor for turbulent flow (Ft) as the function of
(V/U), as shown in eq. 4.2.9. U represents hydraulic loading rate or overflow rate, based on
total flow and bottom area. For effect of short circuit, API recommends the safety factor (Fs)
182
III-65
of 1.2. Then the total safety factor (F), by API recommendation, is the product of Ft and Fs
(eq. 4.2.9c). Factor F will be used to multiplied the value of S, calculated from eq. 4.2.6.
Ft = 0 . 0005 (
V 2
V
) + 0 . 0355 ( ) + 0 . 9617
U
U
F = Ft F s = 1 . 2 Ft
4.2.4
{4.2.9a}
{4.2.9b}
There are many variations of simple decanters, as shown in fig. 4.2.4-1. The most
famous one is API tank, which is the rectangular tank. However, they use the same working
principles, can be calculated by the same equations and consists of relatively the same
components.
To design the decanter, besides the sizing stated above, proper details of construction
of decanter components are also important to guarantee good efficiency. Design
considerations for important components of decanter are described hereby.
1.
Inlet chamber
Inlet section, as shown in fig. 4.2.4-2, is an important of decanter for it helps

assuring that uniformly distribution of oil droplet is achieved. For this purpose, the inlet
chamber should be equipped with baffles or energy dissipation devices or structure. Widely
used structures include vertical columns, perforated wall or vertical partition. Design of inlet
section is a state of art process. So it is recommended to study the successful design from
many references and adapt to fit with the condition considering.
2.
Separation section
Sizing of this section is obtained from the equations. In this section, not only the
oil will be separated, suspended solids will also settle. So sludge hopper or sludge draw-off
pipe, or other provisions for sludge removal should be provided. Geometry of this section
should be as recommended in the previous section to ensure good hydraulic condition. This
section may be covered, if necessary, to prevent accidental ignition and to prevent the loss of
volatile hydrocarbons by evaporation. Sludge hopper, sludge scrapper and surface skimmer,
should be provided, as shown in fig. 4.2.4-2.
3.
Effluent and oil removal devices
Effluent and oil will be removed at the downstream end of the tank. Normally oil
retention underflow baffle is installed to prevent the oil to flow out with the effluent. API
recommends that this baffle should be installed with a maximum submergence of 55% of the
water depth and should be located as close as possible to the oil removal device. The baffle
should be extended to the top of the tank or, at least, higher than water surface.
For oil removal devices, in small unit, the weir or slotted pipe is sufficient. For
upscale tank, those simple devices may draw the water off along with the oil. So the separated
oil still contains some water, and may not be suitable for downstream reuse or recycle
process. In this case, the device with more selective property, such as rotating slotted pipe or
oil skimmer, is required. There is a chapter in this book, devoted to oil skimming process.
183
III-66
Chapter 4 Decanting
For effluent, it is normally removed from the tank by a weir. In some small units,
bell mouth pipe is acceptable. Design consideration for effluent removal device is that it
should be of sufficient size to prevent undesired turbulence and provide good flow
distribution in the tank. Normally, the weir across the width of the tank is sufficient.
a) Example of up-scale simple decanter with inlet diffuser wall, equipped with
mechanical skimmer (Source: Monroe)
b) Example of small to medium size simple decanter with simple elbow type inlet
diffuser and weir for collecting oil (Source: Pan American)
Fig. 4.2.4-1 Variations of simple decanters
a) Graphic image shows important components of API tank (Source: US filter)

Fig. 4.2.4-2 Important components of simple decanter
184
III-67
Flow
15o
Plan
Elevation
b) Example of inlet diffusion wall (Source: API [45])
c) Example of inlet diffusion nozzle

(Source: API [45])
d) Chain and flight skimmer (and

scrapper)(Source:
Envirinmentalleverage.com)
e) Example of rotating skimmer pipe

(Source: Environmentalleverage)
f) Chain and flight scrapper and oil drum

skimmer (Source: US Filter)
Fig. 4.2.4-2 Important components of simple decanter (Cond)
185
III-68
Chapter 4 Decanting
4.3
Compact decanter
4.3.1
Working principles
This type of decanter is the modification of the simple decanter. The concept is to
decrease the rising distance of droplet to intercepting surface without decreasing the retention
time. This can be achieved by inserting plates into the simple decanter to act as the
interceptors for the rising oil droplets. Rising or travelling distance (H) is the distance
between the plates, not the depth of water (D) as shown in fig. 4.2.1-1. There are several
variations of this type of decanter. Normally they are named after configurations of their
inserted plates, such as:
Parallel plate interceptor (PPI), which its inserted plates are flat sheets, placed
parallel to each other.
Tilted plate separator (TPS), which its inserted plates are tilted or inclined.
Corrugated plate interceptor (CPI), which used corrugated plates instead of flat
plates.
The equation that governs the operation of the process is modified from the model of
simple decanter, as shown in Eq. 4.3.1. From the equation and the figure, it is implied that, in
a compact decanter, the simple tank is divided into (N+1) small decanters but the flow
velocity through the tank remains the same.
Separated oil floats
to surface
L
Q
H
Influent
Effluent
D
Inserted plates
(No. of plates = N)
Fig. 4.3.1-1 Schematic of PPI decanter

1/2
18Qc
d c =
gS P (N + 1)
Where Sp
N
L
H
=
=
=
=
{4.3.1}
Inserted plate area

Numbers of inserted plates
Length of inserted plates
Rising distance of oil drop, in this case, distance between inserted
plates
Removal efficiency can be calculated using eq. 4.2.5. Typical characteristic of the
removal efficiency of the compact decanter is identical to the simple decanters, as shown in
186
III-69
fig. 4.2.1-1.But the cut size of this tank will be smaller than the simple decanters, providing
that they are of the same geometry.
4.3.1.1 General model of plate-inserted decanters
According to the concept of decanting model that derived from comparing detention
time with rising time of droplet to intercepting surface, we can formulate the general model to
calculate dc for any decanter as shown in eq. 4.3.2
General model for calculating the cut size, when H, L and A can be clearly defined, is
as shown in eq 4.3.2.
18 HQ c
d c =
gLA
Where Q
H
L
A
1/2
{4.3.2}
=
Wastewater flowrate
= Rising distance of oil drop, depends on the configuration of decanter
= Length of interceptor surface
= Flow area (or cross section area) of decanter
4.3.1.2 Plate-closely-inserted decanters

GPI lab has also developed a decanter, called Spiraloil (see fig. 4.3.1-2) This special
decanter has its lamella plates placed very close to each other. Then the rising distance is
reduced dramatically. For the spiraloil, the plates are rolled into cylindrical shape, so it is very
compact in size. However, it is difficult to determine the rising distance (H). GPI lab has been
studies the model that governs this type of decanter and found that the modified theoretical
model, as shown in eq. 4.3.3, can provide good result. This model is developed from the
general model (eq. 4.3.2) by neglecting the complicated analysis to define H, and using the
concept of decanting area (Sd) instead. Sd is calculated from the sum of every surface area
within the decanter that can intercept oil without considering if the values H of these areas are
identical or not. This model or equation has been confirmed by CHERID [4] for its accuracy,
as shown in fig. 4.3.2-3.
18Qc
d c =
g S d
Annular plates
1/2
{4.3.3}
H
Solid core,
radius = r
e
R
a)
b)
187
III-70
Chapter 4 Decanting
Figure. 4.3.1-2 Spiraloil decanter a) Simple spiral b) Mixed spiral

100.00%
90.00%
80.00%
1'
3'
V = 0.4 cm/s (1, 1')
70.00%
V = 0.8 cm/s (2, 2')
60.00%
V = 1.6 cm/s (3, 3')
50.00%
40.00%
2'
30.00%
20.00%
10.00%
0.00%
0
10
20
30
40
50
60
Fig. 4.3.1-3a
Comparison between observed efficiency (1',2',3') and predicted efficiency (1,2,3) for Simple Spiral
"Spiraloil" decanter
100.00%
90.00%
1'
1 (V = 0.5 cm/s)
80.00%
70.00%
60.00%
2'
2 (V = 1.5 cm/s)
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
0
10
20
30
40
50
60
Fig. 4.3.1-3
Comparison between observed efficiency (1',2') and predicted efficiency (1,2) for Mixed Spiral "Spiraloil"
decanter
From the graphs, it shows that;

1.
Predicted values for cut size are relatively accurate.
2.
Predicted efficiencies of the droplets, smaller than cut size, are always lower
than observed value. This can be explained by the phenomena taking place
within the decanter, which will be described hereby.
3.
Correction factor for efficiency prediction of these small droplets may not be
established accurately. However, the predicted cut size can be used to design the
188
III-71
tank with relatively high accuracy. So it is reasonable to select the cut size to
cover the majority of droplet size distribution. The predicted efficiency of
smaller droplets, which is the minority part, will cause no harm but slightly
underestimation on the total efficiency.
Because of its very close spacing, This type of decanter provides the separation both
from decanting phenomenon and coalescing phenomenon. So the oil drops from the decanter
is relatively big (> 2 mm), and easy to separate at the downstream end of the decanter.
Phenomena taking place in the decanter have also been studied by CHERID. It shows
that, besides the decanting phenomenon, coalescing of oil drop is also taking place. From the
study, it shows that there are 3 parameters that affect the decanting and coalescing
phenomenon in the plate inserted decanter, i.e.,
1.
Wettability of inserted plates
Oleophilic plates: The oil will adhere and then coalesce to form a film at the
surface of the plates. However, when the film is totally coated the plate
surface, it will be more difficult for the following oil drops to coalesce to the
film than adhere to the surface. These following oil drops, sometimes, roll
along the film, rather than coalesce into it, along with the wastewater flow.
However, at the end of plates, the oil film, driven by the hydraulic force of
the wastewater, will form big oil drops. It can be said that these points will
play the roles of the drip points or salting-out points, the same as in the
coalescer. These big oil drops can intercept those non-coalesced oil drops to
form even bigger drops until they reach certain size that can be snapped off
by the water flow.
Hydrophilic plates: The oil will not form a film on the plate surface. But
they will accumulate as an oil droplet and coalesce with other droplets to
form big oil drops. Then they will roll along with the wastewater flow and
coalesce with other drops along their ways like snowballs. These big oil
drops will leave the plate for the surface when they reach sufficient size.
ot co
s do n
p
o
r
d
il
lm
ing o
t he fi
follow roll along
e
m
So
ut
fi l m b
with
O i l fi
alesc
point
Drip
Dr i p
f
ball e
Snow
lm
point
fect
Hydrophilic plate
Oleophilic plate
a) Oleophilic plates
b) Hydrophilic plates
Fig. 4.3.1-4 Effect of wettability of inserted plates

2.
Inclination of inserted plates
189
III-72
Chapter 4 Decanting
In many designs, the plates are tilted for the designers believe that it will help
increasing the oil separation efficiency. CHERID has studied the effect of inclination. From
theory and research result, the influent of the inclination to the decanter can be concluded and
described below:
Effect on decanting phenomena: An inclined decanting channel is

compared with a horizontal channel of the same distance between 2 adjacent
plates (fig. 4.3.1-5). From the figure, it shows that the oil drops in the
inclined decanter will take more time to rise to the intercepting surface since
rising distance is greater (H/cos , instead of H). So, theoretically, inclination
will not help promoting decanting phenomena of oil drop. However, in largescale tank, inclination helps draining the sludge, that is always present in
wastewater, thus, preventing clogging of the decanter.
Effect on coalescing phenomena: CHERID found that the inclination of

plate affects the coalescing phenomena. The decanted oil drops in inclined
decanter may not coalesce into oil film at the surface of the plates, even the
olephilic ones, but roll along with the water flow. Moreover, the inclination
will make the film snap off easier. Thus it will reduce the thickness of film
accumulating at the surface of plates. For big tank, it may not affect the
efficiency much. But in plate-closely-inserted decanter, like spiraloil, this
film helps reducing the rising distance in considerable degree. So, from these
two reasons, CHERID proposes that, for plate-closely-inserted decanter,
inclination should be zero. Or the decanter should be installed horizontally.
U (Rising velocity)
Rising distance =
(H/ cos ) >
=V( Flow velocity)
a) Horizontal decanter
U
V
b) Inclined decanter
Fig. 4.3.1-5 Schematic of inclined and horizontal decanter

3.
Presence of surfactants
The presence of surfactant will decrease the sizes of decanted oil drops, thus
hinder good decanting phenomenon. Furthermore, it will prevent coalescing between oil
drops. As a result, the total efficiency of decanter will be decreased. It has been reported that
[4], when tested with kerosene-water emulsion at the concentration of 100 mg/l with the
concentration of surfactants around 100 mg/l and the average droplet size of 40 microns, the
efficiency of spiraloil will decrease about 15 20%. The interfacial tension between kerosene
and water will drop from 42 N.m to 8.5 32.1 N.m, depending on the type of the surfactants.
Non ionic surfactant is the most effective surfactant for lowering the interfacial tension. The
second best is cationic surfactant, then anionic surfactant, respectively.
4.3.2
Design calculation
190
III-73
Design procedure for compact decanter is relatively similar to the simple decanters
and based upon the equations shown in the previous section.
1.
from the limitation of the decanting processes. Cut size determination from degree of
treatment is described in chapter 3. For the limitations of the decanting process, they come
from 2 main parts, i.e., theoretical and economic limitations, as stated in section 4.2.2.
2.
Decanter sizing
The size of the decanter can be determined, based on the equation in section
4.3.1, as follows:
Decanting area (Sd), inserted plate area (Sp), footprint area (S): The decanter
area of the compact decanter depends on the types or configuration of the decanter. However
the decanting area (Sd) in this case is not equal to footprint area (S).
Parallel plate interceptor, Corrugated plate separator or the decanter of
identical concept
Q
S d =
U dc
U dc =
{4.3.4a}
g d c2
18 c
{4.3.4b}
S d = S p ( N + 1)
{4.3.4c}
S =Sp
{4.3.4d}
N represents the number of plates. Please note that the plates must be inserted at
an evenly interval throughout the water depth.
General compact decanter that rising distance (H) can not be exactly specified.
Q
S d =
U dc
U dc =
{4.3.5a}
g d c2
18 c
{4.3.5b}
In this case, the footprint area has to be specially calculated, based on the
geometry of the decanter. Sd can be specifically calculated, depending on the shape of the
decanter. Surface of material or free water surface that can intercept oil drops will be
accounted for calculating the decanting area (Sd). In case of commercial decanter, required Sd
calculated from eq. 4.3.5a will be used to select the model and/or the number of the product
required for the design flowrate.
Flow velocity (V): Flow velocity means the velocity of total wastewater along
the decanter, determined from wastewater flowrate and full cross sectional area of the
decanter. Velocity is the main parameter that governs flow regime and hydraulic condition,
191
III-74
Chapter 4 Decanting
such as hydraulic force, head loss, etc., in the decanter. CHERID [4] recommends the value of
0.4-1.6 cm/s or 14.4-54 m/h., 2.6 to 10.6 times higher than simple decanter.
3.
Removal efficiency
To determine the removal efficiency, the graded efficiency (d) will be

calculated first by eq. 4.3.6a and b. For graded outlet concentration (Cd), flow splitting effect
between treated water outlet port and separated oil outlet flow must be taken into account, as
shown in eq. 4.2.7c and 4.2.7d. Then, the total removal efficiency (t) can be determined from
eq. 4.3.6c.
d = 100 %
{4.3.6a}

d =
Ud
100 %
U dc
{4.3.6b}

t =
1 d max
( d C od ) 100 %
C o d min
{4.3.6c}

Qout = Treated water outlet flow (eq. 4.2.7d)
5.
Energy required
The compact decanter does not require extra energy to make it function. The
energy is required only to feed the water through the decanter. Pressure drop across the
decanter and piping system depends on decanter and piping design. This pressure drop can be
calculated by general hydraulic equations, such as Darcy-Weisbachs, Mannings, or HazenWilliams equation, thus will not de described here. However, velocity through decanter is
relatively low, compared to velocity in pipe (0.6-2.5 m/s). So the estimated value of pressure
drop across the decanter around 0.5-1.0 m. is normally acceptable, regardless of its size and
configuration.
4.3.3
1.
The equations described above are developed from the following assumptions
and limitations. Thus, it is necessary to ensure that these assumptions are valid when design
your decanter.
1)
The tank is operated under laminar flow regime. Reynolds number, Re, is
between 10-4 to 1, which is the range that STOKES law is valid.
2)
the tank, which can be achieved by the proper design of inlet chamber.
192
III-75
2.
3)
4)

Material selection
There is no evidence that provides strongly recommendation or rule to select the

decanter material, esp. its inserted plates. CHERID has studied the effect of hydrophilic and
oleophilic material but did not point out which one is suitable. Moreover, in his spiraloil
decanter, he used the combination of corrugated oleophilic plates with smooth hydrophilic
insertions. However, theoretically, olephilic material may provide more benefit for it
promotes formation of oil film on its surface, which helps reducing the rising distance, as
described in section 4.3.1.3. Oleophilic property can be achieved by selecting the material
with very low surface energy, such as PTFE, Teflon. It can also be archived by coating the
surface of any material by oleophilic coating, such as silicone. In the latter case, we can select
base material that provides good machinability and cost-effectiveness, regardless of its
wettability, and then have it coated later.
4.3.4
Variations, advantage and disadvantage of compact decanters
There are many variations of compact decanters. However, the components of the
decanter can be designed by the same concept as that of the simple decanter. Nowadays, there
are several suppliers that commercialize these products, such as ELF, Johnson lamella
separator, etc. So designers can find further information from these suppliers. Some examples
of these decanters are shown in fig. 4.3.4-1
Advantages: Main advantage of compact decanter is, of course, its compactness. It
requires 2.6 10.6 times (or more) of footprint area less than simple decanter at the same
capacity. The concept of plate insertion can be used to upgrade the existing simple tank
without constructing the new tank.
Disadvantages: Because of its relatively small flow passage, esp. for closely inserted
decanter, it may have a chance of clogging by suspended solids. So this fact should been taken
into account before design or select the decanter.
193
III-76
Chapter 4 Decanting
a) Spiraloil test (Source: GPI lab)
b) Spiraloil installation on off-shore platform

(Source: ELF, GPI lab)
c) Graphical drawing of parallel plate

interceptor (Source: Anch Tank)
d) Parallel plate interceptor aboveground

installation (Source: Anch Tank)
e) PPI in form of cylindrical tank

(Source: Knitmesh)
f) Parallel plate module for cylindrical

tank(Source: Knitmesh)
g) Parallel plate module

(Source: Industrial heating.com)
h) Corrogated plate module

(Source: Brentwood)
Fig. 4.3.4-1 Examples of compact decanters
194
III-77
Chapter 5 Coalescer
Chapter 5 Coalescer
5.1
General
From STOKES law, particle or oil droplet diameter is the most influent parameter because
it is powered by 2. Thus, if we have a process that can increase the size of the oil droplet 2 times,
the rising velocity will be 4 time higher. This can be achieved by making the oil drops combine
or coalesce to each other. Coalescer is the process that is designed to promote coalescing of oil
droplets into bigger oil drops, which can be separated easily by relatively small decanter. Because
of its working principle involves the modification of parameters of STOKES law. So it is one of
accelerated or adapted separation process, along with other processes such as hydrocyclone and
flotation. There are several types and modification of coalescers. However, they can be
categorized into 2 groups, based on the type of the media used, i.e.,
Granular bed coalescer: This group of coalescer uses granular material, such as
resin, sand or glass beads, as a coalescer bed.
Fibrous bed coalescer: This group of coalescer uses fibrous material, such as metal
wool or plastic brush, as a coalescer bed.
The pictures of various coalescers are shown in fig. 5.1-1.
5.2
5.2.1
Working principles
This type of coalescer uses granular material as a bed to promote coalescing between oil
droplets. The concept of the process is that the oily wastewater will flow through the coalescer
bed, as shown in fig. 5.2.1-1. Oil droplets in the wastewater will undergo several steps to coalesce
them into big oil drops. Then, these big oil drops will be separated by a small integrated decanter
at the downstream of the bed.
Professor AURELLE [3] is the pioneer on coalescer research. He establishes the 3-step
working mechanisms of the coalescer and the model for efficiency prediction, based on YAOs
filter model [35]. Then there are several follow-up researches on coalescer , based on
AURELLEs research
To understand the working principles of coalescer, the 3-step working mechanisms of the
coalescer ise described hereby.
195
III-78
a) Graphical image of Granular bed coalescer

(Source: Elf, GPI lab)
b) Graphical image of one type of fibrous bed

coalescer (Source: Knit mesh)
c) Granular bed coalescer installation for

refinerys condensate treatment
(2x125m3/h)(Source: Donges refineries, Elf)
d) Photo of coalesced oil drop of dynamic

(rotating) fibrous bed coalescer
(Source: GPI lab)
Fig. 5.1-1 Examples of coalescer

OUT:
Large drop
Collector
size =dp,
Void ratio =
H
IN:
Micro drop
Dia. = d
Discharge
screen
Inlet
screen/support
Fig. 5.2.1.1 Schematic diagram of granular bed coalescer

196
III-79
Chapter 5 Coalescer
Mechanisms taking place inside the coalescer bed
AURELLE divided the mechanisms taking place with in coalescer bed into 3 steps, i.e.;

sedimentation, direct interception and diffusion.

wettability of bed material.
Step 3: Salting out or enlargement of coalesced liquid. This step depends on 4

parameters, such as wettability of bed material at the discharge surface, empty bed
flow velocity, interfacial tension and ratio of dispersed phase and continuous phase in
emulsion treated.
Details of each step is described hereby.

5.2.1.1 Step 1: Interception
This step is the step of transportation of the oil droplets through the bed of coalescer.
AURELLE considered that this step is identical to the mechanism of in-depth filtration. So he
applied the phenomena taking place in the filter to the colescer. This step will be divided into 3
transport phenomena, i.e., sedimentation, direct interception and diffusion. Other transport
phenomena, such as that of electrical force, might take place, but it is proven that their effect is
small, thus, negligible. To simplify the model, we will consider the phenomena, taking place at 1
collector or 1 piece of media. Schematic diagram of the 3 phenomena is shown in fig. 5.2.1-1.
Stream line
Media,
Collector
Oil droplet
V U
V
U
a) Direct interception
U= Rising velocity
V= Flow velocity
b) Sedimentation
c) Diffusion
Fig. 5.2.1-2 Schematic diagram of the 3 transport phenomena

1.
Direct interception
When oil drops of diameter d flow along with the streamline, the oil drops that
pass within the distance less than d/2 from the media will be intercepted by the media, as shown
in fig. 5.2.1-1a. The efficiency factor for this phenomenon can be calculated by eq. 5.2.1. dp is the
diameter of collector or media particle.
197
III-80
Int =
2.
3 d 2
( )
2 dp
{5.2.1}
Sedimentation
Consider oil drops of diameter d flow along with the streamline. Because of its
density, the droplets will be subjected to rising velocity (U), calculated by STOKES law. When
they are far from the media, the rising velocity and flow velocity (V) will have the same
direction. When they come close to the media, the flow velocity will deviate, as shown by the
streamline, while the oil drops will be subjected to both flow velocity and their own rising
velocity. So the resultant velocity will not totally conform to streamline. And in some cases, it
will make the oil drops collide to, thus, sediment on the media. The efficiency factor for this
phenomenon can be calculated by eq. 5.2.2.
U gd 2
sed = =
V
18 cV
3.
{5.2.2}
Diffusion
For very small droplets (d < 5 microns), They will be subjected to Brownians
motion. These random motions can cause the droplets to collide to the media. The efficiency
factor for this phenomenon can be calculated by eq. 5.2.3. K , in this equation, represents the
Bolzmann constant and T represents the absolute temperature.
KT
Diff = 0.9
c d dpV
4.
2/3
{5.2.3}
Combined efficiency of step1 : Interception
From steps 1 to 3, we can calculate the efficiency factors of each transport

phenomena for single collector. Theoretical efficiency factor of interception step for single
collector is the summation of the efficiency factors of those three transport phenomena, as shown
in eq. 5.2.4. From the equation, it shows that, at the same operation condition, the theoretical
efficiency factor of the single collector will vary with the droplet diameter, as shown in fig. 5.2.12.
theo = Int + Sed + Diff

Thus
gd 2 3 d 2
KT
theo =
+ ( ) + 0.9
18 cV 2 dp
c d dpV
198
2/3
{5.2.4}
III-81
Chapter 5 Coalescer
1.00E-01
Effciecncy factor
1.00E-02
1.00E-03
1.00E-04
1.00E-05
0.01
0.1
10
100

Diffusion efficiency factor
Sedimentation efficiency factor
Fig. 5.2.1-3
Interception efficiency factor

Theoretical efficiency factor
Relation between oil droplet diameter and efficiency factors of each

transportation phenomena
From the graph, the range where the theoretical efficiency factors are minimal is
between 0.25 to 5 microns. So the droplets in this range is theoretically the most difficult to
separate.
To adapt the efficiency of a single collector to the entire coalescer bed, we will
consider the simplified diagram of single spherical collector, placed in laminar flow regime, as
shown in fig. 5.2.1-3a. V represents the flow velocity. The fraction of wastewater flowing pass
the single collector will be the flow that passes through the projected area of the collector (q), as
shown in eq. 5.2.5a. Then, some oil drops in this fraction of the wastewater will be intercepted by
the collector. The quantity of intercepted oil drops of the single collector (c) will be calculated
from the theoretical efficiency factor, as shown in eq. 5.2.5b.
q=
d 2p V
c' = theo
{5.2.5a}
d 2p V C
{5.2.5b}
199
III-82
OUT:
Large drop
Discharge
screen
dp
Collector
size =dp,
Void ratio =
IN:
Micro drop
Dia. = d
q = Vdp2/4
a)
Inlet
screen/support
V
b)
Fig. 5.2.1-4 Schematic of a single collector and the entire bed of coalescer
C is the inlet concentration of oily wastewater. For the entire coalescer bed, we will
consider a very small slice of bed of the height dH (see fig. 5.2.1-3b). The number of collector
particles in this slice can be calculated from the cross sectional area of bed (Ao), the size of
collector (dp) and the void ratio of the bed (), as shown in eq. 5.2.5c.
Then, the total concentration of intercepted oil for this slice of bed will be equal to
the product of c and the number of collector particles. However, not all of the intercepted oil
drops will adhere to the collector. So the probability coefficient () will be applied to adapt the
quantity of intercepted oil drops to the quantity of adhered oil drops (c), as shown in eq. 5.2.5d.
The number of collector particles in the slice dH =
dH (1 ) Ao
6
c" = theo
d 2p V C
dH (1 ) Ao
,<1
{5.2.5c}
d 3p
{5.2.5d}
d 3p
If dC represents the concentration of oil reduced after passing through the bed dH,
then we have got eq. 5.2.5e and f;
V Ao dC = c"
V Ao dC = theo
{5.2.5e}
d 2p V C
dH (1 ) Ao
{5.2.5f}
d 3p
Therefore,
dC
3
=
(1 ) theo dH
C
2d p
{5.2.5g}
Integration of eq. 5.2.5g will give the value of the oil concentration reduced by the
entire bed, as shown in eq. 5.2.6.
200
III-83
Chapter 5 Coalescer
log(
3
C
H
) = (1 ) theo
2
Co
dp
{5.2.6}
Thus, the theoretical removal efficiency of the coalescer, based on step 1:

Interception, can be written as shown in eq. 5.2.7.
d ,theo
C
= 1
Co
H
3
(1 ) ( theo )
dp
100 % {5.2.7}
100 % = 1 e 2
5.2.1.2 Step 2: Adhesion and coalescence
After being intercepted from step 1, the oil droplets will be separated from the wastewater
stream if they can adhere to the surface of the collectors. After that, in good coalescers, the
adhering oil drops will coalesce to each other and flow separately from the water stream, as oil
stream within the bed. Phenomena taking place in this step is shown in fig. 5.2.1-4. So the
mechanism in this step depends mainly on the wettability of the bed. AURELLE had tested the
effect of wettability, using hydrophilic and olephilic material as coalescer bed for secondary o/w
emulsion treatment. The result shows that:
For Oleophilic material: The oil droplets will adhere to the collector surfaces then
form the oil film around the collectors. The oil films will accumulate in the bed until it
reaches saturate level at certain height of the bed, called critical height (Hc). After
that the oil will start to flow as a separated oil stream, called channeling.
For Hydrophilic material: The oil droplets will be trapped in the void between
collectors. These trapped oil droplets will, then, be play the role of collectors by their
own to intercept the following oil droplets. Then they will coalesce into bigger drops
and flow through the void with the wastewater stream.
Even though both materials can cause coalescence, from test result, the oleophilic material
yields good efficiency up to higher range of flow velocity. It means that oleophilic bed coalescer
can be used at higher loading rates, thus makes it more compact in size. So it is recommended to
use oleophilic material as the bed for direct emulsion treatment.
5.2.1.3 Step 3: Salting out or enlargement of coalesced oil
The coalesced oil that flows through the bed in the manner of channeling will finally
reach the topmost of the bed. Then it will leave the bed for the water surface. In good coalescer,
the coalesced oil will leave the bed in the form of big oil drops (diameter 2-3 mm or more).
Characteristic or size of the oil drops that leave the bed depends on the phenomenon, taking place
at the top surface of the bed. AURELLE has studied this phenomenon, comparing between
oleophilic material and hydrophilic material. The result shows that:
201
III-84
a) Oil drops adhere to collectors
b) Several oil drops coalesce to form oil film or

stream, separating from water stream
Oleophilic bed
a) Oil drops are intercepted or lodge between

interceptor. Note that contact angles > 90o.
b) Intercepted oil drops coalesce to form bigger

drops in the void between collectors
Hydrophilic bed
Fig. 5.2.1-5 Phenomena in step 2: Adhesion-Coalescence
For Oleophilic material: The coalesced oil will flow along its preferable channels
out of the bed, called drip points. At the drip point, the oil will adhere and cover the
top surface of the material as a film. To flow out of the bed, the water has to flow
inevitably through the covering oil film, then forms the oil mousse, as shown in fig.
5.2.1-5. The separated oil will contain high content of water. The water flow will also
cause re-fragmentation of the oil into small oil droplets again when the mousses
rapture, esp. in case that the interfacial tension is low. Thus, the efficiency is
decreased.
202
III-85
Chapter 5 Coalescer
a) Oil mousse forming. Note that contact

angle < 90o.
b) Re-fragmentation of oil when the

mousse raptures
Oleophilic salting out surface
c) Formation of big oil drops. Note that contact

angle > 90o.
d) Oil jet and re-fragmentation of oil at high

velocity or high oil concentration
Hydrophilic salting out surface

Fig. 5.2.1-6 Phenomenon in step 3: Salting out or enlargemant of coalesced oil
For Hydrophilic material: The drip points will appear as well. But the oil will not
form the film over the collector surface. But the film will locate between the collectors
and will grow to big oil drops and, then, be snapped off as big oil drops, without
forming oil mousse. However, at high flow velocity or high concentration of oil,
hydraulic force from water flowing out of the bed will be high. The oil will be
snapped off as a jet of oil and then, from the high hydraulic force, will be refragmented to small droplets.
203
III-86
From the result described above, it shows that efficiency of this step depends on 4
parameters, i.e., wettability of discharge surface, flow velocity or empty bed velocity, interfacial
tension, and concentration or ratio of oil to water. To optimize the efficiency of this step,
AURELLE suggestd the following methods:
Design the coalescer at the proper velocity to avoid the re-fragmentation effect.
Use hydrophilic material as the top layer of the bed or use top grill of hydrophilic
material, to avoid mousse formation. At the same removal efficiency, it is proven that
the bed with hydrophilic material on the top layer can be operated at higher velocity
than that with the oleophilic top layer.
5.2.1.4 Comparison between observed efficiency and theoretical efficiency
The 3 steps mechanisms, proposed by AURELLE, can effectively describe the

phenomena taking place within the coalescer bed. However, to apply it for efficiency prediction,
we have to use many assumptions to simplify them. The most important assumption is that the
efficiency mechanisms in steps 2 and 3 are optimized, so their efficiency is 100%. It means all of
oil that has been intercepted and adhered to collectors in step 1 can be separated. So the removal
efficiency of coalescer can be calculated by eq. 5.2.4 and 5.2.7.
AURELLE had studies the relation between observed efficiency (.exp) and the
theoretical efficiency and found that the observed values are quite different from the calculated
value in complex fashion, as shown in fig. 5.2.1-6. Relation between observed efficiency and
theoretical efficiency, suggested by AURELLE, is shown in eq. 5.2.8a. So the theoretical
efficiency in eq.5.2.7 can be modified by replacing theo with .exp. The efficiency of granular
bed coalescer, then, can be calculated by eq.5.2.8b.
exp = 0.5484(theo ) 0.5143
C
d = 1
Co
{5.2.8a}
H
3
(1 ) ( exp )
dp
2
100 %
100 % = 1 e
{5.2.8b}
AURELLEs model is developed under these following assumptions and conditions:
The key assumption of this model is that mechanisms in step 2 and step 3 of the
coalescer are optimized.
The shape of the collector is relatively spherical. The size of the collector tested (dp)
is between 0.2 1 mm.
The collector shall be wetted by dispersed phase. In case of direct (oil in water)
emulsion, the collector, then, shall be oleophilic. For inverse emulsion, oleophilic
resin is recommended.
Range of empty bed velocity (V) shall be not greater than 0.35 cm/s (12.6 m/h)
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Chapter 5 Coalescer
Density difference between dispersed phase and continuous phase () is

approximately 200 kg/m3.
The model is developed for inlet oil concentration between 100-200 mg/l.
At velocity < 0.35 cm/s, the efficiency of the coalescer is independent of velocity.
Beyond this range, The efficiency will decrease when the velocity increases. The rate
of efficiency decreasing varies with size, wettability and surface roughness of
collector.
If the result from eq. 5.2.8b is greater than 100%, then it will be rounded up to 100%.
Experimental efficiency factor
1.00E+00
1.00E-01
1.00E-02
1.00E-03
1.00E-04
1.00E+00
1.00E-01
1.00E-02
1.00E-03
1.00E-04
Theoretical efficiency factor
Fig. 5.2.1-7 Relation between experimental (or observed) efficiency factor and
theoretical efficiency factor
5.2.1.5 Empirical model of granular bed coalescer
From fig. 5.2.1-6 and eq. 5.2.8, the relation is not in linear fashion, then it can be
interpreted that some assumptions in theoretical model are violated or not exactly true. Many
researchers had tried to fine-tune the assumptions. HAPPEL [44] had changed the flowrate
corresponding to single collector (eq. 5.2.5b) by replacing the value dp with an imaginary
diameter called b to account for the void area between collectors. The value of b is calculated
from the cross sectional area of bed (Ao) and the number of collectors by eq. 5.2.9.
N =
b 2 = Ao
{5.2.9a}
Ao (1 )
{5.2.9b}
d 2p
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DAMAK [9] used HAPPELs theory to adapt AURELLEs theoretical efficiency

equation, however, the accuracy is not improved. So it seems that the mechanism taking place in
the coalescer bed is so complex that it cannot be simplified to develop an accurate theoretical
model. Thus, when the exact theoretical based model can not be found. DAMAK proposed an
empirical equation for coalescer efficiency prediction, based on the dimensional analysis, as
shown in eq. 5.2.10. Typical characteristic curve between efficiency and droplet size is shown in
fig.5.2.1-7.
dpV 0.08 d 0.09 0.09

d
H
)
( ) ( ) 100%
d = 0.58( ) 0.2 ( ) 0.12 ( c
o/w
c
c
dp
dp
{5.2.10}
The model is developed under these conditions i.e.;
The model is tested at the range of dp from 0.36 to 0.94 mm. and interfacial tension
(ow) of 11 to 42 dyne/cm. (T.I.O.A, Heptane, Anisole, Toluene and Kerosene)
The velocity (V) tested is in the range of 0.09 to 0.54 cm/s.
The density difference between dispersed phase (oil) and continuous phase (water)
() is between 83 to 314 kg/m3.
The bed used is spherical glass bead with silicon coated to achieve oleophilicity.
The inlet concentration of hydrocarbon tested is around 1,000 mg/l.
If the result from eq. 5.2.10 is greater than 100%, it will be rounded up to 100%.
Verification result, using AURELLEs experimental data, confirms that DAMAKs model
can predict the removal efficiency with only 10% error. It implies that the model is also valid at
the operating condition tested by AURELLE. From these test conditions, it seems that this
empirical model covers the range of the oily wastewater commonly found in real situation. Thus,
it is recommended to use this model (eq.5.2.10) for granular bed coalescer calculation.
Main parameters that affect the efficiency of the granular bed coalescer include:
1.
Bed height (H)
Typical relation between the bed height and the removal efficiency is as shown in
fig. 5.2.1-7. From the graph, the efficiency of coalescer will increase with increasing height, then
it will stay relatively constant. This height is called critical height (Hc). The occurrence of
critical height can be described by phenomena in step 2 : adhesion- coalescence, as described
before in section 5.2.1.2. If the bed height is shorter than the critical height, it can be said that
there is not enough accumulated oil film to trap the oil droplets and provide continuous coalesced
oil stream to form perfect channeling. Hc depends on wettability, roughness and size of media.
From eq. 5.2.10, it shows that the efficiency is proportional to H0.12
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Chapter 5 Coalescer
Efficiency ()
Efficiency ()
100%
Increase V, dp
More hydrophilic
Less roughness
Lower limit of
the model:
10 microns
Droplet size (d)
Hc
Bed height (H)
Fig. 5.2.1-8 Typical relation between efficiency of granular bed coalescer and various
parameters
2.
Size of collector or media particle (dp)
The effect of the size of media is shown in fig. 5.2.1-7. Under the same operating
condition, the smaller the collector size, the better the efficiency. From eq. 5.2.10, it shows that
the efficiency is proportional to dp-0.4
3.
Flow velocity or empty bed velocity (V)
The effect of velocity is relatively small, compared to other parameter. From eq.
5.2.10, it shows that the efficiency is proportional to V-0.08. However, this is true only within the
valid range of the model. At higher velocity, mousse or jet formation will occur, thus the
efficiency will drop rapidly and no longer conform to eq. 5.2.10. The velocity that the mousse or
jet starts appearing is called critical velocity. It is recommended to use velocity not more than
0.54 cm/s to avoid mousse and jet formation.
4.
Wettability of bed material
The effect of wettabiblity of media is shown in fig. 5.2.1-7. It is recommended to

use oleophilic material as the coalescer bed with the thin top layer of hydrophilic material as drip
point surface.
5.
Ratio of oil to water
Even though this parameter is not included in eq. 5.2.10, but it is an important
parameter that limit the working range of coalescer. In fact, the model in eq. 5.2.10 is valid for oil
concentration not greater than 1,000 mg/l. Higher oil concentration will result in mousse or jet
forming, which will greatly lower the efficiency of the coalescer. To expand the working range of
granular bed coalescer, it is necessary to modify basic granular bed coalescer by additional
installation of oil guide, which will be described in the following section.
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6.
Interfacial tension and presence of surfactants
Surfactant will lower the interfacial tension, then make the oil droplets more
stabilized. This leads to poor adhesion between droplets and surface, ineffective collision
(collision without coalescence), and re-fragmentation of oil drops. So the presence of surfactant
directly limits the efficiency of step 2 adhesion-coalescence. To optimize the efficiency of step
2, it is recommended to destabilize (or breaking or cracking) the emulsion before sending to the
coalescer.
7.
Temperature
Properties of oil and water, such as viscosity, change with temperature. So

temperature is inevitable an important parameter that affects coalescer efficiency. Then it is
important to design the process by taking the possible range of temperature into account.
Normally, the efficiency will, more or less, increase with the temperature. The equations in this
section are developed under the temperature range between 15 to 25oC, which is the general
practical operating range.
8.
Surface roughness of bed material
Surface roughness affects adhesion of oil on the surface of the solid, as shown in
chapter 2. The roughness makes the wettablity of the surface more eminent. So oleophilic
material will show more oleophilicity if its surface is rough. Contact angle of oil on the material
surface will be lower. In this case, it helps promoting direct emulsion separation.
5.2.1.7 Pressure drop
Pressure drop across coalescer bed (p), in metre, can be calculated by Kozeny-Carmans
equation (eq. 5.2.11) (use SI unit, e.g. m, kg, second).
p=
180 H cV (1 ) 2
g dp 2 3
{5.2.11}
All variables except porosity () will be determined by designer. For the porosity of
coalescer bed, from many researches [3], [26], [27], it shows that bed porosity varies with bed
depth and can be divided into 2 zones, i.e.,
Lower zone or critical zone: This zone represents an effective zone of coalescer bed.
The maximum height of this zone is called critical height (Hc). When bed height is
greater than the critical height, the efficiency will increase only slowly (from eq.
5.2.10: H 0.12). In this zone, the bed will be soaked with oil so the effective
porosity will be low.
Upper zone: If the bed is higher than Hc, practically, all of oil will be trapped in
critical zone. Then in the higher zone, there will be enough oil in lower zone to flow
continuously through the bed in form of channeling. So the effective porosity in this
zone will be lower than critical zone.
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Chapter 5 Coalescer
From data of various researches [3], [26], [27], it can be concluded that the pressure drop
of granular bed can be calculated by Kozeny-Carmans equation, using the following
recommendations, i.e.,
5.2.2
When Hc is known (from literatures, etc.), pressure drop lower and upper part of bed
can be calculated separately, using eq. 5.2.11 and corresponding H of each zone. For
example, if Hc is 0.1 m. and total bed height is 0.15 m, H for lower zone will be equal
to Hc because Hc is lower the total height. And H for the upper zone will be 0.15 - 0.1
= 0.05 m.
Recommended porosity for the lower (critical) part of bed (H<Hc) is between 0.14 to
0.19.
Recommended porosity for the upper part of bed (H>Hc) is between 0.23 to 0.30.
If it is certain that H design < Hc, use single step calculation with = 0.14 - 0.19.
However, Hc is usually unknown, then it is recommended to use the single step
calculation with = 0.13 and 0.23 to estimate minimum and maximum pressure drop,
respectively.
The value of described above can be used for the range of dp from 0.20 to 1.0 mm.
Design calculation
Design procedure for granular bed coalescer is based upon the equations, shown in the
previous section. To design the coalescer, the required cut size will be determined first. After that,
the size of the coalescer can be calculated. Then, graded efficiency (efficiency of each size of
droplet) and, hence, the total removal efficiency can be determined. Calculation procedure for
each step is described below.
1.
from the limitation of the coalescing processes. The cut size determination from degree of
treatment is described in chapter 3. For the limitations of the process, it is mainly model
limitation. Since the model used for calculation is based on empirical data, it can be applied only
within its valid range. Extrapolation of model may cause unpredictable errors. The limitation of
model will be described in section 5.2.3. It should be noted that the cut size must be greater than
10 microns since it is the lower limit of the model. For smaller droplets, the efficiency will be
very low and unpredictable.
2.
Coalescer sizing
The size of the granular bed coalescer can be determined, based on the equation in
section 5.2.1. The main equation for coalescer designed will be based on the empirical model, as
shown is eq. 5.2.10. Design cut size will be used to calculate the dimension of the coalescer by
assuming that the graded efficiency at the cut size is 100%.
dpV 0.08 d 0.09 0.09

d
H
d = 0.58( ) 0.2 ( ) 0.12 ( c
)
( ) ( ) 100%
dp
dp
ow
c
c
209
{5.2.10}
III-92
Dimension of the coalescer can be arbitrarily selected under the limitations of the
model, as shown in section. 5.2.3, to make eq. 5.2.10 consistent. However, it is recommended to
select the lowest possible media diameter and highest velocity for the first trial because it will
give the most compact diameter of the coalescer. If the result is acceptable, it can be fine-adjusted
to get the most suitable dimension. If the result is unacceptable, normally too big, it may be
necessary to increase the number of units.
Bed height (m)
Fig. 5.2.2-1 shows the result of calculation from eq. 5.2.10 at various cut sizes. The
calculation is based on kerosene-water emulsion, which may be used as a guideline for coalescer
size estimation. The collector diameter, used in the graph, is 0.35 mm.
1.4
1.3
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
V = 1.94 m/h
V = 3.2 4m/h
V = 11.3 m/h
10
20
30
40
50
60
Cut size (micron)
Fig 5.2.2-1 Relation between cut size and coalescer dimension

3.
Removal efficiency
To determine the removal efficiency, the graded efficiency (d) will be calculated
first by eq. 5.2.10. If the result from eq. 5.2.10 is greater than 100%, then it will be rounded up to
100%.
It must be noted that the graded efficiency from the equation is not yet accounted for
effect of flow splitting between water outlet flow and separated oil outlet flow. To calculate
graded outlet oil concentration, the effect must be taken into account, as shown in eq. 5.2.12a.
Cd =
Q
(1 d ) C od
Q out
{5.2.12a}
Qout is outlet flow at treated water outlet port of the process. Qout is calculated from
difference between inlet flow and separated oil (in relatively pure condition) as shown below.
d max
Q out = Q
Q ( d C od )
{5.2.12b}
d min
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Chapter 5 Coalescer

d max
t =
C od
d min
Co
)
{5.2.12c}
100 %

4.
Pressure drop
Pressure drop (in metre) can be calculated from Kozeny-Carmans equation (eq.
5.2.11). Recommended value of bed porosity () and other criteria are as shown in section
5.2.1.7. For diluted wastewater, the values of and can be replaced by those of water (c, c).
p =
5.2.3
180 HV (1 ) 2
m
g dp 2 3
{5.2.11}
1.
The equations described above are developed from the following assumptions and
limitations. Thus, it is necessary to make sure that these assumptions are valid when design your
coalescer.
1)
Coalescer bed shall be oleophilic and relatively spherical in shape.
2)
Tested size of bed media (dp) is between 0.20 1.0 mm. The larger the media
size, the lower the efficiency.
3)
Tested range of bed height (H) of the model is between 1 to 10 cm. However,
bed height as low as 1 cm is not recommended. The greater the bed height, the
safer the coalescer operation. However, it also results in higher pressure drop.
4)
The velocity (V) should be in the range of 0.09 to 0.54 cm/s or 3.2 to 19.4 m/h.
5)
Tested interfacial tension (ow) is between 11 to 42 dyne/cm or 0.011 to 0.042

N/m. (such as, T.I.O.A, Heptane, Anisole, Toluene and Kerosene)
6)
Different density between dispersed phase (oil) and continuous phase (water)
() is between 80 to 315 kg/m3 (approx.).
7)
The equation is valid for droplet size (d) of 10 microns or bigger. For smaller
droplets, result from eq. 5.2.10 may not be accurate because it is beyond the
data that has been used to verify the model.
8)
The model is valid for inlet concentration between 100 to 1,000 mg/l. At
higher concentration, mousse or jet formation may occur, resulting in
unpredictable decreasing of the efficiency.
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2.
Construction and material selection
Granular bed coalescer consists of 2 major components, i.e., casing and bed.
1)
The casing
The casing is the component that contains the bed and other important
appurtenances, such as wastewater inlet, wastewater outlet, oil outlet, clean out, etc. Researches
in GPI lab normally emphasize on working mechanisms and developing of a model so there is no
direct study on characteristic of the casing. However, because of the fact that the coalescer is
usually designed as a pressure vessel in the same manner as a pressure filter, then, casing or tank
construction criteria of the pressure filter can be readily applied to the coalescer. However, some
details, such as oil outlet pipe, water outlet pipe and internal baffle should be adapted to ensure
good separation between oil and water. As outlined in chapter 4 Decanting, the internal baffle
should be installed in the manner that it can promote oil drop decanting, prevent short circuit of
oil drops to the water outlet pipe. The pipe and baffle arrangement shown in fig. 5.1-1 can be
used as a guideline for casing design.
2)
The bed
From many GPI researches, it is recommended that resin is the most suitable
material for coalescer bed, because:
It is widely used in many industries, and available in every country.

It is produced in wide range of size and normally spherical.
It can be coated to achieve required wettability.
Its cost is competitive.
Its physical properties, such as hardness, etc., are also good.
Other materials that have been used as coalescer bed include glass beads, small
stainless steel balls. Material that is heavier than water, such as stainless steel, has an advantage
for it can be used without installation of top grille to prevent it from carry-over. So it can be
cleaned by backwash process or scouring process because the material is not retained by top
grille, then can be expanded or floated freely.
For wettability, oleophilic bed with thin layer of hydrophilic material on the
top or with hydrophilic top grille is recommended (see section 5.2.1.2). Guideline on
oleophilicity of materials is described in chapter 2. Some hydrophilic material that has good
mechanical properties can acquire oleophilic property by coating with proper substance, such as
silicone. Oleophilicity of bed may change with time from deterioration of the coating or reaction
with wastewater. It may need re-coating or replacement if decreasing in efficiency is
unacceptable.
5.2.4
Variations, advantage and disadvantage of granular bed coalescer
Variations of granular bed coalescer: There are several modifications of granular bed
colaescers, normally, on bed materials, such ad resin bed coalescer, glass bead bed coalescer.
There are 3 major modified granular bed coalescer studied at GPI lab, i.e., mixed bed coalescer,
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Chapter 5 Coalescer
down-flow coalescer and guide coalescer. The latter will be fully described in the next section.
Mixed bed coalescer is another modified form of granular bed coalescer, used for mixed
direct/inverse emulsion separation, which is usually found in liquid-liquid extraction process. In
mixed bed coalescer, the bed will consist of separate layers of oleophilic and hydrophilic
materials, placed in series in the same column. From research [6], ratio of oleophilic and
hydrophilic material and order or configuration of column (upper hydrophilic layer/lower
oleophilic layer or vice versa) depends on wastewater characteristic. So it is difficult to
determine the efficiency of the coalescer by fixed equation. In this case, it is recommenced to
perform pilot test to find optimum design criteria.
Furthermore, there are also variations of coalescers, based on flow patterns i.e., up-flow
coalescer and down-flow coalescer. The researchs conducted in GPI lab are generally based on
up-flow coalescer. For down-flow coalescer, the flow pattern in this case will be identical to that
of deep-bed filter. This type of coalescer is intentionally designed to use with the oily wastewater
that contains suspended solids. The wastewater will be fed from the top of the bed. The oil will be
coalesced in the same manner as the up-flow coalescer. However, the coalesced oil will flow up
against the wastewater stream to the inlet water surface, then be skimmed out of the reactor. This
flow patterns can eliminate the top grille that is used for preventing carry-over of bed media in
up-flow coalescer. This allows us to clean the bed by air scouring, back washing or any proper
mechanism, such as pneumatic pulsation that can make the bed move up or partially fluidize to
unclog the trapped solids. Working principles of this coalescer is generally identical to that of upflow coalescer. However, there is not enough research data to develop the math model. So it is
recommended to use the equation of up-flow coalescer for roughly estimation of efficiency.
Anyway, the exact efficiency would be obtained from pilot scale testing.
Advantage: Granular bed coalescer has a major advantage in its compactness. Tested
loading rate of coalescer is 3.2 19.4 m/h and it can be used with the droplet size from 10
microns while, for simple decanter, the loading rate is about 0.04 m/h for 10-micron droplet
separation.
Disadvantage: The bed of this type of coalescer has relatively low porosity (0.14-0.19).
So, at high loading rate, the pressure drop may be very high. Moreover, it can make the bed clog
relatively easily. So the granular bed coalescer is sensitive to the presence of suspended solids.
5.3
Guide coalescer
5.3.1
Working principles
Guide coalescer is the modified form of simple granular bed coalescer. In guide coalescer,
high-porosity oleophilic material, such as woven metal fiber or woven mesh, will be placed next
to downstream end of the granular and extended up to water surface. Coalesced oil drop will be
guided along this material until it combines with oil layer at the water surface. So, this material is
called guide. Structure of the guide shall be self-sustained or installed in perforated structure,
so the treated water can flow freely out of the guide structure, then be discharged from the
coalescer. The pictures of guide coalescer are shown in fig. 5.3.1-1.
213
III-96
Working principles of guide coalescer is relatively identical to those of basic granular bed
coalescer. However, iinstallation of guide helps preventing formation of oil mousse or jet, which
normally occurs in classical coalescer at high velocity or high concentration of oil because it
virtually eliminates the drip point (step 3 of the 3 mechanisms, see section 5.2.1). Thus, the
maximum velocity before formation of mousse or jet will occur (so called critical velocity) of the
guide coalescer is 1.5 times greater than usual [6]. Furthermore, it can be operated at ratio of oil
to water (Phase ratio) as high as 6 [6].
a) Graphic image of guide coalescer
b) Steel wool or steel mesh that can be used as a guide
Fig. 5.3.1-1 Guide coalescer
From literature review, there is no proposed model for guide coalcescer. However, it is
proven that, at velocity range below critical value, the efficiency is approximately velocityindependent [3], [6]. It, also, can be confirmed by eq. 5.2.10, which shows that the exponent of V
is very low (0.08). Then, at recommended range of velocity, V-0.08 is approximately constant.
So, from this fact, the efficiency of guide coalescer could be calculated by the model of
basic granular bed coalescer (eq. 5.2.10) with additional precautions or assumptions as follows,
When V < 0.54 cm/s: Use eq. 5.2.10 directly.
When 0.54 < V < 0.8 cm/s (1.5 times of 0.54): Use eq. 5.2.10 by using V = 0.54 cm/s
for calculation. Using the real velocity instead of 0.54 cm/s will result in higher
efficiency. However, because of lacking of support data, it is recommended using low
prediction value for safety.
Velocity 0.8 to 1.9 cm/s may still be applicable at low concentration of inlet oil (phase
ratio around 1-2).
For inlet oil concentration, guide coalescer is tested in liquid-liquid extraction

application [6] with maximum phase ratio (oil/water) of 6, the result shows that it can
operate effectively. So, for oily wastewater treatment process, which the concentration
is much lower, installation of guide can assure that the coalescer should be operate
214
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Chapter 5 Coalescer
efficiently. To apply to higher concentration or beyond the limit stated above, bench
scale or pilot scale testing is highly recommended
This type of coalescer have been developed for 2 purposes, 1) to increase the hydraulic
loading rate of the granular bed coalescer, 2) to make it possible to use the granular bed with the
water containing very high concentration of oil, such as in liquid-liquid extraction process.
5.3.2
Design calculation
Steps of calculation, as well as cut size determination, for the guide coalescer is identical
to those of basic granular bed coalescer. However, there are some difference in details of sizing
and pressure drop calculation as described below.
1.
Coalescer sizing
The size of guide coalescer can be calculated by eq. 5.2.10. For velocity less than
0.54 m/s, actual velocity will be used in the equations. However, if design velocity is greater than
0.54, the velocity of 0.54 m/s will be used, regardless of the actual velocity. The size from the
calculation can be, theoretically, used at velocity from 0.54 to 0.8 cm/s.
2.
Removal efficiency
The removal efficiency can be calculated from the selected dimension, using eq.
5.2.10 and 5.2.12.
3.
Pressure drop
Because of the fact that the guide in guided coalescer has relative high porosity
(0.9 approx.), then, The pressure drop is very low, compared to the granular part, and can be
negligible. So Kozeny-Carmans equation (eq. 5.2.11) and recommended value of porosity from
section 5.2.2 can also be used to predict pressure drop of guided coalescer.
5.3.3
1.
The limitations in this case are identical to those of granular bed coalescer (see
section 5.2.3) except for the velocity and oil concentration, which will conform to section 5.3.1.
2.
Material selection
For direct emulsion treatment, granular bed in guide coalescer shall be oleophilic
material. However, instead of top layer or grill of hydrophilic media, guide will be placed on the
top of the granular bed. The guide should be made of metal or rigid material and properly coated
to obtain oleophilic property. It should have high porosity and self-sustained structure because it
is not supported by the wall of the coalescer. If the selected guide is not self-sustained, perforated
oleophilic material shall be provided to support the guide. Commercial woven wire-meshes or
metal wool, such as MuitiKnit, Knit meshTM, 3MTM, etc., can be efficiently used as a guide.
215
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5.4
Fibrous Bed coalescer
5.4.1
Working principles
This type of coalescer uses high porous fibrous material, such as fibrous bottle brush, as a
bed to promote coalescing between oil droplets. Due to its high porosity, this type of bed is
hardly clogged and can handle wastewater containing suspended solids efficiently. It also causes
much less pressure drop than granular bed coalescer. However, fibrous element, which is
normally very small, may deflect at its tip, especially in large-scale unit, and causes unpredictable
channeling of untreated wastwater, then decreasing in efficiency.
From other point of view, this coalescer can be considered as a modified form of guide
coalescer that granular bed is removed and the guide is additionally used to intercept oil, besides
its role to provide coalesced oil flow channel.
Three basic steps for granular bed coalescer, proposed by AURELLE [3], can also be
used to describe phenomena taking place within the coalescer. However, mathematics models,
derived from dimensional analysis, are proven to be more accurate.
There are 2 main categories of fibrous bed coalescers, i.e., Simple fibrous bed coalescer
and dynamic (or rotating) fibrous bed coalescer, as shown in fig. 5.4.1-1. The latter is the
modified form of the former, by installation of driving unit to drive the bed.
5.4.1.1 Simple fibrous bed coalescer model
This type of coalesceruses uses fibrous material, normally, in the form of bottle brush
as a coalescer bed. The brush has relatively high porosity, compared to granular material. So this
coalescer causes much lower pressure drop and is hardly clogged. Furthermore, from the threestep phenomena of coalescer, described in section 5.2.1, it shows that the efficiency of coalescer
will increase if the size of the bed media is small. For fibrous bed coalescer, the size of fiber is
around 100- 200 microns, much smaller than granular medias. By this way, the efficiency can be
improved.
GPI lab has been studied the possibility to use this type of material as a bed for some
times. However, the researches on this type of coalescer are based mainly on its application and
design consideration, rather than model development. So there is no model proposed for this
coalescer. Anyway, these researches, especially the study of SRIJAROONRAT [10], provide
sufficient raw data to formulate an empirical model. This newly formulated model, which will be
called SRIJAROONRATs model, is as shown in eq. 5.4.1. The model has been verified, using
data from MAs and WANICHKULs researches, as shown in fig. 5.4.1-2.
VD
d
d
0 . 35 H
d = 104 . 5 ( c ) 0.77 ( ) 0.18 ( F ) 0.18 (1 ) ( ) 0.694
c
D
D
D
216
100 %
{5.4.1}
III-99
Chapter 5 Coalescer
a) Simple fibrous bed coalescer [11]
b) Graphical image of dynamic fibrous bed

coalescer
c) Examples of brush
d) Coalesced oil drops from dynamic fibrous bed

coalescer
Fig. 5.4.1-1 Fibrous bed coalescer (Source: GPI lab)
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III-100
Where
dF
d
D
H
V
C
c
=
=
=
=
=
=
=
=
Diameter of fiber
Diameter of dispersed phase, in our case, oil
Diameter of coalescer bed, such as diameter of brush
Height of bed, or bed depth
Empty bed velocity
Porosity or void ratio of the bed
Dynamic viscosity of continuous phase, in our case, water
Density of continuous phases
The model is developed and verified under these conditions i.e.;
48 < Re < 1100. Re is the term (cVD/c) in the equation.
1 < H/D < 10.
Diameter of coalescer bed (D) tested is around 5.0 cm. Using bigger coalescer
diameter may cause deflection at the tips of fibers because of longer overhung length,
which may cause channeling of untreated wastewater and error in efficiency
calculation.
The model is valid for droplet size (d) of 1 microns and greater.
Empty bed velocity (V) used in the researches [10], [11], [16] is between 0.5 to 5.0
cm/s (1.8 to 180 m/h). However available raw data used to verify the model is
between 0.5 to 2.0 cm/s. Using velocity > 2.0 cm/s may cause unpredictable error on
Fiber size (dF) used in the researches [10], [11], [16] is between 40 to 200 microns.
However available raw data used to verify the model is between 100 to 200 microns.
Using fiber size < 100 microns may cause unpredictable error on calculated
efficiency.
Void ratio of the bed () is around 0.845 to 0.96.
The model is verified at inlet oil concentration up to 1000 mg/l. Applying the model to
the concentration > 1000 mg/l will cause underestimation of predicted efficiency, as
shown in fig. 5.4.1-2 for WANICHKULs data (C = 7950 mg/l) [11].
The beds used in these researches vary from bottle brush type, simple spiral type
and combination of internal bed of simple spiral and concentric coil springlike
external bed with the tip of the fibers pointed to the centerline. However, they are all
oleophilic. There is some difference in efficiency between each type, but there is too
few data to make a conclusion. However, because of its rigidity, the simple spiral in
coil springlike bed tends to operate more stable without decreasing in efficiency
with time, while others tend to be deflected by weight of accumulated oil drops. In
fact, this type of bed is invented to take advantage of spiral bed for its non-clogging
and disorderly bed (section 5.4.1.3) for its rigidity and good interception efficiency.
218
III-101
Chapter 5 Coalescer
100.0%
90.0%
80.0%
70.0%
60.0%
+20 %
50.0%
40.0%
-20 %
30.0%
SRIJAROONRAT's data
MA's data
WANICHKUL's data
20.0%
10.0%
0.0%
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%
100.0%
Fig. 5.4.1-2 Comparison between observed efficiency and predicted efficiency from
SRIJAROONRAT's model, Verified by MA's and WANICHKUL's data.
5.4.1.2 Dynamic fibrous bed coalescer model
Dynamic brush coalescer is the modified form of simple fibrous brush coalescer by
installing the prime mover to drive the brush. From TAPANEEYANGKUL [8], rotating motion
of the brush provides 2 major benefits, i.e.,
It can increase the probability of interception or collision between fiber elements and
oil droplets. Thus, the efficiency will be improved. Furthermore, if the variable speed
driving system is installed, the efficiency of the coalescer will be adjustable.
Rotating motion also helps reducing possibility of clogging.
The equation for efficiency prediction of this coalescer is proposed by

TAPANEEYANGKUL [8]. It is based on classic dimensional analysis, which is the efficient tool
when exact theory of the processes can not be established. The equation will be as shown in eq.
5.4.2.
VD
d
d
H
D N 0.53
d = 1.76( c ) 0.21 ( ) 0.58 ( F ) 0.58 (1 )0.35 ( ) 0.35 (
) 100% {5.4.2a}
c
D
D
D
V
Or
0 . 67 d
d =
(1 ) 0.35 H 0.35 N 0.53

D 0.03 d F0.58V 0.74
0 . 58
219
100 %
{5.4.2b}
III-102
The equation is developed and verified under these conditions i.e.;
1 < H/D < 2. However, the maximum H/D shown in TAPANEEYANGKULs

research [8] is 6. Using H/D > 2 in the model can be also applied for comparison
purpose only.
Rotating speed of the bed (N) is between 0.167 to 3.33 rps (10 to 200 rpm). Please
note that N is in form of revolution per unit time, not radian per unit time).
Recommended minimum rotating speed is 75 rpm. Using lower speed may not
provide any additional benefit over simple fibrous bed coalescer because the effect of
rotating on interception probability may be cancelled out by the shear effect, which
causes fragmentation of oil drops.
Empty bed velocity (V) is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h) .
Diameter of fiber (dF) is around 100 to 300 microns
Diameter of coalescer bed (D) is not greater than 11.5 cm. Using bigger diameter may
cause deflection at the end of fibers from longer overhung lengths, which may cause
channeling of untreated wastewater and error in calculation.
It is recommended to use the model only for the droplet size (d) of 10 microns or
greater. For smaller droplet, the model can also be applied, but for comparison
purpose only.
The beds, used in the experiment, are bottle brush types, made of oleophilic
polyamide or polypropylene with stainless steel shaft, as shown in fig. 5.4.1-1c.
5.4.1.3 Random or disorderly fibrous bed coalescer
There is another special case of simple fibrous bed coalescer that uses random or
disorderly fibrous material (such as metal wool, etc.) as coalescer bed. SRIJAROONRATs
research shows that removal efficiency of this coalescer is higher than that of coalescer that uses
brush type bed. For this, it can be concluded that tortuosity of bed also affects the removal
efficiency. From SRIJAROONRATs raw data, an empirical model, based on dimensional
analysis, can be derived as shown in eq. 5.4.3. However, this model is developed from rather
small set of data. There is an effort to verify if the simple bed model (eq. 5.4.1b) is still valid for
random fibrous bed coalescer. Comparison between efficiency from eq. 5.4.1b, eq. 5.4.3 and
observed value is shown in fig. 5.4.1-3.
VD
d
d
H
d = 3 . 35 ( c ) 0.23 ( ) 0.03 ( F ) 0.. 03 ( ) 0.36 100 %
c
D
D
D
220
{5.4.3}
III-103
Chapter 5 Coalescer
110.00%
100.00%
Predicted Efficiency (%)
90.00%
80.00%
70.00%
60.00%
+10%
50.00%
40.00%
30.00%
-10%
20.00%
10.00%
0.00%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Fig. 5.4.1-3
Relation between observed efficiency and predicted efficiency from

random fibrous bed coalescer model and simple fibrous bed model
From the graph, it shows that SRIJAROONRATs random fibrous bed model (eq. 5.4.3)
can accurately predict the efficiency of the coalescer while the result from the simple bed model
(eq. 5.4.1b) tends to underestimate the efficiency from 2 to 6 times. This confirms that tortuosity
of the bed plays very important role in efficiency of fibrous bed coalescer. However, tortousity
can not be effectively established in form of numerical value so it can not be included as a
parameter in mathematics model. Eq. 5.4.3, then, can be applied only when design condition is
close to the test condition from SRIJAROONRATs research.
Eq. 5.4.3 is developed and verified under these conditions i.e.;
The beds used in the experiment are highly disorderly bulk of stainless steel fiber, dF =
75 microns, and steel wool, dF = 40 microns (see fig. 5.4.1-4). However, only the
latter case, which raw experimental data is available, is used to develop the model.
The minimum size of oil droplet tested is 1 micron.
Tested Reynolds number is between 840 to 2470.
Porosity of the bed () is around 0.95.
Diameter of the coalescer (D)= 5 cm.
Height of the coalescer bed (H) is between 0.07 to 0.21 m.
Velocity (V) is between 1 to 2.5 cm/s or 36 to 90 m/h.
In case that the conditions stated above are not fully compliant, it is recommended to use
eq. 5.4.1b to calculate the efficiency of the coalescer because it is proven to be valid within wider
range. In this case, predicted result from eq. 5.4.1b tends to underestimate the efficiency of the
coalescer.
221
III-104
a) Highly disorderly stainless steel fibers
b) Steel Wool
c) Magnified picture of (a)
d) Magnified picture of (b)
Fig. 5.4.1-4 Random or disorderly fibrous bed, used in the research of SRIJAROONRAT
Even though each type of fibrous bed coalescer is governed by different equation, all of
the equations is in about the same mathematics form, as shown in eq. 5.4.4. Thus, main
parameters that affect the efficiency of the fibrous bed coalescer can be commonly summarized
as shown in fig. 5.4.1-5.
1 1 1
,
, d , H , N , (1 ))
V D dF
d = f ( ,
222
{5.4.4}
III-105
Chapter 5 Coalescer
Efficiency ()
Efficiency ()
100%
100%
Increase V, D, dF
Decrease H, (1-), N
Less tortousity
Lower limit of
the model:
1 micron
Droplet size (d)
Droplet size (d)
Fig 5.4.1-5 Typical relation between efficiency of fibrous bed coalescer and various
parameters
However, besides the parameters shown in eq. 5.4.4, there are some important parameters
that affect the efficiency of the coalescer, i.e.,
1.
Tortousity
If the bed is more tortuous, the probability to intercept oil droplets will be increased.
The efficiency, then, is increased, as clearly shown in the case of wool coalescer. However, it will
tend to be clogged if suspended solids are present in wastewater.
2.
Wettability of bed
From the 3 mechanisms of AURELLE [3] (section 5.4.1.1), wettability of the bed is
the key parameter that governs the step 2 adhesion-coalescence. In case of direct (oil in water)
emulsion treatment, he bed material shall be oleophilic to optimize the adhesion-coalescence
phenomena.
3.
Interfacial tension and presence of surfactants
Surfactant will lower the interfacial tension, then make the oil droplets more
stabilized. This leads to poor adhesion between droplets and surface, ineffective collision
(collision without coalescence), and re-fragmentation of oil drops. So presence of surfactant
directly limits the efficiency of step 2 adhesion-coalescence. To optimize the efficiency of step
2, it is recommended to destabilize, (breaking or cracking) the emulsion before sending to the
coalescer
4.
Temperature
Properties of oil and water, such as viscosity, change with temperature. So

temperature is inevitable an important parameter that affect coalescer efficiency. Then it is
important to design the process by taking the possible range of temperature into account.
Normally, the efficiency will, more or less, increase with the temperature. The equations in this
223
III-106
section are developed under the temperature range between 15 to 25oC, which is general practical
operating range.
5.
Size of bed shaft
Another precaution about the bed is the ratio of bed center shaft to diameter of bed.
Since the effective part of the bed is its fibers, efficiency of coalescer of the same diameter will
decrease it the shaft is relatively large. Equations in sections 15.4.1 already include the effect of
center shaft. The sizes of the shafts used in those researches are around 1.0 to 1.5 cm., or about 20
to 30% of diameter of the bed. If the selected shaft does not conform to this criterion, diameter of
shaft used in the equations will be adapted to the equivalent diameter that has the same effective
area of fiber as the real bed with the shaft size conforms to the criterion.
5.4.1.5 Pressure drop of fibrous bed coalescer
Many researcher [8], [10], [11], [16] observe pressure drop of fibrous bed coalescers and
report that these coalescer causes very low pressure drop due to very high porosity of their beds.
However, there is not any proposed model on pressure drop.
In order to calculate the pressure drop, it is recommended to use any general piping loss
equations, such as Darcys, Colebrook-Whites or Hazen-Williams equation with the safety
factor of 2 to 5, multiplied to the actual length of the bed. However, the pressure drop of fibrous
bed coalescer is normally low (< 104 N/m2), compared to piping system pressure drop.
5.4.1.6 Size of coalesced oil drop
Observed size of coalesced oil drop from fibrous bed coalescer with oleophilic bed is
reported [3], [10] to be between 0.3 mm to 8.4 mm with the average value between 1.8 to 6.8 mm
(table 5.4.1-1). The size of the oil drop depends on operating condition, esp. velocity, and
material properties, such as interfacial tension, fiber wettability. The size will decrease if the
velocity increases or interfacial tension decreases or the fiber is hydrophilic.
From STOKES law, rising velocity of the droplet of 1.8 mm diameter is around 0.33 m/s,
which is greater than maximum tested velocity in the fibrous bed coalescer (around 5 cm/s). So
the oil drop is positively separated. Furthermore, if oil and water discharge pipes of the coalescer
is properly arranged, even the smallest drop of 0.3 mm can still be separated. So, it can be safely
said that all of coalesced oil can be decanted by downstream end of the coalescer because it
requires less decanting area than the size of the coalescer itself. However, using moderate
velocity (around 2.0 cm/s) and sufficient height (H/D>2) will guarantee sufficient size of
coalesced oil drop for good decanting.
Anyway, it is interesting to consider granulometry of remaining oil droplets that are not
fully coalesced to form big oil drops. To help considering this, there are some researches on
coupling or combination of coalescer and hydrocyclone [10], [11]. Example of the result from
[10] is show in table 5.4.1-2. From the table, it shows that the observed total efficiency of the
coupling is higher than the product of the two separate processes. So it may be implied that the
size of the smallest droplets from coalescer is increased. Therefore, with these bigger oil droplets,
the efficiency of the hydrocyclone is increased. However, there is not enough data for further
224
III-107
Chapter 5 Coalescer
analysis. Furthermore, if this partial coalescing exists, its effect should be already included in the
efficiency prediction models (eq. 5.4.1 to 5.4.3). So, for calculation, it is safer to assume that
there is no partial coalescing. Prediction of coupling of processes would be calculated from the
product of the efficiency of each individual process.
Table 5.4.1-1 Coalesced kerosene droplet size at various velocities and bed heights from
oleophilic bottle brush coalescer (dF = 100 microns, D = 0.05 m, Co = 1 g/l,
120oC) [10]
Bed
height
Empty bed
velcity
min
max
weighted average
cm
cm/s
mm
mm
mm
1.8
1.4
3.3
2.8
0.6
2.2
4.25
0.4
3.3
5.3
0.3
3.3
1.8
1.8
2.8
1.4
3.5
4.25
0.8
2.3
5.3
0.6
1.8
1.8
7.2
8.4
2.8
6.4
7.6
6.8
4.25
7.2
6.5
5.3
0.6
6.4
2.7
14
21
Coalesced oil diameter
Table 5.4.1-2 Comparison between the individual efficiency of oleophilic bottle brush coalescer,
hydrocyclone, theoretical and observed efficiency of the coupling of
coalescer/hydrocyclone [10]
Initial
droplet
diameter
Empty
bed
velcity
Observed
efficiency of
hydrocyclone
(a)
Observed
efficiency of
coalescer
(b)
Theoretical
efficiency of
the coupling
1-(1-a)(1-b))
Observed efficiency
of the coupling
micron
m/s
11
0.02
35%
54.19%
70%
82%
11
0.03
50%
39.65%
70%
82%
11
0.04
61%
31.78%
73%
82%
11
0.05
69%
26.76%
77%
82%
225
III-108
5.4.2
Design calculation
Steps of calculation, as well as cut size determination, for fibrous bed coalescer is
identical to those of basic granular bed coalescer. However, there are some difference in details of
sizing and pressure drop calculation as described below.
1.
The ut size can be determined from the degree of treatment required as well as from
the limitation of the coalescing processes. Cut size determination from degree of treatment is
described in chapter 3. For the limitations of the process, it is mainly model limitation. Since the
model used for calculation is based on empirical data, it can be applied only within its valid
range. Extrapolation of model may cause unpredictable error. The limitation of each model is
described in section 5.4.1.
2.
Coalescer sizing
The size of various types of fibrous bed coalescer can be calculated by eq. 5.4.1 to
5.4.3. Design cut size will be used to calculate the dimension of the coalescer by assuming that
the graded efficiency at the cut size is 100%. Dimension of the coalescer can be arbitrarily
selected under the limitations of each equation, as described in section 5.4.1.1 to 5.4.1.3.
However, it is recommended to select the possible lowest fiber diameter and highest velocity for
the first trial because it will give the most compact diameter of the coalescer. If the result is
acceptable, we may try to fine-adjust the parameters to get the most suitable dimension. If the
result is unacceptable, normally too big, we may have to increase the number of units.
3.
Removal efficiency
After the dimension of the coalescer is determined, graded efficiency (d) can be
calculated by eq. 5.4.1, 5.4.2 or 5.4.3. If the result from eq. 5.2.10 is greater than 100%, then it
will be rounded up to 100%.
It must be noted that the graded efficiency from the equation is not yet accounted for
effect of flow splitting between water outlet flow and separated oil outlet flow. To calculate
graded outlet oil concentration, the effect must be taken into account, as shown in eq. 5.2.12a.
Cd =
Q
(1 d ) C od
Q out
{5.2.12a}
Qout is outlet flow at treated water outlet port of the process. Qout is calculated from
difference between inlet flow and separated oil (in relatively pure condition) as shown below.
d max
Q out = Q
Q ( d C od )
{5.2.12b}
d min
226
III-109
Chapter 5 Coalescer

d max
t =
C od
)
{5.2.12c}
100 %
d min
Co

4.
Pressure drop
As stated in section 5.4.1.5, in order to calculate the pressure drop, it is

recommended to use any general piping loss equations, such as Darcys, Colebrook-Whites or
Hazen-Williams equation (eq. 5.4.5) with the safety factor of 2 to 5, multiplied to the actual
height (H) of the bed. CHW is Hazen williams constant, depending on surface roughness of
coalescer. Recommended value is 110-130 for steel column.
V
P = 6.82
CHW
5.4.3
1.85
1.167
5H
{5.4.5}
1.
The equations described above are developed from the following assumptions and
limitations. Thus, it is necessary to make sure that these assumptions are valid when design the
coalescer. Limitation of each design equation (eq. 5.4.4 to 5.4.3) is described in section 5.4.1.
2.
Construction and material selection
Fibrous bed coalescer consists of 2 major components, i.e., casing and bed.
1)
The casing
The casing is the component that contains the bed and other important
appurtenances, such as wastewater inlet, wastewater outlet, decanting section, oil outlet, clean
out, etc. Researches in GPI lab normally emphasize on working mechanisms and developing of a
model so there is no direct study on characteristic of the casing. However, the size of the fibrous
bed coalescer is usually small to avoid deflection at the tip of fibers, it is, then, designed as inline
unit or in the form of pipe (see fig. 5.4.1-1 and 5.4.3-1). Batteries or multi-coalescer unit is also
available. Downstream decanter may be integrated or placed separately from the coalescer as
shown in fig. 5.4.3-1. As described in section 5.4.1, diameter of the decanter is normally equal to
that of coalescer or a bit bigger to facilitate placement and construction of internal baffle, water
and oil outlet pipe.Casing of coalescer can be made of any material (plastic, steel, glass, etc.) that
can withstand the operating condition. If possible, it should be oleophilic.
227
III-110
a) Lab scale coalescer with integrated

decanter (The bed is placed in the steel
column just below the decanter)
b) Inline-style fibrous bed coalescer [11]
c) Assembly of the coalsecer and separated

decanter (Source: Elf, GPI lab)
Fig. 5.4.3-1 Examples of fibrous bed coalescer casing

2)
The bed
The bed is the most important part in the coalescer. From section 5.4.1, there
are 2 major types of fibrous beds, i.e., simple or brush type and random or disorderly type.
Difference in operating efficiency between the two is already discussed. However, one property,
which both beds have in common, is that, for direct emulsion treatment, the bed shall be
oleophilic.
Material of the bed varies from steel, stainless steel and variety of plastic, scuh
as polyamide, polypropylene as shown in fig. 5.4.1-1, 5.4.1-4 and 5.4.3-2. For simple brush type,
the efficiency of the coalescer varies only slightly for various types of bed shown in the figure.
The factor that governs the efficiency for this type of bed is its oleophilicity. Guideline on
wettability of material is described in chapter 2. To preliminary test olephilic property of the bed,
it can be done easily by dip or have the bed contact with oil or water. If the drop of oil or water is
almost sphere, it can be approximately concluded that the material is hydrophilic or oleophilic
respectively (see fig. 5.4.3-3)
228
III-111
Chapter 5 Coalescer
Fig. 5.4.3-2 Various types of bed tested by WANICHKUL [11]: From left, a) Simple spiral, b)
Double spiral, c) Solid plastic spiral, d) A module of multi-stage bed [No. of stage
can be added by increase the number of module into the same center shaft
a) water drop on b) water drop on non- c) oil drop on silicon

silicon coated fibers
coated fibers
coated fibers
d) oil drop on noncoated fibers
Fig. 5.4.3-3 Characteristics of oil and water drops on silicon coated (oleophilic) steel fibers and
non-coated (hydrophilic) steel fibers
5.4.4
Variations, advantage and disadvantage of fibrous bed coalescer
Variations of fibrous bed coalescer: There are several modifications of fibrous bed
colaescers, normally, on bed type and materials, such as simple fibrous bed, steel wool bed,
rotating or dynamic bed, as described in section 5.4.1. Each type of bed can be sub-divided into
sub-types, characterized by specific features of beds. The efficiencies of these brush beds are
almost identical, as discussed before. However, there are some variations of these coalescers
worth to mention here for their initiative idea.
Double spiral bed (fig. 5.4.3-2b) is one of the innovations of GPI lab [10], [11]. It is
designed to mitigate the fiber tips deflection effect. The bed provides homogeneous void ratio at
any radial distance. External coil spring-like part will help intercepting oil droplets without the
problem about defection since the fibers just protrude a short distance from their coil spring-like
support. This type of bed can also reduce undesirable channeling, taking place at high velocity at
the tips of simple fiber bed. Anyway, it tends to clog easier if suspended solids are presence.
229
III-112
Multi-stage simple brush coalescer is another initiative idea to improve the efficiency of
simple fibrous bed coalescer [11]. Eq. 5.4.1 to 5.4.3 show that efficiency varies with Ha, when 0<
a <1. If a coalescer of bed height H and efficiency of one stage 1-stage is divided into n sets of
bed height (H/n), theoretical total efficiency of the series of these coalescers will be as shown in
eq. 5.4.5.
n stages = 1 (1
1 stage
n
)n
{5.4.5}
From the equation, when 1-stage and a is lower than 1, the value of n-stages is always
higher than 1-stage. From this fact, WANICHKUL [11] had been developed annular brush module
(fig. 5.4.3-2d) that could be placed close to each other or with some spacing between them. When
there is a sufficient distance between modules, it can be assumed that the coalescer becomes
multi-stage. Theoretically, the efficiency will increase as shown in eq. 5.4.5. WANICHKUL use
spacing of 1.0 cm. between each module. The result shows that the total efficiency of this multistage coalescer is actually higher than the single stage one. However, efficiency of the multi-stage
coalescer is approximately equal to efficiency of the single stage coalescer plus 10%, not as high
as calculated from eq. 5.4.5. This is simply because the efficiency is also a function of oil
concentration. After each stage, the oil concentration for the next stage will decrease, so eq. 5.4.5
will be no longer valid. However, this research confirms the idea of efficiency improvement by
simply adding some spacing between each module of bed.
Coupling coalescer and cyclone is another simple modification of 2 well known
processes that can give an impressive efficiency. This coupling is designed on the basic
knowledge that.
Efficiency of hydrocyclone increases with increasing velocity.
Hydrocyclone can not work efficiently at droplet size less than 20 microns.
Efficiency of coalescer decreases with increasing flowrate.
At high velocity, coalescer can intercept these tiny droplets and, somehow, form
bigger droplets, even though the efficiency is low.
Combination of upstream coalescer with downstream hydrocyclone makes the system

work at relatively high and constant efficiency, regardless of the velocity, as shown in table 5.4.12. This combination will be described again in chapter 12.
Advantage:
Major advantages of fibrous bed coalescer are summarized below;
Fibrous bed has high porosity, so it is hardly clogged. Then regeneration or

backwashing is normally not required.
Hydraulic loading rate is very high (up to 72 m/h), compared to simple decanter. So
the size is very compact.
Pressure drop is very low for the bed has high void ratio.
230
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Chapter 5 Coalescer
Very small size of fiber ensures good interception of oil droplets.
The coalescer in form of in-line unit can be designed as a preliminary treatment for
other downstream oil/water separation process, such as hydrocyclone.
Disadvantage: Major disadvantage of fibrous bed coalescer is undesirable channeling of

untreated wastewater from fiber deflection, either by hydraulic force form wastewater flow or
accumulation of oil and solids on the fibers. From this constraint, size of the coalescer is limited
at several centimeters, normally less than 10 cm. So, at high wastewater flowrate, it may require
too many units to be economical. For disorderly bed, inspite of its good efficiency, it is sensitive
to presence of suspended solids. Moreover, from its tortuosity, it is very difficult or impossible to
unclog.
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III-114

6.1
General
Flotation is an accelerated separation process, operated by increasing density

difference between continuous phase and dispersed phase. This is accomplished by mean of
adding gas or air into the wastewater to promote formation of air-solids or air-oil
agglomerates. There are several researches on flotation, its modification and applications of
various types of flotation such as mechanical flotation, diffused air flotation, dissolved air
flotation (DAF), etc. Among these, DAF, with its finest air bubble size, is the most efficient
process. So it became the main flotation process studied in GPI lab.
6.2
Working principles
From STOKES law (eq. 6.2.1), difference density between dispersed phase and
continuos phase () is one of the parameters that governs rising or decanting velocity of the
dispersed phase. Flotation is the separation processes of which aims to increase the density
difference to increase the decanting velocity.
U=
gd 2
18 c
{6.2.1}
For dissolved air flotation, pressurized water which is (or almost) saturated with air or
gas will be fed to wastewater at lower, usually, atmospheric pressure. The air or gas will be
released from the pressurized water in form of tiny bubbles. These bubbles, while rise up to
the surface, will collide with dispersed phase, in case of oily wastewater oil droplets, in the
wastewater. Some will attach to the droplets and form oil-bubble agglomerates. Since the
bubble has much less density than oil and water. Density of these agglomerates will be lower
than that of oil droplets alone, thus, make the rising velocity increase. General schematic
diagram of DAF process is as shown in fig. 6.2-1.
Fig. 6.2-1 Example of schematic diagram of DAF (Source: Aquatec Maxcon)

232
III-115
There are many attempts to predict the efficiency of DAF or to formulate mathematics
model of DAF. However, there is no general model so far that can predict the efficiency of the
process accurately at any operating condition. Almost all of the models are on empirical.
However, there are some researches in GPI lab to formulate the models of DAF that are semiempirical or based on some theories. So they can be used as tools to understand the effect of
some parameters on DAF operation and to adapt empirical data on DAF efficiency at one
condition to estimate, only roughly, the efficiency at other condition. There are 2 approaches
to formulate such a model, studied in GPI lab, i.e.,
Filtration based model

The two approaches are described in section 6.2.1 and 6.2.2.

6.2.1
Filter based model
From the concept that air bubbles are used to intercept oil droplets and form oil-bubble
agglomerate, AURELLE and SIEM [12] considered that this concept is relatively close to that
of filtration with the air bubbles play the role of collector. So they formulated model of DAF
based on the filtration model, proposed by YAO et al. [35]. Details of model formulation are
as shown in the following sections.
6.2.1.1 Applying filtration model to DAF
From filtration model, interception of dispersed phase by a collector of filter media is
based on 3 transport phenomena, i.e., sedimentation, direct interception and diffusion. Other
transport phenomena, such as that of electrical force, might take place, but it is proven that
their effect is small, thus, negligible. However, for DAF, the collectors, which are air bubbles,
are not stationary but have their own rising velocity and also carried along with the water. So
concept of relative velocity will be applied in stead of absolute velocity.
To calculate relative velocity of air bubble/ oil droplets in flotation column, consider a
flotation column which wastewater and pressurized water are fed at the bottom. This causes
flow velocity V in the column (see fig. 6.2.1-1). Air bubbles generated from pressurized
water, as well as, oil droplets in the wastewater will be carried along with the liquid.
However, from STOKES law, the air bubble and the oil droplets also have their own rising
velocities, Uband Ud respectively. So, for the observer looking from outside of the
column, the absolute velocity of bubble and oil droplets will be equal to V+Ub and V+Ud
respectively. Then relative velocity between air bubble and water (Vr) will be as shown in eq.
6.2.2a while the relative velocity between bubble and oil droplets (Ur) is shown in eq. 6.2.2b.
Vr = (V + U b ) (V ) = U b
{6.2.2a}
U r = (V + U b ) (V + U d ) = U b U d
{6.2.2b}
From above equations, if an observer stands on the bubble, it will seem to him that the
water is flowing past him at velocity Ub, while oil droplets move toward him at slightly
lower velocity Ub-Ud. To apply filtration model to DAF, we will consider, firstly, the
phenomena, taking place at 1 collector (or 1 bubble). Assume that frame of reference is on the
bubble, schematic diagram of the 3 transport phenomena is shown in fig. 6.2.1-2. Efficiency
of each phenomenon is described as follow.
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V
x
Ub
Ud
y
Bubble, Oil droplet
Collector
Fig. 6.2.1-1 Diagram for considering relative velocity of bubble and oil in flotation
column
Vr= Relative flow velocity
Ur= Relative decanting velocity
Ur
Vr
Vr
Ur
Oil droplet
Bubble,
Collector
Stream line
a) Direct interception
b) Sedimentation
c) Diffusion
Fig. 6.2.1-2 Schematic diagram of the 3 transport phenomena

1.
Direct interception
When oil drops of diameter d flow along with the streamline, the oil drops that
pass within the distance less than d/2 from the bubble will be intercepted by the bubble, as
shown in fig. 6.2.1-1a. The efficiency factor for this phenomenon can be calculated by eq.
6.2.3. db is the diameter of bubble.
3 d 2
)
2 db
Int = (
2.
{6.2.3}
Sedimentation
Consider oil drops of diameter d flow along with the streamline. When they
are far from the media, the relative decanting velocity (Vr) and relative flow velocity (Ub) will
have the same direction. When they come close to the media, the flow velocity will deviate, as
shown by the streamline, while the oil drops will be subjected to both flow velocity and their
own decanting velocity. So the resultant velocity will not totally conform to streamline. And
in some cases, it will make the oil drops collide to, thus, sediment on the bubble. The
efficiency factor for this phenomenon can be calculated by eq. 6.2.4.
sed =
oil / water gd
{6.2.4}
18 cV r
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3.
Diffusion
For very small droplets (d < 5 microns), They will be subjected to Browniens
motion. These random motions can cause the droplets to collide to the media. The efficiency
factor for this phenomenon can be calculated by eq. 6.2.5. K, in this equation, represents the
Bolzmann constant and T represents the absolute temperature.
Diff
4.
KT
= 0.9
c d d bV r
2/3
{6.2.5}
Combined theoretical efficiency
From 1 to 3, we can calculate the efficiency factors of each transport phenomena

for single collector (or bubble). Theoretical efficiency factor of single collector is the
summation of the efficiency factors of those three transport phenomena, as shown in eq. 6.2.6.
theo = Int + Sed + Diff

Thus
theo =
oil / water gd
18 cV r
KT
3 d
+ ( ) 2 + 0 . 9
2 db
c d d bV r
2/3
{6.2.6}
Assume that frame of reference is on the bubble, it can be implied that the bubble is
stationary within the flow of wastewater. Then, consider one bubble as shown in fig. 6.2.1-3,
The fraction of wastewater flowing past the single collector will be the flow that passes
through the projected area of the collector (q), as shown in eq. 6.2.7a. Then, some oil droplets
in this fraction of the wastewater will be intercepted by the collector. The quantity of
intercepted oil drops of the single collector (c) will be calculated from the theoretical
efficiency factor, as shown in eq. 6.2.7b.
q=
d b2 Vr
c' = theo
{6.2.7a}
d b2 Vr C
{6.2.7b}
q = Vrdb2/4
Vr
Effective
Concentration
=C
(include dilution) Relative velocity between
bubble and water = Vr
Flow velocity = V
db
dH
Concentration after
intercepted by bubbles
= C- dC
a)
Column height
=H
Bubble
size = db
Cross section
area = Ao
b)
Fig. 6.2.1-3 Schematic of single bubble and entire height of flotation column
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C is inlet concentration of oily wastewater. For the entire flotation column, we will
consider a very small slice of rising bubbles of the height dH (see fig. 6.2.1-3b). The number
of bubble particles in this slice can be calculated from the cross section area of bed (A), the
size of the bubble (db) and the ratio of volume of water to total volume (), as shown in eq.
6.2.7c.
Then, the total concentration of intercepted oil for this slice of rising bubbles will be
equal to the product of c and the number of bubbles. However, not all of the intercepted oil
drops will adhere to the bubbles. So the probability coefficient () will be applied to adapt the
quantity of intercepted oil drops to the quantity of adhered oil drops (c), as shown in eq.
6.2.7d.
The number of bubbles in the slice dH =
c" = theo
d b2 V C
dH (1 ) A
dH (1 ) A
{6.2.7c}
3
b
,<1
{6.2.7d}
3
b
If dC represents the concentration of oil reduced after past through the slice of bubbles
dH, then we have got eq. 6.2.7e and f;
V A dC = c"
V A dC = theo
d b2 V C
dH (1 ) A
{6.2.7}
{6.2.7f}
3
b
Therefore,
dC
3
=
(1 ) theo dH
C
2d b
{6.2.7g}
Integration of eq. 6.2.7g will give the value of the oil concentration reduced by the
entire column height, as shown in eq. 6.2.8a.
log(
3
C
H
) = (1 ) theo
2
Co
db
{6.2.8a}
However, void ratio (e) of DAF system can be calculated directly from air flowrate
discharged from pressurized water and total water flow as shown in eq. 6.2.8b.
1 =
=
Qt
AV
{6.2.8b}
Thus, the theoretical removal efficiency DAF, based on filtration model, can be
written as shown in eq. 6.2.8c.
d ,theo
C
= 1
Co
3 H

( theo )
2 AV dp
100 % {6.2.8c}
100 % = 1 e
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The filtration based model, proposed by AURELLE and SIEM, can be effectively
described the phenomena taking place within DAF reactor and effect of parameters to DAF
efficiency. However, formation of bubble-oil agglomerates, which is rather complex
phenomenon into itself, is simplified to only one parameter . The value of would vary
with many parameters such as characteristic of wastewater, operating condition, etc, which
may not be included in the 3 transport phenomena. This causes some discrepancies between
theoretical efficiency and observed efficiency. So the efficiency from eq. 6.2.8c should be
corrected by a correction factor.
SIEM had studies the relation between observed efficiency (.exp) and the theoretical
efficiency and found that the observed values are quite different from the theoretical value
from eq. 6.2.8c. Relation between observed efficiency and theoretical efficiency, suggested by
SIEM, is shown in eq. 6.2.9a and fig. 6.2.1-4. So the theoretical efficiency in eq.6.2.8c can be
modified by replacing theo with .exp. The efficiency of DAF, then, can be calculated by
eq.6.2.9b.
exp = 0.009005( theo ) 0.5919
C
d = 1
Co
{6.2.9a}
3 H

( exp )
2 AV dp
100 %
100 % = 1 e
{6.2.9b}
(t) = 0.009005 (t theo)0.5919
-9.0E+00
ln (Observed efficiency)
-8.0E+00
-7.0E+00
y = 0.5919x - 4.71
2
R = 0.9821
-6.0E+00
-5.0E+00
-4.0E+00
-3.0E+00
-2.0E+00
-1.0E+00
0.0E+00
0.0E+00
-1.0E+00
-2.0E+00
-3.0E+00
-4.0E+00
-5.0E+00
-6.0E+00
-7.0E+00
ln(Theoritical efficiency)
Fig. 6.2.1-4 Relation between theoritical efficiency factor and observed efficiency factor
6.2.1.3 Limitation of filtration based model of DAF
From eq. 6.2.3 to 6.2.5, it shows that the three efficiency factors does not depend on
flowrate because there is no parameter relating to the flowrate, such as velocity, etc. in the
equations. Furthermore, from eq. 6.2.9b, the term /AV can be rewritten in form of
pressurized water (Qpw) and wastewater (Qt) flowrate, as shown in eq. 6.2.10.
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Q pw Conc(air )
AV
Qt
air
{6.2.10a}
Or
=
Q pw
Qt
X =
RQ
X
1 + RQ
{6.2.10b}
Normally, under certain design condition, Qpw/Qt or Qpw/Q (= R)is constant. Solubility
of air in water (X) and air density are intrinsic (internal) properties, which are constant at any
given pressure and temperature. So, from eq. 6.2.10, it shows that /AV is flow-independent.
From these, it seems that predicted DAF efficiency from the filtration-based model is
mathematically flow-independent. However, In fact, effect of wastewater flowrate,
sometimes, described in form of velocity or retention time, is studied by many researchers. It
is widely accepted that DAF efficiency varies with retention time. So, considering SIEMs
research, it can be interpreted that the effect of retention time is already included in eq. 6.2.9a.
Since eq. 6.2.9a is evaluated from one set of operating condition (/AV = 0.0516) and
retention time (25 minutes (approx.)), it may be valid only for that condition. To expand valid
range of SIEMs model, some criteria or model that contains flowrate-dependent parameter
(such as retention time, etc.) is required.
6.2.2
Population balance model is one of popular concepts, used by many researchers, to

develop DAF model. In GPI lab, DUPRE [14] uses this method in her research on application
of DAF for liquid-solid separation. Concept of this method is that rate of change in the
number of pollutants which is free or attached by 1, 2 or more air bubbles is the function of
the number of air bubble and oil droplet, as shown in eq. 6.2.11. Oil droplet that is attached by
at least 1 bubble, so-called oil-bubble agglomerate, will be separated. So rate of change in
number of oil droplets represents removal efficiency.
Main assumption of population balance method is that the number of bubble is
assumed to be constant. From many researches [14], [34], It is proven that, for liquid-solid
separation, the number of bubble (N) can be safely assumed as constant without serious error,
because there are a lot more bubbles than pollutant if normal range of (Qpw/Qt) is applied.
However, in case of oily wastewater, many researches [12], [13] show that bubble-oil
agglomerates are in form of oil shell with air inside and these agglomerates are still able to
intercept more oil droplets. Those researches also show that coalescence of oil and bubble is
more effective than that of the same species. So it should be safely assumed that the number
of bubble in this case is more or less constant and the population balance method is, then,
applicable.
dn0
= k 0 n0 N
dt
{6.2.11a}
dni
= k i 1ni 1 N k i ni N
dt
{6.2.11b}
i = 0 to imax
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N=
db
Where
{6.2.11c}
3
Collision rate constant for population balance equation (T-1)

Adhesion efficiency between bubbles and oil drop/ bubble
agglomerate at the number of bubble of the oil/bubble agglomerate
= i
the number of bubble
=
i =
N =
no and ni represent the number of oil droplet which is free and attached by i bubbles
respectively. represents collision rate constant, from Saffman and Turners (1956)
coagulation theory, and represents adhesion efficiency or probability that the collision
between oil drop and bubble will be successful. Removal efficiency can be written as (ni/n0),
which can be achieved by integrating eq. 6.2.11.
To integrate eq. 6.2.11, complex numerical method is required. MATSUI and
LEPPINEN [34], [37] solve the equation by Laplace transforms and suggest the solution as
shown in eq. 6.2.11.

d 2 / d 2
ni
b 1
= x : i e ( ) e
{6.2.11a}
i = 0 to imax 1
x :i =
x ( x 1)...( x (i 1))
i (i 1)...( 2 )(1)
{6.2.11b}
x = d 2 / d b2
When
i
=
Where
=
6
{6.2.11c}
0, the above function will be equal to 1.

{6.2.11d}
aG (1 + ( d / d b )) 3 0
numerical constant
G is a measure of turbulence intensity, which is normally proportional to V but the

exact relation depends on DAF design and operating condition. For i = 0, ni will become n0,
which represents the number of free oil drop remaining from contacting with air bubble. So 1(n0/N) represents removal efficiency of the process. Using i > 0 will result in greater value of
efficiency. So, to be on the safe side, we will use i = 0. Then eq. 6.2.11, when i = 0, can be
rewritten as shown in eq. 6.2.12. Removal efficiency of DAF is, then, can be written in form
of eq. 6.2.13.
n0
= e ( )
N
=1
{6.2.12}
n0
= 1 e ( )
N
{6.2.13}
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It should be noted that eq. 6.2.13 is about the same form as eq. 6.2.9b, but the value of
, represented by eq. 6.2.11d, clearly represents effect of every interesting parameter,
including retention time. So population balance model is flow-dependent and, then, can be
used to extend the valid range of SIEMs model, as described in section 6.2.3.
6.2.3
Generalized model of DAF from combination of filtration based model and

population balance model
From section 6.2.1, it shows that SIEMs filtration based model can be used to predict
the efficiency of DAF at any diameters of oil droplets and bubbles, as long as design retention
time and F/AV still conforms to SIEMs condition. And from section 6.2.2, it shows that
population balance model gives the equation that is flow-dependent. So it is possible to use
these two models to extend the valid range of SIEMs model to another operating condition.
To do so, firstly, SIEMs model will be used to calculate the efficiency at his operating
condition. Then, at any d and db, eq. 6.2.11d and 6.2.13 can be rewritten in form of a function
of a parameter that we want to vary from SIEMs condition, i.e., retention time and gas
flowrate. while other parameters still conform to SIEMs (eq. 6.2.14). When the efficiency at
SIEMs condition is known, the efficiency at other condition can be predicted from eq. 6.2.14
and relation between design value and SIEMs value of that parameters (eq. 6.2.15 and
6.2.16).
{6.2.14a}
{6.2.14b}
= const .G = 2
= 1 e = 1 e ( 2 )
If x represents the variable or that we want to vary from SIEMs while another
variable still conforms to SIEMs condition, eq. 6.2.14b can be rewritten as show below.
= 1 e A x
Where
A =
{6.2.14c}
constant
If
{6.2.15}
x = B.x ref
Where
B =
Constant
Xref = x at SIEMs condition

Then
1 e ( Ax )
=
ref 1 e ( Ax )
{6.2.16a}
ref
( ABx ref )
1 e
=
ref 1 e ( Ax )
= 1 (1 ref ) B
{6.2.16b}
ref
{6.2.16c}
However, changing of of will also cause some parameter in eq. 6.2.11d change.
For example, increasing of retention time from SIEMs condition will make V decrease. Then
G will decrease. So the constant A at design condition is not equal to A at SIEMs
condition. In this case, eq. 6.2.16 is not valid. And it is not possible to know the value of A
at design condition. So, the best estimation in this case is to use the value of A at some
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condition that we are sure that will underestimate efficiency at design condition. Design
reactor in this case will be larger than it should be. Then it can be considered as safety factor.
Guideline to predict the efficiency from combination of SIEMs model and population
balance model will be described again in details in section 6.3.
6.2.4
Influent parameters
From models described in section 6.2.1 and 6.2.2, main parameters that affect the
efficiency of DAF can be summarized as shown in fig. 6.2.4-1.
Efficiency ()
Efficiency ()
100%
100%
Increase db
Decrease , , H
Lower limit of
the model:
2 micron
Droplet size (d)
Droplet size (d)
Fig. 6.2.4-1 Typical relation between efficiency of DAF and various parameters
From the models, it can be summarized that, efficiency of DAF can be improved by:
Increase the size of oil droplets. This can be done by coagulation-flocculation

process.
Decrease the size and quantities of bubbles. This can be achieved by using high
performance injection valve.
Increase quantity of air/pollutant ratio by increasing pressurized water flowrate or

using higher saturator pressure. However, operating cost should be considered.
Increase column height to increase retention time.
However, there are some more phenomena and parameters that also effect the
efficiency of DAF, which will be described below,
1.
Characteristic of bubble-pollutant agglomerate and transfer compound

Characteristic of bubble-pollutant agglomerate
Since DAF performance depends on formation of bubble-pollutant agglomerate,

some researches in GPI lab [13], [14] had been conducted to study characteristics of the
agglomerate. Fig. 6.2.4-2 shows characteristic of bubble-solid and bubble-oil agglomerate.
For bubble-solid agglomerate, certainly, bubbles will attach to the surface of
solid in side-by-side manner. On the contrary, for bubble-oil agglomerate, side-by-side
characteristic is only temporary or intermediate condition. Finally, oil and bubble will
integrate in form of spherical thin film or shell of oil with air core inside. This can be
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explained by the concept of spreading, described in chapter 2, section 2.2.2.2. Consider

interfacial tension between kerosene, water and air as shown below,
Oil-water: ow
Air-water: w
Air-oil: o
= 35 dynes/cm
= 72 dynes/cm
= 28 dynes/cm
From chapter 2, oil will spread over the air bubble when w > o+ow. From the
values of interfacial tension, it clearly shows that this condition is confirmed (72 > 28 + 35).
So the oil will spread over air bubble and form a thin film around the air.
The four ways to improve the efficiency of DAF described earlier in fig. 6.2.4-1
is actually the way to improve collision probability. However, one of the most encountered
problems in DAF operation is collision between bubble and pollutant without attachment.
According to the study in static transparent model [13], to form agglomerate, bubble and
pollutant must be collide or come close to each other at some certain distance for sufficient
period of time to drain water film between them and made bond to each other. To solve this
problem, some chemically active agents are used to adapt properties of bubble and
wastewater. The chemicals are called transfer compound.
Effect of transfer compound on bubble-pollutant agglomerate
Transfer compound is chemical added either as gas to bubble-forming air or as

chemical to water. Major role of the compound is to help promoting bubble-pollutant
agglomerate and strengthen the bond between them. It will cause mass transfer, where it got
its name, from bubble to water or vice versa that change local interfacial or surface tension of
pollutant or bubble. This change will facilitate agglomerate formation. This effect of local
change in surface tension is known as the Marongoni effect. There are 2 major types of the
compounds, i.e., transfer gas and transfer compound for water.
Transfer compound for water is practically a surfactant added to

pressurized water. The surfactant will reduce surface tension of water. In
case of solid separation, the effect is relatively the same as that when using
surfactant in a washing machine. Bubbles and solids will attach to each other
easier and stronger. Efficiency will be improved. This idea is actually
commercialized by many companies, such as SAFTM (suspended air
flotation) from Enprotec.
Transfer gas is typically a gas of highly soluble chemicals, such as

ammonia, which is added to bubble-forming air. The concept is that the gas
would transfer from bubble into water and make the water film rapture
easier. This will help interaction time between bubble and pollutant and
make them attach immediately after collision. In GPI lab, AOUDJEHANE
[13] shows that small amount of ammonium gas added into the air actually
helps reducing coalescence time between bubble and oil droplet. However, it
also promotes coalescence between bubble and bubble. So, these effects tend
to cancel out each other. The efficiency is relatively the same.
In case of oily wastewater, however, presence of surfactant in water causes the

droplet smaller and more stable. So it make the efficiency decrease. Anyway,
AOUDJEHANE shows that if the surfactant is firstly added to oil and mass transfer of
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surfactant is in the direction from oil toward water. It will help rupturing the water film then
improving efficiency of coalescence between bubble and oil. However, doing so in real
situation may not be possible because we cannot add surfactant into oil before it becomes
wastewater.
a) Solid-bubble agglomerate. Please notice side-by-side formation. [14]
b) Bubble and oil droplet come close to

each other.
c) The bubble and droplet collide. Water

film between them is draining.
d) Water film rapture after been draing for

some times. Oil starts to enclose air bubble
in very brief time.
e) Then, oil-bubble agglomerate is form of

thin oil film around air core is generated.
Fig. 6.2.4-2 Solid-bubble agglomerate and formation of oil-bubble agglomerate [14]

2.
Turbulence in flotation column
As shown in eq. 6.2.11 and 6.2.13, the efficiency of DAF depends on gradient or
turbulence within the reactor. If turbulence increases, probability of collision between bubble
and pollutants will also increases. However, turbulence also causes adverse effect on
fragmentation of oil droplets or flocs. AOUDJEHANE had studied the effect of turbulence in
special DAF model equipped with mechanical mixer, reported that efficiency of DAF
increases with increasing turbulence or mixing intensity until some certain limit. Then the
efficiency will be stable or slightly decrease with increasing turbulence. It seems that
turbulence has both advantage and disadvantage. Normally, DAF is designed in smooth
laminar flow region. Increasing the efficiency of DAF by increasing turbulence is to be done
very carefully. Pilot-scale observation or CFD analysis should be conducted.
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3.
Presence of surfactant
Effect of surfactant in wastewater is as discussed in effect of transfer

compound. In presence of surfactant, oil droplets will become more stable and their sizes
will be smaller. Efficiency of DAF, then, will decrease. So it is recommended to destabilize
(or break or crack), coagulate/flocculate the wastewater before using DAF.
4.
Formation of air bubbles
From, filtration-based model efficiency of DAF will increase if the size of

bubbles decreases. So pressurized water system shall be designed to make majority of very
tiny droplets and avoid generating big bubbles. DUPRE [14] had studied bubble generation in
venturi-style injection vale and reported that using hydrophobic material for valve
construction may result in bigger bubbles. She also reported that addition of surfactants in
pressurized water causes augmentation of population of microbubbles, while addition of
polyelectrolyte gives the opposite result. Details of pressurized water system or saturator will
be described in section 6.5.
6.3
Design calculation
From previous sections, it shows that there are many parameters, such as wastewater
characteristic, reactor configuration and operating condition, that effect efficiency of DAF
reactor. So, design of DAF reactor is generally based on hydraulic loading rate and some
proven reactor configuration. However, to valorize the researches conducted in GPI lab,
design procedure for DAF, recommended in this section, will be based upon the models,
shown in the previous sections as well as general design practices. Calculation in each step is
described below.
1.
Cut size determination and required efficiency
from the limitation of the DAF processes. Cut size determination from degree of treatment is
described in chapter 3. However, in general practice, DAF is hardly used alone but will be
combined with coagulation-floculation process (see chapter 10). After coagulationflocculation process, granulometry of size distribution of dispersed phase in the wastewater
will be changed from that of initial wastewater. The size distribution after coagulationflocculation may be roughly estimated, as shown in chapter 10. However, it is clear that it is
no longer possible to determine the cut size from the initial size distribution. Then the degree
of treatment (such as effluent oil concentration, etc.) will be used to calculate the required
efficiency. This required efficiency or the required degree of treatment would be used to
compare to general recommended criteria of DAF to determine if it is feasible to use DAF for
such wastewater.
In case that there is no general design criteria or recommended efficiency for the
wastewater to be treated, it is strongly recommended to perform DAF test, such as Flota-test,
to evaluate the feasibility and efficiency of DAF before designing the real unit.
2.
DAF reactor sizing
The size of the DAF can be determined based on (1) mathematics models from
section 6.2, (2) general design criteria and (3) pilot-scale test result. Designing an efficient
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DAF reactor, as well as other processes, is the state-of-art and requires experience. However,
result from the models and some useful criteria acquired from many researches, esp. GPI
researches, will be provided here to be a guideline for DAF reactor sizing.
2.1. General design criteria
Recommended design criteria from various literatures and manufacturers are

summarized in table 6.3-1. It should be noted that the values in the table are summarized from
experiences and researches with various operating conditions and types of wastewater, then,
should be used as a guideline. It is recommended to review related researches for the type of
wastewater to be treated. If possible, DAF test, using lab-scale batch test, such as flota-test, or
pilot-scale test with the real wastewater should be performed.
2.2. DAF design by combination of filtration based model and population
balance model
From the 2 models in section 6.2, they can be used to size DAF reactor and
estimate graded efficiency of DAF process at any operating condition. If direct scale-up of
SIEMs model ( the same V and /AV) is used, the cut size at H =0.70 m. is around 35
microns.
If DAF is used alone without coagulation-flocculation process and cut size can
be determined, the cut size can be used to calculate surface area of DAF reactor (A) by
assuming that the efficiency at the cut size is 100%.
If cut size can not be determined, approximate size of DAF reactor can be
calculated from general criteria, described in table 6.3-1. It is recommended to use the reactor
size calculated from the general criteria as a guideline to calculate the efficiency. Then, it can
be fine adjusted again to fit specific constraint of each project.
Calculation procedure and model limitation will be as described below.
2.2.1. Design DAF at SIEMs condition ( /AV is at SIEMs condition. H can
be varies)
1. To predict removal efficiency of DAF, reference graded efficiency
(based on Qt) can be calculated by SIEMs model. If the result
from the equations is greater than 100%, then it will be rounded up
to 100%. The values of (/AV) have to be the same as SIEMs
condition (see item 3).
d ,ref
= 1 e
3
H
( exp )
)
2 AV
db
100 %
( exp ) = 0.009005( theo ) 0.5919
{6.2.9b}
{6.2.9a}

Int =
3 d 2
( )
2 db
{6.2.3}
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III-128
sed =
oil / water gd
18 cV r
Diff = 0 . 9 (
Vr = Ub =
Where
c
K
T
KT
)2 / 3
dV r d b
air / water gd b2
18 c
{6.2.4}
{6.2.5}
{6.2.2a}
= viscosity of continuous phase (water) (L2/T)

= Boltzman constant (1.38*10-23)
= Absolute temperature (Kelvin)
2. To use the equations described above, the following conditions will

be satisfied;
1) Inlet oil concentration should not be greater than 1,200 mg/l
(before dilution) or 435 mg/l (after dilution). Using the model
with higher oil concentration will result in underestimating of
efficiency.
/AV = 0.0516. Only this value must be used in the
equations. As long as this value is fixed, SIEMs operating
condition still holds and the model is still valid.
Retention time, based on total flowrate (Qt), is around 25
minutes.
Diameter of air bubbles (db) varies from 15 to 130 microns.
Tested average bubble diameter is 70 microns, which is used
to verify the model, and standard deviation of bubble
diameters is 34.5 microns. The range of bubble sizes is
common for commercial pressurized water system or
saturator. The pressure of the test system is 4 atm (absolute).
3
3
Tested air flowrate () is 0.42 cm /s (4.2e-7 m /s).
3
3
Tested wastewater flowrate (Q) is 3.9 cm /s (3.9e-6 m /s)
Tested effective water depth (H) is 0.70 m. The value of H
can be freely changed as long as (/AV) is fixed. However,
H between 1.8 to 2.7 is recommended by API [45].
Diameter of flotation column is 0.15 m Cross section area of
column (A) is 0.01767 m2.
Ratio of number of bubble/ oil droplet tested is around 1.4
oil droplet/ 1 air bubble.
Hydraulic loading rate or flow velocity (V), based on Qt, is
1.6 m/h
2) he model is tested at the following operating condition;
246
III-129
Table 6.3-1 General design criteria of DAF from various literatures and manufacturers (hydraulic loading rate is based on total flowrate)
247
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Table 6.3-1 General design criteria of DAF from various literatures and manufacturers (hydraulic loading rate is based on total flowrate)
248
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3. To apply SIEMs condition to other wastewater flowrate, area (Aref)

and gas flowrate (ref) corresponding to that flowrate can be
calculated from the following equations. The subscript of A and
in this case is ref to indicate that SIEMs condition (or reference
condition) still holds.
Aref =
ref =
Qreq
Qmod el
Areq
Amod el
Amod el =
Qreq
3.9 10 6
mod el =
0.01767
4.2 10 7 Areq
0.01767
m2 (Q as m3/s) {6.3.1}
m3/s
{6.3.2}
4. If H is changed from 0.70 m. to Hreq, will be changed from 25

min. to ref by the following equation. The subscript of in this case
is ref to indicate that SIEMs condition (or reference condition)
still holds.
ref =
H req
H mod el
mod el =
H req
0 . 00046
1
3600
hour
{6.3.3}
5. Because of limitation of the pilot model, tested ratio of pressurized

water to wastewater is quite high (around 92%), compared to that of
general DAF for solid/liquid separation (less than 50%) [13].
However, API [45] recommended air/wastewater ratio of 0.35 std.
ft3/ 100 gal of total flow for full-flow DAF process. This value is
equivalent to 84% of 4-atm (abs) pressurized water/ wastewater.
Anyway, it is interesting to adapt the model to calculate the
efficiency at lower ratio of pressurized water by the procedure in
item 2.2.2.
6. Tested hydraulic loading rate or overflow rate (based on Qt) is 1.6
m/h, which is relatively low, compared to normal rate of 3-15 m/h
for domestic wastewater treatment. The value recommended by the
American Petroleum Institute (API) [45] is between 4.8-6.1 m/h. So
it is also interesting to adapt the model to calculate the efficiency at
higher overflow rate by the procedure in item 2.2.2.
2.2.2. Design DAF at other condition from SIEMs condition
To calculate graded removal efficiency at other operating condition
than SIEMs model, esp. at higher overflow rate or lower ratio of pressurized
water/wastewater, calculation procedure will start from direct scale-up of
SIEMs condition (the same as 2.2.1). After that, adaptation by population
balance model will be applied.
Direct scale-up of SIEMs condition (/AV is at SIEMs condition. H
can be varied.)
1. Calculate the reference efficiency (d,ref) of the model at required

height (Hreq), average bubble diameter (db) and droplet sizes (d)
using eq. 6.2.2 to eq.6.2.5 and eq. 6.2.9. Use /AV = 0.0516 in
order that the operating condition of SIEM still holds.
249
III-132
2. Scale up the area from 0.01767 m2 to required area (Areq). Other

operating condition from section 2.2.1 still holds. So efficiency
from section 2.2.1 remains the same. This required area could be
approximated from recommended hydraulic loading rate (Vreq) and
ratio of pressurized water to wastewater ((Qpw/Q)req) as shown in
table 6.3-1.
Areq
Q req 1 + ( pw ) req
Q
=
V req
{6.3.4}
3. Find ref, corresponding to the area Areq, by following equation,

ref =
Areq
Amod el
mod el =
4.2 10 7 Areq
m3/s
0.01767
{6.3.2}
4. Find ref, corresponding to the height Hreq, by following equation,

ref =
H req
H mod el
mod el =
H req 25
0.70 60
Hour
{6.3.3}
Change and from SIEMs condition by population balance

model
5. From population balance method, calculate 2,ref corresponding to
Areq, Hreq, ref and ref from the reference efficiency (from item 1)
by the following equations. Please note that, at this point, SIEMs
condition still holds. 2,req has to be calculated separately for each
droplet diameter.
2, ref =
ln(1 d , ref )
{6.3.5a}
ref ref
Or
d ,ref = 1 e
( 2 , ref ref ref )
{6.3.5b}
6. Find req from required ratio of pressurized water to wastewater

(see table 6.3-1 for the recommended value) by following
equations.
req =
Volume
Volume
air
Q pw =
pw
Volume
Volume
air
{6.3.6a}
R Q
pw
Then, from Henrys law (section 6.5)

req = y H 'R Q (P Patm )T ( 0 . 082 10 3
m3
)
mol K
{6.3.6b}
For air, y =1. H in this case in in the form of molair/(m3 water. atm).
Henrys constant of air at any temperature can be calculated from
an empirical equation, shown in section 6.5.
7. Choose req from recommended criteria (see table 6.3-1).
8. To change and from SIEMs, the following procedure is
recommended and precautions should be noted.
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III-133
This will cause decreasing of V, so G will decrease. Then 2

(see eq. 6.2.11, 6.2.14) will be lower. However we do not know
how much exactly. So, to be on the safe side, we will assume
that only decrease but = ref. In this case, 2 will remain the
same and be equal to 2,ref. The efficiency can be estimated by
eq. 6.3.7a.
d = 1 e
( 2 , ref req ref )
{6.3.7a}
Because we use ref, instead of req, the calculated efficiency will

be lower than the real value.
This will cause increasing of V, so G will increase. Then 2 (see

eq. 6.2.11, 6.2.14) will be higher. Again, we do not know how
much exactly. So, to be on the safe side, we will assume that 2
= 2,ref. The efficiency can be calculated by eq. 6.3.7b. And
again, the calculated efficiency will be lower than the real value.
d = 1 e
( 2 , ref req req )
{6.3.7b}
This can be done by increasing pressurized water flowrate.

However, the ratio of pressurized water/ wastewater is already
high (92%). So there is only a small gap to increase (from
Qpw/Q = 92% to 100%). In this case, 2(see eq. 6.2.11, 6.2.14)
will be higher. Like the former case, the efficiency can be
calculated by eq. 6.3.7b.
This case is not feasible because it means that we have to

decrease wastewater flowrate and increase pressurized water
flowrate. As stated above, the ratio of pressurized water/
wastewater is already high (92%). If we decrease wastewater
flow, quantity of pressurized water flow will exceed that of
wastewater, which is not feasible because we have to recycle
effluent at 100% plus additional makeup water to feed the
pressurized water system.
There is no obvious limit for the 4 adaptations, shown above.
However it is recommended to use the values of each parameter
(d, db, C, etc.) within general range, shown in item 2.2.1 and
table 6.3-1.
The procedure described in paragraph 2.2 will result in efficiency of
DAF reactor corresponding to firstly approximate size. If the calculated
efficiency dose not meet the required efficiency, the reactor size will be
adjusted until it gives a satisfying efficiency.
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2.3. DAF test
It must be noted that there are many other parameters that can affect efficiency
of DAF, such as presence of coagulation-flocculation process, reactor hydraulic design,
contact zone configuration, design of pressurized water system (or saturator) and injection
valve, etc. These parameters can cause some discrepancies in efficiency prediction especially
when coagulation-flocculation is used since the granulometry of influent will be totally
changed. In this case, pilot-scale or small batch experiment, such as Flota-test, will provide
valuable data for design propose and can be used to compare with model result to determine
the final design criteria. In fact, it is strongly recommended to perform DAF test, if possible,
every time before designing DAF system. Pictures of DAF test are as shown in fig. 6.3-1
a) Pilot-scale for DAF test
b) Flota-test set (Source: GPI lab)
c) Flota-test of cutting oil emulsion with

coagulant addition. Notice the float at the
surface of the reactors. (Source: GPI lab)
d) Magnified photos of non-coagulant float

(left) and flocculated float from Flotatest(Source: GPI lab)
Fig. 6.3-1 Pilot-scale DAF test and Flota-test

3.
Removal efficiency and outlet concentration
3.1. Outlet concentration
Outlet concentration and graded concentration of oil after DAF (C and Cd) can
be calculated by the following equation
Cd =
Q
(1 d )C od
Q out
{6.3.8a}
, dil
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III-135

C =
Q
Q out
d max
(1
)C od
, dil
C od
, dil
{6.3.8b}
d min
Q out = Q
d max
{6.3.8c}
d min
Co,dil and Cod,dil are the inlet concentration after dilution with pressurized water.
Q/Qout represents the effect of flow splitting between treated water and oil outlet port. In lab
scale, where pressurized water comes from oil-free water, outlet concentration can be written
in form of Co and Cod, which are the initial concentration of oil in wastewater before dilution
by pressurized water, as shown in eq 6.3.8d. However, in this case, effluent quantity will
increase from the initial wastewater flow (Q) to total flow (Qt), which is summation of
wastewater flow and pressurized water flow.
C =
d max
Q
Q
(1 d )C od (
)
Q out d min
Qt
{6.3.8d}
If pressurized water comes from treated effluent, remaining oil in the effluent
will effect the inlet concentration after dilution. The value of Cod,dil and Co,dil in this case can
be calculated with accounting for mass balance, as shown in item 3.4.
3.2. DAF efficiency
DAF efficiency (DAF), which is the efficiency based on flotation effect alone,
can be calculated by the following equation.
DAF =
1 d max
((1 d ) C od , dil ) 100 %
C o d min
{6.3.9a}
In lab scale, where pressurized water comes from oil-free water. DAF efficiency
can be written in form of Co and Cod, which are the initial concentration of oil in wastewater
before dilution with pressurized water, as shown in eq 6.3.9b.
((1
d max
DAF =
) C od , dil
d min
C o , dil
) (1
d max
d min
) C odl (
Q
Qt
Q
Co ( )
Qt
1
Co
d max
((1
) C od ) 100 %
{6.3.9b}
d min
However, if treated water is recycled to the pressurized water system, the values
of Co,dil and Cod,dil will be affected by remaining concentration in recycled stream and will be
required more complex calculation as shown in item 3.4.
3.3. Total removal efficiency
When pressurized water comes from DAF effluent: Total removal efficiency
(t), which is defined as ratio between oil mass removed from water and initial oil mass, can
be calculated by the following equation.
t =
Co C
100 %
Co
{6.3.10a}
When pressurized water comes from additional clean water: Total removal
efficiency (t) can be calculated by the following equation. Please note that effluent quantity
in this case is equal to Qt, not Q.
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III-136
C Q C Q t
= o
=
C oQ
Co C (
Co
Qt
)
Q
100 %
{6.3.10b}
3.4. The value of Cod,dil and Co,dil when DAF effluent is used in the pressurized
water system
If the effluent from DAF is recycled to pressurized water system, some oil left in
the effluent will be returned to the system. In this case, mass balance of oil has to be taken
into account. Thus, Cod,dil will be modified by adding this return oil repeatedly, as shown in
eq. 6.3.11. Theoretically, rmax in eq.6.3.11 should be infinity. The value of Cod,dil will
eventually convert to an asymptote. Anyway, using rmax around 30 will practically give the
result sufficient accuracy, esp. when d > 20%. However, if coagulation-flocculation is used
before DAF process, the value of d will be so high that Cod,dil in this case is only slightly
higher than Cod.Q/Qt.
C od
, dil
r max x Q pw
C Q
=
(1 d ) r 1 od
r =1 Q t
Q t
{6.3.11a}
Where Qpw = R.Q. Above summation can be simplified as shown in eq. 6.3.11b.
C od
, dil
C o , dil =
((
R
(1 d )) r max 1 1 )
C Q
1+R
od
R
Qt
(1 d ) 1
1+R
(C
d max
od , dil
{6.3.11b}
{6.3.11c}
d min
4.
Energy required
DAF reactor does not require extra energy to make it function. The energy is
required only to feed the water and pressurized water into the tank, then the water will flow,
naturally, through the tank by gravity. Pressure drop across the tank and piping system depend
on tank and piping design. This pressure drop can be calculated by general hydraulic
equations, such as Darcy-Weisbachs, Mannings, or Hazen-Williams equation, weir
equation, orifice head loss equation, thus will not de described here.
However, it is the pressurized water system that requires most energy in DAF
system. Design of pressurized water system or saturator will be described separately in section
6.5
6.4
Design consideration and Construction of DAF reactor

1.
Reactor material
DAF reactor can be made of concrete, steel or any material that can withstand
wastewater characteristic and operating condition. Special protective coating may be
necessary in case of corrosive wastewater. Otherwise normal coating is sufficient.
254
III-137
2.
Reactor geometry and internal baffle configuration
As shown in section 6.2.4 that turbulence in reactor effects efficiency of DAF for
it effects probability of collision between oil droplets and air bubbles. Theoretically,
efficiency increases with increasing turbulence or velocity gradient (G). This concept could be
applied in DAF without coagulation. However, for DAF with coagulation-flocculation, high
gradient may result in re-fragmentation of flocs, which makes efficiency decrease. Besides,
more turbulence may cause some undesirable eddy, which can cause carry-over of droplet
along with effluent. So geometry or configuration of internal baffle in the tank are usually
designed to minimize undesirable turbulence. However, to maximize contact or collision
between bubbles and oil droplets, as well as, to ensure uniform flow distribution in the tank,
DAF reactor is normally equipped with inlet baffle as shown in fig. 6.4-1. The configuration
of internal baffle is based mainly of experience. Nowadays, as computerized fluid dynamics
(CFD) tool is easier affordable, it is wildly used as a tool to design or perfect the configuration
of DAF reactor
There are some attempts to design of DAF reactor to imitate the condition
within the flota-test, which is closest to quiescent condition. Examples of this design are
KROFTA reactor and DAF Corp. reactor, as shown in fig. 6.4-2. In KROFTA tank,
wastewater and pressurized water are fed by the rotating arm into the reactor in order that
there is least lateral velocity.
For tank geometry, DAF reactor can be designed as rectangular or circular tank.
Both shape of tank, when properly designed, can operate at about the same efficiency, even
though some literatures [49] might claim that circular shape is superior for its better bubble
and water distribution. So other factors, such as shape of land, convenience of construction,
availability and O&M cost of necessary equipment, such as scraper, skimmer, etc. should be
taken into account to determine the most suitable shape of tank.
3.
DAF necessary equipment and component details
Like other treatment processes, DAF performance depends both on proper

calculation and proper equipment and component design. Nowadays, there are a lot of
packaged DAF systems and commercial products related to DAF process. Designer or owner
can contact various suppliers for more details. However, in this chapter, some details of
necessary equipment and component details will be provided as a guideline of what is
necessary to consider in DAF process.
Fig. 6.4-1 is a good example to show necessary equipment and components of
DAF system. Brief of each equipment and component will be as described as follow.
Inlet port or inlet channel: Inlet port or inlet channel should be designed to
guarantee well bubbles and water distribution. Details of inlet port might
vary from simple branch pipes with throttling valves to big manifolds with
flow control devices (fig. 6.4-2). For circular tank, water is normally fed at
the center feed well of the tank. In this case, annular perforated pipe will be
used. Combination of good inlet port and inlet baffle, described in previous
item, will contribute to good performance of DAF system. Pressure reducing
valve or injection value or injector of pressurized water is one of the most
important component of DAF system for it plays important role in bubble
255
III-138
formation. The finer the bubbles, the better the efficiency. The pressure
reducing valve will be described in section 6.5.
4.
Effluent outlet: Effluent outlet is normally designed as weir or bell mouth

pipe. It plays important role to control water level in the reactor so it should
be designed to be adjustable. Effluent from DAF will overflow off the weir
of bell month into gutter or trough, which is normally equipped with a pipe to
recycle some portion of effluent to saturator system. For rectangular channel,
outlet port normally locates at the opposite end of inlet port. However, in
some designs, outlet port will locate at the same side as inlet port to
maximize agglomerate paths. Internal baffle or lateral draw-off pipe should
be properly located to ensure that only clarified water will be withdrawn to
the weir or bell mouth.
Scum or float skimmer: air-pollutant agglomerate will float and form a

layer at the surface of the tank. The float layer is normally removed by means
of skimmer. Typical skimmer for rectangular tank is chain and flight type.
For circular tank, skimmer is normally rotating skimmer blade, attached to
the same central driving unit or rotating bridge as the bottom scraper. In
some designs, skimmer for circular tank is designed as a rotating scoop (see
fig. 6.4-2) to scoop off the scum and transport via its center trough that also
serves as a shaft to scum hopper. Scum hopper or scum receiving structure
will be placed a little higher than water outlet port in order to prevent water
from overflow into the structure.
Sludge draw-off: Settleable solids are normally present in the wastewater

and will be settled within any tanks, include DAF reactor. So sludge draw-off
system should be provided. Components of the system might vary from
simple draw-off pipes to sludge hopper with sludge scrapper. For circular
tank, scraper will be either peripheral driven or central driven type. For
rectangular tank, there are several types of scraper, i.e., chain and flight,
auger or screw conveyor.
Add-on process of DAF
Coagulation-flocculation: Efficiency of DAF depends on many factors included

influent oil droplet sizes. Even though DAF can be used as stand alone process, its
performance is normally erratic esp. when oil droplet size is very small. To make the
performance rather steady, coagulation-flocculation process is usually included to increase the
size of pollutant to be floated. Coagulation-flocculation process consists of 2 main
components, i.e., rapid (or flash) mixing part for coagulant-water mixing, and flocculation (or
slow mixing) part for floc formation. There are a lot of coagulants using for wastewater
treatment, such as metal salts, polyelectrolyte. Type and dosage of coagulant vary with
wastewater characteristic and can be archived by pilot testing, such as jar test or flota-test.
Details of this add-on process will be described in chapter 10. Pictures of coagulationflocculation from flota-test of cutting oil emulsion are shown in fig. 6.3-1. Examples of case
studies on oily wastewater treatment are shown in table. 6.4-1.
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Fig. 6.4-1 Example of necessary equipment and component details of DAF system (Source: Environ Treatment System)
257
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Table. 6.4-1
Data on efficiency and coagulant concentration of various oily wastewater

treatments by DAF [51]
Wastewater
Oil concentration
Coagulant
(mg/l)
Influent
Effluent
%Removal
125-170
35-52
70-72
100 alum
100
10
90
130 alum
580
68
88
Oil tanker ballast water
100 alum + 1 polymer
133
15
89
Paint manufacture
150 alum + 1polymer
1900
100
30 alum + 10 activated silica
250-700
20-50
>90
3830
270
93
4360
170
96
Refinery
Aircraft maintenance
Meat packing
Addition of transfer compound: Sometimes, efficiency of DAF is limited by

probability of air-pollutant agglomerate. In case of oily wastewater, the most frequent
encountered problem is ineffective collision between bubble and oil droplets (collision
without agglomerate forming). There are some attempts to solve this problem by adding
chemically active agent, called transfer compound, to change some properties of bubble or oil
droplet to facilitate oil-bubble agglomerate forming. These chemicals can be added to either
wastewater or as a gas to bubbles. Examples of these chemicals are ammonium gas,
surfactants, etc. In GPI lab, DUPRE [14] had studied the effect of various transfer compound
and concluded that addition of surfactant in pressurized water can cause augmentation in
population of microbubbles. On the contrary, addition of polyelectrolyte will cause decreasing
in electrical charge, then favor coalescence of bubbles.
Even though this method is used with some success for water-solid separation,
which the chemical helps forming stronger bond between bubble and solid surface, there is no
clearly evidence, at least in GPI lab, that it is feasible on oily wastewater treatment (see
section 6.2.4). So it is recommended to perform DAF test with the real wastewater before
design this add-on system. Otherwise, coagulation-flocculation may be more suitable.
a) KROFTAs inlet manifold with flow

control devices (Source: KROFTA)
b) Example of inlet branch pipes

(Source: Leopold)
Fig. 6.4-2 Necessary equipment and reactor components of DAF system

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III-141
c) Inclined inlet baffle at the center of the

tank (Source: WR DAF)
d) Perforated pipe inlet

(Source: HUBER)
e) Bell mouth pipe outlet (Source: ETS)
f) Example of weir outlet (Source: HUBER)
g) Lateral perforated pipes for effluent

draw-off (Source: Leopold)
h) Chain and flight scum skimmer
Fig. 6.4-2 Necessary equipment and reactor components of DAF system (Cont)
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III-142
i) Rotating scoop skimmer

(Source: DAF corp.)
j) Detail of rotating scoop skimmer

(Source: DAF corp.)
k) Example of CFD analysis on bubble

density in DAF reactor
(Source: InfilcoDegrmont)
l) Example of CFD analysis on velocity

distribution in DAF reactor
m) Typical flow pattern in DAF system

(Source : InfilcoDegrmont)
n) Folded flow pattern in DAF reactor

(Source: WR DAF)
o) Rectangular DAF reactor

(Source: WR DAF)
p) Circular DAF reactor

(Source: KROFTA)
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III-143
q) Example of shallow DAF reactor

(Source: WR DAF)
r) Graphical image of shallow DAF reactor

(Source: KROFTA)
s) Feed manifold and rotating internal baffle t) 4 effluent draw-off pipes in shallow DAF
in shallow DAF reactor (Source: WR DAF)
reactor (Source: WR DAF)
u) Flocculation tank (Source: Aquapak systems)
v) Flocculation pipe (the array of pipe

beside DAF reactor) (Source: WR DAF)
5.
Characteristic of float or scum
Characteristic of float or scum of DAF depends on characteristic of wastewater.

Fig. 6.4-3 shows some examples of scum from DAF. However, for refinery wastewater,
petroleum or oil-related industries, which oils are components of the wastewater, scum will be
261
III-144
rich in oil. Some literatures [50] report that oil concentration in DAF scum is as high as 50%
by weight for DAF process with coagulation-flocculation. For oil-rich scum, it could be
possible to use oleophilic oil skimmer, which is widely used for API tank.
However, solids and other pollutants are usually present in oily wastewater, the
scum, then, contains these solids and pollutants and is in form of thick froth layer. DAF
system can produce scum, which is normally more dense than settled sludge from settling
tank. Average concentration of 1% (solid content) could be expected. Higher concentration,
such as 3%, is reported by many sources [51].
a) Scum for petroleum industry (Source:

www.environmentalleverage.com)
b) Scum from high rate DAF reactor

c) Scum from circular DAF reactor

(Source: KROFTA)
d) Example of side window of DAF tank. Notice

float layer and bubble (Source: KROFTA)
Fig. 6.4-3 Examples of characteristics of scum from DAF processes
6.5
6.5.1
Working Principle and design calculation
Because air bubble is the heart of DAF operation, pressurized water system, then, is a
very important component of DAF for it is the source of air bubbles. Basic principle of
pressurized water system or saturator is to dissolve the air into the water at high pressure.
After that the pressurized water will be injected into the wastewater at operating pressure,
normally ambience. When the pressure decreases, solubility of air in water will decrease so
the excess air will become gas and cause air bubble within the water.
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There are 3 major modes of pressurization in DAF process, i.e.,
Full-flow pressurization: In this mode, whole wastewater is pressurized. It might

operate at lower pressure since the quantity of pressurized water is high, low
dissolved concentration of air is sufficient. Reactor in this case is designed only to
handle wastewater quantity. However, pollutants, esp. suspended solids, may cause
some problems to the saturator system, esp. injection valve and packed saturation
tank. It can not be used if coagulation-flocculation is employed for it may cause refragmentation of floc by the saturator packing.
Partial flow pressurization: In this mode, only some portion of wastewater is
pressurized and then sent to mix with the rest of wastewater to reactor. However,
pollutants in wastewater might still cause some problem to the saturator system.
Recycled flow pressurization: This mode of operation is the most popular. Some
portion of treated water is recycled to use as pressurized water. Quantity of the
water is relatively good for it has been treated. So it does not cause any problem to
the packed saturation tank. However, the reactor has to handle wastewater plus
recycled flowrate.
However, the pressurized water system for every mode of pressurization is identical.
Good saturator system has to provide a number of very tiny bubbles. Characteristic of good
pressurized water is that, when it is discharged into the reactor, it will have cloudy and milk
appearance for relatively long period of time, as shown in fig. 6.5-1.
a) Example of propagation of bubbles generated by pressurized water when injected

into the top of test tank.
b) Cloudy, milky appearance of bubbles generated by pressurized water

Fig 6.5-1 Example of good bubble formation from pressurized water (Source:
Cornell DAF pump)
263
III-146
From GPI research [12], theoretical equations, such as Henrys law and Daltons law,
can be used to calculate pressurized water system with relatively high accuracy. To size the
pressurized water system, the following procedure is proposed.
1.
Quantity of air or gas in pressurized water
Solubility or concentration of air in water in saturator is practically governed by

Henrys law (eq. 6.5.1).
x =
Where
{6.5.1}
yP
H
x = molar fraction of dissolved gas in water (mol/mol)

Y = molar fraction of gas in air (mol/mol) For air: y = 1 For oxygen:
y(O2) = 0.21 (=0.11 in permanent regime) For nitrogen: y(N) =
0.79 (= 0.89 in permanent regime)
P = absolute pressure of saturator (atm, or conforms to unit of H
used)
H = Henrys constant, depending on type of gas (20oC), i.e., For air:
H = 4.04x104 atm/mol For oxygen: H = 8.04x104 atm/mol For
nitrogen: H = 6.64x104 atm/mol
Eq. 6.5.1 can be used to calculate the value of x or molar solubility of gas in
saturator at any given pressure (P). Normally, saturator is operated at around 4 atm (abs).
Concentration of air or gas discharged within DAF reactor at ambience condition can be
calculated by eq. 6.5.2.
Conc .( gas ) =
x MW ( gas ) water
1000
MW (water )
mg/l
{6.5.2a}
Where MW(gas) and MW(water) are molecular weight of gas and water
respectively.
Substitute x from eq. 6.5.1.
Conc .( gas ) =
A =
y P MW ( gas ) water
1000 = A P
MW (water ) H
y MW ( gas ) water
1000
MW (water ) H
{6.5.2b}
{6.5.2c}
To facilitate calculation of dissolved air or gas, Henrys constant can be

expressed in the form of molair(or gas)/(m3 water.atm), called H. Eq. 6.5.2d can be used to
calculate the value of H at any temperature. Temperature is in Kelvin. From this concept, eq.
6.5.2b can be rewritten as shown in eq. 6.5.2e.
H ' = 0 . 000002 (T 273 ) 3 + 0 . 00039 (T 273 ) 2 0 . 02745 (T 273 ) + 1 . 2472
y P MW ( gas ) H ' mg/l
Conc .( gas ) =
1000
{6.5.2d}
{6.5.2e}
For quantity of gas discharged in DAF reactor, it can be calculated from

difference between concentration of dissolved gas in at saturators pressure and that at
ambience pressure, 20 as shown in eq. 6.5.3.
264
III-147

= y H 'R Q ( P P atm ) T ( 0 . 082 10
/( mol K ))
m3/s
{6.5.3a}
at T = 20oC (293 K)
gas = y H 'R P ( gauge
( 24 . 026 10
/ mol ) = B P ( gauge
m3/s
{6.5.3b}
Every constant in eq.6.5.2 and the value of A for eq. 6.5.2c, as well as, B for
eq. 6.5.3b are tabulated in table 6.5-1. Table 6.5-2 shows the value of A at various
temperature. The value of A and B in the table are theoretical value under an assumption
that the water is saturated by gas. In fact, general saturator can dissolve gas into water at
around 70-95% of saturated concentration. So value of Conc.(gas) and gas from eq. 6.5.2c
and 6.5.3b should be multiplied by the factor of 0.70 to 0.95 to yield the practical or observed
value.
Table. 6.5-1 Constant for calculation of concentration and quantity of gas for saturator
design (Operating pressure of DAF = Patm, T = 20oC)
Gas
Y
H
MW(g/mo
A
B
(mol gas / mol
(atm/mol)
l)
((mg/l)/atm) ((l gas/l water)/atm. gauge)
water)
Air
1.0
4.04x104
28.95
24.17
0.020
Oxygen
(O2)
0.21
8.04x104
32
9.222
0.0076
Table. 6.5-2 Air characteristic and solubility at Patm [51]

Temperature(
o
C)
Weight solubility:
A((mg/l)/atm.)
Volume solubility: B
((ml gas/l water)/atm gauge))
Air density
(g/l)
37.2
28.8
1.293
10
29.3
23.5
1.249
20
24.2
20.1
1.206
30
20.9
17.9
1.166
40
18.5
16.4
1.130
50
17.0
15.6
1.093
60
15.9
15.0
1.061
70
15.3
14.9
1.030
80
15.0
15.0
1.000
90
14.9
15.3
0.974
100
15.0
15.9
0.949
2.
Energy required
Main energy consumption for saturator is the energy for 1) compressing the gas
into water at required rate and 2) pumping the water at design pressure and flowrate.
Normally, pressure drop of piping system is relatively low, compared to working pressure of
the saturator, then can be negligible.
265
III-148
Energy for compressor can be practically calculated by adiabatic process

equation (PV1.4 = Constant) with satisfactory accuracy (see eq. 6.5.4). comp is overall
efficiency of compressor, which can be safely assumed to be around 60-70%.
Power =
comp
RT
0 .4
1 . 4 1
(
)
1 .4
P
Conc ( gas ) Q
pw
MW ( gas )
Patm
{6.5.4}
Using R = 8.314 Pa.m3/(mol. K), Conc(air) in g/l and Qpw in m3/s will result in
power as Watt. Molecular weight (MW) of air is 28.95 g/mol. Fig. 6.5-2 shows relation
between calculated power required for compressor and absolute pressure of saturator (P) for
10 m3/h of pressurized water.
Energy for pressurized water pump can be practically calculated by general
equation by assuming overall efficiency of the pump (pump) around 60-70%.
Power =
Q pw ( P Patm )
pump
Q pw P( gauge )
{6.5.5}
pump
Using Qpw in m3/s and pressure (P) in Pa. will result in power as Watt. Fig. 6.5-2
shows relation between calculated power required for pump and absolute pressure of saturator
(P) for 10 m3/h of pressurized water.
Energy for DAF pump The DAF pump is a special type of saturator that
integrate the function of compressor and pressurized water pump into a single machine.
Details of the pump will be described in the next section. Its energy required is theoretically
equal to summation of energy for compressor and energy for pressurized water pump.
However, single step estimation, using eq. 6.5.5 alone with pump around 50-60% is
acceptable. The exact energy required can be obtained from manufacturers information.
Power required for compressor

(Watt / 10 m3/h of water)
180
160
140
120
100
80
60
Pump
= 70%
2000
Pump
( = 100%)
1500
Compressor
= 70%
1000
Compressor
( = 100%)
40
Power required for pump

(Watt / 10 m3/h of water)
2500
200
500
20
0
0
0
Saturator pressure (atm. (absolute))
Fig. 6.5-2
Relation between power required for pump, compressor and absolute pressure of saturator for
pressurized water flowrate of 10 m3/h (assume %air saturation = 95%)
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III-149
6.5.2
Type of saturator and injection valve

1.
Saturator
Saturator can be divided into 2 main categories, i.e.,
2.
Combination of pump and saturation tank: Schematic diagram of this

system is generally as shown in fig. 6.5-3. Working principle of the system is
relatively the same as packaged booster pump or pump/pressure tank system
in water distribution work. However, the saturation tank has to be specially
designed to maximize air dissolution into water. For conventional system, the
tank is designed as packed column, using ring packing or likewise, as shown
in fig. 6.5-4. Saturation tank in this case is classified as pressure vessel, so, in
some countries, its design must conform to applicable law or regulation of
pressure vessel.
In some designs, the pressure tank is replaced by other air-water mixing

device, which is equivalent in performance but less complex and less
expensive. An example of this device is mixing pipe as shown in fig. 6.5-4.
Generally, air compressor for DAF is installed. However, in case that there is
common compressed air supply, it can be readily used in DAF. In few
design, the pressure tank with automatic air intake system, which is widely
used in packaged pump-pressure tank system, is used.
DAF pump: This device is combination of pump and air saturation system
into one machine. Air will be either sucked from ambience by the pump itself
or supplied by compressor into pump suction or pump casing. The air will
mix with the water within the pump. It eliminates the use of saturation tank.
Schematic diagram and examples of DAF pump are as shown in fig. 6.5-3
and 6.5-4.
Injection valve
Injection valve or pressure reducing valve or pressure release valve is a device

that practically generates air bubbles at the working point. The valve will reduce the pressure
of pressurized water to ambience, which cause excess dissolved gas to convert to gas bubbles.
In GPI lab, there are few researches on the value [14], [15]. From the researches, it shows that
the gas will be firstly generated in form of large gas pocket and then will be fragmented by
hydrodynamic force to form microbubbles (see fig. 6.5-5). So geometry of the valve, which
determines hydraulic condition, is the key parameter to obtain microbubbles. Many types of
valves are shown in fig. 6.5-5. Selection of the valve is based mainly on experience. However,
it is recommended to install the value as close to mixing zone between wastewater and
pressurized water as possible.
267
III-150
a) Conventional pressurized water system or saturator system
b) Saturator system using DAF pump

Fig. 6.5-3 Schematic diagrams of saturator systems (Source: Edur pump)
268
III-151
a) Packed tower to air saturation

(Source: Leopold)
b) Packed column for air saturation

(Source: Enprotec)
c) Air mixing tube for air saturation

(Source: DAF corp.)
d) Installetion of DAF pump

(Source: WR DAF)
e) Example of DAF pump

(Source: Edur pump)
f) Graphical image shows working principle

of DAF pump (Source: Hellbender pump)
Fig. 6.5-4 Examples of saturator system
269
III-152
a) Examples of injection valves [14]
b) Magnified photos of air pocket formation and fragmentation in convergencedivergence nozzle type injection valve [14]
Fig. 6.5-5 Examples of injection valve
6.6
There are many variations of DAF system in many ways such as tank shape, flow
pattern, equipment, loading rate, as described before in this chapter. So selection and design
of DAF is state-of-art, like many other processes, and based mainly on experience. However,
data from DAF test, such as Flota-test, and studies on successful projects for the same or
related type of wastewater are useful to design DAF system.
Advantages:
1.
It requires less footprint area than conventional decanter.
2.
Since it is accelerated process, we have some control over many operating

parameters, such as coagulant dosage, quantity of pressurized water, etc. Then it
has more flexibility to handle variation of wastewater characteristic.
3.
DAF is less effected by temperature, compared to other processes.

270
III-153
Disadvantages:
1.
Capital cost and operating is higher than conventional decanter.
2.
DAF system consists of a lot of equipment, so the maintenance is higher than

conventional decanter. Moreover, it may require more skill of the operator.
3.
Its efficiency depends on many parameters as described before, so it may

decrease if some parameters in not optimized.
4.
Coagulation-flocculation process is normally required. This causes more expense

on chemicals.
271
III-154
7.1
General
Hydroyclone is an accelerated separation process. Its main working concept is to

replace the gravitational acceleration that governs decanting velocity by higher centrifugal
acceleration. Hydrocyclones are widely used in many processes, i.e., classification and
separation between solid-liquid and liquid-liquid. Unlike other centrifugal machines, driving
force of hydrocyclone is generated solely from its inlet velocity. The higher the velocity (or
flowrate), the higher the efficiency. Or it can be implied that, at the same flowrate, smaller
will have higher performance that the smaller one. This is the most interesting advantage of
hydrocyclone.
Commercial hydrocyclones come in various shapes (single conical, long double
conical, etc.) and configurations (co-current or counter current, based on direction of water
and oil outlet flow). However, because it is used to make the separation between 2 phases
(such as, liquid-liquid, solid-liquid.), it will be called here as two-phase hydrocyclone. In
GPI lab, almost all of the researches are based on this type of hydrocyclone. In this chapter,
we will consider particularly on application of hydrocyclone on oil/water separation. For
oil/water separation, the hydrocyclones usually come in the form of elongated conical
hydrocyclone, as shown in fig 7.1-1a. Vortex or spiral movement in hydrocyclone will make
oil move inward to the center where it is purged to an overflow port, as shown in fig. 7.1-1.
Treated water will flow out at an underflow port. Studies on two-phase hydrocyclone for
oil/water separation will be described in section 7.2.
However, there is another type of hydrocyclone that is initiated by AURELLE and
MA [16] in GPI lab. This special hydrocyclone is an innovation designed for simultaneous
separation of oil and suspended solids from water. Studies on this three-phase hydrocyclone
will be summarized in section 7.3.
a) Graphical image shows vortex and oil

core in 2-phase counter current hydrocyclone
(Source: Ultraspin)
b) Graphical image of three-phase

hydrocyclone [16]
Fig. 7.1-1 Basic flow pattern and examples of hydrocyclones

272
III-155
50
Entre
Entre
53
Surface intrieure
428
255
Surface extrieure
120
Tube d'aspiration
Sortie eau
10
c) Industrial scale counter current 2phase hydrocyclone (Source: Krebs)
Sortie eau
Sortie huile
Sortie huile
d) Co-current lab scale 2-phase

hydrocyclone (Source: GPI lab)
Fig. 7.1-1 Basic flow pattern and examples of hydrocyclones (Cond)

7.2
7.2.1
Working principles
As mentioned earlier, working principle of hydrocyclone is based on modifying an

acceleration in STOKES law (eq. 7.2.1). From the law, rising or decanting velocity (Ud) of oil
droplet is proportional to acceleration (a). Generally, this acceleration means gravitational
acceleration (g). However, in centrifugal machine, liquid is forced to spin or centrifuged
around the axis of the machine. So the liquid is subjected to another acceleration, which is
centrifugal acceleration. If the liquid spins fast enough, the centrifugal acceleration (ac) will
overcome the gravity acceleration. The decanting velocity of oil droplets, as well as, removal
efficiency, will increase. The higher the centrifugal acceleration is, the better the efficiency is.
Ud =
a d 2
18 c
{7.2.1}
Where d = Diameter of dispersed phase, in this case, oil droplets

a = Corresponding acceleration of oil droplets
= Difference between density of dispersed phase and continuous phase
C = Dynamic (or absolute) viscosity of continuous phase, which is water, for
oily wastewater
Ud = Rising or decanting velocity of the droplet diameter d
So, efficiency of hydrocyclone can be described in term of ratio between centrifugal
and gravity acceleration, called the factor of acceleration (), as shown in eq. 7.2.2 .For
hydrocyclone, the driving force that makes the liquid rotate or spin comes from energy of its
own inlet flowrate. Theoretically, pressure head of feed flowrate can be converted to velocity
by energy conservation law, as shown in eq. 7.2.3.
ac =
2V 2
D
{7.2.2a}
a c 2V 2
=
g
gD
{7.2.2a}
{7.2.3}
V = 2 gH
273
III-156
From eq. 7.2.2a and 7.2.3, can be rewritten as follow,

=
2( 2 gH ) 2
{7.2.4a}
gD
4H
D
{7.2.4b}
Where = Factor of acceleration

V = Tangential velocity in hydrocyclone
D = Diameter of rotation, in this case, hydrocyclone diameter
H = Head or pressure drop across hydrocyclone
Eq. 7.2.4b signifies that,
Efficiency of hydrocyclone is direct proportional to its pressure drop.

As stated earlier in section 7.1, efficiency of hydrocyclone will increase if the size
of hydrocyclone decreases. It can be implied that, at the same flowrate, smaller
hydrocyclone is always more efficient than the bigger one.
7.2.1.1 General flow pattern and feature of hydrocyclone

General feature
Generally, hydrocyclone consists of cylindrical section, where inlet port(s) is
tangentially placed, and conical section, which may be a smooth cone (fig. 7.1-1d and 7.2.11a) or has an inflection point (fig. 7.1.1a,c and 7.2.1-b).
There may be one or two inlet ports. And it may have circular or rectangular opening.
For typical hydrocyclone, there will be an outlet port at the center of the cover of cylindrical
section. This port is always called overflow port. The port locate at the pointed end of conical
section is called underflow port. The wall of overflow port is, usually but not always,
protruded into the hydrocyclone. If it exists, this part is called vortex finder.
However, many manufacturers had separately engineered the shapes of their
hydrocyclones to fit their applications. For examples, there might be another cylindrical
section at the end of the conical section. Or there might be 2 concentric underflow without
overflow ports. Anyway, their working principal is always based on centrifugal acceleration.
Liquid-liquid hydrocyclone for oil/water seperation
Because of relatively low density difference between oil and water, compared to that
of solid and water, shape of liquid-liquid hydrocyclone for oil/water seperation has to be
adapted from typical solid-liquid hydrocyclone as shown in fig. 7.1-1 and 7.2.1-1f. The shape
of the oil/water hydrocyclone shown in the figure was researched and proposed by Prof.
THEW of University of Souththamton, UK. From the figure, another conical section with
small cone angle is added, and then followed by another cylindrical section. Overflow oil
outlet port is smaller than that of solid-liquid one. And there is no vortex finder since it is not
essential to prevent short circuit of oil to oil outlet. Moreover, THEW also shows that
presence of vortex finder resulted in lower efficiency. This hydrocyclone is widely accepted
274
III-157
as a typical design of oil/water separation. In GPI lab, MA [16] also used THEWs type
hydrocyclone for his model development.
General flow pattern
As mentioned earlier, general spiral flow pattern of typical hydrocyclone, which has 1
overflow and 1 underflow port, is as shown in fig. 7.2.1-1a. From the figure, there are both
upward and downward flow. Upward and downward flow pattern might be difference in case
of co-current hydrocyclone, which has 2 concentric underflow ports. Nevertheless, flow
pattern will always be spiral, which causes centrifugal acceleration.
From centrifugal acceleration and density difference between oil and water, oil
droplets will tend to move toward the axis of hydrocyclone and form an oil rich zone or oil
core at the axis (fig. 7.2.1-1d) that can be purged to an oil outlet port. Water, on the other
hand, will be centrifuged outward and flow out at water outlet port, as shown in fig. 7.1-1a
and 7.2.1-1b. Oil core normally contains both oil and water (fig. 7.2.1-1e). So oil removed
from hydrocyclone still contains some amount of water. Then hydrocyclone is rather oil
concentrator than oil separator. To separate oil from this concentrated mixture, other
separation process, such as coalescer, may be required.
Sometimes, there is an air core forming at the center of oil core (fig. 7.2.1-1c). It does
not provide any separation efficiency and, sometimes, makes the operation unstable. Presence
of air core can be avoided by providing back pressure, such as valve throttling, at the outlet
port.
Concentrated oil
Overflow port
Inlet port
Oily wastewater
Underflow port
Treated water
a) General spiral flow

pattern in typical
hydrocyclone [30]
b) Typical trajectory of oil droplets

in liquid-liquid hydrocyclone
c) Example of
presence of air core
[30]
Fig. 7.2.1-1 General flow pattern and features of hydrocyclones
275
III-158
d) Oil core formation (thin red strip at

the center of the hydrocyclone) [11]
e) Magnified photo of oil core, shows tiny

oil droplets suspending in water [16]
L1
L3
Do
Ds
Dn
Di
Dn/D=0.5, Ds/D=0.25, Do/D<0.05, L1/D=1, L3/D=15-20 , =1.50o, =20o

Di/D=0.25 for 1 inlet and 0.175 for 2 inlet ports, total length/D =45 (approx.)
f) THEWs type liquid-liquid hydrocyclone for oil/water separation

Fig. 7.2.1-1 General flow pattern and features of hydrocyclones
7.2.1.2 Velocity distribution in hydrocyclone
Flow pattern in hydorcyclone, as shown in the previous section, can be described in
the form of velocity within the hydrocyclone. Velocity at any point in the hydrocyclone can
be divided into 3 components, i.e., tangential, radial and axial velocity (fig. 7.2.1-2).
Characteristic of each velocity components will be described as follow.
R
lo
Hydrocyc
Vr = Radial velocity
Vt = Tangential velocity
Vz = Axial (or vertical) velocity
Vr
ne wall
Vt
Vz
Z
Axial axis
Fig. 7.2.1-2 Velocity components in hydrocyclone
276
III-159
1.
Tangential velocity
Outer zone: When water is fed tangentially into the hydrocyclone, it will cause
vortex flow pattern around axial axis on the hydrocyclone. Generally, in accordance with
conservation of angular momentum, tangential velocity (Vt) will increase as radial distance
from the axis of the hydrocyclone (R) decreases. Relation between tangential velocity and
radial distance in this zone is as shown in eq. 7.2.5.
{7.2.5}
Vt R n = const.
If n is equal to 1, this means conservation of the momentum is complete. The

vortex formed under this condition is called free vortex. However, for general
hydrocyclone, there is some loss within the hydrocyclone so there is no complete conservation
of the momentum. Normally, the value of n is between 0.5 1.0, depending on
configuration of hydrocyclone. This type of vortex, when n in not equal to 1.0, is called
semi-free vortex.
Inner zone: When small values of R are reached, flow pattern will change in the
manner that tangential velocity decreases with decrease in radial distance. The relation
between tangential velocity and radius becomes that of solid body rotation, corresponding to
constant angular velocity, as shown in eq. 7.2.6. This flow pattern is called forced vortex.
Vt R 1 = const.
{7.2.6}
Then, tangential velocity profile within general hydrocyclone will be as shown in

fig. 7.2.1-3c, where tangential velocity profiles of various types of vortex are also shown.
VtRn = Const.
Vt/R = Const.
n=1
n<1
Vt/R = Const. VtRn = Const
Ra
R
a) Free vortex (n=1) and

semi-free vortex (n<1)
b) Forced vortex
c) Combined vortex (general

case of hydrocyclone)
Fig. 7.2.1-3 Tangential velocity profile in hydrocyclone and various typed of vortex
Driving force of hydrocyclone come from inlet velocity. Theoretically, tangential
velocity at the wall of hydrocyclone at the inlet port level (Vc) should be equal to inlet
velocity (Vi). However, since there is some loss within the hydrocyclone, there is some
reduction of the tangential velocity from the inlet velocity. The ratio of the tangential velocity
to inlet velocity is called .
=
Vc
,<1
Vi
{7.2.7}
277
III-160
The value of varies with the shape of hydrocyclone. From eq. 7.2.5 and 7.2.7,
tangential velocity at any radial distance can be written as shown below.
D
D
Vt R n = V c ( ) n = Vi ( ) n
2
2
Vt = Vi (
Where
D n
)
2R
{7.2.8a}
{7.2.8b}
VI = Velocity in the inlet port of hydrocyclone

D = Diameter of hydrocyclone (measured at the same level as the
inlet port)
R = Radial distance
It should be noted that tangential velocity depends on radial distance (R), and is
independent of axial distance (Z). The velocity at the same R will be practically identical at
any axial distance from inlet level of hydrocyclone (Z), as shown in fig. 7.2.1-4.
R= r1
Vr1
Vr1
Vr1
Vr1
a) Source: Krebs
b) Data from KELSALL[30]
Fig. 7.2.1-4 Examples of tangential velocity profile

2.
Axial velocity
As shown in fig. 7.1-1 and 7.2.1-1 that the outer and inner layers of liquid in
hydrocyclone move in opposite direction, axial velocity (Vz) profile will consist of both
upward and downward velocity, as shown in fig. 7.2.1-5. Axial velocity profile depends on
shape of hydrocyclone, such as angle of cone, and operating condition, such as presence of air
core. Even in the same hydrocyclone, characteristic of axial velocity profile at various zones,
such as conical zone, inlet cylindrical zone or near apex zone. etc., are not similar. However,
typical axial velocity profiles at the effective conical section of hydrocyclone can be
simplified as shown in fig. 7.2.1-5b and 7.2.1-5c. Fig. 7.2.1-5b is typical axial velocity profile
for solid-liquid separation, proposed by RIETEMA [quoted by [16]]. For fig 7.2.1-3c, it is the
278
III-161
axial velocity profile, proposed by THEW and COLMAN [quoted by [16]] for of liquid-liquid
hydrocyclone, as well as, proposed by KASSELL [quoted by [30]] for solid-liquid separation.
There is no general relation or equation of axial velocity for hydrocyclone.
However, equations of axial velocity profile for specific shapes of hydrocyclone are available,
such as COLMANs equation for THEWs type liquid-liquid hydrocyclone. The equation
(shown in the next section) will be used for 2-phase hydrocyclone model development.
(Source: Krebs)
(Source: [52])
(Source: Bradley [30])
a) Examples of axial velocity profiles from various sources

Axial axis
wall
Hydr
o
Locus of zero
vertical velocity
Locus of zero
vertical velocity
cyclo
ne
Locus of zero
vertical velocity
b) Axial velocity profile

with 2 downward and 1
upward flows
c) Axial velocity profile

with 1 downward and 1
upward flows
d) Axial velocity profile

predicted by COLMANs
equation
Fig. 7.2.1-5 Example of axial or vertical velocity profile
279
III-162
3.
Radial velocity
Radial velocity (Vr) normally has a maximum value near to the wall of
hydrocyclone in inward direction. Then it will decrease with decreasing of radial distance. It
might or might not reach zero value and become outward radial velocity, depending on the
shape and axial position considering. Example of radial velocity profile is shown in fig. 7.2.16. KELSALL [30] proposed the estimated value of radial velocity in the conical section as
shown in eq. 7.2.9.
U = W tan( )
2
{7.2.9}
Fig. 7.2.1-6 Example of radial velocity profile [30]

7.2.1.3 Forces on particle in hydrocyclone
From the velocity fields of liquid or continuous phase decsribed above, dispersed
particles, in this case, oil droplets, suspended in hydrocyclone will subject to many
components of forces. Consider an oil droplet (or particle) in hydrocyclone as shown in fig.
7.2.1-7. The oil droplet will subject to several clearly-defined forces, such as,
R
F3
F5
F2
F4
lone wall
Fr
R
Hydrocyc
F1
Fig. 7.2.1-7 Forces on oil droplets or

particles in hydrocyclone
U
V
W
Resulting V
Z
Axial axis
Fig. 7.2.1-8 Components of velocity of oil

droplets or particles in hydrocyclone
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III-163
Centrifugal force in radial axis (F1)

V 2 d 3
F1 =
Drag force or hydraulic force in radial axis (F2)

F2 = Cd
d 2
1
cU 2
2
4
d 3
{7.2.5c}
Drag force or hydraulic force in axial axis (F4)

F4 = Cd
{7.2.5b}
Gravity force (F3)

F3 = g
{7.2.5a}
d 2
1
cW 2
2
4
{7.2.5d}
Drag force or hydraulic force in tangential direction (F5)

F5 = Cd
Where
U =
V =
W =
d 2
1
cV 2
2
4
{7.2.5e}
Radial velocity (or decanting velocity) of oil droplets

Tangential velocity of oil droplets
Axial velocity of oil droplets
Please note that three components of velocity are of oil droplets (fig 7.2.1-8), which
are not exactly the same as the three velocities (Vx, Vy, Vz) of liquid, described in the previous
sections. There are also other forces, such as lift force, etc. These forces will make the oil
droplets move in hydrocyclone and determine if those droplets can be totally, partially
separated or can not be separated by the hydrocyclone. Normally, it is not possible to exactly
calculate some components of forces or account for all forces to find the exact resultant force
that governs movement of oil droplets.
Thus, to predict if oil droplets can be separated by hydrocyclone or, on the other hand,
efficiency of hydrocyclone, there are 2 major approaches, i.e.,
Theoretical based model, such as trajectory analysis, equilibrium orbit or

retention time based model. Well proven laws, such as STOKES law, are applied
to these models under some assumption or simplification. This type of model
might or might not be very accurate, compared to empirical model derived from
experimental data. The accuracy of the type of model depends on degree of
simplification used by the researchers. But it is useful tool to understand the effect
of parameters to the effciency of hydrocyclone.
Empirical based model, such as the model and reducing efficiency curve,
proposed by Yoshioka and Hotta [30], Dalstorms, and Plitts , as well as THEWCOLMANs model.
7.2.1.4 Trajectory analysis model

GPIs trajectory analysis model for oil/water separation is the work of MA [16].
Concept of MAs model is adapted from the concept of decanter. Major assumptions that
underlines this model are that;
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III-164
The concept of decanter that oil droplets will be separated by hydrocyclone, if the
oil droplets can reach the decanting surface before flowing out with water is
applied (see fig. 7.2.1-9). Decanting surface in this case is assumed to be the locus
of zero vertical velocity (LZVV). If the droplets can reach this line, next moment,
they will start to travel upward to oil outlet port, then, are separated from the
wastewater.
There is equilibrium of forces in radial direction and oil droplet travels in the radial
direction at terminal velocity of immersed object in fluid stream.
Radial velocity is governed by STOKES law.
For tangential and axial velocity of oil droplet, it is assumed that oil droplets are
entrained by the water and have the same tangential and axial velocity as the water
at that point. So V = Vt and W = Vz.
THEWs type hydrocyclone is used. So tangential and axial velocity profiles are
calculated from the equations proposed by THEW, COLMAN [quoted by [16]] for
this type of hydrocyclone.
Three velocity components, used for model development, are governed by eq. 7.2.6 to
7.2.8.
Radial velocity: derived from STOKES law;
U =
{7.2.6}
d 2 V 2
18 c R
Tangential velocity: derived from energy conservation law (see eq. 7.2.8) and verified
by experimental data to find and n. For THEW hydrocyclone, = 0.50 and n = 0.65. Please
note that eq. 7.2.7b is valid only for 2-inlet ports hydrocyclone only.
V = 0.50Vi (
Or
D 0.65
)
2R
{7.2.7a}
Q
(
) D 0.65
V = 0.50 2 n
2 R
Di
4
{7.2.7b}
Axial velocity: COLMAN [quoted by 16]] observed axial velocity profile in lower
conical section of THEW hydrocyclone, which is the effective section, and developed axial
velocity equation in form of the 3rd order polynomial equation, as shown in eq. 7.2.8. Z-axis
starts from the bigger end of lower conical section, where R is equal to Dn/2, toward the lower
cylindrical section.
2
R
R
W
R
= 3.33 + 12
8.63 + 1.19
Wz
Rz
Rz
Rz
Q
Wz =
(0.5 D n Z tan( / 2)) 2
D
R z = n Z tan( )
2
2
282
{7.2.8a}
{7.2.8b}
{7.2.8b}
III-165
Q represents wastewater inlet flowrate. Dimensions of the hydrocyclone (Di, Dn, etc.)
conform to fig. 7.2.1-1f. To find trajectory, relation between R and Z has to be found. Firstly,
consider equation of U and W as follow;
R
t
U =
W =
{7.2.9a}
Z
t
{7.2.9b}
From above equations, we have;
R U
=
Z W
R Z
=
{7.2.10a}
{7.2.10b}
Integration of eq. 7.2.10b will result in the relation between R and Z, as shown in eq.
7.2.10c.
RZVV
=
0
{7.2.10c}
RZVV represents any points on the locus of zero vertical velocity (LZVV), which is
normally in conical shape. However, since conical angle of the lower cone is very small
(1.5o), it can be safely assume that LZVV is cylindrical with the radius of RZVV at the small
end on the cone (Z=L). At Z = L, from eq. 7.2.8, RZVV is equal to 0.186(Dn/2). So relation
between R and Z or trajectory of oil droplets can be rewritten as shown in eq. 7.2.11.
Integration of the equation is transcendental and requires complex numerical method, such as
Runge-Kutta. However, it can be done by advanced calculator or computer program,
including the program being developed in this research.
0.186 ( Dn / 2 )
{7.2.11}
R
Hyd r o
0.5Dn
Rd
cy cl o
ne wa
ll d > d
c
d < dc
LZVV
d = dc
0.186Dn
d
100%
Zone 1
Zone 2
d < dc
d = or > d c
dc
Fig. 7.2.1-9 Trajectories of oil droplets and typical efficiency curve

from trajectory analysis model
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III-166
Efficiency determination
Fig. 7.2.1-9 shows the trajectories of oil droplets in lower conical section of
hydrocyclone. As stated before, decanting surface in this case is the locus of zero vertical
velocity (LZVV), which can be calculated from eq. 7.2.8, where W = 0. To simplify the
calculation, it is assumed that LZVV is cylindrical with R = 0.186(Dn/2).
From the figure, the longest path to reach the LZVV is the path starting at the wall of
the hydrocyclone at larger end of the cone to the zero-vertical-velocity point at the lower end
of the cone (fig. 7.2.1-9a). The smallest droplet size that can reach this point is called the cut
size (dc). The droplets of cut size or bigger are always separated from wastewater stream with
100% removal efficiency (eq. 7.2.12a).
d = 100%
For d dc
{7.2.12a}
The smaller droplets can be also separated providing that they enter the cone near to
the axis of the hydrocyclone. When uniformly distributed influent flow is valid, which is
practically true, the removal efficiency of the droplets smaller than cut size are proportional to
corresponding radial distance (Rd) that makes the droplets reach the ZVV point at the lower
end of the cone, as shown in eq. 7.2.9b. Typical efficieny curve of the trajectory analysis
model is shown in fig. 7.2.1-12b.
Dn 2
)
2
d =
100 %
Dn 2
Dn 2
(
) ( 0 . 186
)
2
2
R d2 ( 0 . 186
For d < dc
{7.2.12b}
7.2.1.5 Other models

There are several researches that suggests the model to predict the efficiency of
hydrocyclone, both theoretical and empirical based, such as Bradleys, Rietemas,
Dahlstroms, Chebelins, Plitts, Lynchs, etc. [16],[28]- [34]. However, most of models are
developed from solid-liquid hydrocyclone. Some models are developed for specific
commercial oil/water hydrocyclone, such as Vertoils. So it should be applied only with that
specific hydrocyclone. Extrapolation of model is normally not guaranteed.
For THEWs type hydrocyclone, used by MA in his research, Prof. THEW, himself,
and his colleague, COLMAN, have proposed the model for the hydrocyclone (eq. 7.2.13a).
However, it is empirical model, which seems to be obtained from curve fitting. The equation
for estimation of d75% for THEWs hydrocyclone, quoted by CHEBELIN [29], is as shown in
eq. 7.2.13b (use unit in kg, m, second.)
d = 1 e
d 75%
( 1 . 8 (
d
d 75 %
0.01 ( D n ) 3
=
0 . 19 ))
{7.2.13a}
0.5
{7.2.13b}
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MAs model was verified by observed data obtained from crude oil/water treatment.
Fig. 7.2.1-10 shows the efficiency curve from MAs trajectory analysis model (eq. 7.2.6 to
7.2.8, 7.2.11), THEW-COLMANs model (eq. 7.2.10 and 7.2.11) and observed efficiency
[16]. From the figure, it shows that, at droplet size > 20 microns, MAs and THEWCOLMANs models give relatively accurate result ( 10% error). However, at d > d 80%,
THEW-COLMANs model seems to cause higher degree of error and predict too high value
of cut size. This may because the researchers used different assumptions or operating
condition to develop their models.
Difference between MAs model and observed value can be explained by effect of the
assumptions used to develop the model as follow;
Radial velocities of oil droplets are not exactly governed by STOKES law.
STOKES law is valid only in laminar flow regime (Re of droplets < 1). However,
in some cases, esp. when droplet size is large, Re might be greater than 1. And
from very short retention time, the droplets may not reach the terminal velocity,
governed by STOKES law. Furthermore, radial velocity of water, which can carry
the oil droplets along and add-up to the decanting velocity from, is not accounted.
So the value of U used in the model is, generally, lower than actual value. This is
the reason why the predicted efficiency is lower than the observed value.
Effect of eddy current, lift forces, drag forces in vertical and tangential direction is
assumed to be negligible and cancelled. Anyway, they, in fact, can cause some
discrepancies in the prediction result.
Effect of hinder settling, esp. near to the center of hydrocyclone
However, Mas model is developed from theoretical assumption and does include
many parameters, such as viscosity, feed flowrate, and size of the hydrocyclone, etc., which
can be used to explain or verify the effect of these parameters to the efficiency. So, it provides
valuable tool to designer and will be used in the computer program being developed under the
scope of work of this research. Furthermore, the trajectory analysis model is developed under
the assumptions that give underestimated result. So the predicted efficiency is on the safe side.
110%
100%
90%
Efficiency (%)
80%
70%
60%
50%
40%
30%
Thew-Colman's model
Observed data
Ma's trajectory analysis
20%
10%
0%
0.00
10.00
20.00
30.00
40.00
50.00
60.00
Note: Dn = 0.02 m, Q = 1.943 m3/h, Vi = 7.12 m/s: Wastewater used is crude oil/water emulsion: =
98 kg/m3, = 0.0011 Ns/m2, = 15o, d = 15 to 50 microns
Fig. 7.2.1-10 Comparison between observed efficiency and predicted efficiency form
MAs model and THEW-COLMANs model
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III-168
There is no tested evidence about the valid range of MAs model. However, from the
assumptions used, the model should be valid for every THEWs type hydrocyclone as long as
operating condition is in valid range of STOKES law (laminar flow region: Re < 1). Anyway,
working condition and performance of hydrocyclone are also governed or limited by other
parameters or factors. So it is more suitable to state that the model is valid in laminar flow
region when other factors also confirm to working limit of hydrocyclone, as described in
section 7.2.1.7.
Parameters that affect the performance of hydrocyclone are those presenting in model,
as shown in section 7.2.1.4. However there are some factors that have influent on the
efficiency of hydrocyclone that can not be expressed in form of numerical function. Influent
parameters of hydrocyclone, collected from GPI researches and many literatures, can be
summarized as follow;
1.
Droplet size (d)
Efficiency of hydrocyclone increases with increasing of droplet size, as clearly

shown in fig. 7.2.1-10. So it is recommended to avoid any action that can cause oil drops to
break-up into smeller droplets, such as using high-shear feed pump (Ex. high speed
centrifugal pump, or regenerative turbine pump). On the contrary, putting some process that
can increase the size of droplets at upstream of hydrocyclone, such as high-rate coalescer, will
help increasing hydrocyclone performance.
2.
Feed flowrate (Q)
From eq. 7.2.4, efficiency of hydrocyclone will increase, if feed flowrate

increases for it will make inlet velocity, which is a driving force of hydrocyclone, increase.
However, this is true before velocity in the cyclone reaches the value that droplet refragmentation occurs. There are evidences [16], [28] that the inlet velocity (Vi) as high as 7
m/s is used without causing any adverse effect on efficiency. This value of Vi can be
compared to velocity of 1.7 m/s, using nominal diameter (Dn) of the cyclone. Please note that
increasing of flowrate also cause pressure drop to be increased, which effects operating cost.
Pressure drop will be described separately in section 7.2.1.8.
3.
Shape of hydrocyclone
Shape of hydrocyclone substantially effects its velocity profiles and vortex

formation. So it certainly effect its performance. But it can not be expressed in form of
numerical equation. Many researchers have studied effect of dimension of each component of
solid-liquid hydrocyclone (such as inlet port, overflow, underflow port, vortex finder, etc.).
For oil/water hydrocyclone, THEW has thoroughly studied the effect of geometry and
proposed the optimized shape of the cyclone, which is used in GPI researches. In fact, we
usually design hydrocyclone system from standard commercial product, which, more or less,
conform to THEWs geometry. Anyway, MA [16] had carried out some profound studies of 2
components. The result is as shown below.
Conical angle : Using lower (from 20o to 8o) result in decreasing of

pressure drop about 11% (from 4.5 to 4.0 bar at 1.6 m3/h, Dn = 16 mm, crude
oil/water emulsion) while the efficiency is relatively unchanged.
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III-169
Ratio Dn/D: Lower Dn/D from 0.5 to 0.43 can increase efficiency (+5% for
Q = 1 to 1.6 m3/h) but pressure drop is also considerably increased (+0.5 bar
for Q = 1 to 1.6 m3/h, D = 32 mm, Dn = 16 and 14 mm).
It must be noted that the models in section 7.2.1.4 and 7.2.1.5 are valid only for
THEWs type hydrocyclone only.
4.
Inlet oil concentration (Co)
For low concentration oily wastewater (Co < 1%), the concentration has
practically no effect on efficiency. For higher concentration, theoretically, it should effect the
performance from hinder settling effect and changing of viscosity. However, THEW [28]
shows that the efficiency is little affected even at the concentration as high as 10 15%.
5.
Purge ratio or split ratio(Rf)
For oily/water separation, oil will be purged to outlet overflow port. Purge ratio
(Rf) (or split ratio) is the ratio between oil outlet flowrate (overflow) to water feed flowrate
(Q). Theoretically, flowrate of overflow should be as close as possible to the flowrate of oil
components in the water to get relatively pure separated oil. However, in practice, it is
impossible to do so because pressure drop will be too high and some oil will entrain to
underflow port. It is recommended to use Rf around 1.8 to 2.0 times of flowrate of inlet oil
[28]. For general oily wastewater, which inlet oil concentration less than 5% (by volume),
purged oil flow is relatively small compared to the whole flow. So it does not effect velocity
profile and efficiency of hydrocyclone. But it effects pressure drop, which will be described in
the next section.
6.
Wastewater characteristic and presence of surfactant
Wastewater characteristic inevitably affects efficiency of hydrocyclone. The

model in section 7.2.1.4 has included general parameters that represent characteristic of
wastewater, such as , c, etc. So it is useful tool to understand effect of parameters on
cyclone performance. Some indirect parameters can be determined if it effects the
performance or not by considering its effect on those parameters included in the equation.
For example, presence of salinity will increase density difference, so it favors
efficiency. Presence of surfactant will lower interfacial tension, resulting in fragmentation of
droplets, so it causes adverse effect on hydrocyclone.
7.
Temperature (T)
Proporties of oil and water always change with parameter. So it is inevitable that
temperature will effect hydrocyclone efficiency. Rising in temperature make water viscosity
decrease, then favors the efficiency. However, it will decrease interfacial tension and density
difference, then has adverse effect on the efficiency. So effect of temperature on individual
waster will be accounted on these facts. Anyway, for petroleum/water emulsion at normal
working condition (<40o C), increasing of temperature, more or less, favors hydrocyclone
efficiency.
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III-170
8.
Presence of air core
Air core could form at the axis of hydrocyclone from presence of low-pressure
region generated by vortex, especially when it is purged directly to atmosphere. It is also
formed by changing in solubility of gas in water from decreasing of pressure. Presence of air
core might partially block the overflow port and result in instability of performance. Air core
formation can be suppressed by avoiding direct purge to atmosphere and the use of
backpressure. However, many system operating with several percent of air core (by volume)
still give satisfactory result. So throttling should be made until the efficiency is optimized
without over-emphasizing on air core formation. In fact, its formation could not be visible in
commercial opaque hydrocyclone.
Pressure drop is very important parameter since it directly relates to driving force of
the hydrocyclone, as shown in eq. 7.2.4. Furthermore, purge ratio and back pressure control to
suppress the air core is normally be done by valve throttling at the two outlet ports, which
directly effects the pressure drop.
Pressure drop can be divided into 2 types, i.e., pressure drop across inlet and overflow
port (Po) and pressure drop across inlet and underflow port (Pu).
Like the case of efficiency, equations of the pressure drop of hydrocyclone were
proposed, based on both theoretical and empirical approach. However, there is no pressure
drop model for THEWs type hydrocyclone, which we knew of. Anyway, many literatures
[16], [28] [34] show that general model of pressure drop relation is as shown in eq. 7.2.14.
P = f (Q 2 . xx / D n 4 )
{7.2.14}
From GPI researches, there are sufficient data to formulate semi-empirical models of
pressure drop from the general model, as shown below.
For pressure drop (bar) across inlet and overflow port (oil outlet);
Q 2.3 2.6
Po = 16 4
Dn (1 R f )
0.1611
{7.2.15a}
Flowrate and hydrocyclone diameter are in m3/s and m, respectively. Rf is lower than
1.0. However, effect of purge ratio is verified from relatively small set of data, so it might
cause some error. Firthermore, for low concentration wastewater (Co<5%, Rf <10%), effect
or Rf is very small. Eq. 7.2.15a can be rewritten as eq. 7.2.15b, which can be safely used
without causing serious error.
Po = 16
Q 2.3
Dn
1.17
{7.2.15b}
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For pressure drop (bar) across inlet and underflow port (water oultet);
Pu = 4 . 6
Q 2.2
{7.2.15c}
Dn 4
From above equations, it should be noted that:
Pressure drop of overflow is always higher than that of underflow. So it is used for
pump sizing. If multi-stage hydrocyclone system is used, available pressure for the
next stage is equal to (Po-Pu). The unit of Q is in m3/s, D in meter.
Underflow pressure drop is practically independent of split ratio. While overflow

pressure drop is slightly affected by the split ratio.
For oily wastewater treatment, which involves low concentration of oil,

characteristic of wastewater does not affect the pressured drops.
General working pressure range of hydrocyclone is up to 6.5 bar. THEW [28]

recommended the value of 1-5 bar. Hydrocyclone selection is to be compromised between
efficiency, size (capital cost) and pressure drop (operating cost).
7.2.2
Design calculation
Design procedure for hydrocyclone is based upon the equations, shown in the previous
sections. To design two-phase hydrocyclone for oily wastewater treatment, the required cut
size will be determined first. After that, the size of the hydrocyclone can be preliminary
selected. Then, graded efficiency (efficiency of each size of droplet) and then total removal
efficiency can be determined. The procedure will be repeated until the optimum size is
selected. Calculation in each step is described below.
1
from the limitation of the decanting processes. Cut size determination from degree of
treatment is described in chapter 3. For theoretical limitation, since the model is based on
STOKES law, it can be applied only when the droplet behavior conforms to the law. Thus, it
can not be used with very small droplet sizes for they are subjected to Brownians motion and
their rising velocity are not governs by STOKES law. There are also some limitations from
characteristic of hydrocyclon itself that governs the cut size selection. Generally,
recommended smallest diameter that can be separated (but only partially) by hydrocyclone is
about 20 microns. For smaller droplets, the efficiency will be very low and erratic.
To design the hydrocyclone by MAs model, it is recommended to select the cut
size that covers majority of oil droplet in the wastewater and provide a safety factor around
10% to 20%, because the model is apt to predict too small cut size. For example, if the desired
cut size is 50 microns, it is recommended to select 50(1-0.20) = 40 microns.
2
Hydrocyclone sizing
The size of the hydrocyclone could be roughly estimated by general design

criteria, such as maximum working pressure, hydraulic loading, etc. Fig. 7.2.1-1 shows the
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III-172
relations between flowrate, inlet velocity, velocity at lower conical section (at dia. = Dn) VS.
diameter of the cylindrical part of hydrocyclone (D) at Po = 3 and 5 bars, which are generally
used as design pressure. For the exact size, the mathematical model can be used. Then the
model will be used again to find the graded efficiency of the hydrocyclone. After that, the size
may be fine adjusted again to obtain the required efficiency.
14.00
Flowrate (m3/h) and Velocity (m/s)
12.00
Inlet V at P = 5 bar
10.00
Q at P = 5 bar
8.00
Q at P = 3 bar
Inlet V at P = 3 bar
6.00
4.00
V at Dn
at P = 5 bar
2.00
at P = 3 bar
0.00
0
10
20
30
40
50
60
70
80
90
100
Diameter of cylindrical section of hydrocyclone (D) (mm)
Fig. 7.2.1-1 Corresponding flowrate and velocities of various sizes of hydrocyclones at

overflow pressure drop (Po) = 3 and 5 bars
To size the hydrocyclone and calculate greaded efficiency of the hydrocyclone,
the following procedure, based on MAs model, is recommended.
2.1
Calculate the size of hydrocyclone (Dn)
The size of the hydrocyclone can be calculated by integrating eq. 7.2.11, using
the design cut size from item 1. The corresponding R will be equal to (Dn/2). The integration
can be done by the use of a scientific calculator, general mathematical software or the
computer program developed in the scope of work of this research.
0.186 ( Dn / 2 )
R
U
U =
{7.2.11}
d 2 V 2
18 c R
{7.2.6}
Q
(
) D 0.65
V = 0.50 2 n
2 R
Di
4
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
{7.2.7b}
2
R
+ 1.19
Rz
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{7.2.8a}
III-173
{7.2.8b}
Q
(0.5 D n Z tan( / 2)) 2
D
R z = n Z tan( )
2
2
0.25( D n )
L=
tan(1.5 o / 2)
Wz =
2.2
{7.2.8b}
{7.2.16}
Calculate corresponding radial entering distance (Rd)
For the droplet smaller than the cut size, it is necessary to calculate the
corresponding Rd that makes the droplet reach the radial distance R = 0.186(Dn/2) at Z = L.
To calculate Rd, eq. 7.2.11 need to be integrated again, using every value of d that is smaller
than the cut size.
3
Outlet concentration and removal efficiency

Graded efficiency
Graded efficiency (or centrifugal efficiency), in this case, represents the

efficiency calculated from the trajectory analysis method. For d dc, graded efficiency will be
equal to 100%.
d = 100 %
For d dc
{7.2.12a}
For the droplet smaller than the cut size, the theoretical graded efficiency can be
calculated, using the Rd from item 2.2, by the following equation.
Dn 2
)
2
d =
100 %
Dn 2
Dn 2
(
) ( 0 . 186
)
2
2
R d2 ( 0 . 186
For d < dc
{7.2.12b}
Outlet concentration
Outlet oil concentration at the underflow (water) and overflow (oil) outlet can be
calculated from theoretical efficiency and purged ration as shown in eq. 7.2.17a and b,
respectively. The equation is valid only when the purged flow is greater than the oil
quantity in the wastewater. Otherwise the oil that can reach the oil core will not be purged
entirely and then entrain with the underflow.
C d , overflow
( 1 d ) C od
(1 R f )
=
d C od
{7.2.17a}
{7.2.17b}
Rf
Global efficiency and removal efficiency

Graded efficiency is not the actual efficiency of hydrocyclone because it does
not account for purged or split flow. Even though this split flow is small and hardly affects the
flow regime in the hydrocyclone, it, somehow, affects the oil concentration calculation. As
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described in section 7.2.1.7, the purged flow must be greater than the oil quantity in the
wastewater. Otherwise the oil that can reach the oil core will not be purged entirely.
Total removal efficiency (t) of the hydrocyclone represents ratio of oil
concentration between underflow and inlet flow, which can be calculated from the following
equation.
1
1 d
{7.2.18}
t =
d C od 100 %
max
(1 R f ) C o
d min
Co = Inlet oil concentration of the wastewater

Rf = Split ratio (= Qoverflow/Q)
4
Pressure drop and energy required
The pressure drop (in bar) can be calculated from the following equations.
Generally, the overflow pressure drop is greater than that of underflow and will be used as
design pressure for feed pump selection. The unit of Q is in m3/s, D in meter.
Q 2.3 2.6
Po = 16 4
Dn (1 R f )
Pu = 4 . 6
7.2.3
0.1611
{7.2.15a}
Q 2.2
{7.2.15c}
Dn 4
1.
The equations described above are developed from the following assumptions
and limitations. Thus, it is necessary to ensure that these assumptions are valid when design
your hydrocyclone.
1)
2)
3)
The model is valid only for THEWs type hydrocyclone or other cyclones
with relative identical geometry.
comparison only.
Eq. 7.2.7a is valid for the hydrocyclone with 2 inlet ports only. If the
hydrocyclone has only 1 inlet port, Q in the equation will be modified as
shown in eq. 7.2.7a. However, using 2 inlet ports is recommended for its
hydraulics stability. Please note that the size of 2 inlet ports will be smaller
than a single inlet port to keep the inlet area constant.
V = 2(
4)
D
)( n ) 0.65
D 2 R
i
Q
{7.2.7a}
For general oily wastewater with the oil concentration of 5% or less,

overflow quantity is small, not greater than 10%. So its effect on velocity
profiles and efficiency is small, thus, negligible.
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5)
6)
7)
8)
2.
From the assumptions used for model development, the model prediction
has some discrepancies from the actual value. However, as stated in section
7.2.1.6, it is a useful tool for understanding the effect of each parameter.
The hydrocyclone should be designed within the limitations shown in
section 7.2.1.7. The size of hydrocyclone should conform to commercial
standard sizes.
From eq. 7.2.4b, it is recommended to select the smallest possible
hydrocyclone. However, the pressure drop, clogging problem from the
presence of suspended solids and cost should be taken into account.
From the high shear characteristic, it is reasonable to assume that there is
no coalescense taking place within the hydrocyclone. Re-fragmentation can
be avoided by following the recommended range for pressure and flowrate.
So it can imply that the overall size distribution of oil droplets is not
affected by the hydrocyclone. This assumption is useful for considering the
size distribution of each stage of multi-stage hydrocyclone system.
Construction and system integration
Normally, we select the hydrocyclone from commercial products. So we cannot

do anything about its design and fabrication. However, it is necessary to study the product to
make sure if it conforms to our model limitation.
Hydrocyclone efficiency depends on the sizes of the oil droplets, so the
processes that can make the droplets smaller, such as pumping, should be avoid or kept to
minimum, at the upstream of the hydrocyclone. Or the hydrocyclone should be installed as
close to the wastewater source as possible.
Generally, oily wastewater contains some suspended solids. So the hydrocyclone
system is designed as a coupling of soild-liquid and liquid-liquid hydrocyclone, as shown in
fig.7.2.3-1. In this case, the feed pressure of the first stage hydrocyclone should be sufficient
for the next stage hydrocyclone(s). Installation of booster pump between each stage is
possible but not recommended since it will make the oil droplets smaller.
a) schematic diagram
b) An example of commercial set
Fig. 7.2.3-1 An example of the coupling between solid-liquid and liquid hydrocyclone for the
treatment of oily wastewater containing suspended solids (Source: Ultraspin)
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7.2.4
Variations, advantage and disadvantage of hydrocyclone

Variation of two-phase hydrocyclone
There are some variations of liquid-liquid hydrocyclone, for example in flow pattern
(counter current, co-current), etc. (see fig. 7.1-1). In any case, the majority of the liquid-liquid
hydrocyclone still conforms or relativelty close to THEWs type. Nowadays, there are several
suppliers that commercialize these products, such as Neyrtec, Dorr Oliver, Krebs, Ultraspin,
etc. So designers can find further information from these suppliers.
However, there is another type of liquid-liquid hydrocyclone preliminary tested in GPI
lab [11] that should be mentioned here, i.e. the co-current hydrocyclone (fig. 7.1-1d). Main
advantage of this hydrocyclone comes from its shape which is considerable shorter (around
8.5 times of D) than THEWs type (about 45 times of D). So it requires less installation space.
There is no study on comparison between THEWs and the co-current cyclone efficiencies in
GPI lab. However, WANICHKUL [11] proposed useful relation between oil and water outlet
velocity of the co-current hydrocyclone. He used an oil extract pump, instead of typical outlet
valves, to control oil outlet flowrate. From fig. 7.2.4-1, the effects of relation between water
outlet velocity (V1) and oil outlet velocity on oil removal efficiency are summarized below.
V1
V2
Oil outlet
tube, dt
Water outlet
Oil outlet
Case I: V1V2 and

dt > Oil core
Case II: V1<V2 and

dt > Oil core
Case III: V1V2 and

dt < Oil core
Case IV: V1>>V2 and

dt < Oil core
Fig. 7.2.4-1 Relation between oil and water outlet velocity in co-current hydrocyclone
V1 V2 and the concentric oil outlet tube is greater than diameter of oil core
The oil will be largely removed. The efficiency is high.
V1 < V2 and the oil outlet tube is greater than diameter of oil core The oil will
also be largely removed. But some oil will be entrained with the water. The
efficiency is slightly lowered.
V1 V2 and the oil outlet tube is smaller than diameter of oil core The oil will
flow out at both oil outlet and water outlet ports. The efficiency is low.
V1 >>V2 and the oil outlet tube is smaller than diameter of oil core The
efficiency is, somehow, relatively high from the effect of high oil outlet velocity.
These facts are useful for the co-current cyclone operation. However, the efficiency of
the co-current hydrocyclone cannot be calculated by MAs trajectory analysis model. To
design this cyclone, designers should consult the manufacturers or find more researches on
this type of hydrocyclone.
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Advantages: Main advantages of the hydrocyclone include.
Its compactness and it has no moving part.

Its efficiency increases with flowrate (eq. 7.2.4b). This is the most distinguished
advantage of the hydrocyclone.
No additional chemicals (such as coagulant, floccuclants) required.
The operation is not complicate.
Its modular construction facilitates upgrading or optimization.
Disadvantages: Main disadvantages of the hydrocyclone include,
It is a pollutant concentrator, rather than a separator. However, GPI lab has

developed the oily wastewater treatment system which is the combination of
hydrocyclone and coalescer to make it possible to obtain relatively pure separated
oil. The details will be discribed in chapter 12.
The hydrocyclone cannot remove the oil and the suspended solids simultaneously.
So it needs at least 2 hydrocyclones of different shape. To overcome this
disadvantage, GPI lab has initiated a special hydrocyclone that can separate both
the oil and suspended solids at the same time. The details will be described in the
following section.
7.3
7.3.1
Working principles
As mentioned in the previous section, a limitation of general hydrocyclone is that it

cannot be used to separate solid and liquid pollutant from the wastewater simultaneously.
Coupling of standard solid-liquid and liquid-liquid hydrocyclones are normally used for this
purpose (fig. 7.2.3-1). To obtain these two separations simultaneously, AURELLE and MA
[16] had initiated a new type of hydrocyclone, known as three-phase hydrocyclone, as
shown in fig. 7.3.1-1. The idea behind its geometry is the fusion between liquid-liquid cyclone
of THEW and solid-liquid cyclone of RIETEMA. The vortex created by inlet flow will be
used as a driving force for the 2 parts of the hydrocyclone. Three-phase hydrocyclone does
not require an inter-connecting pipe between 2 cyclones like typical 2-cyclone system (fig.
7.2.3-1). Theoretically, it means the energy loss of the system is reduced. Thus the efficiency
should be better. Installation space is also reduced.
Solid-liquid part

Di
Du
Dp
D Do
Ds
L4
L2
L1
L5
L3
Note: Di/D=0.25 for 1- inlet and 0.175 for 2- inlet, Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid part cone angle=12o, for liquid-liquid part=1.5o
Fig. 7.3.1-1 Three-phase hydrocyclone

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Fig. 7.3.1-2a shows the trajectories of oil droplets and suspended solids. The solids
will be centrifuged outward to the wall of cyclone and be purged at the annular solid outlet
port at the apex of RIETEMAs conical section. The oil droplets will move toward the axis in
the RIETEMA part and flow up into THEW part, where they will join the oil core. The oil
core will spirally flow at the axis down to the RIETEMA part again, and then be purged to oil
concentric outlet tube.
Generally, working principle of this hydrocyclone is still similar to that of two-phase
hydrocyclone. However, The result from MAs Plexiglas model showed that the vertical
velocity in RIETMA part is slightly changed to account for the central oil core, as shown in
fig. 7.3.1-2b.
Wastewater inlet
Concentric oil outlet tube

Water inlet
Solid annular outlet port
Wastewater inlet
Fig. 7.3.1-2a Oil drop (sphere) and particle (cube) trajectories in three-phase hydrocyclone
Solid-liquid
(RIETEMA) part
Liquid-liquid
(THEW) part
Fig. 7.3.1-2b Typical vertical velocity profiles in three-phase hydrocyclone

7.3.1.1 Model for liquid-liquid part
MA reported that the flow pattern and formation of the oil core inside the THEW (oil)
part of three-phase hydrocyclone is identical to THEWs hydrocyclone. But no mathematical
model had been proposed. However, from the identical flow pattern compared to THEWs
cyclone, it can be safely assumed that the driving force of this hydrocyclone is identical to
THEWs type hydrocyclone and MAs trajectory analysis for THEWs type hydrocyclone
should be applicable for this cyclone as well.
From the assumption that two and three-phase hydrocyclone have identical driving
force, which is the fraction of their own inlet velocity, we have the following equation;
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3 V
=
V
Thew i(Thew)
i(3 )
4Q
3
)2
(D
i(3 )
4Q
= 0.5
2
(D i(Thew) )
From the geographies of the cyclones (fig. 7.2.1-1f and 7.3.1-1),

Dn in fig.7.2.1.1f = Do in fig. 7.3.1-1 = ND.
4Q
3
ND 2
))
(0.25(
0.43
4Q
= 0.5
ND 2
))
(0.25(
0.5
2
0.5
3 = 0.5
= 0.676
0.43
{7.3.1}
The subscript 3 and THEW represent that the variables belong to three-phase
hydrocyclone and THEWs type hydrocyclone, respectively.
From above equations, MAs model as shown in section 7.2.2 can be adapted for
three-phase hydrocyclone design by changing the value of in eq. 7.2.7b from 0.50 to 0.676.
Dn in the equations of 2-phase hydrocyclone is replaced by Do in case of 3-phase
hydrocyclone. L in those equations is also replaced by L5. The model was verified by the
observed data from MAs research. The result showed that the model could predict the
theoretical oil removal efficiency of the three-phase hydrocyclone with 20% accuracy.
7.3.1.2 Model for solid-liquid part
MA did not propose model for solid-liquid part either. Anyway, since the geometry of
this part of three-phase hydrocyclone is similar to RIETEMAs cyclone, the assumption that
the driving force of this cyclone is identical to standard RIETEMA hydrocyclone should be
valid. So the model derived for RIETEMA hydrocyclone, which is general form of solidliquid hydrocyclone, should be applicable to three-phase hydrocyclone.
RIETEMA [30] defined the performance of the hydrocyclone in the form of d50% and
the dimensionless number Cy50, as shown in eq. 5.9. To find graded efficiency besides d50%,
correlation of YOSHIOKA and HOTTA [30], for 2% < d <98%, may be applied (eq. 5.10).
2
d 50 ( ss c )(L 2 L 4 ) p
= Cy 50
c cQ
(
d,SS
=1 e
{7.3.2}
0.115)3
50%
{7.3.3}
RIETEMA recommended the value of Cy50 around 3.5 for RIETEMA type
hydrocyclone, which MA used as one part of his hydrocyclone. So it is recommended to use
Cy50 =3.5 to calculate the efficiency of solid part of three-phase hydrocyclone.
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MA proposed the model for pressure drop calculation for his prototype hydrocyclone.
For the prototype, he used Do = 14 mm and D = 32 mm. Pressure drops across various ports of
the prototype (in bar) can be calculated from the following equations,
Pwater = 1.364Q 2.11
{7.3.4a}
Pss = 0.951Q 2.34
{7.3.4b}
Poil = 3.140Q 2.03
{7.3.4c}
The equations are valid only for 14/32-mm. three-phase hydrocyclone. Thus, to extend
the valid range of the equations or to develop generalized model. We consider 2 approaches.
Similarity approach
From TRAWINSKY [33], he suggested that hydrocyclone, like other centrifugal

machines, is subject to concept of similarity or affinity law.
P D 1d 50%
{7.3.5}
So combination of eq. 7.3.4 and 7.3.5 can be used to predict the pressure drops of
any size of three-phase hydrocyclone by calculating the pressure drops of 14/32-mm.
hydrocyclone at given flowrate by eq. 7.3.4 first, then use eq. 7.3.5 to find the flowrate at
given hydrocyclone diameter and given characteristic of wastewater.
Empirical approach
Similarity approach is theoretical based. In practice, many factors may cause some
discrepancies from theoretical value. To account for these factors, empirical approach is
introduced. We base our model on eq. 7.2.14 that we successfully applied for two-phase
hydrocyclone.
To develop and verify empirical model, we use the data from MAs and THEWs
research [16], [18]. The empirical models for predicting of the pressure drop across inlet and
various outlet ports are as shown in eq. 7.3.6 (P in Bar, Q in m3/s, D in m.).
Pwater = 49.8
Pss = 21
Q 2.12
D4
{7.3.6a}
Q 2.34
D4
{7.3.6b}
Q 2.03
D4
{7.3.6c}
P = 55
oil
The equations are in the similar forms to MAs models. However, substituting the
value of D = 32 mm in eq. 7.3.6 will not result in the exact eq. 7.3.4 because eq. 7.3.6 are
verified from wider range of data.
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Comparisons between the predicted pressure drops of the 2 approaches, using data
from [16], [28], are as shown in fig. 7.3.1-3. The graphs show that the two approaches give
very accurate results. However, using eq. 7.3.4 and 7.3.5 may cause some difficulty because it
requires calculation for d50% first. So using eq. 7.3.6 may be more convenient.
9.00
7.00
5.00
4.00
3.00
Semi-empirical
6.00
Similarity
8.00
= Pressure drop across oil outlet port
2.00
= Pressure drop across water outlet port
1.00
0.00
0.00
= Pressure drop across SS outlet port
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
Fig. 7.3.1-3 Comparison between observed pressure drop and predicted valued from the 2
approaches (similarity and semi-empirical model)
7.3.2
Because the mathematical models of three-phase hydrocyclone is adapted from twophase hydrocyclone, design procedure as well as design consideration for the three-phase
hydrocyclone will be identical to that of the two-phase, as shown in section 7.2.1 and 7.2.2.
But the efficiency and pressure drop across solid outlet port of the solid-liquid part will be
calculated additionally by eq. 7.3.2, 7.3.3 and 7.3.6b.
7.3.3
Advantage and disadvantage of three-phase hydrocyclone
Advantage: Main advantage of this hydrocyclone is that it can remove solid and oil
simultaneously. It can replace typical two-stage system. The installation space is reduced. It
also helps saving the piping work
Disadvantage: Various types of three-phase hydrocyclone are developed and
patented, such as AURELLE and MAs and few American designs. However, it is available
as custom-made equipment, rather than mass product. So it may not be cheap and may cause
some inconvenient in maintenance or part replacement. The oil and solids removal
efficiencies are also inter-related for they share the same driving force. So, in some case, to
obtain one good removal efficiency (either oil or solid), the other removal performance may
not work at the optimized condition. So the flexibility of the system is, somehow, less than
that of the coupling between 2 cyclones.
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8.1
General
Membrane process is a separation process based, mainly but not entirely, on filtration
concept. Physically, membrane is permeable or semi-permeable material, which restricts the
motion of certain species [54]. Theoretically, we can always separate one or more components
from fluid stream providing that the membrane chosen is suitable for size difference.
Membrane process becomes one of the most promising separation process due to its
characteristics that fulfill modern needs, proposed by AURELLE [56], i.e.,
Its efficient
Its compactness
Its closed-system characteristic, no odor, no noise pollution
Its automatic control capability
Nowadays there are a lot of books, literatures and researches on membrane processes.
Membrane manufacturers can also provide useful data from their own experiences. Thus, in
this chapter, the main context will emphasize on the researches of GPI lab on the treatment
of oily wastewater by membrane processes. Only some basic principles and mathematical
model, related to the researches, will be present to provide basic understanding. UF is the
main membrane process of the GPI researches on oily wastewater treatment since its
separation characteristic practically covers the range of oil droplets found in general oily
wastewater, esp. macro- and microemulsion. Thus, majority of this chapter devotes to UF
study. For other processes, only some basic knowledge and the significant findings from the
GPI researches will be presented.
8.1.1
There are several types of membrane separation processes. Here will be considered
only the pressure-driven membrane processes. Other processes that use other forms of driving
forces, such as electrodialysis (electrical potential), dialysis (concentration gradient),
pervaporation (concentration and vapor pressure), will not be considered here. Pressure-driven
membrane processes can be categorized by their separation characteristics, i.e.,
microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO). An
example of relation between material sizes and their corresponding membrane processes is as
shown in fig. 8.1.1-1. From the relations shown in the figure, separation characteristic of each
membrane process can be summarized as shown in fig. 8.1.1-2. Membrane are classified
either by pore size or molecular weight cut-off (MWCO). The latter is determined by
relation between the sizes of materials to be separated by the membranes and their molecular
weights. It should be noted that manufactures, sometimes, use different kinds of material to
determine the MWCO, i.e., proteins (globulin, albumin, etc.), saccharides (dextrans), etc.
Thus there is some difference in the relation between the pore size and molecular weight. It is
recommended to confirm with the manufacturers. The size of material, defined by MWCO,
may not be exactly equal to the pore size of the membrane. But it is the size that the
membrane can be separated with acceptable efficiency (about 90%), not absolute (100%). So
it is usually called normal MWCO or NMWCO, to distinguish from absolute MWCO
that which is normally not specified.
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MF and UF have relatively large pore sizes, so they work rather like screens or sieve
filters. While separation by NF and RO, which have very tiny pore sizes, is not simply by size
alone but involves more complex factors, such as osmotic pressure. So we can group the
membranes processes into 2 categories, i.e., (1) MF and UF, (2) NF and RO.
Fig. 8.1.1-1 Material sizes and corresponding membrane processes (Source: Osmonics)
Fig. 8.1.1-2 Separation characteristic of membrane processes

(Source: Koch membrane system)
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8.1.2
In membrane process, wastewater or mixture that contains the objects or materials to

be separated (called feed) will be fed to membrane module. Only certain component of feed
will be able to pass through the membrane. The component that can pass through the
membrane is generally called permeate or filtrate. The rest, which is retained by the
membrane, will remain in the feed side and be called retentate or concentrate.
Mode of operation, categorized by flow direction of feed, can be generally divided
into 2 modes, as shown in fig. 8.1.2-1, i.e.,
Dead-end mode- Flow direction of feed is perpendicular to the membrane surface.

Retained component will accumulate on the membrane surface so its operation is
rather like a cake filtration. This cake could obstruct the permeate flow, resulting
in lower permeate flowrate. However, because of its simplicity, no complex piping
required, it is normally used in slab-scale for preliminary testing of membrane.
Anyway some upscale dead-end membrane, such as pleated MF, is also available.
Cross-flow or tangential flow mode- Unlike dead-end mode, the feed is pumped
over the surface of the membrane, resulting in two product streams i.e., permeate
and retentate. The later is sometimes recycled to the feed side and fed to the
membrane again until it reaches the design concentration, esp. in case that the
concentrate is the required product. General commercial membranes are
configured to be operated in this mode of operation. It is practically used in real
life situation. So, in this chapter, we emphasize only on the cross flow mode.
a) Dead end
b) Cross-flow
Fig. 8.1.2-1 Mode of operation of membrane process [11]

8.1.3
Membrane structure
Application of a membrane depends on its mechanism, which, in turn, based upon its
structure. Many authors may suggest difference number of membrane structures. By some
criteria, some structures may be only sub-types of other structure. However, it can be
generally summarized into two major structures, i.e. symmetric and asymmetric membrane.
Symmetric membranes are the membranes of uniform structure. Their separation

mechanism can be compared to in-depth filtration. Microporous membrane is
categorized in to this type of the structure. Normally, inorganic membranes, such
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as ceramics, microporous glasses, metals, come under this structure. This type of
membrane may be produced by these manufacturing processes, i.e.,
Sintering or stretching
Casting
Phase inversion and etching
Extrusion
More details can be provided by membrane manufacturers or from literatures and

books. Sometimes, symmetric membranes are undergone coating process to
achieve some specific properties. In this case, it will become asymmetric
membrane with composite structure.
Asymmetric membranes are the membranes of non-uniform structure, which

separation process takes place a thin denser skin layer of the membrane. Their
separation mechanism can be compared to screening or sieving. They can be
produced of a single polymer. In this case, they will be called integrally skinned.
Sometimes, a thin dense polymer skin is formed on the microporous support.
Then, it will be called composite or non-integrally skinned membrane.
Asymmetric membrane may be produced by these manufacturing processes, i.e.,
Casting of skin and laminating to support film

Dip-coating of skin-forming polymer onto microporous support
Phase inversion
Gas-phase deposition of the barrier layer from a glow-discharge plasma
Interfacial-polymerization of reactive monomers on the surface of support film
a) Symmetric structure
b) Asymmetric
Fig. 8.1.3-1 Membrane structures (Source: SCT, Millipore)

8.1.4
Membrane material
Membrane material plays very important role on separation. To obtain efficient

separation, the membrane material should posses the following properties;
Chemical resistance to feed and cleaning agents

Mechanical and thermal stability
High selectivity and permeability
Stable operation
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The properties mentioned above depend on types of membrane material as well as

feed or, in our case, wastewater. Membrane materials can be divided into 2 groups, i.e.,
Polymeric material
Inorganic material
Some polymeric membrane materials and their properties are briefly summarized, as
shown in table 8.1.4-2. For inorganic materials, they generally include ceramics, glasses and
metals. Almost all of inorganic membranes are in tubular form, either single-channel or multichannel module. For ceramic membranes, they are generally of asymmetric (composite)
structure with fine-grain skin, such as titania (TiO2) or zirconia (ZrO2), over porous support,
such as alumina (Al2O3) or zirconia. There are many variants of these composite materials,
such as zirconia/alumina, titania/alumina, carbon/zirconia, carbon/carbon, etc. For metal
membranes, stainless steel is used as support layers with sintered or coated skin, such as
zirconia. Inorganic membranes are, sometimes, coated with polymeric skin to produce the
membranes of required pore with very durable support layer, which can be re-coated when the
skin is damaged. General advantages and disadvantages of inorganic membranes are as
tabulated in table 8.1.4-1.
Properties and characteristic of the two types of membranes described in this section
can be used as a preliminary guideline for material selection. However, its properties may be
modified by modern coating or other process to obtain required characteristic of each
application. Furthermore, there are other materials that can be used for membrane production.
So it is recommended to consult the manufacturers and perform feasibility test before design
the system.
a) Regenerated CA, regenerated PS (above),

effect of surface thickness on void formation
b) PP(above) and Polycarbonate from

irradiation and chemical process
Fig. 8.1.4-1 Membrane materials (Structures depend on manufacturing processes.)

(Source: Millipore, Orelis, WWW.Scienceinafica.co.za)
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e) Polysulfone UF
d) Ceramic
Fig. 8.1.4-1 Membrane materials (Structures depend on manufacturing processes.)

(Source: Millipore, Orelis, WWW.Scienceinafica.co.za) (Cont)
Table 8.1.4-1 Advantages and disadvantages of inorganic membrane [38]
Advantage
Disadvantage
Very good chemical resistance to chlorine,

acids, alkalis, common solvents. However,
even though the membrane is very durable,
chemical resistance of other accessories, such
as seals, must be considered.
Initial cost is much more expensive than

polymeric membranes. However, lifetime and
saving in replacement cost must be taken into
account.
Wide range of pH (0.5-13, even 0-14 for Ceramic membranes are naturally brittle. It
some types) and temperature (up to 125o C, could be damaged if dropped or subjected to
even 350o C for some types).
severe vibration.
High pressure limit (up to 10 bar), which is Require high tangential velocity (2-6 m/s). So
usually the limit of seals.
large pumping capacity is required.
Extended operating lifetime, more than 10 Narrow range of pore size, normally available
years-lifetime is reported.
only in MF and UF forms.
Backflushing capability
cleaning of membrane.
allows
effective
In general, high permeate flux.
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Table 8.1.4-2 Summary on membrane polymeric materials [38], [54], [57]

Material
Cellulose
(CA)
Type of
membrane
acetate MF, UF, RO
Advantage
Inexpensive
Wide range of pore size,
Hydrophilicity
Disadvantage
Narrow pH (3-6) and
temperature range (<40oC),
Moderate chlorine resistance
(<1 mg/l free Cl)
Good fouling resistance to oil

Biodegradable
and fat.
Polyamide ,
aromatic (PA)
MF, UF, NF, Wide range of pH (2-12) and

temperature (to 70 oC)
RO
More permselectivity than
CA
Polysulfone (PS)
MF, UF, RO Wide range of temperature

substrate
(up to 75oC 125oC) and pH
(1-13)
Good chlorine resistance (to
200 ppm)
Good chemical resistance to
alcohols, acids, halogenated
hydrocarbons
Polyacrylonitrile
(PAN)
Polypropylene (PP)
MF, UF, RO Hydrophilicity

substrate
form)
MF, UF
Low resistance to free

chlorine, esp. in alkali solution
Biodegradable.
Hydrophobicity,
Low range of pressure (< 7 bar
for plate, <1.7 bar for hollow
fiber)
Moderate chemical resistance
to aromatic hydrocarbons,
ketones, ethers, esters
(modified Narrow range of pore size
Good chemical resistance
Require co-polymer to make

less brittle
Inexpensive
Hydrophobicity
Wide range of temperature

Good chemical resistance
Polytetrafluoroethylene (PTFE)
MF, UF
Polyvinylidene
fluoride (PVDF)
MF, UF
Very good chemical and

thermal stability
Hydrophobicity
Very good chemical

resistance to chlorine, acid,
alkali, common solvents
Hydrophobicity (can be
modified to obtain
hydrophilicity), Expensive
Expensive
Note: Bold letters are most usual application. [57]

8.1.5
There are several types of membrane module available. However, they can be divided
into 5 types (fig. 8.1.5-1), categorized by their geometry, i.e.,
Tubular module
Hollow fiber module
Plate module
Spiral wound module
Other types, such as dead-end pleated module, rotating disc module, etc.
306
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Here will be described only the first 4 types for they are normally applied on oily
wastewater treatment. General characteristic of each type of membrane module can be
summarized as shown in table 8.1.5-1. Please be noted that technologies are improved
everyday. So some data (cost, efficiency, some features, etc) need to be updated regularly.
a) Tubular (Source: Orelis, Koch)
b) Hollow fiber (Source: Koch, Romicon)
c) Plate (Source: Millipore, Orelis)
d) Spiral wound (Source: Orelis, ALTO japan)
Fig. 8.1.5-1 Membrane modules

307
III-190
e) Pleated module
(Source: Vivendi water, Sentry)
f) Rotating disk system (above) and vibrating

membrane system (Source: IGB, VSEP)
Fig. 8.1.5-1 Membrane modules (Cont)
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309
Module cost
High ($1300 1500 / m2) [38]
Low [57]
10000-20000 : outside in RO
1500-5000 : inside-out UF
150-300
Membrane area to
volume ratio (m2/m3)
Laminar but high shear rate

from its small diameter (2,00016,000sec-1). V of 0.5-2.5 m/s.
Re > 10,000. Velocity of 2-6 m/s

for UF.
Flow regime
Moderate ($500-100 / m2)
100-300
Moderate ($800-1,000 / m2)
800-1200
Re varies from 100-13,000.
Feed channel height varies

from 0.5-3.0 mm., depending
on the presence of suspended
solids.
Average feed channel height is

0.5-1.5 mm. Support grid of
channel spacer helps promoting
turbulence which increases the
permeate flux.
Very small, 0.2-3.0 mm for

UF and MF and as small as 40
microns for RO. Prefilter is
necessary. Because of its self
support
structure,
Backflushing is possible
Large ( 12.5 mm). They can

handle
wastewater
with
relatively
large
particles.
However, the particles of 10% of
tube diameter or larger should be
screened out.
It is backflushable.
Flow passage
Laminar in general.
Equivalent to that of plate

module. But SS in feed may
deposit at the channel
spacers. Some tubular or
corrugated spacer is being
developed.
Feed is distributed to each

rectangular feed flow channel.
The permeate will flow through
the membrane plates and flow
in permeates channels to the
outlet ports.
Like the tubular module, feed

is distributed to the cores of
the
fibers.
(Only
few
manufacturers do vice versa.)
Feed is distributed to each

membranes tube. It flows inside
the tube and the permeate flows
through the tubular walls and out
off the outer shell at outlet port.
It can be viewed as a rolledup plate module around a

center perforated pipe that
act as a permeate channel.
The rolled-up membrane is
then placed in the shell.
Spiral wound (fig. 8.1.5-1d)
Flow pattern
A module consists of a flat

sheet, a support grid used as a
permeate flow channel and a
membrane plate. Above the
membrane is a feed flow
channel. Several groups of
layers may be stacked to form a
multi channel module. Due to
its shape, it is relatively easy for
on-site replacement.
Plate (fig. 8.1.5-1c)
The membrane materials are

cast as tiny tubular shape like
the tubular module but much
smaller and there is no support
insert. They are also come in
the form of shell-and-tube.
Hollow fiber (fig. 8.1.5-1b)
Polymeric materials, acting as

membrane surface, are cast on
the inside of porous tubular
inserts. For ceramic membranes,
they are usually monolith and
self-supporting. They usually
come in the form of shell-andtube. The outer shell is also used
as permeate collector.
Tubular (fig. 8.1.5-1a)
General
Characteristic
Table 8.1.5-1 General characteristic of various membrane module [38], [54], [57]
III-192
8.2
8.2.1
8.2.1.1 Pore size and molecular weight cut-off (MWCO) of UF

Ultrafiltration (UF) membrane can retain material of the size larger than 0.001-0.02
microns (1-20 nm) [38], which is the size of finely dispersed oil droplet in emulsions. So the
researches in GPI lab emphasized on the application of UF, rather than other membrane
processes. UF membranes are normally specified by the molecular weight cut-off MWCO.
To relate the membrane to MWCO, PORTER [59] proposed the relation based on globular
proteins as shown in fig. 8.2.1-1. Please note that if the specified MWCO is not based on the
proteins, the graph will not be valid. Hence, the exact pore size information should be
confirmed by the manufactures.
Poer size (microns)
100
10
1
1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
Molecular weight cut-off (MWCO) as Kilo Daltan (kd)
Fig. 8.2.1-1 Relation between pore sizes and MWCO [59]

Removal or retaining efficiency of membranes are usually described in the term of
rejection (R), which is defined by eq.8.2.1.
R =1
Where CP
CR
=
=
CP
CR
{8.2.1}
Solute or pollutant concentration in permeate
Solute or pollutant concentration in retentate
If the pollutants are completely rejected by the membrane, CP will become zero and R
will be equal to 1 or 100%.
Typical characteristic of rejection or removal efficiency of a membrane and molecular
weight is a shown in fig. 8.2.1-2. Existing UF membranes often posses diffuse cut-off,
rather than sharp cut-off, characteristic because of its wide distribution of pore sizes. .
NMWCO is the molecular weight at the rejection of 90%. This percentage may not be
practically exact but it is the generally accepted value. So the pore size shown in fig. 8.2.1-1 is
the effective value, corresponding to its NMWCO.
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Rejection or
Removal efficiency
100 %
Ideal cut-off
90 %
Sharp
cut-off
Diffuse
cut-off
0%
1,000
Log (molecular weight)

NMWCO
10,000 100,000
Fig. 8.2.1-2 Typical characteristic curves of UF membrane

To select the appropriate membrane to separate the oil droplet or particles from the
wastewater, AURELLE summarized and proposed 3 basic considerations as follows,
Pore size of membrane: To prevent oil droplets to pass through the membrane
pore, the size of the pore, firstly, must be smaller than the droplets. From
researches in GPI lab, it is recommended that minimum pore size should be 1/4 to
1/3 of average droplet size. Some researches [38] even proposed the ratio of 1/10.
Characteristic of membrane: for oil/water separation, membrane should be

hydrophilic. Membrane material should not react with the wastewater, which can
cause pour clogging. Hydrophilic material, such as polyacrylic, cellulose acetate,
zirconium oxide, etc., is recommended. Naturally without special treatment or
coating, polysulfonate tends to be fouled by oil, resulting in low flux and frequent
washing.
Operating condition: Operating pressure should be less than capillary pressure

required to force the oil droplets through the membrane pores. Capillary pressure
increases with the hydrophilicity of membrane and decreasing of pore size.
However, if pore size and hydrophilicity are carefully selected, the capillary
pressure is normally higher than recommended maximum pressure of the
membrane. The capillary pressure of oil drop can be calculated by the modified
form of the capillary equation (see chapter 2), proposed by NAZZAL (quoted by
[10], [11]) as shown in eq. 8.2.2.
cos
o/w
Pcap = 2
o/w
r
rd
4
r
1/3
3cos
cos 3
2
o/w
o/w
1
cos
+ (2 sin
+ sin 3
)
o/w
o/w
o/w
311
{8.2.2}
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Where rd
r
o/w
=
=
=
=
Oil droplet
rd
Membrane
Radius of oil droplet (L)

Pore radius (L)
Contact angle
interfacial tension of
2r
Pore
oil and water (MT-2)
Fig. 8.2.1-3 Oil drop at membrane pore

8.2.1.2 Characteristic of cross-flow ultrafiltraton
Because almost all of the ultrafiltration processes in real life situation are in cross-flow
mode, characteristics and theories presented in this chapter, then, will be based on cross-flow
ultrafiltration. For wastewater treatment process, the aims of the process are (1) to separate
the pollutants from the water and (2) to reduce the volume of the retentate as much as
possible. So the UF processes are normally designed as a batch system, shown in fig.8.2.1-4,
which will be used to describe the characteristics of cross-flow UF in this section. In this
section, only characteristic curves are presented but the explanation and the models that
govern the characteristics will be described in the next section.
Retentate
Po
Storage
tank
Membrane
Pp
Permeate
Pi
Feed
Feed
pump
Heat
exchanger
Fig. 8.2.1-4 Typical schematic of cross-flow UF for wastwater treatment

1.
Permeate flux and transmembrane pressure
From fig. 8.2.1-4, the feed will be pumped by feed pump into the cross-flow UF
module. The pressure on the feed side (PF) will be higher than the pressure on the permeate
side (Pp), which is normally equal to atmosphere. So the solvent and the solutes that cannot be
retain will be forced through the membrane as permeate. Difference between the pressure on
feed and permeate sides (eq. 8.2.3) is called the transmembrane pressure (Pt). Since the
feed inlet pressure (Pi) and outlet pressure (Po) is not identical due to losses in the membrane
module, PF is an average value of Pi and Po (eq. 8.2.4). Flowrate of permeate is usually
defined as permeate flux, which is the flowrate per unit area of the membrane, such as litre
per square meter per hour (LMH).
{8.2.3}
Pt = PF Pp
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PF =
Pi + Po
2
{8.2.4}
Water flux
If pure water is fed to the membrane, the relation between permeate flux and
transmembrane pressure will be or almost linear, as shown in fig. 8.2.1-5a.
Flux of mixture, solution, or wastewater
If the feed concentration is constant, which can be obtained by either recycling
the permeate and retentater or not returning both of them back to the feed storage tank, typical
characteristic curves of permeate flux and transmembrane pressure will be as shown in fig.
8.2.1-5b. From the figure, the graph can be divided into 2 major zones, i.e.,
Pressure controlled region- the flux is proportional to pressure.

Mass transfer controlled region- the flux is nearly constant and relatively
independent to pressure.
The graph also shows the effects of various parameters on the flux/pressure
relation. Other types of graphs also exist for some types of feed. But they are minority (fig.
8.2.1-5a).
Typical
water flux
An example of variants
of water flux
Typical solution flux
Flux
An example of variants
of solution flux
Fig. 8.2.1-5a Examples of pure water flux and solution flux characteristics
Higher recirculation flow

or cross-flow velocity
Higer temperature
Lower concentration
Wate
r
Flux
Mass transfer
controlled region
flux
Pressure controlled
region
Fig. 8.2.1-5b Typical characteristic curves of water and solution flux VS. transmembrane
pressure when feed conc. is constant
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2.
Permeate flux and feed concentration
Relations between feed concentrations and permeate fluxes in log/normal scale

are as shown in fig.8.2.1-6. The typical relation is linear, as shown in curve 1. However, in
case of oily wastewater, the curve is proven to be as shown in curve 2 [11], [18]. Other shapes
of graphs also exist but are scarcely found.
Flux
1
Cg
Cg
case 1 case 2
Cg
case 2
Log (Concentration)
Fig. 8.2.1-6 Characteristic curves of permeate flux and feed concentration

3.
Permeate flux and time

Constant feed concentration
Evolutions of flux with time when the feed concentration is kept constant are
shown in fig. 8.2.1-7. The flux will decrease rapidly at first, then the rate of decrease will be
slower. After that the flux will be relatively constant or steady. The fluxes shown in fig. 8.2.14 are the value of flux in this steady zone. The period of time before the flux reaches steady
value may take few minutes or several minutes, depending on the type of wastewater, type of
membrane and operating conditions, as shown in fig 8.2.1-7. In fig. 8.2.1-7a, the relation that
the flux increases with time is scarcely observed. It occurs when the feed concentration is very
low and the cross-flow velocity is high.
Flux
Flux
Higher cross-flow velocity

Lower concentration
Higher Pt
Time
Time
a) Effect of velocity and feed concentration
b) Effect of transmembtane pressure
Fig. 8.2.1-7 Typical characteristics of permeate flux VS. time for constant feed conc. system
314
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Non-constant feed concentration

Evolution of flux with in this case will be varied with wastewater characteristic,
membrane properties and operating condition. For oily wastewater treatment, the retentate is
returned to the storage tank where fresh wastewater may and may not be added, as shown in
fig. 8.2.1-4. Then it is fed repeatedly to the membrane until it reaches a required
concentration, or the flux is unacceptable low. In this case, the concentration of feed, as well
as flux, varies with time.
General characteristic of UF of oily wastewater in batch process described above
is as shown in fig. 8.2.1-8. At first, the flux drops relatively rapid, then rate of decrease is
lower. The flux decreases slower until it reaches a certain concentration. Then rate of decrease
in flux is higher until it become about zero.
Flux
Time
Fig. 8.2.1-8 An example of characteristic of flux VS. time for non-constant feed conc. system
8.2.1.3 Flux model in pressure controlled region
From characteristics of UF processes described above, Many researchers had tried to
explain them in term of related theories and established mathematical models to predict the
characteristics of UF. To predict flux of UF in pressure controlled region (fig.8.2.1-5b), the
widely accepted model is the one based on flow through porous channel, which is governed
by Hagen-Poiseuille law, as shown in eq. 8.2.5.
d p2 Pt
= A Pt
J =
32 x
{8.2.5}
Flux (L3L-2T-1, i.e. LMH or gallon per ft2 per day (GFD))
Surface porosity of the membrane
Pore diameter (L)
Transmembrane pressure (LT-2M-1)
Length of the channel, in this case, the thickness of skin layer of
the membrane (L)
Dynamic viscosity of feed (ML-1T-1)
Membrane permeability coefficient (L)
Where J
dp
Pt
x
=
=
=
=
=
315
III-198
The model is valid the following assumptions are satisfied [38];

1.
2.
3.
4.
5.
The flow is in laminar regime. Re < 2100. It is usually true under certain
conditions, such as (1) low pressure (2) low feed concentration, (3) high crossflow velocity.
Density is constant. The liquid is incompressible.
The flow is independent of time (steady state condition).
The liquid is Newtonian.
End effects are negligible.
This equation can also be used to calculate the water flux of the membrane. Normally,
it is difficult to determine geometry parameters in the equation, such as , x, dp. However,
these parameters are constant. So the group of parameters in the parenthesis can be
determined experimentally by UF test with a known liquid, such as water. After that, it can be
applied to other liquids by changing the viscosity.
From the equation, the flux varies linearly with the transmembrane pressure.
However, when the pressure is higher, the properties of liquid, such as viscosity, etc., and the
effect of mass transfer phenomena is prevailing. Characteristic of UF will change to mass
transfer controlled region. Eq. 8.2.4 will be no longer valid.
For the water flux, it is usually governed by eq. 8.2.4. However, deviation may occur
in some cases, as shown in fig. 8.2.1-5a. This can be described by the deformation of the
membrane pores under high pressure or pore blocking due to trace material in the water. The
latter case usually occurs when tap water is used to determine the water flux.
8.2.1.4 Concentration polarization
In mass transfer controlled region, the flux is relatively constant and independent of
pressure, as shown in fig. 8.2.1-5b. To explain this, mass transfer phenomena in the UF
module should be considered. One of the important transport phenomena is the formation of
concentration polarization.
When the mixtures, solution, or wastewater is fed to the UF, particles, solutes,
macromolecules or pollutants are rejected by the membrane. These materials, then, tend to
accumulate and form a layer of high concentration of the materials at the membrane surface
(fig. 8.2.1-9). This layer is called polarization layer, CP layer, or gel layer [38].
However, gel layer is usaually refered to a layer of gel, which concentration is quite constant,
while polaization layer is the transition zone which concentration increase from bulk
concentration to that of gel. Characteristic of the layer depends on the type of the materials.
This layer is believed to hinder and restrict permeate flow by one of the two mechanisms, i.e.,
1.
High solute concentration increases the osmotic pressure within the polarization
layer. The osmotic pressure will oppose or counter the transmembrane pressure
and make the effective driving force of the process decrease. So the flux is
decreased.
2.
High solute concentration in the polarization layer causes the solute to transport
back into the bulk liquid by concentration gradient. At certain concentration, the
transport of solute to the layer by convection and the back-transport will
counterbalance, resulting in steady flux.
316
III-199
Important notes on polarization layers are,

1.
It is assumed to be dynamic. Changes in operating condition, such as cross-flow

velocity, pressure, will change the polarization layer. The layer will disappear if
the system does not operate. This fact makes it different from the fouling of
membrane, which will not disappear unless the membrane is cleaned.
2.
It is believed to make the flux pressure-independent in mass transfer controlled

region. Change in pressure will change the polarization layer, thus, the osmotic
pressure or back-transport will be changed accordingly, resulting in
counterbalance of the system. For example, if the pressure is higher, the flux will
be briefly higher and then drop back to the previous value.
8.2.1.5 Mathematical model for mass transfer controlled region: film theory
One of the widely used model for flux prediction in mass transfer controlled region is
film theory model. It is derived by balancing the convection mass transfer and the
concentration-gradient back-transfer. The model is as shown in eq. 8.2.6a
J=
ln(
Where J
D
K
Cg
CP
C
Cg CP
C CP
=
=
=
=
=
=
=
) = K ln(
Cg CP
C CP
{8.2.6a}
Flux (L3L-2T-1, i.e. LMH or gallon per ft2 per day (GFD))
Diffusion coefficient or diffusivity (L2T-1)
Thickness of polarization layer (L)
Mass transfer coefficient (L3L-2T-1)
Gel concentration
Permeate concentration, (= 0 since oil rejection is normally100%)
Bulk concentration
Gel concentration is theoretically the concentration of gel layer at the surface of

membrane. Cg is assumed to be constant for a given solution or wastewater. From fig. 8.2.15b, it shows that the flux in mass transfer controlled region still varies with cross-flow
velocity. Many researchers including GPIs [11], [18] proposed that the model could be
modified to account for the effect of cross-flow velocity (V) as shown in eq. 8.2.6b. The effect
of V on the flux is as shown in fig. 8.2.1-9. The values of k, K, and Cg depend on the type
of wastewater and membrane and are usually obtained by experiment.
Gel layer
Polarization layer
Flux
V2>V1
Cg
V1
Permeate
Bulk concentration
CB
Cp
Cg
Log (Concentration)
Membrane
Fig. 8.2.1-9 Diagram of polarization layer and effect of velocity on flux in film theory
317
III-200
J = kV ln(
Cg
C
{8.2.6b}
The equations for determining the value of K, based on Buckingham theory are also
widely used (eq. 8.2.6c - e) [38]. However, to use the equations, it is necessary to know the
value of Cg and D. The value of D also depends on the type of solution or wastewater.
For turbulent flow, Re>4000
Sh = 0.023 Re 0.8 Sc 0.33
{8.2.6c}
For laminar flow,

Re< 1800, Lv<L, Lc>L
Sh = 1.86 Re 0.33 Sc 0.33 (d h / L) 0.33
{8.2.6d}
For laminar flow,

Lv>L, Lc>L
Sh = 0.664 Re 0.5 Sc 0.33 (d h / L) 0.50
{8.2.6e}
Where Sh
Re
Sc
dh
Lv
=
=
=
=
=
Lc
L
=
=
Sherwood number =
kdh/D
Reynolds number =
dhV/
Schmidt number
=
/D
Hydraulic diameter =
4. flow area / wet perimeter (L)
Entrance length, based on velocity profile or the distance from the
entrance of membrane module flow channel that the velocity profile
becomes steady (L)
Entrance length, based on concentration profile (L)
Length of membrane module flow channel (L)
Eq. 8.2.6c to 8.2.6e are universal models, derived from many assumptions. So they can
provide only the approximate value of K. Eq.8.2.6a and b are also developed from
concentration-gradient assumption, described in the previous section. So it may not exactly fit
real flux/pressure curve. Some researches [54] reported that the concentration at the
membrane surface is not constant, but varies with operating condition. However the model is
accepted as an effective mathematical tool to estimate the flux in mass transfer controlled
region.
8.2.1.6 Resistance model
The porous flow model and film model cannot be used to predict the flux in both
pressure and mass transfer controlled region. So other models ware developed to govern the
whole range of flux/pressure behavior, such as resistance model and osmotic pressure model.
Here will be described resistance model for its mathematical simple that facilitates its use.
For resistance model, the concept of resistance-in-series, like in heat transfer, is
adapted. General form of the model is as shown in eq. 8.2.7.
J=
Pt
{8.2.7}
R represents the summation of various resistances (see fig. 8.2.1-10) i.e.,
318
III-201
Feed
PF
Gel /Polarization
layer
Permeate
Gel resistance (Rg)

Me
mb
ran
e
Fouling resistance (RF)

(Adsorption)
Pp
Fouling resistance (RF)

(Pore Blocking)
Membrane
resistance (Rm)
Fig. 8.2.1-10 Various resistances in UF processes

1.
Membrane resistance or intrinsic membrane resistance (Rm): It is the

resistance of membrane determined using pure water as the feed. It is the inverse
of A in eq. 8.2.5. Rm is theoretically constant and depends only on the type of the
membrane.
Rm =
2.
Pt
JW
{8.2.8}
Fouling resistance (RF): Membrane fouling, unlike concentration polarization,

is characterized by irreversible decline in flux, caused by interaction between
feed and membrane as well as deposition and accumulation of some feed
components on the membrane surface (external fouling) and/or with in the
membrane pores (internal fouling). The nature and extent of membrane fouling
as well as evolution of fouling with time are strongly influenced by nature of
membrane and characteristic of the feed. Many forms of equation to predict the
fouling are proposed, such as Hermias [54], Cheryans [38], etc. Generally, it
can be characterized by powered or exponential equation as examples shown in
eq. 8.2.9.
R F = Ro t n : n > 0
{8.2.9a}
Or
R F = Ro e nt : n > 0
{8.2.9b}
319
III-202
Ro is initial fouling resistance. However, since fouling from feed/membrane

interaction is assumed to be because of physicochemical, it will be unaffected by
operating condition. So RF in this case can be included in Rm as Rm, as shown in
eq. 8.2.9c. Many researchers [10], [11], [18] studied applications of UF on oily
wastewater treatment, using newly prepared cutting oil emulsions. They
concluded that fouling resistance of membrane, in this case, scarcely occurs,
and if any, can be assumed to be constant without varying with time. So the
concept of Rm in eq. 8.2.9c is valid. However, in case of real wastewater,
fouling from foreign material deposition may be present Thus RF, in this case,
will vary with time and should be observed by pilot-scale test.
R ' m = Rm + R F
3.
{8.2.9c}
Polarization or gel resistance (Rg): This resistance is caused polarization layer.

In some literatures, it is divided into 2 separate resistances, i.e., gel resistance
and polarization resistance. However, many researches and literatures also prove
that using the resistance in a single term of Rg provides sufficiently accurate
result. As described in section 8.2.1.4, the resistance is reversible and changes
with operating condition. General equation of Rg is as shown in eq. 8.2.10, which
and are empirical constants.
R g = V Pt
{8.2.10}
Thus, from the equations of various resistance and assumptions stated above, the
resistance model of UF on oily wastewater treatment can be rewritten as shown in eq. 8.2.11
J=
Pt
R ' m + V Pt
{8.2.11}
Eq. 8.2.11 provides a flux/pressure curve that more or less fits the observed data both
in pressure and mass transfer controlled region. Like film model, the values of and
depend on type of wastewater as well as membrane and have to be obtained by experiment.
Apart from feed concentration, velocity and pressure, of which effects on described in
the previous section, important parameters that affect the performance of UF process are
summarized below.
1.
Viscosity
Viscosity is an important parameter that affects flow regime and shear rate. Thus
it affects the polarization layer and make the mass transfer coefficient (k) in eq. 8.2.6 change.
Generally, viscosity increases with increasing feed concentration. This can explain the
inflection point in flux/concentration curve in fig. 8.2.1-6, which is the case of general oily
wastewater. For oil/water mixture, when the concentration reaches certain value, viscosity,
thus mass transfer coefficient, changes dramatically (see fig.8.2.2-7). So the graph is shifted
from a straight line.
320
III-203
2.
Temperature
Since many physical properties, such as viscosity, density, change with

temperature, it is inevitably one of the influent parameters on UF performance. Permeate flux
generally increases with increasing temperature. So it is beneficial to operate the UF process
at the highest possible temperature, providing that there is no unusual effect such as extra
fouling due to high temperature precipitation. CHERYAN [38] proposed water fluxtemperature correlation as shown in eq. 8.2.12a. In the research on cutting oil emulsion
treatment, both fresh and used conditions, WANICHKUL [11] used permeate fluxtemperature relation as shown in eq. 8.2.12b. It was proven to be quite accurate. However, it
should be noted that higher temperature may also result in lower interfacial tension of feed
components, thus lower size of liquid dispersed phase, such as oil droplets in water.
3.
J 25o C = 0.615 J 50 o C = 1.276 J 15o C
{8.2.12a}
J Ao C = J B o C e ( 0.0239 ( B A))
{8.2.12b}
Membrane properties
Major membrane properties that affect the performance of UF are as shown
below,
Hydrophilicity: For UF of aqueous feed, generally, the membrane should be

hydrophilic to avoid absorption of hydrophobic or amphoteric components in
the membrane, which can cause fouling. Hydrophilicity can be roughly
determined by measurement of contact angle of oil drop on the surface of
membrane, as described in chapter 2. Membrane material can be used to
estimate membrane hydrophilicity. However, surface-coating process, which
can modify its original properties, should be taken into account.
Surface roughness: The membrane with smooth surface is likely to foul

less. Surface roughness of membrane also affects the contact angle
measurement and may cause error in hydrophilicity determination.
Charge of the membrane: To separate charged particles, the membrane

should be of the same charge to take advantage of mutual repulsive force.
Pore sizes: As described in section 8.2.1.1, the pore sizes of membrane

should be suitable for the pollutants to be separated. GPI recommended pores
size is around 1/3 to 1/4 of the size of the pollutants (see some exception in
section 8.2.3.1). Too large pore size may affect in higher initial flux but it is
clogged easily, resulting in lower flux in long term and frequent washing
process. Too small pore size also results in low flux and high energy
consumption.
Turbulence: As described before, flux increases with increase in turbulence.

Normally, turbulence or flow regime is controlled by cross-flow velocity.
However, there are some attempts to enhance the flux by the use of turbulent
promoters, such as inserting wire mesh or grid in membrane flow channel.
Caution is that it also promotes clogging. Some techniques choose to move
membrane, rather than liquid, to increase turbulence, such as rotating disc
membrane module.
321
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4.
Interaction between feed and membrane
Some components in feed may react or coat membrane of certain material,

resulting in adverse affects, such as fouling or decrease in rejection. For example, oils can
cause fouling to PVDF membrane for the oil structure is similar to the functional group of the
material. So it is recommended to perform UF test with real feedstream before designing the
process.
8.2.2
In this section, Design procedure and design consideration as well as some significant
findings about application of UF on oily wastewater treatment, based mainly on GPI
researches, are described.
8.2.2.1 Membrane selection
Pore size or MWCO: Under proper operating condition, UF membranes with MWCO
of 40 to 150 kilo-Dalton were proven to be effectively used to separate oil from secondary and
macroemulsion with rejection of 100% [10], [11], [18], [19], [20]. The oily wastewater tested
were both in fresh and used condition with the droplet sizes around 0.11-0.21 micron for
macroemulsion and 11 microns for the secondary emulsion. For microemulsion (droplet size
of 20 100 nm or 0.02 0.1 ), the membranes of MWCO of 40 50 kD can be used with oil
rejection of 100%. From GPI researches, it is recommended that pore size should be around
1/3 1/4 of droplet size to be separated for stabilized emulsion. For non-stabilized emulsion,
it is recommended to use maximum pore size of 100 nm. to prevent the oil from passing
through the membrane (see section 8.2.3).
Membrane material: Apart from the pore size, membrane material and module are
important parameters that affect membrane selection. Every research in GPI lab confirms that
hydrophilic material is the most suitable choice for oily wastewater treatment. For
polymeric materials, cellulose acetate, acrylics and polyacrylonitrile (PAN) are hydrophilic,
while PVDF and polysulfone are generally hydrophobic. In GPI lab, most experiments were
carried out by PAN membrane. For inorganic membrane, composite membranes with zirconia
(zirconium oxide) and alumina skin also provide good hydrophilicity. However, other factors,
such as limiting pressure, chemical resistance, fouling, and cost, should be taken into account
for membrane material selection. These data can be obtained from pilot scale test. It must be
noted that the membranes of the same pore sizes may give different performance it they are
made of different materials.
Membrane module: In GPI lab, all of the UFresearches were based on plate and
tubular modules. The tubular modules used in the experiments were inorganic membrane
while the plate modules were polymeric types. Thus the result can not be directly compared.
However, from many literatures, every type of module, described in section 8.1.5, is reported
to be effective for oily wastewater treatment [38]. Hence the flux obtained, fouling and cost
should be considered to select the most suitable membrane.
8.2.2.2 Prediction of permeate flux
The size of membrane is determined from the quantity of wastewater, permeate flux
and required operating cycle of the system (such as continuous 48 hours, etc.). Permeate flux
of UF membrane can be determined based on (1) mathematics models from section 8.2.1, (2)
322
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general design criteria and (3) pilot-scale test result. The latter, if available, is the most
significant data for final decision on membrane process design since modular structure of
membrane makes it possible to scale-up the process from the test data in relatively linear
manner. However, flux result from the models and general criteria acquired from many
researches, esp. GPI researches, will be provided here to be a guideline to narrow the choices
of membranes to be test or for preliminary technical and economic analysis.
1.
General design criteria
Recommended design criteria from various literatures and manufacturers are

summarized in table 8.2.2-1. It should be noted that the values in the table are summarized
from experiences and researches with various operating conditions and types of wastewater,
then, should be used as a guideline. It is recommended to review related researches for the
type of wastewater to be treated.
2.
UF flux prediction by mathematical models
In case that the data required for mathematical models are available, the models
can be used for permeate flux estimation. Many literatures provide the values of important
parameters for the models, obtained from various types of wastewater and operating
conditions, which can be adapted to design the membrane process for similar wastewater.
Since almost all of GPIs researches were interpreted using film model and
resistance models. In this section is emphasized on these 2 models. Summaries of important
parameters for film model and resistance model from GPIs researches are tabulated in table
8.2.2-2 and 8.2.2-3. Applications of the models are summarized as follows,
(1) Film model: The model (eq. 8.2.6a and b) can be used to predict the flux in
mass transfer controlled region, where the flux is theoretically pressure-independent. It can
be used to calculate the flux at any wastewater concentration, which is very useful because
volume reduction of the wastewater, that makes the concentration change, is one of major
objectives of oily wastewater treatment process.
Flux/pressure relation graph for UF of macroemulsion contains an infection
point as shown in fig. 8.2.1-6 [11], [18]. In this case, it can be said that there are two Cg. The
first one is obtained from extending the steeper part of the graph to cross the X-axis. But it is
not the real Cg and used only for flux calculation at lower range of retentate concentration.
The real Cg is obtained from the graph after inflection point. For macroemulsion, the real Cg
crosses the X-axis at approximately 100% concentration (fig. 8.2.2-1). This can imply that,
theoretically, we can use UF to filter it until the retentate becomes water-free oil [18].
However, the flux will decrease and become so low that it may become uneconomic.
323
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324
1-2% oil
< 0.5 % oil
Oily wastewater containing

emulsified oil
Food wastewater, wastewater

containing surfactant,
chemical
2-stages system of
Membrex (spiral
wound + rotating disc)
Carbosep M9
1,000 ppm FOG,

500 ppm SS
20 ppm total HC,

30 ppm SS
Automobile manufacturing
plant wastewater
Effluent of biological
treatment of petroleum oil
refinery
Spent coolant
Membrex ESP, spiral
Koch 252, 1 tubular ,

60 m2
Koch 252, 1 tubular ,

60 m2
Conventional UF
Membrane used
5-6% V oil
General oily wastewater
3-5% oil
0.1-10% oil
Cutting oil wastewater or

stabilized oily wastewater
Wastewater containing spent

coolant and lubricants
Inlet oil/ droplets

size
Wastewater
50-200
kD
40 GFD for
spiral, 160120 GFD for
disc, no other
data
specified
100 LMH,
25oC, 3.5 bar
50 LMH,
25oC, 3.5 bar
Pore
Flux/
size or Operating
MWCO condition
100%
rejection
30-50%
75 ppm
FOG
50% oil, 10%

SS, 99.5%
volume
reduction
Up to 100%
60%
Up to 40% V
oil
40-80%
Retentate
conc.
<10-100
ppm oil
<10-50
ppm
Rejection
or outlet
oil conc.
Table 8.2.2-1 General design criteria of UF process from various literatures

Ref.
GM plant,
Maxico
The author
recommended
Kochs data
Kochs data
[38]
[38]
[38]
[38]
[38]
[38]
[54]
Free oil must [38], [59]

be removed
first.
Remark
III-207
Table 8.2.2-2 Summary of parameters of film model from UF researches on oily wastewater treatment (reference temperature = 20oC)
325
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Table 8.2.2-3 Summary of parameters of resistance model from UF researches on oily wastewater treatment (ref. temperature = 20oC)
326
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80.00
Permeate flux (l/m .h)
70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
1
100
10
Retentate concentration (% V of oil)
P = 1 bar, V = 1.17 m /s
P = 1.5 bar, V = 1.4 m/s
Fig. 8.2.2-1 Examples of flux VS. oil concentration in UF of macroemulsion
Flux
JC,V
Vref
Flux
JC,V
At Pref
JC,Vref
JC,Vref
Vref
C Cg
Log (C)
Pref
a) Graph from film model
Pt
a) Graph from resistance model
Fig. 8.2.2-2 Case 1: find flux/pressure relation when k, , Cg and Rm are known
Table 8.2.2-4 Procedure to predict flux/pressure relation for case 1: Know k, , Cg and Rm
Item
1
Procedure
Find JC,V,Pref
Variables
Equation
C, V
Find JC,Vref,Pref
Rm (or Rm)
Find C ,derived from
resistance model at one
value of C and two values
of V
Find C
J C ,V , Pr ef = kV B ln(
C,Vref
J C ,Vref , Pr ef = kVref
Cg
C
Cg
ln( )
C
J
V
C,V R m Pref ( V )
ref
ln
J C,V R m P
ref
C =
V
ln( ref )
V
C =
327
{8.2.13a}
J
P
R
ref
C,V,Pref m
V c P J
ref C,V,Pref
{8.2.13b}
{8.2.13c}
{8.2.13d}
III-210
Flux/pressure relation at
conc. = C
Pt
J C,V,P =
c
t R m + C V Pt
{8.2.13e}
The subscript ref represents the parameter at reference condition that the graph
8.2.2-2a is derived from. Normally the reference condition is in mass transfer control region.
Otherwise the graph will not be a straight line as shown in the figure. However the equations
are proven to provide acceptable result even when the reference pressure is in the transition
zone between pressure- and mass transfer control region. In any case, it is recommended to
select the reference pressure as high as possible and should be greater than 50% of
recommended operating range.
Eq. 8.2.13e can be used to predict flux at concentration C and cross-flow velocity
V over the entire range of working transmembrane pressure Pt, usually recommended by
membrane manufacturers. Examples of prediction result from this concept are shown in fig.
8.2.2-3. The graphs show that the results are relatively accurate (10%).
180
160
140
120
100
80
60
40
20
0
0
0.5
1.5
2.5
Transmembrane Pressure (Bar)

Observed, C = 2%
Fig. 8.2.2-3
(3.1)
Predicted, C = 2%
Observed, C = 8%
Predicted, C = 8%
Reference, C = 4%
Relation between UF permeate flux and Transmembrane pressure at Cref = 4% by volume of oil , V = 1.4
m/s and Predicted relations at C = 2 and 8% (Oil: Elf SeraftA cutting oil macroemulsion, Membrane: IRIS
3042 PAN )
Case 2: Know , , Cg and Rm
The procedure to find flux/pressure relation (JC,V,Pt) at any concentration and

pressure is as described in table 8.2.2-5.
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Table 8.2.2-5 Procedure to predict flux/pressure relation for case 2: Know , , Cg and Rm
Procedure
Variable
Find JCref,V,Pref
Cref, V
Find JC,V,Pref
Find JC,Vref,Pref
4
5
Find C, C
Flux/pressure
relation at
conc. = C
C,V
Rm (or
Rm), Vref
Equation
J
Cref,V
P
ref
R 'm +
{8.2.14a}
V Cref P
Cref
ref
Cg
ln(
)
C
J C,V = J
Cref,V
Cg
ln(
)
C
ref
Cg
ln(
)
P
C
ref
J C,V
=
ref '
ln( C g )
Cref P
R
+
V
m
C
ref C
ref
ref
ref
{8.2.14b}
{8.2.14c}
Use eq. 8.2.13c and d

Pt
J C,V,P =
c
t R m + C V Pt
{8.2.14d}
The value of Vref in this case can be chosen arbitrarily. For Pref, it is recommend to
used the maximum recommended pressure.
(2) Special case: Flux prediction for mixture of cutting oil macro- and
microemulsion: Treating Wasted cutting oil emulsion is one of the main applications of UF
on only wastewater treatment. Parameters related to treatment of cutting oil macro- and
microemulsion are provided in table 8.2.2-2 and 8.2.2-3. However, in real life situation, many
mechanical workshops of factories may use more than 1 type of cutting oil to the requirement
of individual manufacturing process.
GPI lab has devised an approach to estimate permeate flux of the mixture.
The approach is based on the concept that, when 2 types of emulsion are mixed, oil
concentration of mixture will be the summation of the 2 initial concentration. Surfactant and
co-surfactant in the microemulsion will reduce the droplet size of the macroemulsion in the
mixture. However the quantity of the surfactant/co-surfactant will not be sufficient to convert
all oil to microemulsion. The resultant flux, then, will be neither the same as the flux of pure
microemulsion, nor that of pure macroemulsion. But it will surely fall between these 2
extreme cases. Accurate prediction may require the knowledge of the chemistry of
surfactants/co-surfactants.
However, since the excess amount of surfactants/co-surfactants in the
mixture is directly proportional to the ratio of the microemulsion presenting in the mixture, it
can be estimated that flux of the mixture is the weighted-average of the fluxes of two
emulsions.
To estimate the flux of the mixture according to the concept described
above, the following procedure is recommended.
329
III-212
Calculate total oil concentration of the mixture (Coil,mix)
C oil .mix = C oil .mac + C oil , mic
{8.2.15a} or
C oil , mix = C mac R mac + C mic R mic
{8.2.15b}
Where Coil,mix, Coil,mac, Coil,mic are oil concentration of the mixture,

macroemulsion portion and microemulsion portion, respectively. While Cmac and Cmic
represents the concentration of cutting oil concentrate of macro- and microemulsion
portions. Rmac and Rmic are the ratio of oil in the emulsion concentrate. For macroemulsion, the
majority part of concentrate is oil, Rmac is around 80%. While Rmic is around 20-30%.
For example, when macroemulsion at concentration of 4% by volume of
concentrate mixes with microemulsion of 2% by volume of concentrate, if Rmac and Rmic =
80% and 20%, total oil concentration in the mixture (Coil,mix) will be (4x0.8)+(2x0.2) =
3.6% by volume of oil.
Calculate permeate flexes of whole macroemulsion and whole

microemulsion at the oil concentration of Coil,mix (Jmac:Coil,mix and
Jmic,Coil,mix) by the procedure decribed in table 8.2.2-4 and 8.2.2-5.
Estimate the flux of the mixture by the following equation. Error of

prediction is around 20%.
mix
J
+C
J
oil,mic mic,Coil,mix
C
oil,mix
{8.2.15c}
8.2.2.3 Prediction of evolution of flux, wastewater and permeate volume with time and
membrane size for batch cross-flow UF system
In real situation, UF process may be designed as batch process, continuous process,
single stage process or multi stage process, depending on objectives. However, for wastewater
treatment process, UF is normally designed as batch system, as shown in fig. 8.2.1-4. In batch
process, the concentration of retentate will be increased up to required limit or as much as
possible. Then the process will be stopped and the retentate will be hauled away for final
disposal or recycling. After that the batch will start over again.
Process flux will decrease continuously with increase of the concentration. The models
and procedure described in the previous paragraph can be used to predict the permeate flux at
any concentration. Thus it is possible to estimate evolution of retentate volume, permeate
volume, and flux with time. These data is important to design UF process to meet the required
operating time. However, it must be noted that predictions are based on the assumption that,
Flux at any moment is equal to the value calculated by the model described in the
previous section.
There is no fouling from any other foreign materials.
To find permeate volume, we consider that a small volume of permeate (dVol),

passing through a UF membrane of area A at a small time (dt), will be defined by the
following equation.
330
III-213
{8.2.16}
dVol = J(c) Adt
If the system is operated in the mass transfer controlled region, the film theory (eq.
8.2.6b) can be applied. Eq. 8.2.16, then, can be rewritten as follows,
Cg
dVol = kV ln
C
Adt
{8.2.17}
If we start with initial wastewater volume Volo and concentration Co and the rejection
of oil is totally completed, which is true from our every test, the concentration C will be the
function of the permeate volume at that moment V.
C=
C o Vol o
(Vol o Vol)
{8.2.18}
Eq. 8.2.17 can be rewritten as,

dVol = kV ln
(Vol o Vol)C g
Adt
C o Vol o
Vol
final
dVol
(Volo Vol)Cg
Volo
ln
C o Volo
t
= kV Adt
0
{8.2.19a}
{8.2.19b}
However, the system may not be operated in the mass transfer controlled region for
the whole time. In this case, the function J(c) in eq. 8.2.16 can be calculated by eq 8.2.11. Eq.
8.2.19b is in the form of integration of [1/ln (x)], so it can not be written in general form since
the equation will be infinity at x =1. However, a definite integration is possible, using
numerical method that can be calculated by computer.
An example of flux/time prediction is shown in fig. 8.2.2-4. The flux is predicted
based on the data (Cg, k, , , , Rm ) of fresh Seraft ABS cutting oil macroemulsion and
IRIS 3042 membrane, shown in table 8.2.2-2 and 8.2.2-3. The membrane area used is 1 m2.
However, in this example, it is assumed that the system is in mass-transfer controlled region.
So eq. 8.2-19b is used.
The predicted flux/time relation is compared with the results from UF test on used
cutting oil macroemulsion (Co = 3% V of concentrate or 2.4%V of oil, from Willamette SAS
factory) from WANICHKULs research [11], as shown in fig. 8.2.2-4. The x-marked circles
indicate the observed flux of fresh emulsion. From the graph, it shows that the model can
accurately predict flux of fresh (unused) emulsion as the circles are closed to the theoretical
flux curve.
Comparing with observed flux of the used emulsion, the graph shows that, at low
concentration, theoretical flux is greater than observed value. This is simply because of
additional fouling from foreign materials in the emulsion. From the data, the system was
undergone rinsing for 5 times, every 300-400 l of permeate volume on the average.
Furthermore, at low concentration, the system does not fully reach mass transfer controlled
region so the predicted flux from film model is higher than the actual.
331
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However, at high concentration, theoretical flux is, somehow, lower than observed
value. This can be explained by partial degradation of the used emulsion. During its working
lifetime, cutting oil emulsion will subject to many foreign material and operating factors, such
as coated oil on specimen surface, small scraps of specimen, leaked lubricant, and heat. So its
quality, as well as its stability, will gradually deteriorate. This is proven by milky appearance
of used emulsion, compared with the translucent or transparent characteristic of fresh
emulsion. When partial oil is destabilized to be free oil, this means the concentration of oil in
emulsion form may be lower than its initial value. At lower concentration, the effect of
fouling overwhelms the effect of reduced concentration, so the theoretical flux is higher than
the observed value. However, at higher concentration where the concentration effect is
stronger, the theoretical flux shows lower value.
Evolution of permeate volume with time, calculated from integration of eq. 8.2.19b is
shown in fig. 8.2.2-5. From the observed data, it confirms that the macroemulsion can be
ultrafitrated until the retentate is relatively pure oil. In this case, initial volume of 1643 l of
2.4%V of oil is ultrafiltrated to the final volume of 40 l. The theoretical time required to do so
is 45 hours, compared to observed value of 34 hours. However, the theoretical volume of
permeate is higher until almost at the end of the operation. Evolution of theoretical flux with
concentration is shown earlier in fig. 8.2.2-1. It must be noted that eq 8.2.16 to 8.2.19 are
based on the assumption that no additional emulsion is added to the storage tank during the
operation. If the emulsion is added, eq. 8.2.16 must be modified to account for it.
initial concentration 2.4% by volume of oil (not concentrate): Module UFP10: membrane IRIS 3042)
70.00
P = 1.0 bar, v = 1.17 m/s
P = 1.5 bar, v = 1.40 m/s
60.00
50.00
flux (l/(sq.m.h))
1
2
40.00
30.00
20.00
10.00
0.00
0
200
n
400
600
= Rinse membrane with water
800
1000
Permeate volume (l)
Observed data
1200
1400
1600
1800
= Observed data from UF test of new

cutting oil at the same condition
Fig. 8.2.2-4 Relation between Flux VS. theoretical and observed permeate volume
332
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1800
1600
Permeate volume (l)
1400
P = 1.5 bar, v = 1.40 m/s
P = 1.0 bar, v = 1.17 m/s
1200
1000
800
600
400
200
0
0.000
5.000
10.000
15.000
20.000
25.000
30.000
35.000
40.000
45.000
50.000
Time (h)
Observed data
Fig 8.2.2-5 Relation between time VS. theoretical and observed permeate volume
Average process flux estimation: Since the equations stated in this section is very
complex and could not be solved without calculation or computer program, a rough approach
to estimate average flux has been devised and, actually, used even for real design. Average
process flux (Javg) can be calculated from the flux at the beginning (Jbegin) and the end of batch
(J end). In this case, the fluxes at these only 2 points are required. If the final concentration is
relatively Cg, J end can be assumed to be zero. This Javg will be preliminary used to calculate
evolution of permeate volume (eq. 8.2.20b) in stead of the integration result from eq. 8.2.19.
Observed and calculated average flux from beginning to zero-flux from UF of macroemulsion
at 4% of concentrate volume, as shown in the example, are around 47 and 44 LMH,
respectively [11].
J avg =
J begin + J end
{8.2.20a}
Acc. Vol permeate = J avg t
{8.2.20b}
These estimated evolution data also provides the idea about the approximate size of
membrane required. If the estimated operation time is not suitable, the area of membrane can
be adjusted until it results in the required operating time. If should be noted that the predicted
result does not include the time for rinsing or cleaning the membrane, which may take as 1-2
hours per cycle, depending on method and cleaning agent.
8.2.2.4 Sizing of related facilities
General components of UF system for wastewater treatment are shown in fig. 8.2.1-4,
i.e.,
333
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1.
Equalization or storage tank
Here, only single-stage batch process is considered. Details of other types of the
processes, such as continuous process, multi-stage process, etc. can be found in many
literatures, listed in the bibliography.
For batch process without addition wastewater during UF operation, the
volume of the equalization or storage tank is simply equal to the volume of wastewater
generated during the operating cycle of the UF process. In this case, the system must have at
least 2 tanks. While one tank is being feed to the membrane, another is used to received the
incoming wastewater. Then they will be switched over when the wastewater on the first tank
is completely treated. Flux/time and wastewater volume/time relations in this case can be
directly calculated by the equations described in section 8.2.2.3. Final volume of retentate in
this case is not used for volume calculation. It is the simplest method for UF process
calculation. However, the volume of the tanks in this case will be relatively large.
For batch process with continuous or intermittent incoming wastewater into
the same tank, the volume of the storage tank can be calculated by mass balance. Minimum
required storage volume is equal to the maximum difference between accumulated permeate
volume and accumulate influent wastewater volume. Graphical presentation for minimum
storage volume calculation is shown in fig. 8.2.2-6. Evolution of accumulated influent
wastewater depends on influent wastewater flow characteristic, such as constant discharge
continuously for 8 hours/ day, etc.
Accumulated
volume
Influent
wastewater
Volume
required
for storage
tank
Permeate
Influent stops
Final retentate
volume required
End of batch Time

End of filtration
Start cleaning
Fig. 8.2.2-6 Calculation of required storage volume of equalization tank by graphical method
Final retentate volume required can be estimated from recommended Cg for
similar wastewater, For evolution of accumulated permeate volume, it is more difficult to
achieve. It can be preliminary estimated by the concept described in section 8.2.2.3. However,
since the permeate flux depends on retentate concentration, which, in turn, depends on mass
balance of recycled retentate, remaining wastewater in the tank and addition influent, eq.
8.2.19b is not valid and needs to be modified. This will complicate the calculation process
even more. However, the concept of average process flux, also described in section 8.2.2.3,
can be used to simplify the calculation.
334
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2.
Feed pump
Here will consider only the system with single feed pump, which is generally
used in UF process of wastewater treatment. The feed pump is an equipment that supply
wastewater to the membrane as well as maintain recirculation flowrate, thus cross-flow
velocity, in UF module.
For the flowrate, the pumping system is sized to cover the maximum
recirculation flowarate, which is normally higher than permeate flowrate and capable of
turning down to handle the minimum flowrate.
For the pressure, the pump is sized to handle the design working pressure of the
system, which may need to be varied to optimize the system performance. There are key
values of pressure that should be aware of in pumping system design, i.e.,
Capillary pressure of the membrane: Transmembrane pressure must be

lower than the capillary pressure between oil droplets and membrane, as
shown in eq. 8.2.2. So this pressure should be taken into account for pump
selection. However, for properly selected membrane, this value is normally
higher than recommend maximum operating pressure of the membrane.
Pressure drop from membrane module friction and piping system: The
pressure drop has to be taken into account in pump design. Otherwise it may
not be able to provide the design working transmembrane pressure. For feed
and return piping system, the pressure drop can be calculated by general head
loss equations.
For membrane module, the major loss from wall friction of flow channel in
membrane module can be calculated from well-known formula, such as Darcy-Weisbachs
(eq. 8.2.21a).
L V2
h
=f
l major
D 2
{8.2.21a}
For laminar flow, f = 64

Re
{8.2.21b}
For turbulent flow (Colebrooks equation),

1
e/D
2.51
= 2 log(
+
)
0.5
3.7 Re f 0.5
f
{8.2.21c}
e/D is ratio of roughness to diameter. For plate membrane, the flow channel is
usually rectangular. D of this channel can be calculated as hydraulic diameter, as shown in eq.
8.2.21d. H and W are height and width of the rectangular channel respectively.
D=
4HW
2(H + W)
{8.2.21d}
The minor loss can be estimated using standard minor loss equation (hl minor (in
metre) = KminorV2/(2g)). The latter becomes the majority of head loss when the recirculation
velocity is high.
335
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Even though this pressure drop is not high (normally < 0.5 bar), it may become
of significant effect when the UF is operated at low transmembrane pressure, such as 0.5 to1
bar or when the concentration of retentate is high. For oily wastewater, viscosity will vary
rapidly in some range of concentration, as shown in fig. 8.2.2-7. This will cause extra pressure
drop. So, maximum viscosity expected during the operation should be accounted in pump
selection.
o
(Elf SeralfABS cutiing oil macroemulsion, 20
C, 100% = pure cutting oil concentrate = 80% V(approx) oil )
350.00
300.00
Viscosity (cp)
250.00
200.00
150.00
100.00
50.00
0.00
0
10
20
30
40
50
60
70
80
90
100
Oil concentration (% V of cutting oil concentrate in water)
Fig. 8.2.2-7 Relation between oil concentration VS. viscosity of emulsion

For the power requirement of UF system, main power consumption is the
power required to maintain transmembrane pressure at require flowrate (or recirculation
velocity). This power can be calculated straightforwardly by the basic equation
Power =
PQ
overall
PVA
overall
{8.2.21e}
Q in this case means recirculation flowrate, not the permeate flowrate. V is the
recirculation velocity and A is the flow area of liquid in UF module (the channel between the
membrane surface and the UF module wall). P in the equation is pump discharge pressure,
which is the summation of transmembrane pressure and other headloss from pipe and values
system. It should be noted that transmembrane pressure is average value of the pressure at
the inlet and outlet of UF module. Overall efficiency of pump depends on pump type. For
progressive cavity pump or progressive screw pump, the efficiency should be around 50-70%.
In case that the data required for mathematical models are available, the models
can be used for permeate flux estimation. Many literatures provide the values of important
parameters for the models, obtained from various types of wastewater and operating
conditions, which can be adapted to design the membrane process for related wastewater.
3.
Heat exchanger
For oily wastewater treatment, when the retentate is repeatedly pumped into
membrane process, it will accumulate heat loss from feed pumps and friction so it will gain in
temperature. If the temperature is too high, it may cause adverse affect to the membrane and
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seals. Thus, heat exchanger is required to maintain the temperature of feed stream within the
recommended temperature range of membrane or at the design temperature. Heat load of the
system depands on piping and components design.
To estimate the maximum heat load, it can be assumed that energy loss from
input power supply is converted solely into heat. Thus the heat load can be roughly calculated
from modification of eq. 8.2.21e as follows,
1
Heat =
1 PQ
overall
{8.2.22}
Rising in temperature (T) can be roughly calculated by basic heat capacity

equation (Heat = M.C.T). C is specific heat. M is mass flowrate of feed pump. When the
heat, T, and the required temperature are known. It is possible to design or select the heat
exchanger. But the design of the heat exchanger is a science into itself, which will not be
described here. It can be selected from commercial product of specially designed by heat
exchangers designers.
8.2.2.5 UF efficiency on oily wastewater treatment
From many researches in GPI lab, it clearly shows that, with appropriate UF
membrane pore size hydrocarbon or oil, even in the form of very tiny droplets in
macroemulsion and microemulsion, cannot pass the membrane. It can be said that the removal
efficiency of UF is 100%. By the way, the efficiency will be lowered after prolonged
operation, mainly from normal wear and tear problem. Characteristics of wastewater, such as
presence of free-oil or non-stablized oil may lower the oil rejection of the membrane (see
section 8.2.3-1). So oil concentration in permeate can be expected in the range of 0-100 ppm,
depending on wastewater characteristic and membrane (see table 8.2.2-1).
Even though the oil rejection is generally complete, it does not mean that there is no
residual pollutant in the permeate since there may be other components of pollutants in the
wastewater that can pass through the membrane, such as surfactants and co-surfactants. Extent
of residual pollutants depends on components of the wastewater. Examples of residual
pollutants of cutting oil emulsions permeate are shown section 8.2.3. These residual
pollutants need to be further treated, such as by RO, distillation, biological treatment,
which will be described later in the related chapters.
8.2.3
Design consideration and significant findings from GPIs researches
In this section, design consideration and significant findings from related researches of
GPIs lab on oily wastewater treatment by UF will be described.
8.2.3.1 Design consideration and significant finding on secondary emulsion treatment
Almost all of the researches on oily wastewater treatment by UF are based on
stabilized emulsion since it cannot be separated effectively by other single process. However,
SRIJAROONRAT [10] has researched on UF of non-stabilized secondary emulsion. Her
study provides useful information to understand the performance of UF when free-oil is
present, which is frequently found in general oily wastewater. Significant findings of the
research can be summarized as follows,
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Flux
1.
Flux/pressure curve of non-stabilized emulsion shows some decline at high

pressure (fig. 8.2.3-1a). For this, SRIJAROONRAT described that it causes by
pore clogging of the oil film. Since the oil is not stabilized, it can be coalesced
and coated the membrane surface. At high pressure, the oil film is pinned against
the membrane and causes the blocking more predominant. Flux was reported to
range from several hundreds to few thousands LHM [10]. However, its
feasibility should be considered comparing to other possible processes, such as
coalescer.
2.
If the pore size of membrane is selected by the same criteria as for stabilized
emulsion, i.e. 1/3 to1/4 [GPI] or 1/10 [38] of droplet size, the pore will be
relatively large, which causes lowering in capillary pressure. Thus the working
pressure may high enough to overcome the capillary pressure, resulting in
presence of oil in permeate. Permeate flux in this case will be very low.
Evidence on coalescing of oil drop in the permeate is also observed. Thus it is
recommended to select the pore size of 50-100 nm for non-stabilized emulsion
treatment. If the pore size is properly selected, oil rejection will be or almost
100% (fig. 8.2.3-1b)
3.
Presence of surfactant causes adverse affect on flux and oil rejection.

SRIJAROONRAT showed that, at ratio of surfactant to oil of 2% and Pt = 3 bars,
the oil can pass through the membrane and present in the permeate even when
the membrane of 100 nm is used. Operating at low-pressure (i.e. 1 bar) help
alleviating this problem. Her research can be used to explains why the rejections
of UF of real wastewaters are not equal to 100%, unlike in the lab result. This is
because free oils or tramp oils are usually present in real wastewater while they
are usually not present in synthetic wastewater used in the experiment.
4.
Residual pollutant, measured in term of TOD, varies with membranes efficiency

or oil rejection as well as presence of surfactants/co-surfactants or other soluble
components in the wastewater. In case that the surfactants are present, it will
tribute to main TOD in the permeate. And if their concentration are high enough,
they will make the oil pass through the membrane. The TOD in this case will be
very high from presence of oil in the permeate.
Flux of
stabilized emulsion
Flux of nonstabilized emulsion
Pt
Fig. 8.2.3-1a Flux of non-stabilized

emulsion
Fig. 8.2.3-1b Photographs of non-stabilized emulsion

influent, retentate and permeate (from left) [10]
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8.2.3.2 Design consideration and significant findings on macroemulsion treatment

Cutting oil emulsion is the major source of this type of wastewater. All of related
GPIs researches prove that UF process is very efficient for treatment of this wastewater.
Design consideration and significant findings from GPIs lab on macroemulsion treatment are
summarized as follows,
1.
The value of Cg
Flux/pressure curve of macroemulsion follows the typical pattern as shown in

fig. 8.2.1-5b. But for the flux/concentration relation, BELKACEM [18] proven that the
relation can be approximated as being linear with an inflection point, as shown in fig.8.2.2-1.
The real Cg is about 100% of oil. It means that we can recycle the retentate to the UF module
until it is about pure oil. This result was also confirmed by WANICHKUL [11] (see example
in section 8.2.2.3). BELKACEM explained the lower values of Cg from other researches by
the assumption that they are tested within relatively short periods of time. Thus extension of
the results in log/normal scale will intersect the concentration axis at the first virtual Cg (Cg in
fig. 8.2.1-6 and 8.2.2-1) or somewhere between Cg and Cg.
2.
Flux enhancement by salt addition
Flux enhancement by salt addition was confirmed by many researches [11], [18],
[20]. The salt used in the experiments was CaCl2. Working principle of the process is that the
salt will be added to the wastewater in a certain amount to cause partial, not complete,
destabilization of the emulsion. Typical effect of salt concentration on the flux from dead-end
batch test at low Pt is as shown in fig. 8.2.3-2a. In cross-flow module, the graph is almost
identical but the difference between complete and partial destabilization is relatively smaller
and the salt requirement for partial destabilization is slightly higher from the effect of crossflow to polarization layer formation.
Flux
Partial
destabilization
Flux
Complete
destabilization
Partial
destabilization
Complete
destabilization
Lower initail
oil concentration
CaCl2 concentration
a) From dead-end mocule
CaCl2 concentration
b) From cross-flow module
Fig. 8.2.3-2 Typical relation between CaCl2 concentration and flux at low Pt
The effect of salt that cause changing in stability of the emulsion is reducing the
repulsive forces between droplets as well as potential barrier by modification of Zeta potential
and conductivity of the solution. This favors coalescence of oil droplets (see fig. 8.2.3-3).
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Ca+
Surfactant/
Co-surfactant
Oil
Ca+
Fig. 8.2.3-3a Partially destabilization by salt and coalesce of oil droplets
Fig. 8.2.3-3b Magnified images (x100) of oil droplets from original (left) and partially
destabilized macroemulsion (right) [11]
Fig. 8.2.3-3c Magnified images of new membrane surface (left) and the surface after UF of
macroemulsion at 3 bars without salt (middle) and with salt addition (600 mg/l CaCl2) [11]
The amount of salt for partial destabilization is not enough to destabilize all of
the oil droplets. But in polarization layer, which the concentration is locally high, oil droplets
are closely packed. The effect of this amount of oil is enough to provoke coalescence. The
coalesced droplets will become free-oil, floating on the top of storage tank. Thus the
concentration of emulsion fed to the membrane is relatively lower than the value calculated
from volume reduction (or concentration factor) (fig. 8.2.3-4). So the flux is higher.
The extent of flux increase depends on wastewater characteristic and
operation condition as shown in fig. 8.2.3-2 and 8.2.3-4. Flux enhances up to 2-3 time of nosalt condition were reported [18]. For residual salt pollutant, if the optimal dose of salt is
added, 20% of the added amount will be found in the permeate. The salt exceeding the
optimal dose will pass through the membrane without any retention and found in the
permeate. Optimum dose of CaCl2 for macroemulsion, based on Elf Seraft A cutting oil
macroemulsion [18], is about 34 mg/l of Ca++ or 125 mg/l of CaCl2 per 1% by volume of oil
in wastewater.
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Flux
Observed
concentration
Flux of
stabilized emulsion
Flux of partially
destabilized emulsion
Theoretical
Free-oil is not separated

from storage tank.
Free-oil is separated.
Co
Pt
Calculated
concentration
Fig. 8.2.3-4 Relation between fluxes VS. pressure and calculated VS. observed oil
concentration in retentate for partially destabilized emulsion
Other significant findings and precautions on flux enhancement by salt addition
are summarized below.
3.
Other types of salt can be used, such as NaCl, ferric salt or aluminium salt,
etc. The higher the valence electron of the salt, the better the destabilization
as well as the lower the salt concentration required. Thus NaCl is considered
not suitable for it required concentration is high and cause high chloride in
permeate. For Fe and Al salts, they are more expensive than CaCl2.
Furthermore, laws and regulation in many countries limit presence of highvalence ions in effluent.
Presence of free-oil may cause some problem at high Pt and V, as described

in section 8.2.3.1. It can cause pore blocking, resulting in decrease in flux at
high Pt (see fig. 8.2.3-4), esp. at high value of V because it can cause high
mixing effect and turbulence, so the free-oil in the surface of tank is drawn
back with the feed stream to the UF module. This effect is also more eminent
when the membrane is hydrophobic (such as PVDF or Polysulfone). Thus, it
is recommended to separate this free-oil off the recycled stream, by
coalescer.
Some membrane material, such as ZrO2, may interact with calcium

complexes and cause serious decrease in flux. Furthermore, membrane with
large pore size (i.e., 150 kD) will be blocked relatively easily by free-oil, as
described in section 8.2.3.1.
Residual pollutant in permeate
Oil rejection or removal efficiency is about 100%. Theoretical oil concentration

in permeate is 0 ppm (see fig. 8.2.3-5). However, actual oil concentration in permeate may
greater than 0 ppm, depending on condition of equipment, wastewater characteristic and
operating condition, such as presence of free-oil or fouling materials (foulants).
Even though the oil is about completely rejected by UF. Permeate still contains
surfactants/co-surfactants and some additives that, naturally, can pass through the membrane.
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Some surfactants may react with other substances and form complex or integrates with its
species to form micelles that can not pass the membrane. However, it can be safely assumed
that the concentration of surfactants/co-surfactants in permeate is equal to free
surfactants/co-surfactants in inlet wastewater. For example, Elf Seraft A concentrate
contains 10% by weight of surfactant (sodiumsulfone, sodium carboxylate, triethanolamine
carboxylate), 5% of co-surfactant (benzylic alcohol), and 4% additives. Its permeate contains
pollutant, measured as TOD, around 650 mg/l per 1% by volume of oil in the inlet
wastewater. Many researches [10], {11], [18] pointed that TOD removal efficiency of UF for
macroemulsion is greater than 95%.
In case that the salt is added to the wastewater, surfactants/co-surfactants will
react with the salt to form complex. However, there is not enough data to conclude its effect
on residual pollutants in permeate. So, to be on the safe side, it can be assumed that the TOD
in this case is identical to the no-salt case. And the salt will also be present in the permeate as
described in the previous paragraph.
a) Fresh macroemulsion
b) Used macroemulsion
c) Microemulsion
Fig. 8.2.3-5 Examples of feed emulsions and their corresponding UF permeates

8.2.3.3 Design consideration and significant findings on microemulsion treatment
Design consideration and significant findings from GPIs lab on microemulsion
treatment are summarized as follows,
1.
Flux/pressure relation and Cg
Flux/pressure relation of microemulsion is of typical pattern, like

macroemulsion. Even though the droplet size of microemulsion is always smaller that that
of macroemulsion, Its flux may be higher or lower than macroemulsions, depending on its
components. For example, Elf Seraft A macroemulsion (dE 150- 200 nm) has higher flux
than Elf Emulself G3 microemulsion (dE = 50 nm.) but lower than Emulself XT (dE = 20 nm)
at the same oil concentration and operating condition. For the Cg of microemulsion, there is
no experiment that was conducted until the flux was about zero. The maximum value,
proposed by BELKACEM and based on Elf Emulself G3, (see table 8.2.2-2), is 45% by
volume of oil.
2.
Oil rejection and residual pollutants in permeate
Recommended MWCO of UF membrane for microemulsion treatment is around

40-50 kD. Oil rejection, based on fresh emulsion, is 100%. For used emulsion, presence of
free-oil or foulant may cause decrease in oil rejection.
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Permeate of microemulsion contains much more residual pollutants than that of

macroemulsion since it contains very high concentration of surfactants/co-surfactants and
additives (around 80% by weight). For example, Elf Emulself G3 microemulsion contains
surfactants/co-surfactants and additives around 80-85%. Its permeate contains TOD of 2,660
mg/l per 1% by volume of oil in the inlet wastewater. Many researches [10], {11], [18]
pointed that TOD removal efficiency of UF for microemulsion is around 80-90 %. Because of
high residual TOD, the permeate need to be further treated by RO or other feasible processes.
Flux enhancement by salt addition had never been studied in GPIs lab.
Theoretically, the effect of salt in this case should be identical to that of macroemulsion.
However, since concentrations and types of emulsifier of the two emulsions are greatly
different. Salt requirements should be different. Thus it is recommended to perform UF test to
find salt requirement, rate of increase in flux and residual salt in the permeate before design.
8.2.3.4 Fouling and cleaning of membrane
Fouling is a major problem of membrane process. Unlike polarization, Decrease in
flux from fouling is irreversible. The flux will decrease with time, even when operating
condition is constant, and not recover unless proper regeneration or cleaning process is
applied. Fouling is represented in the resistance model in the form of fouling resistance RF
(see section 8.2.1.6). Its mathematical equations are of power or exponential types. The exact
equation for each wastewater is achieved only from the experiment.
There are several references, literatures and books about fouling and cleaning of
membranes, as listed in bibliography. Here, only fouling and cleaning related to oily
wastewater will be mentioned.
1.
Typical foulants
Fouling materials, which are usually found in oily wastewater, include.
2.
Hydrocarbons, fats, oils and grease: These substances are usually listed as
a major foulant for UF process. Their presence should be avoided or
minimized. However, for oily wastewater treatment, its rejection becomes
the objective of the process. Free-oil cause more problems than emulsified
oil, as described in section 8.2.3-1. To reduce the fouling from oil, one
should start with the right membrane material. Hydrophilic membrane, such
as PAN, is recommended. Free oil should be removed from UF feed stream.
Suspended solids: For cutting oil wastewater or wastewater from mechanical

workshops, scraps or small bits of materials from manufacturing processes
are major source of SS. Extent of clogging depends mainly on the size of the
SS. It is recommended to separate these materials from UF feed steam.
Heavy and relatively larger scraps can be settled. For smaller SS, it may be
separated by physical processes, i.e. hydrocyclone or prefilter. Generally, the
materials, which are larger than 1/10 of membrane flow channel, should be
prefiltered.
Flux enhancement
Many techniques are invented to slow down fouling process, resulting in longer
period of high flux. Examples of these techniques, shown in fig. 8.2.3-6, include,
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Back flushing (sometimes called backpulsing, backwashing) This

method has been tested by SRIJAROONRAT [10], using Membralox T170 inorganic tubular module, active surface of 0.005 m2, equipped with
automatic backflushing equipment. After normal UF operating of 1-3
minutes, the permeate of 3 ml is automatically injected in the direction of
permeate side to feed side every 0.7 to 5 seconds. For UF of kerosene/water
secondary emulsion with backflushing, increases in flux up to 2 times were
reported. In present, this technique is commercially available, esp. for
ceramic membrane.
Turbulence promoter: Moving of membrane, such as in rotating disc

module, or insertion of wire, mesh into the membrane flow channel can
increase turbulence, thus increase permeate flux.
Other techniques, such as (1) co-current permeate flow, which required a

permeate pump, (2) permeate backpressure by throttling of permeate outlet
valve to optimize Pt or (3) use of pulsating feed, etc.
Fig. 8.2.3-6 Examples of flux enhance techniques [38]

3.
Cleaning of membrane
When flux decreases to an unacceptable level, the membrane needs to be cleaned

to restore the flux up to or almost to the original value. Cleaning procedures always involve
combination of these means, i.e.
Chemical, in the form of detergents, acids, alkalis, water or cleaning reagents

Thermal, in the form of heat
Mechanical, in the form of hydrodynamic force.
To remove oil from the membrane, many reagents are recommended such as
alkali, alcohol, detergents or even pure water. Selection of cleaning reagent depends on type
of product (for manufacturing process), type of foulants, chemical and thermal resistance of
membrane material.
For oily wastewater treatment, rinsing with water and/or cleaning with detergents
or surfactants are generally used. Rinsing with water is proven to be efficient enough for
cleaning UF membrane of used macroemulsion treatment from mechanical workshop [12],
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(see fig. 8.2.2-4). Use of surfactants provides better cleaning efficiency pluses that the
surfactants will somehow bond to the membrane surface in the form of oleophobic layer
consisting of micelles, resulting in more hydrophilicity of membrane. This oleophobic layer,
formed by surfactants, will prevent the oil from attaching to the membrane. Thus, it helps
reducing fouling, resulting in prolonging period of high flux [18], (see fig. 8.2.3-7).
Fig. 8.2.3-7 Example of evolution of flux of macroemulsion UF with periodical cleaning with
macroemulsion (membrane IRIS 3042, P = 1 bar, V=1.5 m/s. 25oC) and schematic of
interaction between membrane/surfactants [18]
Cleaning of UF membrane by microemulsion
GPI lab had researched on the use of microemulsion as a cleaning reagent [18],
[11], since it contains high concentration of surfactants. Recommended cleaning procedure
starts with rinsing of the membrane with water for 20-30 minutes, then circulation of the
microemulsion for 15 minutes. WANICHKUL [11] recommended another water einsing after
the emulsion circulation. Throttle valves in the system should be fully open during the
cleaning process. Recommended concentration for the cleaning solution is Around 2% by
volume of concentrate. The used cleaning emulsion can be stored and used for several times
until it is saturated by oil. The result shows that the procedure can restore the flux up to 98%
of original value. Advantages of this concept include;
Microemulsion is normally available in factories or mechanical workshops.

No need to purchase surfactants. Its efficiency is very good. It also helps
forming micelles as described in the previous paragraphs.
The result is relatively identical to the use of surfactants since it can prolong
period of high flux as shown in fig. 8.2.3-7.
For its very high surfactant concentration, it can be reused for several
cleaning cycles until it is saturated by oil. Thus this concept is quite
economical.
Used cleaning microemulsion can be treated by chemical breaking, following

by UF.
Apart from the use of commercial microemulsion, BELKACEM also

recommended a formula of the special cleaning microemulsion, which
generates low-pollutant permeate from its treatment by UF. Its concept is
based on the use of low-solubility surfactants/co-surfactants. The
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components of the cleaning emulsion are as shown in table. 8.2.3-1. The

permeate from treatment of the cleaning emlsion by UF contains TOD of 3
g/l, much lower than that of conventional microemulsions permeate.
Recommmended concentration to create cleaning solution is 4.5% as volume
of the concentrate.
Table 8.2.3-1 composition of the special cleaning microemulsion concentrate [18]
Components
Name/ type
Percent by weight
Base oil
mineral
32%
Surfactant
Alkyl benzene sulfonate
22%
Co-surfactants
Alkyl phenol ethoxylate (non-ionic)
22%
Oleic acid
5%
Anticorrosion
Oramide DL810 (by SEPPIC)
8%
Bactericide
Seppicide HB (by SEPPIC)
4%
Antimousse
Antimouse 411
2%
Water
5%
8.2.3.5 UF test
Since the performance of UF is sensitive to types of membrane and wastewater
characteristics, which may varies greatly from source to source, it is strongly recommended
to perform UF test to obtain the exact data on UF performance for the wastewater to be
treated.
Almost all of membrane manufacturers provide feasibility test service and produce
pilot-scale or lab-scale UF test module. The UF test module can be divided into 2 major types,
i.e.,
Dead-end test module, as shown in fig. 8.2.3-7a, b. This type of test module is
basically operated in dead-end mode, with some equipment or mechanism, such as
mechanical agitator or small recirculation pump, that provide turbulence for
polarization control. Driving pressure generally comes from an air compressor or
compressed air cylinder. This type of model is inexpensive and takes relatively
short test time. However, even though it is equipped with polarization control
device, the effect is not identical to the real module, which is operated in crossflow mode. It is difficult to predict the relation between result from the test module
and real cross-flow module, esp. when free-oil is present in the wastewater. So the
module is normally used to find preliminary result on flux and fouling of
membrane and for comparison purpose between various types of membranes.
Realistic test module, as shown in fig. 8.2.3-8c, d. This type of test module is
practically a scale-down version of the real UF module. So the result from this test
module is more realistic and can be straightforwardly scaled-up for design of the
full-scale system.
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a) Dead- end test module

(Source: Millipore)
b) Plate membrane test module (Source: Orelis, Osmonics)
c) Spiral wound test set (Source: Millipore)
d) Pilot-scale test set (Source: Millipore)
Fig. 8.2.3-8 Examples of UF test modules

Almost all of the researches on oily wastewater treatment by UF are based on
stabilized emulsion since it cannot be separated effectively by other single process. However,
SRIJAROONRAT [10] has researched on UF of non-stabilized secondary emulsion. Her
study provides useful information to understand the performance of UF when free-oil is
present, which is frequently found in general oily wastewater. Significant findings of the
research can be summarized as follows,
8.2.3.6 Miscellaneous design consideration
Most of the design considerations for each category of oily wastewater are described
in the previous sections. In this section, some general remarks and common design
considerations, summarized from synthesis of literatures and GPI researches, will be
presented as follows,
From GPIs researches as well as other literatures, it is recommended to operate

UF system for oily wastewater around a certain flux to prolong the operating
time per cycle (before cleaning) and maintain relatively steady flux. This concept
is called critical flux. At this flux, deposition of foulants can be counterbalanced
by shear force from cross-flow velocity. Thus the fouling resistance is relative
steady (not changing with time). This can be normally achieved by the use of
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moderate pressure (1-1.5 bar). The use of higher pressure may give higher flux
but the rate of decrease in flux is higher to, resulting lower overall flux.
UF performance is sensitive to type of membrane, characteristic of wastewater and

operating condition. So it should be very careful to use the data from literatures or
researches to design the system. Experimental procedures of the researches should
be considered. The common mistakes on the use of researches on UF of oily
wastewater treatment are about, (1) pore size, sometimes MWCO and pore sizes
are confusing, and (2) concentration of oil, they are reported in various forms (%
by volume of oil, % by volume of concentrate in case of cutting oil emulsion, % by
weight, etc.), (3) Effect of concentration factor, some experiments carried out by
recycling the permeate to the feed stream, so the concentration of feed were
constant. The concentration effect is not included.
The cost of membrane system is high and the performance on secondary emulsion
treatment is not better than general separation processes. The UF, then, should be
used for some specific wastewater, separating from main stream wastewater.
8.3
8.3.1
Microfiltration (MF) membrane can retain material in the range of 0.1 to about 5
microns (100-5,000 nm). It is mainly used as a clarification technique, separating suspended
solids from dissolve substance [38]. Size of MF is defined in the form of pore size, rather than
MWCO. MF membranes are available in various geometry and materials as UF. Its main
applications are separation of suspended particles in biotechnology, food and pharmaceutical
industries such as bacteria, red blood cells, latex emulsion, dairy product, etc. Examples of
MF membrane are as shown in fig. 8.3.1-1
Tubular module
(Source: Koch)
b) Plate module
(Source: Millipore)
c) MF membrane structure
(Source: Millipore)
Fig. 8.3.1-1 Examples of MF membranes
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Theoretically, working principle of MF is relatively identical to that of UF. Theories,

models and characteristic curves of UF can be applied to MF. Main difference between MF
and UF is the pore size. Since the pore size of MF is relatively large. Its corresponding
capillary pressure is relatively low (around 0.1 bar). Thus, its maximum or limiting pressure is
much lower than UF. Its pore is about the same size as droplets in macroemulsion, so some oil
droplets can pass the MF membrane and be present in permeate. This is the main reason why
MF had not been studied seriously on oily wastewater treatment.
However, GPI lab had researched on the feasibility of combination between chemical
destabilization and MF for macroemulsion treatments as will be described in the following
section.
8.3.2
Significant findings on MF for oily wastewater treatment from GPI researches
As stated above that MF pore size is close to that of oil droplets in macroemulsion, to
use MF for this wastewater, the droplet size must be increased. MATAMOROS applied the
concept of flux enhancement by salt addition, like the case of UF, to MF. Significant findings
from the research are as described below,
1.
Recommended pore size is around 0.2 for MF (with salt addition) of

macroemulsion treatment. The use of too large pore results in very low or zero
oil rejection. Both oil and water can pss through the membrane. The use of
smaller pore is not possible, since its maximum pressure, calculated from pore
size, is not enough to drive the separation process. Both water and oil cannot
pass the membrane. If we increase the pressure, it can force the oil through the
membrane, resulting in very low or zero oil rejection anyway.
2.
Quantity of salt required is much higher (about 3 times) than that of UF and
relatively close to the quantity required for total destabilization. Optimum dose
of CaCl2 for macroemulsion, based on Elf Seraft ABS cutting oil macroemulsion
[20], is about 95 mg/l of Ca++ or 350 mg/l of CaCl2 per 1% by volume of oil in
wastewater.
3.
Result from dead-end test module of MF with salt addition shows very high flux,
relatively close to that of water flux. However, in case of cross-flow module, the
initial flux is about identical to the water flux at the beginning of the operation.
Then, the flux decreases rapidly within very short time (few hours), more rapid
than that of UF. The steady flux is relatively low and may not be higher than that
of UFs flux (see fig. 8.3.2-1). Steady flux, based on Seralf ABS 4% at 0.1 bar, is
around 25 LMH.
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Fig. 8.3.2-1 Evolution of flux from MF (with salt addition) of macroemulsion [20]
4.
The difference between dead-end and cross-flow model may be caused

difference in test volume since the dead-end module is much smaller than the
pilot scale cross-flow module.
5.
Rapid decrease in flux can be explained by deposition and coalesce of free-oil at

the surface as well as within the pore size of membrane since the pore size of MF
is relatively large.
6.
When the membrane is properly selected, oil rejection is about 100% at low
operating pressure (about 0.05-0.1 bar). Increase in pressure beyond the capillary
pressure results in presence of oil in permeates. Since the pressure is much lower
than (about > 10 times lower) that of UF, energy consumption of MF is very
low, compared to UF.
7.
Residual TOD comes from the surfactants/co-surfactants. Concentration of

residual salt and TOD are relatively identical to that of UF with salt addition,
described in section 8.2.3.2.
8.
To reduce fouling, MATOMAROS recommends the use of other separation

process, such as coalescer or hydrocyclone, to separate the free-oil from MF feed
stream.
9.
Since quantity of salt added into the wastewater is high, the emulsion is largely
destabilized already since it is in the storage tank, indicated by presence of oil
layer on the surface. Thus, the use of MF should be compared to the combination
of destabilization and other basic process, such as decanter, coalescer.
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8.4
Reverse osmosis is the ultimate pressure driving membrane process that capable of
retaining ionic-range materials, the range of 0.1 nm. Structure of RO membrane is dense,
compared to porous structure of UF and MFs (see fig 8.4-1). Its main application is
production of ultra pure water for many industries, such as, pharmaceutical, electronic, food,
and nuclear (water for reactor). RO membranes are available in various materials and
modules, i.e. plate, etc., as described on section 8.1.
Cutaway-view of RO module
(Source: Desal)
RO pure water system

(Source: Koch)
Fig. 8.4-1 Examples of RO membranes

8.4.1
Working principles of RO is based on the concept of osmosis. Osmosis phenomenon

can be explained by considering the system of 2 compartments, separating by dense
membrane, as shown in fig. 8.4.1-1. Each compartment contains the solution at different
concentration.
Osmosis phenomenon is defined by mass transfer of the solvent through the
membrane, from the diluted solution to the concentrated one. Increase in pressure on the
concentrated side can lower or stop the mass transfer. To stop the mass transfer, the pressure
required shall be equal to osmotic pressure, as shown in fig. 8.4.1-1b. If the applied
pressure is higher than the osmotic pressure, the solvent will inversely travel from concentrate
side to the diluted side (fig. 8.4.1-1c). This is the phenomenon taking place in RO and give the
process its name.
Posmotic
a) Osmosis phenomenon
P = Posmotic
P = Posmotic
b) Osmotic pressure
c) Reverse osmosis
Fig. 8.4.1-1 Working principles of reverse osmosis

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Osmotic pressure is the function of concentration and usually defined by Vant hoff as
shown in eq. 8.4.1.
= A1C + A2 C 2 + A3 C 3 + ...
Where
C
An
=
=
=
{8.4.1}
Osmotic pressure
Concentration of solution
Virial coefficients of the solution
The value of A1, A2, A3, etc. depends on type of solution. The virial coeeficients of
large molecules or materials are relatively small. Thus the osmotic pressure is low and usually
negligible, as in case of MF and UF. For low molecular-weight molecules, supposed to be
separated by RO, the values of high-ordered A are high so the osmotic pressure becomes
significant.
Mathematical model for RO
Mathematical model of RO can be written in the form of resistance model, as shown in
eq. 8.4.2. For RO, transmembrane pressure is countered by osmotic pressure, so the effective
driving force for the process is the difference between the two pressures. RO resistance
mainly consists of the membrane resistance. Mass transfer resistance in the boundary layer
may be accounted in some cases.
J=
Where J
Pt M
RM
=
=
RM =
{8.4.2}
Permeate flux
Osmotic pressure, calculated from the concentration at the
membrane surface
Membrane resistance
RO may find its application in industrial water reuse process. However, due to its
minuscule pore size and very high osmotic pressure, pressure requirement, thus energy
consumption, of RO is very high. So it is scarcely used on general wastewater treatment. In
GPI lab, RO had been studied for its performance on treatment of highly polluted permeate
from UF of wasted emulsion. The studies will be summarized in the following section.
8.4.2
Significant findings on RO for oily wastewater treatment from GPIs researches
BELKACEM [18], MATAMOROS [20] and WANICHKUL [11] had studied on

application of RO on treatment of highly polluted permeates from treatment of wasted cutting
oil emulsion. Significant findings of the researches are as summarized below,
1.
RO is proven to be an efficient process for treatment of UF permeate of macro-or

microemulsion, which contains very high concentrations of surfactants/cosurfactants that are not retained by the UF membrane. When retentate and
permeate are recycled, relation between flux and pressure from RO of
microemulsions permeate from UF is linear up to the maximum test pressure of
60 bars as shown in fig. 8.4.2-1a.
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Flux
Flux
Lag due to
osmotic
pressure
Min recommended
pressure
Pt
Log (conc.)
Fig. 8.4.2-1a Typical relation between flux

and pressure of RO
2.
Fig. 8.4.2-1b Typical relation between flux

and log of concentration
Evolution of RO flux from treatment of microemulsions and macroemulsions

UF permeate, both in used and fresh condition, are relatively identical as shown
in fig. 8.4.2-2. The graph is for RO operation in batch process (see fig.8.2.1-4)
without return of permeate so effect of factor of concentration is already
included.
180
160
Flux (L/(m2.h))
140
120
100
80
60
40
20
0
0
2000
4000
6000
8000
10000
12000
14000
Time (sec)
Microemulsion
Macroemulsion
Used macroemulsion
Fig. 8.4.2-2 Examples of flux evolution from RO of the UF permeates of various emulsions (the
RO permeate are not recycled) [11]
3.
Flux decreases with increase in concentration factor (fig. 8.4.2-1b). There is no

clear evident if the relation between flux and factor of concentration will have
inflection point like that of UF of macroemulsion (fig. 8.2.1-6) since the
experiments were usually stopped before the zero-flux was reached. The
maximum factor of concentration (or volume reduction factor) ever tested in GPI
lab is 2.5 (at 25 bars, 30oC, V = 1.8 m/s)[18].
4.
BELKACEM [18] reported that permeates TOD generally increases with time
or concentration factor (shown in fig. 8.4.2-3a). However, WANICHKUL
showed [11] that TOD may decrease with time or concentration factor, as shown
in fig. 8.4.2-4. Decrease in permeate TOD, in this case, may be explained by
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formation of micelles on the membrane surface when the concentration of feed is

continuous increased along the process time until it reaches the critical micelle
concentration (CMC) [11]. These micelles cannot pass through the membrane so
the quantity of pollutant in permeate is decreased. Formation of micelles depend
on type and concentration of surfactants/co-surfactants in the permeate, as well
as interaction between those pollutants and other material such as calcium that
may cause formation of complexes as well as electrical charge of membranes.
Thus, exact result should be obtained from RO test.
5.
Typical relation of rejection or removal efficiency with pressure, based on salt, is

as shown in fig. 8.4.2-3b [59]. But MATAMOROS [20] indicates that, for UF
permeate of microemulsion, the rejection decreases at high pressure (the dashed
line in fig. 8.4.2-5b). There is not sufficient data to evaluate the cause of this
decrease. However, it is recemmeded to use moderate transmembrane pressure
(about 20-25 bars) to obtain good rejection.
Rejection
Rejection and
TOD permeate
Rejection
TOD
1
Min recommended
pressure
Concentration factor
Fig. 8.4.2-3a Relation between rejection,

TOD of permeate and concentration factor
Pt
Fig. 8.4.2-3b Relation between rejection and

transmembrane pressure
TOD of permeate (mg/l)
0
0
2000
4000
6000
8000
10000
12000
14000
16000
Time (sec)
Microemulsion
Macroemulsion
Used macroemulsion
Fig. 8.4.2-2 Examples of permeate TOD evolution from RO of the UF permeates of various
emulsions (the RO permeate are not recycled) [11]
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6.
8.5
Guidelines for RO design or evaluation, summarized from various GPIs lab, are
as shown in table 8.4.2-1. Membrane material used is polyamide. MWCO is
around 100-150 Daltons.
Nanofiltration (NF)
Nanofiltration is an intermediate membrane process between ultrafiltration and reverse

osmosis. It is a relatively new technology, compared to others membrane processes. NF
membrane pore sizes are between those of UF and RO. It can retain the meterials of the size
around 100 600 nm. Thus it can be used to separate dissociated form of a compound from
the undissociated form [38]. For example, lactic, citric, and acetic acids can pass through to
NF at low pH but are rejected at high pH when in their salt forms. NF is generally used in
many industries, such as biotechnology, food, and drinking water as well as in environmental
applications. Apparently, structure and module of NF are relatively identical to those of RO.
8.5.1
Separation in NF membrane is based on both size difference, like UF, and diffusion
mechanism, like RO. Generally, NF membranes are charged so they can be used for selective
separation of charged materials. Uncharged membranes are available but very rare and not
popular. Separation mechanisms in NF membrane are not well understood. But they are
generally described in 2 approaches, i.e. ionic exclusion and, like RO, solution-diffusion.
For ionic exclusion approach, separation of charged materials by NF depends on the
charges of ions in solution to be separated and of membranes. Ions of the same charge as the
membrane will be pushed while the counter-charged ion will be attracted by the membrane
charges. For uncharged membrane, the modified form of solution-diffusion model, as shown
in eq. 8.4.2-2, was used to explain the separation mechanisms in the NF membranes by some
researchers. Applications of NF on oily wastewater treatment are known of but they are
privately designed and there are not many publications on the issue.
In GPI lab, MATAMOROS [20] performed the feasibility study on application of NF
for cutting oil emulsion treatment. The result will be summarized in the next section.
8.5.2
Significant findings on NF for oily wastewater treatment from GPIs researches
MATAMOROS [20] had studied the performance of NF on the treatment of cutting oil
emulsions as well as permeates from UF of cutting oil emulsions, using cellulose membranes,
i.e. Desal 5 (600 Da), SV10 (100-300 Da) and SG15 (2000 Da). Significant findings of the
research are as summarized below,
1.
From the research, NF is proven to be an efficient process for treatment of UF

permeate of macro-or microemulsion, which contains very high concentrations
of surfactants/co-surfactants that are not retained by the UF membrane.
Rejection is slightly lower than that of RO. But the energy consumption is about
half of ROs, since its pressure range is around 4 20 bars, compared to the
range of 20 60 bars for RO. Evolution of flux with time and with pressure for
NF of permeate are relatively identical to that of RO (fig. 8.4.2-1 and 8.4.2-2).
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Table 8.4.2-1 Summary of RO data on oily wastewater treatment
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2.
NF performances on macro- and microemulsion treatment were also studied.

The result showed that, at constant feed concentration, relation between pressure
and flux of NF for macro- and microemulsion treatment are divided into 2
regions i.e. pressure controlled and mass transfer controlled region (fig 8.5.2-1),
like that of UF.
3.
Relation of flux and theoretical concentration of feed, when permeate is not

recycled, is as shown in fig. 8.5.2-2. The relation is not linear so it is not
governed by film model (section 8.2.1.5). This can be explained by
destabilization in-situ of emulsified oil during NF operation, justified from
presence of oil layer in the storage tank. Destabilization of oil, like the case of
UF with salt addition, makes the real feed concentration lower than theoretical
value.
4.
Results of MATAMOROS are as shown in table 8.5.2-1. From the table, TOD
removal efficiencies of UF are always higher than UF. This means the oil is
completely separated and the surfactants/co-surfactants are retained with higher
efficiency. However, it should be noted that the results are based on fresh
emulsion. For used emulsion, result may differ and should be obtained by pilot
test.
Fig. 8.5.2-1 Relation of flux and transmembrane pressure of NF for macroemulsion

(Elf Seraft ABS) and microemulsion treatment (Elf Emulself G3 EAB), using desal5
membrane at 20oC [20]
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Fig. 8.5.2-2 Relation of flux and theoretical feed concentration of NF for macroand microemulsion treatment [20]
8.6
Comparison of membrane processes on emulsion treatment
Major objective of GPIs researches on oily wastewater treatment by membrane

process is the treatment of stabilized emulsion. From the previous sections, they show that
performance of each process or combinations of processes on emulsion treatment are
different. To compare the performance of processes or combinations of membrane processes,
MATAMOROS had performed pilot test of various processes using the same macroemulsion.
His results are tabulated in table 8.6-1. However, It should be noted that,
1.
The results are based on specific operating conditions, types of wastewater and
membrane. Since performances of membrane processes are sensitive these
parameters, the results can be used as a guideline for preliminary evaluation
only.
2.
Fresh emulsions were use so fouling due to foreign materials was not included.
3.
Evolutions of flux with time are not present. In real design, this data is important
for membrane sizing and determination of operating and cleaning cycle. For
example, NF and MF+CaCl2 may be very interesting from their relative low
energy consumption. But they may foul easily, resulting in low flux for long-tern
operation and more frequent cleaning.
4.
Even though the efficiency of each process is very high. It does not mean that the
permeate always conforms to the related standard. For example, permeates
TOD from RO of UF+RO of macroemulsion at 4% by volume of oil is around
1,250 mg/l, which is still high and may need further treatment or to be mixed
with relatively diluted wastewater and treat by conventional treatment system.
5.
From the previous sections, it is obvious that membrane process is very versatile
and efficient process. But its performance is sensitive to many parameters. So it
is, again, strongly recommenced to perform pilot test before design the real
membrane process.
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Table 8.5.2-1 Summary of NF data on oily wastewater treatment
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Table 8.6-1 Comparison of membrane processes on cutting macroemulsion treatments

(based on Elf Seraft ABS at 4% by V of oil)
MF+CaCl2
UF
UF+RO
UF+NF
NF
MS11107
Iris3042
Iris3042 +MS10
Iris3042
+Desal5
Desal5
Global TOD
removal efficiency
(%)
97.2
95.8
99.1
97.9
97.4
TOD of final
permeate (g/l)
2.76
4.5
0.92
2.2
2.7
Pt (bar)
0.1
1+30
1+10
10
Flux (LMH)
24.9
52.92
52.92/42.12
52.92/30.96
27
Not available
3.2
3.2+40.2
3.2+22.8
22.2
Membrane
Specific energy
consumption
(KWh/m3)
Remark
Note
2
3
See note 1
See note 2
Initial flux of MF is very high, compared to that of water, but the membrane is
rapidly clogged by free-oil. The flux, thus, drops sharply. The final flux is
relatively low.
Evolution of time was not present in the original research. But the membrane tends
to be clogged by free-oil from destabilization in-situ.
No comparison data of microemulsion treatment was proposed.
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Chapter 9 Thermal processes

9.1
General
Thermal processes are separation processes that involve changing of phases of the
materials to be separated. For distillation, it involves liquid and gas. For crystallization and
zone refining, they involve liquid and solid. Since the processes involve phase changing, they
inevitably consume high energy. This is the reason why they are scarcely used for general
wastewater treatment. However, it may become economical alternative if the product from the
treatment can be recycled or relative easier for ultimate disposal.
Oily wastewater is actually binary system, containing, mainly, 2 immiscible liquids i.e.
oil and water. So it could be separated by thermal processes. In GPI lab, there are some
researches on applications of thermal processes on oily wastewater treatment. Most of all
were based on distillation. Only few were based on crystallization. So, in this chapter will be
emphasized on distillation, which can be divided into 2 major types, i.e. conventional
distillation and enhanced distillation, called heteroazeotropic distillation.
It must be noted that the researches are based on lab-scale experiments to study the
theoretical concepts that underline process operation. In real processes, the distillations are
usually carried out in distillation columns, which their designs are a major science into itself.
So it will not be mentioned here. However, the researches can be used as a guideline to
understand and evaluate the feasibility of the processes.
9.2
Since distillation always involves liquid and vapor phase of mixtures, it can be
described by the concept of vapor/liquid equilibrium. The mixtures may have two or more
components. However, to provide basic knowledge of the process, it is sufficient to simply
consider the mixture of 2 components, called binary mixture.
9.2.1
Basic knowledge on vapor/liquid equilibrium of mixtures
Since distillation always involve the mixture of two or more components, it is

necessary to know a certain number of variables to describe or characterize the equilibrium
stage of the system. The number of required variables, called degree of freedom is
calculated by the phase rules, as shown in eq. 8.2.1.
F = 2 + N
{9.2.1}
Where F = Degree of freedom

= The number of phases, for vapor/ liquid system, = 2
N = The number of species in the mixtures
For example, to describe a binary mixture system, required degrees of freedom are 22+2 = 2, which are normally pressure and temperature. Generally, distillation processes
operate at constant pressure, so operating parameter that is used to control the process is
temperature.
To understand vapor/liquid equilibrium of a binary system, consider a binary mixture
of specie A and B in the container, as shown in fig. 9.2.1-1. Assume that overall pressure of
the system is constant at 1 atm. When the mixture is heated, temperature of the mixture will
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increase, as shown in fig. 9.2.1-2. When it reaches a certain temperature, called bubble
point, the first bubble of vapor will appear. From this point, the mixture will exist in both
vapor and liquid phases. Unlike a pure substance, temperature of the system during
evaporation period continuously changes, rather than being constant. When the temperature
reach a certain value, called dew point, the last drop of liquid will disappear.
P = constant
P = const.
Liquid Liq
Vapor phase
Gas Gas
Dew point
Bubble point
Liquid phase
Specie A
Specie B
Time
Heat
Fig. 9.2.1-1 Diagram of a binary mixture

system
Fig. 9.2.1-2 Evolution of temperature of a

binary mixture at a constant P
Dew temperature and bubble temperature of a binary mixture varies with pressure. An
example of relation between pressure and temperature is shown in fig. 9.2.1-3. Characteristic
of P-T curve depends on types of components in the mixture.
Critical locus
100% Methanol
Methanol/Benzene
mixture
C
Bubble curve
Dew curve
0% Methanol
Fig. 9.2.1-3 Examples of P-T diagram

At a binary system at constant pressure, the dew- and bubble points of the system vary
with composition of the mixture. Compositions of the mixture are usually reported in the from
of molar fraction x and y. The value xi represents the ratio of moles of species i in
liquid phase (ni,l) to summation of moles of every species in liquid phase (nl) (eq. 9.2.2). On
the other hand, the value of yi is the ratio of moles of species i in vapor phase (ni,v) to
summation of moles of every species in vapor phase (nv) (eq. 9.2.3).
xi =
n i ,l
yi =
n i ,v
nl
nv
=1
{9.2.2}
=1
{9.2.3}
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When the bubble points at various values of x1 are plotted, the curve is called the
bubble curve or saturated liquid line. On the other hand, when the dew points at various
values of yi are plotted, the curve is called the dew curve or saturated vapor line.
Generally, dew curve and bubble curves are plotted on the same coordinate. They can be
plotted both on T-x-y scale and P-x-y scale as shown in fig. 9.2.1-4a and b. Since distillation
process usually operates at a constant P, T-x-y curve is normally used. Relations between
pressure, temperature, x and y can be combined into a three-dimension coordinate, resulting in
P-T-x-y diagram as shown in fig. 9.2.1-5.
P = const.
T
C
T = const.
Bubble curve
Dew curve
Pure B
xA = 0
yA = 0
xA , yA
Pure A
Bubble curve
Dew curve
Pure B
xA = 0
yA = 0
xA = 1
yA = 1
a) T-x-y diagram
Pure A
xA , yA
xA = 1
yA = 1
b) P-x-y diagram
Fig .9.2.1-4 Examples of T-x-y and P-x-y diagrams

To understand phase changing taking place in distillation process, we will consider a
P-x-y diagram as shown in fig. 9.2.1-6. From the figure, the points on the dew curve represent
saturated vapor. the area above the dew curve (T-yi) is of superheated vapor. The points on the
bubble curve represent saturated liquid. The area below the bubble curve (T-xi) is of
subcooled liquid. The area between the 2 curves is the two-phase region. The two curves meet
at the edges of the diagram where saturated liquid and saturated vapor of the pure species
coexist.
P
T
r
Pu
eB
Superheated vapor
ve
cur
w
P = const.
De
c
b
Critical
T
Pu
re
A
b
Bu
Pure B
xA = 0
yA = 0
0
xA
yA
rv
cu
e
bl
c
b
a
Subcooled liquid
xA= 0.6 xA= 0.8
Pure A
xA = 1
yA = 1
yA = 0.4 yA = 0.6
1
Fig. 9.2.1-5 An example of P-T-x-y diagram

364
Fig. 9.2.1-6 An example of T-x-y diagram

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From fig. 9.2.1-6, if we heat the subcooled liquid of 60 mol-% of specie A and 40 mol% of specie B (so xA = 0.6, xB = 1-0.6 = 0.4) under a constant P from point a, the first bubble
will appear when the temperature reaches the bubble curve at point b. The molar fraction of
specie A in this very first bubble will be determined by drawing the horizontal line from point
b to meet the dew curve at point b. If we continue heating, more vapors will appear while the
quantity of liquid will decrease. The compositions of liquid will follow the bubble curve from
point b (xA = 0.6) to c (xA 0.8) and the composition of vapor will follow the dew curve from
b (yA 0.8) to c (yA = 0.6), respectively. When the temperature reaches point c, the last drop
of liquid disappears. The mixture will become entirely vapor with yA = 0.6. Continuing
heating, the vapor will have higher temperature and become superheated vapor. Cooling of
vapor can be explained by the same manner described above.
9.2.2
Characteristics of vapor/liquid equilibrium curves depend on types of components of

the mixture, pressure and temperature. Examples of various types of vapor/liquid equilibrium
are as shown in fig. 9.2.2-1. The first 3 curves are of miscible mixtures. For some mixtures,
the T-x-y diagrams present a maximum or minimum point where the boiling liquid at this
point produces a vapor of exactly the same composition. This point is called the azeotrope.
At some conditions, liquid/liquid equilibrium (LLE) coexists with vapor/liquid
equilibrium (VLE), this give rise to vapor/liquid/liquid equilibrium (VLLE) [61], as shown in
fig. 9.2.1-1 d to f. The state that VLLE is present is called heterogeneous azeotropic or
heteroazeotropic. As stated before, VLLE varies with intensive properties (P,T) and may
become only VLE at certain conditions as shown in fig. 9.2.2-2.
Locus of
azeotrope
High P
Low P
Pure B
xA = 0
yA = 0
x A , yA
Pure A
xA = 1
yA = 1
Fig. 9.2.2-2 Examples of evolution of VLE and VLLE with pressure
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Example
Type
V
Without azeotrope
Methanol-Water
T
L+V
L
X, Y
X
V
Minimum-temperature
azeotrope
L+V
L
Azeo
Azeo
X, Y
Azeo
Maximum-temperature
azeotrope
Ethanol-Water
Acetone-Chloroform
Y
L+V
Azeo
L
X, Y
V
Heteroazeotrope
(Partially miscible)
N-butanol-Water
Azeo
L+V
L
Azeo
2L
X, Y
V
Heteroazeotrope
(Immiscible)
Azeo
L+V
Decane-Water
Y
L+V
Azeo
2L
X,Y
X
V
Demixtion
Polypropylene oxideWater
L+V
L
2L
X ,Y
Fig. 9.2.2-1 Examples of various types of vapor/liquid equilibrium
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9.3
Heteroazeotropic distillation of oily wastewater
Heteroazeotopic distillation, in this chapter, is technically referred to the distillation

process that a proper substance, called entrainer, is added to the feed to ensure the
formation of heteroazeotrope. It does not include the process that the azeotrope occurs
naturally. However, their working principles are identical. Details of the heterotropic
distillation process are described below.
9.3.1
Working principles
Since hydrocarbons or oils have very low water-solubility, it is generally acceptable to

assume that oily wastewater, which is actually the oil/water mixture, is immiscible binary
mixture. Typical characteristic of T-x-y diagram at a constant pressure (called isobar
diagram) of oily wastewater is as shown in fig. 9.3.1-1. Generally, hydrocarbons have
higher boiling point than that of water.
T
Boiling T A
of B
TH B
P = const.
Boiling T
of Water
D
Vapor (V)
Oil +V
Azeotrope (H)
Pure Oil
xw = 0
yw = 0
W+V
yw,6
yw,5
xw,2
yw,1 to yw,4
= yH
xw,1
xw,1
Oil+water
xw , yw
xw = xH
yw = yH
xw,6=1
xw,5=1
xw,3 xw,4=1
Pure water
(W)
xw = 1
yw = 1
Fig. 9.3.1-1 Typical isobar diagram oily wastewater

From the diagram, it shows that the wastewater can be boiled at the temperature lower
than that of pure water and pure oils. Heteroazeotropic distillation, which is the distillation
when the VLLE is present, makes use of this fact so it requires lower energy than classical
distillation.
From the figure, the bubble curve in this case will look like a figure U with square
legs (Line ABHCD). If the original wastewater contain 70 mol-% of water (xw,1 = 0.70), it
will boil at the temperature TH. The composition of this very first bubble can be determined
by drawing the horizontal line to meet the dew curve (Curve AHD). In this case, they will
intersect at point H. Thus the molar fraction of water (yw) in the bubble is that of azeotrope
(yH, xH). Continuing heating, the liquid volume gradually decreases and its composition
gradually change from xw,1 to x.w,2, xw,3, etc. However, by drawing the horizontal lines from
these values of xw, the compositions of yw are always equal to yH. During this period the
temperature is automatically constant at TH. When xw finally reaches 1, this means the
residue becomes pure water. All of oils are separated from water and in vapor phase.
After this, the temperature rises until it reaches the boiling point of pure water. The
value of xw is constant at 1. The value of yw increases from yH to yw,4, yw,5, etc. since the pure
water continues boiling at add more steam to the overall vapor phase.
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The vapor phase is usually condensed to recover oil vapor. If the vapor is condensed
while xw < 1, the composition of vapor will be constant at yH. From fig. 9.3.1-1,these vapors
will condense at the temperature TH, resulting in the distillate of oil and water at xw = yH.
From GPIs research by TOULGOAT [19], the distillate will not be formed as an
emulsion if the hydrocarbons have high vapor tension and/or their water solubility is very low
and not sensitive to temperature change. This condition is usually satisfied for oily wastewater
treatment polluted by petroleum-base oil or for the carefully selected entrainer (described in
section 9.3.4). Thus the distillate from heteroazeotropic distillation of oily wastewater is
usually in the form of 2 separate layers of water and oil.
9.3.2
To define dew curve and bubble curve of a binary mixture, the following equations are
generally used, i.e. eq. 9.3.1 and eq. 9.3.2 (Daltons law)
p i = x i Pi sat
{9.3.1}
pi = y i P
{9.3.2}
Where pi = Partial pressure of specie i

Psat = Vapor pressure of specie i
P
= Pressure of overall system, which is normally kept constant, e.g. 1 bar
P
From eq. 9.3.1 and 9.3.2, it gives rise to Raoults law (eq. 9.3.3). The equation is
valid under the assumption that the vapor phase is an ideal gas and the liquid phase is an
ideal liquid.
y i P = x i Pi sat
{9.3.3}
If the system is not ideal system, eq. 9.3.3 will be modified as shown in eq. 9.3.4
(modified Raoults law).
y i isat P = x i i f i sat
{9.3.4}
i is called activity coefficient, which is normally obtained from experiments. If =

1, this means the system is ideal. The equation will become Raoults law. The vapor pressure
is replaced by the term fugacity (f) and fugacity coeficienct (). Relation between Psat, f
and are as shown in eq. 9.3.5.
isat =
f i sat
Pi sat
{9.3.5}
For application of oily wastewater treatment, the use of eq. 9.3.3 is proven to be
accurate enough [24], [11]. These equations will be used to determine the dew curve and
bubble curve, as well as azeotropic point of oily/water mixture, as described in the next
section.
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9.3.3
Calculation of azeotropic temperature and composition, dew curve and bubble

curve.
To calculate the isobar diagram of VLLE of oily wastewater or oil/water mixture, the
following procedure, based on the theories described in the previous section, is recommended.
1.
Find the azeotropic temperature (TH) and bubble curve (T-x)
For immisible bunary mixture of A and B, it can be imagined that the two
liquids are separately located in the container. Each liquid exerts the corresponding vapor
pressure. Thus the vapor pressure of the system is the summation of the vapor pressures of
every species, as shown in eq. 9.3.6. On the bubble curve, the mixture will boil when the
vapor pressure of the mixture is equal to the overall pressure of the system (P) (eq. 9.3.6).
PAsat+ B = PAsat + PBsat = P
{9.3.6}
To find the temperature TH that corresponds to eq. 9.3.6. Relation between vapor
pressure and temperature of both liquids must be known. For general liquids, their properties
can be found in many references, e.q. Perrys [2]. If the relations are provided in the form of
data table, it may be more convenient to use graphical method to find TH, as shown in fig.
9.3.3-1. Curves of liquid A and B are drawn, using the data from the reference. Curve of the
mixture A+B is obtained by the sum of vapor pressure of A and B at the same temperature.
This curve is the relation between azeotropic temperature (TH) and pressure. Thus TH at any
given operating pressure of distillation process can always be found.
Pressure
A+B
Pdesign
Pure A
Pure B
TH
Temperature
Fig. 9.3.3-1 Graphical method to find heteroazeotropic temperature

Sometimes, Relation between Psat and T of pure liquid is given in the form of
equation, called Antoine equation (eq. 9.3.7).
ln( P sat ,T ) = A
B
T C
{9.3.7}
T is temperature. A, B and C are numerical constants, depending on the types of

liquids. These constants can be also found in many references. From Antoine equations of the
two liquids, eq. 9.3.6 can be rewritten in the form of T. After solving the equation at a given
P, the resulting T is the azeotropic temperature TH. The bubble curve of an immiscible binary
mixture can de drawn as a straight horizontal line at the temperature TH on the T-x,y
diagram.
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2.
Find the Dew curve (T-y)

At every point on the dew curve, the liquid A and B will condense so,
p A = PA
sat ,T
{9.3.9}
{9.3.11}
pB = P
sat ,T
B
From eq. 9.3.2, the values of yA at any T (yA,T) in the region A-V (fig. 9.3.1-1),
which A will condense, can be calculated from the following equation.
p TA = y TA P = PAsat ,T y TA =
PAsat ,T
P
{9.3.12}
In the same manner, the values of yA at any T (yA,T) in the region B-V
(fig. 9.3.1-1), which B will condense, can be calculated from the following equation
p BT = y BT P = PBsat ,T y BT =
PBsat ,T
P sat ,T
y TA = 1 B
P
P
{9.3.13}
By varying the values of T, yA at various value of T can be calculated. Plotting

the values of yA and T on T-x-y diagram result in a dew curve. The curve will be calculated
easily by graphical method as shown in fig. 9.3.3-2. Generally, specie A represents water. So
the value of x and y represent the molar fraction of water in liquid and vapor phase,
respectively.
Pressure
Water+oil
Temperature
Calculate yA and yB by eq.

9.3.12 and 9.3.13, then, plot
T,yA and T,yB to obtain dew
curves
A (Pure water)
Psat,T1
A
PBsat,T1
Psat,T2
A
PBsat,T2
T1
B (Pure oil)
T2
T2
T1 Temperature
Pure
oil (B)
TH
yB 1 yH yA 1x,y Pure
water (A)
yB 2 yA 2
Fig. 9.3.3-2 Graphical method to find dew curve

3.
Find heteroazeotropic composition (xH, yH)
From eq. 9.3.2, azeotropic composition (yH) in the form of molar fraction of A
can be calculated from the following equation,
yH =
pA
P
{9.3.8}
At TH, liquid A (and B) will condense so,

p A = PAsat ,TH
{9.3.9}
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Thus,
yH =
PAsat ,TH
P sat ,TH
= sat ,T A
P
PA H + PBsat ,TH
{9.3.10}
This means that, at azeotropic point, liquid phase will contain (100yH) mol-% of
specie A and 100(1-yH) mol-% of specie B. For the vapor phase, it will also contain (100yH)
mol-% of specie A and 100(1-yH) mol-% of specie B. Heteroazeotropic temperature (TH) and
composition (yH) of common hydrocarbons, calculated from theoretical equation described
above, are tabulated in table 9.3.3-1. Observed values of yH from LUCENA [24] are also
presented in the table. It shows that the theoretical equations can be used to predict the
characteristic of real process with high accuracy.
Table 9.3.3-1 Heterotropic temperature and composition from various hydrocarbons [24]
Molecular
weight (g/mol)
TH
(deg. C)
yH
(by molar)
yH
(by volume)
C6H14
56
61.6
0.209
0.0351
C7H16
100
79.2
0.452
0.0922
C8H18
114
89.5
0.616
0.188
C9H20
128
94.8
0.827
0.3255
C10H22
142
97.6
0.914
0.495
C11H24
156
98.9
0.959
0.6663
C12H26
170
99.5
0.98
0.7953
C13H28
184
99.8
0.991
0.890
C14H30
198
99.95
0.996
0.9542
C15H32
212
99.999
0.998
0.9702
C16H34
226
100
0.999
0.9840
9.3.4
Extractant
y H observed
(by volume) [24]
0.468
0.767
Application of heteroazeotropic distillation on treatment of inverse emulsion or

concentrated oily wastewater
In spite of its lower energy consumption than the classical distillation,

heteroazeotropic distillation still consumes relatively high energy. So it may not be
economical to treat general wastewater by this process. However, for the wastewater
containing high concentration of oil or inverse (water in oil) emulsion (e.g. slops from
refineries), the portion of water to be separated is relatively small and the residue from
distillation process, which is water-free oil, become valuable for it can be re-processed or
recycled. In these cases, heteroazeotropic distillation may become economically feasible.
GPI had studied applications of heteroazeotropic distillation on treatment of slop [24]
and retentate from UF of cutting oil emulsion [11]. Significant findings from the researches
are summarized as follows,
1.
Addition of entrainer (or extractant)
Even though slop or retentate is naturally oil-water mixture, it may or may not
contain a component that forms an azeotrope. Sometimes, in self-entraining mode, obtained
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distillate is still in the form of emulsion. So to ensure the formation of azeotrope and readily
separated distillate, specific hydrocarbons, called entrainer or extractant, will be added to the
wastewater. So the heteroazeotropic distilltation, in this chapater, means the distillation
process that entrainer is added to promote the formation of azeotrope. This entrainer will
extract the water from the wastewater when the temperature of the system reaches the
azeotropic temterature (TH). The vapor, evaporating at TH, will contain (100yH) mol-% of
water and 100(1-yH) mol-% of entrainer. Performance of entrainer depends on its value of yH.
The higher the value of yH, the better the performance of entrainer. Since it means that only
small amount of entrainer is required to separate relatively large amount of water from the
waste. For properly selected entrainer, the distillate is condensed to form two separate layers
of water and entrainer, which can be reused.
2.
Characteristic of the process
Experiments in the lab were based on simple distillation apparatus, as shown in

fig. 9.3.4-1. Operating pressure of the process is ambience. Typical evolution of temperature
during the heteroazeotropic distillation process is as shown in fig. 9.3.4-2 [11].
Thermometer
TI
Heat exchanger
Feed
container
Distillate
Heater
Fig. 9.3.4-1 Examples of lab-scale apparatus for heteroazeotropic distillation [11], [24]
150
Classical distillation
180
135
160
120
Temperature (oC)
140
105
Heteroazeotropic
distillation
120
90
100
75
80
60
60
45
40
30
20
15
Accumalated diatillate volume (ml)
200
0
0
10
20
30
40
50
60
Time (minute)
Temperature
Distillate volume
Fig. 9.3.4-2 Example of evolution of temperature with time from the treatment of UF
permeate of cutting oil emulsion, using decane as entrainer [11]
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From the figure, the temerature will rise from ambience to azeotropic
temperature (TH), and then remain constant until the water is totally separate. After that, the
temperature will rise up to the boiling point of the entrainer. From the example, the entrainer
is decane, theoretical TH (table 9.3.3-1) is 97.6oC, relatively identical to the observed value.
Then the temperature rises to 174oC, which is corresponding to the boiling point of decane.
The evolution of temperature is natural, without controlling of any kind. It indicates that the
process is relative easy to operate.
3.
Performance of the process
Condensation of the vapor phase results in the distillate consisting of 2

separate layers of entrainer (upper layer) and water (lower layer). The residue is dehydrated
hydrocarbons, which is very fluid, compared to mayonnaise-like, viscous slop or UF
retentate. The pictures of feed, residue and distillate of the slop and UF retentate are as shown
in fig. 9.3.4-3.
a)
b)
c)
d)
Slop (a), distillate and residue (b), magnified pictures of slop (c)
and residue (d)
e)
UF retentate (30% vol of oil),
residue and distillate (e)
Fig. 9.3.4-3 Pictures of feed, residue and retentate of slop and UF retentate of used
macroemulsion (30% by volume of oil) [24], [11]
The entrainer can be simply decanted and then reused for the next distillation
cycle. For the water, even though its appearance is transparent and seems clean, it may
contain some soluble pollutants, such as some volatile chemicals or surfactants, depending
on characteristic of the feed. WANICHKUL [11] reported that TOD of the water from UF
retentate of cutting oil emulsion is around 1,000 2,800 mg/l. In this case, it needs to be
further treated.
In case of slops, the residue can be sent back to refinery process for
reproduction. For UF retentate, the residue, which is mainly base oil from cutting oil
emulsion, has high calorific value so it can be reused. Generally, mechanical workshops or
cutting oil users will send their UF retentates to central treatment facilities, where they can be
treated more economically. Heteroazeotropic distillation can be used in such treatment
facilities to treat these kinds of wastes.
4.
Performance of entrainers
As stated before, the performances of entrainers depend on their capability to

extract water from wastewaters, represented by their corresponding yH. The higher the yH, the
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better the extracting performance. LUCENA had proven that the value of theoretical yH is
close to the observed value, as shown in table 9.3.3-1. Apart from pure hydrocarbons, he also
tested some general commercial hydrocarbons. The results are tabulated in table 9.3.4-1. From
the result, kerosene and gasoline are suitable to use as entrainers.
Table 9.3.4-1 Water extracting performance of various commercial hydrocarbons [24]
Name
Ratio of water in the distillate

or yH (by volume)
Remark
Kerosene
0.635
Gasoline
0.75
BTX cut (or fraction)
0.134
Charge rformat oil
0.15, 0.23, 0.455
See note 1
Cur FCC oil
0.08, 0.144, 0.343
See note 1
Note
1. These oils contain several fractions of hydrocarbons so they start extracting water with the
lowest-yH hydrocarbon. When it is used up, the next higher-yH hydrocarbons are used.
9.3.5
Application of heteroazeotropic distillation on treatment of the wastes polluted by

trace hydrocarbons: Steam stripping
Steam stripping is another, in effect the reverse, form of heteroazeotropic distillation

that the small amount of relatively volatile materials, such as volatile hydrocarbons, hydrogen
sulfide or ammonia, are removed from large amount of less volatile material or wastewater.
In this case, water will be used as an entrainer to extract the pollutants. For wastewater, even
though it contains water and has self-entraining property, steam is normally used to heat the
wastewater and reduce the effective pressure in the distillation apparatus to save the energy
required. Stripping with inert gas is also available.
Stripping reactor is generally a packed column to provide efficient vapor-liquid
contact. The waste is fed at the top of the column while the steam enters at the bottom. The
quantity of steam required to remove pollutants depends on the types of the pollutants. The
vapor of steam and pollutants flows out at the top of the column to further process, depending
on the type of pollutants. Condensate of oil and water is sent to oil separation process for
recovery of oil. Hydrogen sulfide or ammonia may be sent to flare of furnace or disposed off,
if possible. It should be noted that steam stripping is based on different concept from air
stripping, which is based on solubilty of gas governed by Henrys law.
9.3.6
9.3.6.1 Quantity of entrainer required

As stated before that the column design will not be discussed here, the major
calculation of the process is quantity of entrainer required to separate the pollutants. It can be
divided into 2 cases as follows,
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1.
Heteroazeotropic distillation of concentrated oily wastewaters or slops
In this case, the entrainer is selected hydrocarbons and the pollutant is water.
Theoretical quantity of entrainer can be calculated from yH of the entrainer and quantity of
water to be removed by the following equation.
Volume entrainer = S .F Volume water
(1 y H )
yH
{9.3.11}
The yH of various entrainers are listed in table 9.3.3-1 and 9.3.4-1. If other
entrainer will be used, its yH can be determined from experiment or calculated by the
procedure shown in section 9.3.3. If the theoretical value of yH is used, S.F of 1.05 to 1.2 is
recommended [24].
2.
Steam stripping
In this case, the entrainer is steam and the pollutant is volatile material in the
wastes. Theoretical quantity of steam can be calculated from quantity of pollutants to be
removed and their corresponding yH by the following equation.
Volumesteam = S .F Volume pollu tan ts
yH
(1 y H )
{9.3.12}
Please note that the calculated quantity of steam is the quantity required for
heteroazeotropic distillation process only. Additional heat (sometimes, also in the form of
steam) may require to raise the temperature of the system up to the design point.
9.3.6.2 Design considerations
From GPIs researches, design considerations can be summarized as follows,
1.
In case of treatment of slop or concentrated wastewater, quantity of water should

be determined before addition of entrainer. Excess dosage of entrainer results in
more energy consumption. Since the temperature required to recover this excess
entrainer will be equal to the boiling point of the entrainer, not the azeotropic
temperature (see fig.9.3.4-2). Otherwise, this excess part will be wasted with the
residue and not be recycled.
2.
If possible, it is recommended to perform lab-scale tests or pilot-test to evaluate

the type of entrainer, its required quantity and the efficiency of the process, such
as TOD of distilled condensate, before design the real process. Since some
unknown factors, e.g. presence of surfactants, volatile substances, etc., may
affect the performance of the process.
3.
For steam stripping, the components of pollutants, sometimes, may be unknown.

Thus it is strongly recommended to perform lab-scale tests or pilot tests. To
evaluate the feasibility of the system and the quantity of steam required.
4.
The process operates at high pressure. Thus presence of some chemicals, such as
hydrogen sulfide, may give rise to high-corrosive environment. So these
precautions need to be taken into account in the distillation reactor design.
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5.
The distillation system is generally costly and consumes high energy. Economic
analysis of the system should be performed, compared to other competitive
processes, e.g. stripping VS. chemical treatment or solvent extraction or
adsorption.
9.4
Classical or conventional distillation of oily wastewater
9.4.1
Working principles
Classical or conventional distillation in this chapter is referred to the distillation

process that no entrainer is added to the feed to force the formation of azeotrope. Working
principle of classical conventional distillation is similar to that of the heteroazeotropic except
that there is no addition of entrainer to the feed. However it may contain azeotrope in case
that there are some components in the feed that can act as entrainer.
If the azeotrope is not naturally formed, the boiling point in this case will not be
lowered by azeotropism. So, more energy is required to rise the temperature up to operating
value. In case of oily wastewater, the temperature is around than 100oC, which is the boiling
point of the water at 1 atm. Since it consumes high energy, its application on wastewater
treatment is limited. Distillation under reduced pressure is reported to be used for emulsion
treatment in Germany. In GPI lab, WANICHKUL [11] had studied the application of
distillation on oily wastewater, as will be described in the next section.
9.4.2
Significant findings on classical distillation for oily wastewater treatment from

GPIs researches
WANICHKUL [11] had divided his research into 2 parts, i.e. (1) distillation of
stabilized emulsion and (2) distillation of permeate from UF of stabilized emulsion.
Significant findings from the research are as summarized below,
9.4.2.1 Distillation of stabilized emulsion
WANICHKUL [11] had studied the performance of distillation on stabilized
emulsions, using both macro- and microemulsion. The result shows that,
Distillation of cutting oil macroemulsion
1.
The evolution of temperature of macroemulsion (based on Elf Seraft ABS 4% by

volume of concentrate) is as shown in fig. 9.4.2-1. From the figure, the
temperature rises from the initial value to 92oC and remains constant throughout
the experiment. This can be explained that the process contains a self-induced
azeoptrope since the boiling point of the mixture is lower than the boiling point
of water (100oC).
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300
18
250
15
200
12
150
100
50
0
0
20
40
60
80
100
120
140
TOD of distillate (g/l)
Temperature (oC) , Distillate volume (ml).
0
160
Time (minute)
Temperature
Accumulated distillate volume
TOD of water part
TOD of oil+water part
Fig. 9.4.2-1 Evolution of temperature, volume of distillate, TOD of mixed distillate and TOD
of water part of the distillate (Based on Elf Seraft ABS, 4% by volume of concentrate) [11]
2.
Other evidence for self-induced azeotropism is that the distillate consists of two
separate layers of oil and water, as shown in fig. 9.4.2-2. These two parts are
readily separated. The oil part is mainly dehydrated hydrocarbons portion in the
cutting oil and can be reused or recycled.
Fig. 9.4.2-2 The feed, residue and distillate from distillation of the macroemulsion [11]
3.
Some pollutants are found in the water part of the distillate. Evolution of TOD in
the distillate is very complex, resulting from complicate ingredient of the
emulsion, as shown in fig. 9.4.2-1. From the experiment, TOD of the water part
is around 2,000-7,000 mg/l. TOD removal efficiency is around 96%, based on
cutting oil TOD of 120,000 mg/l.
4.
The efficiency of the process is close to that of UF (98%) but the energy
consumption distillation process is much higher. UF, generally, requires energy
around 10-20 kWh.m-3 while energy requirement of distillation is around 625
kWh.m-3 [11]. Thus if the treatment of permeate is not concerned, UF seems to
be more feasible than distillation for macroemulsion treatment.
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5.
From complexity of cutting oil formulation, x-y diagram of the mixture can not
be established. But the result can be used as a guideline to evaluate the feasibility
of distillation on this kind of application
Distillation of cutting oil microemulsion

The evolution of temperature of microemulsion (based on Elf G3 EAB 4% by
volume of concentrate) is as shown in fig. 9.4.2-3. From the figure, the
temperature rises from the initial value to 99oC and remains constant throughout
the experiment. So the process also contains an azeotrope.
120
18
100
15
80
12
60
40
20
Temperature (oC) , Distillate volume (ml).
1.
0
0
10
20
30
40
50
60
70
80
90
Time (minute)
Temperature
Accumulated distillate volume
TOD of water part
TOD of oil+water part
Fig. 9.4.2-3 Evolution of temperature, volume of distillate , TOD of mixed distillate and TOD
of water part of the distillate (Based on Elf G3 EAB, 4% by volume of concentrate) [11]
2.
The distillate also consists of the layers of oil and water, which are readily
separated (fig. 9.4.2-4). Evolution of TOD is complex, like the case of the
macroemulsion. TOD of the water part of the distillate varies from 1,200 to
2,200 mg/l. TOD removal efficiency is around 98%, based on cutting oil TOD of
75,000 mg/l. The efficiency is higher that that of UF (approx. 85%)
Fig. 9.4.2-4 The feed, residue and distillate from distillation of the microemulsion [11]
3.
Energy consumption for microemulsion is relatively similar to that of

macroemulsion (approx. 625 kWh/m-3) . So it consumes much more energy than
UF ( < 20 kWh/m-3) [11].
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1.
The permeate from UF of used macroemulsion was used. Inlet TOD is about
4,400 mg/l. The permeate boils at 100oC so there is no azeotrope. Like the case
of emulsions, the x-y diagram for distillation of the permeate can not be
established, resulting from its complex ingredients.
2.
The distillate is clear and contains. Evolution of TOD is shown in fig. 9.4.2-5.
Final TOD of the distillate at the end of the experiment is around 100-500 mg/l.
It may still exceed the discharge limit of some effluent standards. TOD removal
efficiency is around 90%.
300
1.2
250
200
0.8
150
0.6
100
0.4
50
0.2
Temperature (oC), Distillate volume (ml).
Distillation of permeate from UF of macroemulsion
0
0
20
40
60
80
100
120
140
160
Time (minute)
Temperature
Distillate volume
Series3
Fig. 9.4.2-5 Evolution of temperature, volume of distillate, and TOD of distillate (Based on
UF of used macroemulsion, TOD of feed =4400 mg/l) [11]
379
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Chapter 10 Chemical treatment processes

10.1 General
Naturally, oils or hydrocarbons tend to separate from water. In their natural form,
separation of oil droplets is governed by their size. Large oil droplets separate from water
within a short time while small droplets take longer time to be decanted or separated.
Efficiency of most of physical separation processes aforementioned decreases with the
decrease of oil droplet sizes.
Furthermore, if the droplet sizes are small enough (< 5 microns), the oil droplets will
subject to Brownian motion. Thus theirs rising velocity are no longer governed by STOKEs
law and can be negligible. These droplets will remain dispersing in the water without
decanting. (In fact, they may probably decant but take very long time, such as years.) In this
case, it can be said that the oil is stabilized. The oil/water mixture is called stabilized
emulsion or stable emulsion.
In some applications, it is necessary to disperse oil into water phase and keep it in the
stabilized form. Examples for these applications include some dairy product processing,
washing process using detergents or the use of cutting oil emulsion. In case of machanical
workshops, the stabilized mixture of oil and water, called cutting oil emulsion is needed to
perform very important roles in lubrication of machine tools and specimens, cooling, washing
away the scraps and impurities away and protecting the tools from corrosion. The oil has to be
dispersed homogeneously in the water to provide consistent properties. For washing, greasy
dirt on the clothes needs to be removed and suspended in wash water without coming back to
the clothes again. To make the oil stable, apart from oil and water, the third components
called surface active agents is always required.
When this stabilized emulsion is no longer suitable to use and then wasted, it will
become one of oily wastewater that is most difficult to treat. Thermal and membrane
processes are proven to be applicable for this kind of wastewater.
STOKEs law-based physical separation processes (e.g. decanter, coalescer, DAF),
can not be directly used in this case since the wastewater contains very small and stable
droplets. To use these physical processes, the wastewater needs to be undergone necessary
chemical treatment processes.
Main objectives of chemical treatment processes for stabilized emulsion treatment are,
To destabilize the emulsion and
To make the oil drops ready to separate from the water, e.g. to increase the size
of the droplets.
GPI lab had studied chemical processes for oily wastewater treatment, which can be
summarized as shown in the following sections.
380
III-263
10.2 Basic knowledge

Stability of emulsion refers to the ability of the emulsion to maintain its properties,
esp. its dispersion. Stable or stabilized emulsion can, practically, maintain its oil dispersion
without changing with time. So its required qualities, such as cooling or lubricating capacity,
are relatively consistent. Stability of emulsion are generally based on 2 factors,
Droplet size: The oil droplet size must be very small. So they are not decanted
naturally or by STOKEs law-based separation processes.
Resistance to coalesce: The oil droplets must have good resistance to coalesce. So
their size distribution remain relatively constant.
From section 2.2.1, the droplet size is proportional to effective work and inverse of
interfacial tension (1/o/w). Thus, to obtain stabilized emulsion, it is reasonable to decrease the
interfacial tension between oil and water and prevent the interaction between oil droplets.
However, low interfacial tension is not the only factor that guarantees the stability of the
emulsion. AURELLE and ZHU [21] proposed the properties that give rise to stable emulsion,
which will be described in section 10.2.3. To achieve these properties, the third component,
called surface-active agents or surfactants, is required. Details on surfactants are
described in the following section.
Surface-active agents, or surfactants, are practically the materials that are soluble both
in oil and water. They usually localize themselves and form a layer (generally,
monomolecular layer) at the surfaces or interfaces. This phenomenon is called surface
activity, which give the materials their names. Chemically, they always comprise of large
polar functional groups. One end of the molecules that is soluble in oils is usually a long chain
of aliphatic or aromatic or both forms of organic groups with 8 to 18 carbon atoms. Being a
long chain, this hydrophobic part is usually called tail of the surfactants. Another end,
which is water soluble or hydrophilic, is usually called head of the surfactant. Thus the
symbol of surface-active agents is usually drawn as a circle with long tail as shown in fig.
10.1.2-1.
Hydrophobic
tail
Hydrophilic
head
Micelle
or
Oil
Nonionic
Anionic
+
Cationic
Amphoteric
Fig. 10.2.2-1 Symbols of surface active agent and its localization at oil/water interfaces
381
III-264
Types of surface-active agents or surfactant are categorized by charge of their head as

follows,
1.
Anionic surfactant is the surfactant that ionizes to yield a positive charge, free
ion and a negative charge (surface active ion) which localizes at the interface. Its
symbol contains a minus sign in the head. This type of surfactant is relatively
cheap and widely used in industries. Common anionic surfactants are, i.e.,
Soaps are usually sodium or potassium salt, derived from fats and oils by
saponification (hydrolysis with presence of alkaline agent) with sodium
hydroxide.
Sulfate surfactants are salts of sulfated alcohol, such as dodecyl or lauryl

alcohol. General formula of these surfactants is in the form of R-OSO3-M+,
where M+ represent positive-charge ion, such as sodium or potassium.
Sulfonate surfactants are sulfonated compound, mainly derived from esters,

amides and alkylbenzenes. An example of these surfactants is sodium
alkylbenzene sulfonate. General formula is R-SO3-M+.
2.
Cationic surfactant is the surfactant that the surface-active part is cation. It is

usually salt of quaternary ammonium hydroxide, which its hydrogen of the
ammonium ion have been replaced with alkyl groups. Cationic surfactants are
quite expensive. But they are noted for their disinfecting (bactericidal) property
[1]. The symbol of the surfactant contains plus sign.
3.
Non-ionic surfactant is the surfactant that does not ionize and have to depend
on groups in the molecule to make it soluble [1]. The groups are usually
polymers of ethylene oxide (C2H4O). The symbol of the surfactant, in this case,
contains no sign. Examples of the surfactants are polyethyleneglycol monooleate, nonylphynol ethoxylene of ethylene oxides. The surfactants are noted for
adjustable hydrophil-lipophil properties.
4.
Amphoteric surfactant is the surfactant that contains both positive and negative
surface-active part. Its symbol contains 2 circles, one with minus sign, another
with plus sign.
In production of industrial emulsions, esp. manufacturing of cutting oil, surfaceactive agents are divided into 2 types, i.e.,
1.
Surfactants are the main surface-active agents used to lower the oil/water
interfacial tension, thus, stabilize the oil droplets. They are usually of anionic
type. Thus they forms anionic stabilized emulsion. However, nonionic emulsions
are also available.
2.
Co-surfactants are normally nonionic surfactants such as fatty alcohol. Their

localization at the surface of oil droplets among the main surfactants helps
reducing the repulsive force between the ionic heads of surfactants. Thus they
give rise to smaller droplet sizes and more stable emulsion.
Effect of surfactant: Surfactants lowers the oil/water interfacial tension (as well as
surface tension of water, in case of air/water interface) by the mechanism described in the
next section. Relation between interfacial tension and concentration of surfactant is as shown
382
III-265
in fig. 10.2.2-3. From the graph, interfacial tension decreases rapidly at the beginning. Then
the rate of decrease lowers until the concentration of surfactant reached a certain value, called
critical micelle concentration (CMC). After that, the tension remains relatively constant.
This can be explained by the formation of groups of surfactant molecules called micelle (fig
10.2.2-1). These surfactants will no longer localize at the surface of droplets, so they have no
effect on the tension.
ow or
w
Time
CMC
Fig. 10.2.2-2 Diagram of the electrical double layer

As mentioned in section 10.2.1, emulsion must have one or more of the following
properties, proposed by AURELLE and ZHU [21], to become stable emulsion.
1.
Thermodynamic stability
Normally, interfacial tension of oil is positive. To increase the stability of oil

droplets, the interfacial tension should be lower to increase the area, thus decrease the
diameter of the droplets. Addition of surfactant can lower the interfacial tension by its
localization at the droplet surface. The surfactant will try to stretch or increase the surface of
oil droplets as much as possible in order to locate itself at the surfaces. It results in virtual
force (p) that tries to stretch the surface, countering to the interfacial tension (o/w) that tries to
contract the surface (see fig. 10.2.3-1). Effective interfacial tension is the difference between
these two forces, as shown in eq. 10.2.1.
Surfactants,
co-surfactants
Water
Coalesce
p
Droplet surface
ow
Redistribute
ow = 0
ow
ow < 0
ow = 0
Oil
Fig. 10.2.3-1 Interfacial of oil and water with

the presence of surfactants
383
Fig. 10.2.3-2 Coalescence and redistribution

of droplets in thermodynamiclly stabilized
emulsion
III-266

original
ow = ow
p
{10.2.1}
If the surfactant concentration is high enough, it will lower the tension until it
becomes zero. At thermodynamic equilibrium condition, the system of these small droplets
has zero energy. When they coalesce, the sum of surface area will decrease so the equilibrium
is disturbed. The energy, thus the tension, will become negative. So they will spontaneous
redistribute to their original small diameters to maintain the equilibrium, as shown in fig.
10.2.3-2.
2.
Dynamic stability
From thermodynamic point of view, the system that has zero energy is very
stable. But, actually, some systems that have positive energy are also found very stable. So,
besides thermodynamic stability, the emulsion must have dynamic stability. This stability
comes from 2 equally important factors or resistance, i.e. electrical and mechanical resistances
or barriers.
2.1
Electrical barrier
Electrical characteristic of charged particles (in this case, oil droplets) can be
explained by the double layer theory (proposed and developed by Helmholtz, Stern, Gouy
and Chapman) or the DLVO theory (proposed by Derjaguin, Landan, Verwey and Overbeek).
To describe a charge particle, the two theories are relatively similar and characterize the
charged particle as shown in fig. 10.2.3-3.
The original charge of oil droplet is normally negative, acquired by negative ion
adsorption. From its electrical charge, the oil droplet can attract ions of the opposite charges
(counter ions) to surround it. However the counter ions, in this case, are positively charged
ions, which are usually surrounded by molecule of water. So they can come close to the oil
droplet only at a certain distance called Stern layer thickness (). The stern layer is the
inner layer of the double layer, according to the theories. Other counter ions that locate
outside the stern layer will more dense near the surface and then will thin out until their
concentration are equal to that in bulk liquids. This outer layer is called the diffused layer.
Outside the diffuse layer, the effect from droplet charge is negligible.
+- - -+ - +
+
+
+
+ - Oil w/ +
+
+
+ + -surfactants
-- +
+
+ + + +- + +
+
Stern layer
+
-
+
+
- +
- +
- +
-
- +
+
+
Stern potential
Diffuse layer
Voltage
+
+
+
- +
Plane of shear
Oil w/ adsorbed
surfactants at
the surface
Zeta potential
Distance
Stern layer
Diffuse
layer
+ Positive charge ion with

water solvation
Fig. 10.2.3-3 Diagram of the electrical double layer

384
III-267
Electric force from the charge of the droplet can be measure by its movement
when it is placed in electrical field (Electrophoretic). For the negatively charged particle, it
will move toward anode. The movement can be transformed to the value of electrical voltage.
This voltage is called Zeta potential (Z). The higher the value, the greater its force to repulse
co-ions. So the droplets can not some close to each other.
2.2
Dynamic barriers
Some systems of low Z are found very stable too. This can be explained the
presence of dynamic barriers. The film of surfactants on the surface of droplets is relatively
rigid. Even the droplets collide, the film will not rapture and can prevent coalescence. To
increase the rigidity of film, Non-ionic co-surfactants are added so their molecules can locate
tightly among charged surfactants, resulting in a rigid film. This is the reason why the cosurfactants or muti-surfactants are used in production of cutting oil emulsion.
From the previous sections, the properties to obtain stable emulsion are shown. So, to
destabilize (or crack or break) the emulsion, those factors will be eliminated or
minimize, i.e.,
Increase of interfacial tension to eliminate thermodynamic stability
Minimize or elimination of surfactant films around the droplets
Reduction of charge of the droplets to eliminate or minimize electrical barriers.

When the droplets can come close to each other at some certain distance.
Attractive force between molecules (called Van Der Waal force) overcomes
repulsive force from electrical charges. So the net force will be attractive (fig.
10.2.4-1) and the droplets move toward each other and have a chance to coalesce.
Repulsive force
Repulsive force
+ Van Der Waal
Resulting
force
+
+- - -+ - +
Attraction
+- - -+ - +
-- +
+
-- +
+
+(Short range) + - +
- droplets- droplets-- +
+
--+ + Oil
+ + Oil
-+ +
-+
+ -+ Electrical + + +- - -+ +
+
+ +
+
repulsion
+
(Longer range)
Distance
Val Der Waal
Force
Attrative force
prevails
Attractive force
Fig. 10.2.4-1 Force diagram of oil droplets and relation of repulsive, attractive
and resulting force with the distance between oil droplets
385
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10.2.4.1 Destabilization mechanisms

To achieve above goals, one or more of the following destabilized mechanisms is
needed.
1.
Reduction of diffuse layer thickness
When counter-ions are added into the wastewater, these ions will be attracted
by the droplet charges. Thus they will surround more tightly near the droplets and reduce the
diffuse layer thickness. This effect results in reduction of Zeta potential. So the droplets can
come closer to each other and have a chance to coalesce. For general oily wastewater and
cutting oil wastewater, droplets have negative charges. So counter ions in these cases are
positive charges, e.g. Na+, H+ in the forms of NaCl or H2SO4, etc. The counter-ions can be
added until the system reaches iso-electric condition (potential = 0). However, this mechanism
cannot reverse the droplet charges, no matter how many ions are added.
2.
pH adjustment
If soaps are used as surfactants, such as some microemulsions, the acid added
will neutralize NaOH used in saponification, thus shift the equilibrium of hydrolysis of fatty
acid. So the soaps transform back to fatty acid and loss surfactant effects. The emulsion, then,
is destabilized.
3.
Precipitation of surfactants
Since emulsion stability is based on presence of surfactants, precipitation of

surfactants can certainly destabilize the emulsion. Addition of some chemicals can react with
the surfactants, resulting in complexes of no surfactant property. Bivalent or multivalent salts
are used to precipitate the surfactants, such as CaCl2, MgCl2, MgSO4, alum (aluminium
sulfate) or ferric chloride. Generally, the higher the valence, the better the efficiency to
precipitate the surfactants and the smaller dosage of the salts required. However, precipitation
efficiency also depends on the types of salts and surfactants used in the emulsion, which
should be verified by jar test. Efficient salt for one surfactant may ineffective for other types
of surfactants.
4.
Sweep coagulation
Some metal salts can form complexes with other ions in the water, such as
hydroxide. These complexes can trap the oil droplets, thus the droplets can be separated from
the emulsion. These types of chemicals are normally multivalent metal salts, such as alum.
5.
Adsorption and charge neutralization
Addition of surfactants that have the opposite charges to those used in the
emulsion may result in destabilization of oil droplets by adsorption of the new surfactants and
neutralization of the existing charges. But it must be noted that, if overdose, this mechanism
will cause reversal and re-stabilization of emulsion.
6.
Bridging
There are several commercial chemical products that can be used to destabilize
the emulsion. From their molecule structure and properties, they may trap the oil droplets by
386
III-269
their bridging properties or adsorb the oil droplets and from scum or sludge. They may
contain the salts that can destabilize the emulsion by the mechanism mention above.
Examples of these chemicals are the products of DEGUSSA and Primafloc.
10.2.4.2
Coagulants and destabilization chemicals
Chemicals or materials generally used to archive the destabilization mechanisms

described above include,
1.
Monovalent electrolytes
Examples of this type of salt are NaCl and H2SO4. Main destabilization
mechanism is reduction of diffuse layer. Thus required dosage is quite high in order to
provide sufficient concentration of positive ions in the entire emulsion to destabilize the
droplets. For certain types of surfactants, e.g. soaps, acid can cause destabilization be
neutralization of saponification process that gives rise to the soaps. In this case, required
concentration is much lower. Main disadvantage is the formation of saline or acid pollutants
after destabilization. So it seems like the pollution changes from oily waste to saline or acid
wastes.
2.
Bivalent electrolytes
Examples of this type of chemicals are CaCl2, Ca(COOH)2 (Calcium formiate),

MgSO4 and MgCl2. Main destabilization mechanism is precipitation of surfactants. Free
surfactants in water will react with Ca or Mg ions and form complexes. Equilibrium between
adsorbed, ionized surfactants on the droplet surfaces and free surfactants is shifted. So ionized
surfactants will reverse into free surfactants thus, reduce the stability of droplets. This effect is
practically governed by solubility product of the surfactants. Required dosage in this case is
lower than that of monovalent ones. If inorganic electrolytes are used, they may also cause
high saline waste, depending on required dosage. Organic salts, such as calcium formiate
(Ca(COOH)2) may be more interesting since the residual pollutants is (COOH)2 which is
organic and biodegradable.
3.
Multivalent electrolytes
Examples of this type of chemical are ferric chloride (FeCl3) and alum. They
are generally more effective in destabilization than the previous two chemicals. But it may not
be used with some surfactants, such as certain types of soaps. Main destabilization
mechanisms are combination between precipitation of surfactants as well as sweep
coagulation. So the actual dosage is lower than that calculated from solubility product alone
and usually lowest among the first three electrolytes
4.
Surfactants of opposite charge
Examples of cationic surfactants that may be used for emulsion destabilization

are N-cetylpyridinium chloride and salts of quaternary ammonium hydroxide. Main
destabilization mechanism is adsorption and charge neutralization. Overdose must be avoided
to prevent charge reversal and re-stabilization.
387
III-270
5.
Commercial adsorbents
Oil destabilization and absorbents are commercializes. Destabilization

mechanisms and efficiency vary with its components and emulsion ingredient.
10.2.4.3 Destabilization of emulsion stabilized by nonionic surfactants
The mechanisms stated above are generally based on emulsions stabilized by ionic
surfactants. In case of those stabilized by nonionic surfactants, the mechanisms that involve
reduction or elimination of electrical barrier are invalid since the droplets carry, practically,
no charge. Main destabilization mechanism in this case must base on precipitation of the
surfactants to form insoluble complexes. ZHU proposed original chemical destabilization
method of the emulsion stabilized by nonionic surfactants of fatty acid based by addition of
anionic surfactants (such as alkylsulfate of fatty alcohals) and cationic trivalent electrolytes
(such as alum, ferric chloride).
10.2.4.4 Dosage, efficiency and residual pollution
ZHU had tested various type of chemicals to destabilize many kinds of emulsion,
both macro- and microemulsion, both fresh and used conditions. Efficiency, residual pollution
and examples of optimum dosage are summarized as follows,
1.
The emulsions and destabilization chemicals were tested in lab scale by simple
mixing and decanting.From ZHUs criteria, chemicals are considered to be
effective destabilization reagents for that emulsion when the oil is separated
in the form of free oil at the surface within 1 hours. However, in effective
cases, the decanting is carried out within relatively short time, less than 20-30
min. Oil removal efficiency varies from 0 (cannot destabilized) up to 40-70%
or 99%, depending on types of destabilization chemical and emulsion.
2.
Residual pollutant after decanting of free oil is mainly co-surfactants, esp. in

the form of fatty alcohol, which is highly soluble. Concentration of this soluble
pollutant depends on ingredient of emulsion treated and initial concentration of
concentrate (in case of cutting oil emulsion) in the emulsion. This pollutant
contains high TOD and must be further treated, as previously discussed in
chapter 8 Membrane processes.
If salts, e.g. NaCl, etc. or acids are used to destabilization, they also cause
residual pollutants in form of saline and acid. If the residual TDS
concentration is high, it may not conform to effluent standard. This is the main
disadvantage of destabilization by salt. Effluents from destabilization with
acids, ferric chloride or alum have low pH and must be neutralized before
discharge.
3.
There are no universal chemicals and dosages valid for every emulsion.
Types of effective chemicals, optimum dosages, and residual pollutants level
must be evaluated first in lab scale before design the full-scale chemical
process. However, test result from fresh emulsion can generally be applied for
used emulsion. [21]. Results from ZHUs study on destabilization of certain
emulsions are shown in table 10.2.4-1.
4.
Increase of temperature, generally, helps improving destabilization efficiency

by [21],
388
III-271
Increase of Brownian motion that favors collisions of droplets

Decrease of water viscosity that favors draining of water film around
droplets
Partial dehydration that helps weaken mechanical barriers of droplets
Table. 10.2.4-1 Results from ZHUs research on destabilization of various emulsions

A) Emulsions tested
%
Oil
Type/ appearance
Surfactant
Name
Co-surfactants
%
Name
%
Addi
-tive
5
Milky anioninc
macroemulsion
80
Sodium
alkylbenzene
sulfonate, sodium
carboxylate,
triethanolamine
carboxylate
11
Benzylic
alcohol, PEG
ester.
Milky anioninc
macroemulsion
Soduim sulfonate,
alkylphosphate
33
Butyldiglycol
Transparent
anioninc
microemulsion
25
Mixed soaps of
mono- and
diethanolamine of
fatty acids
38
Butyldiglycol
Transparent
anioninc
microemulsion
Amine caboxylate
and K alcanolamine
30
Butyldiglycol
12
Milky nonioninc
macroemulsion
80
PEG mono-oleate,
nonylphenolethoyla
te (8 moles of
C2H4O)
20
%
Water
27.5
Note: PEG = Pltyethylene glycol
B) Results on destabilization of emulsion A at conc. of 2% by volume of concentrate, 20oC
g/l
meq/l
Oil
removal
eff. (%)
H2SO4
18.3
355
97.1-97.5
99.5-99.9
1.21-1.38
470-543
0.5-0.9
NaCl
20
339
96.3-96.6
99.6-99.7
1.62-1.81
630-705
8.3-8.5
CaCl2
1.5
20
96.3-96.5
99.6-99.9
1.67-1.81
658-705
7.6-8.0
MgCl2
1.8
17
96.3-96.6
99.6-99.8
1.62-1.79
630-696
8.3-8.4
MgSO4
24
96.3-96.6
99.4-99.6
1.65-1.79
639-696
8.3-8.5
1.0
FeCl3
0.6
11
96.4-96.9
99.1-99.5
1.52-1.75
620-714
2.1-2.5
1.8
Alum
96.2-96.7
99.4-99.7
1.60-1.84
724-855
3.8-3.9
2.1
1.5
23
90.8-95.9
1.99-4.45
602-639
7.4-7.5
Dosage
Chemicals
Ca(COOH)2
TOD
removal
eff. (%)
Effluent
TOD
(g/l)
HC in
effluent
(mg/l)
pH
389
o/w
dyn/cm
1.4
III-272
C) Results on destabilization of emulsion B at conc. of 2% by volume of concentrate, 20oC
g/l
meq/l
Oil
removal
eff. (%)
H2SO4
13.7
265
80.5-82.5
6.10-6.69
3.92-4.37
1.8-2.4
NaCl
20
339
75.0-76.5
8.50-9.00
5.27-5.60
8.4-5.8
CaCl2
27
80.5-81.0
6.70-6.90
4.26-4.67
8.0-8.2
MgCl2
19
77.5-80.0
7.10-8.10
4.48-5.04
8.3-8.6
MgSO4
3.5
28
78.5-79.5
7.30-7.70
4.59-4.82
7.6-8.2
FeCl3
1.25
23
80.0-81.0
6.70-7.10
4.26-4.48
2.7-3.8
Alum
27
80.0-81.0
6.70-7.10
4.26-4.48
4.3-4.6
Ca(COOH)2
30
73.5-78.0
7.90-9.60
4.59-5.72
8.3-8.4
Dosage
Chemicals
TOD
removal
eff. (%)
Effluent
TOD
(g/l)
HC in
effluent
(g/l)
pH
o/w
dyn/cm
D) Results on destabilization of emulsion C at conc. of 2% by volume of concentrate, 20oC
g/l
meq/l
Oil
removal
eff. (%)
H2SO4
3.7
71
76.3-87.3
3.90-7.70
2.60-4.90
NaCl
60
1016
10.5-71.5
9.30-9.60
5.80-6.00
CaCl2
27
70.0-71.0
9.40-9.80
5.92-6.12
MgCl2
2.5
24
69.5-70.3
9.70-9.90
6.07-6.22
Alum
6.2
55
71.0-71.5
9.30-9.40
5.81-5.92
46
64.0-70.0
9.80-11.8
6.12-7.34
Dosage
Chemicals
Ca(COOH)2
TOD
removal
eff. (%)
Effluent
TOD
(g/l)
HC in
effluent
(g/l)
pH
0.6-2
o/w
dyn/cm
3.9-4.2
E) Results on destabilization of emulsion D at conc. of 2% by volume of concentrate, 20oC
g/l
meq/l
Oil
removal
eff. (%)
H2SO4
1.83
35
54.0-58.0
11.3-12.6
8.71-9.54
1.9-3.5
NaCl
50
947
46.5-53.0
13.0-15.1
9.75-11.1
9.2
CaCl2
27
50.5-52.0
13.3-13.8
9.95-10.3
8.7-8.8
MgCl2
19
53.5-55.5
12.2-12.8
9.23-9.64
8.7
MgSO4
2.5
20
53.5-54.5
12.5-12.8
9.44-9.64
8.7-8.8
36
52.5-57.0
11.6-13.2
8.92-9.85
4.2-6.2
1.5
23
43.0-52.0
13.3-16.3
9.95-11.8
7.7-8.8
Dosage
Chemicals
Alum
Ca(COOH)2
TOD
removal
eff. (%)
390
Effluent
TOD
(g/l)
HC in
effluent
(mg/l)
pH
o/w
dyn/cm
III-273
F) Results on destabilization of emulsion E at conc. of 2% by volume of concentrate, 20oC

Anionic
surfactants
(%)
Chemicals
(g/l)
Oil
removal
eff. (%)
TOD
removal
eff. (%)
Effluent
TOD
(g/l)
HC in
effluent
(mg/l)
pH
Cmin
Cmax
0.6
0.6
0.8
87.5-89.5
4.85-5.80
1.92-2.29
3.0-3.1
1.0
0.6
1.5
87.1-97.3
1.14-1.32
0.46-0.53
2.7-3.2
1.2
0.6
2.0
96.8-97.7
1.05-1.46
0.42-0.59
1.7-3.0
1.5
0.6
3.0
92.3-97.0
1.37-3.60
0.55-1.42
2.6-3.1
2.0
0.6
3.5
95.2-97.4
1.19-2.22
0.48-0.89
2.7-2.8
79.5-84.5
7.15-9.40
2.84-3.76
3.9
93.0-98.0
0.92-3.30
0.37-1.28
11
93.3-97.7
1.08-3.10
0.43-1.23
4.0-4.1
16
92.5-98.0
0.92-3.35
0.37-1.37
4.0-4.7
o/w
dyn/cm
Ferric chloride
Alum
Note: The anionic surfactant used in the experiments was Melanol CL30 (for FeCl3) and Melanol V90
(for alum). They are products of SEPPIC, contains 30 and 90% of fatty acid alkylsulfate, respectively.
10.3
Process design
Even though there are many types of destabilization chemicals, from the point of
view of process design, the reactions require the same kind of reactors. The reactors in this
case are actually the same as those required for coagulation-flocculation process in potable
water treatment. In fact, destabilization process can be counted as coagulationflocculation
process. Generally, the process is divided into 2 steps, i.e.,
Mixing or rapid mixing

Flocculation
Design of each step is described below,

Destabilization
chemicals
Emulsion
To separation
process
M
Rapid mixing
Flocculator
Fig. 10.3-1 Schematic diagram of chemical process for emulsion destabilization

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10.3.1
Rapid mixing
Rapid mixing is designed to provide complete mixing between wastewater and

destabilization chemicals. There are 2 main types of mixing methods, i.e. hydraulic (e.g. weir,
flume, static mixer) and mechanical (e.g. pumping, mechanical mixer). Main design criterion
of this step is described in the form of velocity gradient (G). Recommend velocity gradient is
300 -1500 s-1[46]. In this chapter we will emphasize on the mixing tank, which is generally
used in industries. The value of 100-300 s-1 is common for mixing tank. Recommended
detention time () is 5-20 second. However, if wastewater flowrate is low, the detention time
will be controlled by the smallest size that can be constructed, which may be greater 20 s.
There is practically no adverse affect about this except capital cost and energy cost is higher.
Important equations to design mixing tank are as shown in eq. 10.3.1 and 10.3.2.
P
G =
V
Where
0. 5
{10.3.1}
Velocity gradient (t-1, normally in second 1)

Dynamic viscosity of wastewater, normally about the same as
water
Mixing power (ML2s-3, normally in watt)
volume of the mixing tank (L3)
G =
=
P =
V =
Power required for mechanical mixers

P = N p n3D5
Where
Np
n
D
=
=
=
=
{10.3.2}
Power number, dimensionless

Density of wastewater, normally about the same as water
Impeller rotating speed (rev/s)
Impeller diameter (m)
Since the mixing tank is usually small, the impeller used is usually propeller or
pitched turbine (fig. 10.3.1-1). The value of Np for propeller and pitched turbine varies with
Reynolds number as shown in fig. 10.3-1.2) [63]. Reynolds number in this case is calculated
from rotation speed (n) and impeller diameter (D) as shown in eq. 10.3.3.
Re =
nD 2
{10.3.3}
Fig. 10.3.1-1 Static mixer (leftmost) and impeller types (from left): flat turbine, pitched blade
turbine, propeller type (Source: Memko, Sharp mixers)
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Fig. 10.3.1-2 Relation between Np and Re [63]

Calculation procedure is as shown below,
1.
Select required gradient (G) and detention time ().
2.
Calculate required volume (V) from and wastewater flowrate (Q). Geometry
of the tank should be cubic.
V = Q /
10.3.2
{10.3.3}
3.
Calculate require power (P) by eq. 10.3.1.
4.
Calculate n and D for required power by eq. 10.3.2. Impeller diameter should
be around of tank width. Mechanical mixers are commercially available,
thus it can be selected from manufacturer catalog to suit the required tank
volume.
Flocculator
Floculator is designed to provide mildly mixing to make the destabilized droplets or

flocs collide and coalesce into bigger drops of flocs. There are many variants of flocculator,
also categorized mainly by their mixing methods, e.g.. Baffle type, mechanical mixer type.
However, for industries, mechanical mixers are widely used for its flexibility (variable speed
drive can be used) and reliability. The industries always have personals that can due with
O&M of these machines. So there is no problem form maintenance point of view. So we will
emphasize on the mechanical mixing flocculation tank. Design criteria of flocculation tank
are based on velocity gradient (G) and detention time (). Recommended values are tabulated
in table 10.3.2-1
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Table 10.3.2-1 Recommended value of gradient and detention time

Parameter
Velocity gradient (G)
Detention time ()
Product of G.
Range
Ref.
20-80 s-1
[46]
20-75 s-1
[41]
20-150 s-1
Kawamura S.
10-30 min
[46]
20-30 min
Kawamura S.
23,000-210,000
[41]
For mechanical mixing flocculation tanks, they are usually divided into 3
compartments of the same volume to avoid short circuit. The gradient will vary from the
highest value at the first compartment to the lowest at the final compartments (e.g. 75 s-1 to
30-40 s-1 t0 20-30 s-1). There are 2 major types of mechanical mixers used in the flocculation
tanks, i.e. impeller type, like the rapid mixing tank, and paddle type, as shown in fig. 10.3.2-1.
Fig. 10.3.2.1 Paddle type mixers (Source: Norfolk WTP, Aqua Pak)
Design procedure of floccuclation tank is relatively identical to that of the rapid
mixing tank. For paddle type mixer, its sizing can be calculated by eq. 10.3.4 [64].
G=
Where
G
n
A
v
Cd
V
=
=
=
=
=
=
=
=
nAv 3 C d
2V
{10.3.4}
Velocity gradient (t-1, normally in second 1)

The number of paddle blades
Surface area of one paddle (m2)
Tip speed of paddle (m/s)
Drag coefficient (normally = 0.6)
Tank volume (m3)
Density of wastewater, normally about that of water, (kg/m3)
Dynamic viscosity of wastewater, normally about that of water
(kg/(m.s))
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10.4
Process design of the chemical treatment is relatively simple. However, it must be

noted that,
1.
There are no universal chemicals and dosages valid for every emulsion.
Types of effective chemicals, optimum dosages, removal efficiency and
residual pollutants level must be evaluated first in lab scale (e.g. jar test) before
design the full-scale chemical process.
Fig. 10.4-1 Jar test equipment (Source: ECE engineering)

2.
Normally, there are residual pollutants in the form of soluble co-surfactants, as

well as residual salt or acid pollutants from destabilization chemical, which
need to be further treated. The extents of residual pollutants depend of type of
destabilization chemical as well as ingredient and initial concentration of
emulsion.
3.
In case of effective destabilization, destabilized oil drops can be decanted

within relatively shorts time (20 min to less than 1 hour). For mathematical
point of view, it is reasonable to use this decanting time to find the diameter of
destabilized droplets. The recommended value is 200 microns (see fig. 10.42), which can be used for further calculation of the downstream separation
process, such as DAF. For the non-stabilized oil droplets (since oil removal
efficiency is < 100%), we can not be sure of its size distribution. To be on the
save size, it may be estimated that the size distribution or granulometry of nonstabilized oil droplets remain the same as that before chemical treatment.
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Fig. 10.4-2 Example of stabilized emulsion before (right) and after chemical treatment (left)
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Chapter 11 Finishing processes

11.1
General
From the previous section, various oily wastewater treatment processes are
described. At their best conditions, most processes can treat the wastewater at the oil removal
efficiency more than 90%. However, in cases of high concentration wastewater, residual
pollutants from those processes may yet conform to related effluent standards. Furthermore,
there are some residual pollutants that are not exactly oils or hydrocarbons but come from
other components usually present in emulsion or oily wastewater. These pollutants are mainly
surfactants, co-surfactants, esp. in the form of fatty alcohol. Some treatment processes also
add residual pollutants to the effluent, such as salt, TDS, or acid from chemical destabilization
processes. Thus these effluents need to undergo finishing treatment processes to ensure that
their qualities meet the effluent standard.
There are 2 common finishing processes, generally used to treat the effluents of oily
wastewater from physico-chemical or physical treatments, i.e. biological treatment and
adsorption.
These processes are extensively studied for long times. Details of the processes are
available in many sources, including books, journals, literatures, as well as references from
users or system manufacturers. For biological treatment, it is actually a science by its own
right. Moreover, the researches of GPI lab, directed by Prof. AURELLE do not emphasize on
these processes. Thus, in this chapter, they are only briefly described to fulfil the whole
content of oily wastewater treatment processes.
11.2
11.2.1
Basic knowledge
Biological treatment processes are referred to the treatment processes that use
microorganisms to eliminate pollutants in wastewater. The pollutants may be utilized by the
microorganisms as substrates (biodegradation), which is, then, transformed to new cells and
non-pollutant substances, e.g. CO2, H2O, etc. Sometimes, the pollutants are trapped (sorption)
in flocs of microorganisms. Biological reactors are designed to provide controlled
environment to suit the microorganisms for their growth and utilization of the pollutants. The
reactors are also designed to prevent most of the microorganisms from carrying over with
effluent, since their presence in the effluent can be considered a kind of pollutants as well.
Biological treatment processes can be categorized by many criteria. According to the
types of microorganisms, they are generally divided into 2 types, i.e.,
Aerobic processes, which microorganisms depend on aerobic respiration. In

these processes, oxygen is an important factor for it is used as the electron
acceptor in the respiratory metabolism of microorganisms
Anaerobic processes, which microorganisms do not depend on oxygen. The

microorganisms in these cases generate energy by fermentation metabolism that
does not require oxygen as an electron acceptor. Some anaerobic
microorganisms use other substances as electron acceptors such as nitrate,
sulfate, or carbondioxide.
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From the point of view of reactor design, biological processes are generally divided
into 2 major types, i.e.,
Suspended growth, which microorganisms are suspended within the water. The
major suspended growth aerobic system is the activated sludge process (AS).
General schematic diagram of AS is as shown in fig. 11.2.1-1. The
microorganisms are controlled to form flocs that can be easily separated from the
water in sedimentation tanks.
Attached growth, which microorganisms are mainly attached to solid surfaces in

the biological reactors. Examples of these processes are trickling filter,
biocontact reactor and anaerobic filter.
Inlet wastewater
Q, So
M
Se
Effluent
QW, XR
QR, XR
Biological reactor
or aeration tank
Wasted sludge
Sedimentation tank
or clarifier
Fig. 11.2.1-1 General schematic diagram of activated sludge

11.2.1.1 Mechanisms of pollutant removal by biological processes
Removal of pollutants in biological treatment are complex and consists of many
phenomena, such as removal of suspended solids by enmeshment in the floc, physico-chemical
adsorption of colloidal material and biosorption or biodegradation by microorganisms [51].
Many researches had studied these mechanisms and proposed many mathematical models to
predict the performance of the processes.
Generally, pollutants are measured in the form of the oxygen demand required to
oxidize them. If the oxygen demand is based on biological reaction, it is called biochemical
oxygen demand (BOD). If it is based on chemical reaction, such as oxidation with
dichromate, it is called chemical oxygen demand (COD). However, pollutant removal can be
written in the form of general mathematical model as shown below [51],
S
dS
= k n X
dt
So
Where
S =
So =
t =
kn =
{11.2.1}
COD (or BOD) concentration at time t (ML-3, normally in mg/l)

Initial COD (or BOD) concentration (t = 0) (ML-3, normally in
mg/l)
Time (T, normally, in day)
Rate coefficient (T-1, normally, in day-1)
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X =
Effective biomass concentration. In case of As, X represents

MLVSS
(Mixed Liquor (the mixture in aeration tank) Volatile Suspended
Solids)
(ML-3, normally in mg/l)
Function power order (e.g. n = 0 zero order, n = 1 first-order,
etc.)
For completely mix reactor where BOD reduction ratedecreases with time since
readily biodegradable is gradually used up. Eckenfelder [51] proposed the simplified model as
follows,
So Se
S
=k e
X t
S
{11.2.1}
Se = COD (or BOD) concentration of effluent (ML-3, normally in mg/l)
Where
Biodegradability of substance is presented by its rate coefficient (k). The higher the
value of k, the better the biodegradability. Examples of rate coefficient for some types of
wastewater are listed in table 11.2.1-1
Table 11.2.1-1 Rate coefficient for selected wastewaters [51]
k (d-1)
Temperature (oC)
Domestic wastewater (soluble)
8.0
20
Potato processing
36.0
20
High nitrogen organics
22.2
22
Organic phosphates
5.0
21
Cellulose acetate
2.6
20
Vegetable tannery
1.2
2.0
Wastewater
11.2.1.2 Biodegradability of oily wastewater

Hydrocarbons or oils are considered biodegradable but the degree of
biodegradability of each type of hydrocarbons are different, depending on their
characteristics, such as molecular structure. Generally, small molecular hydrocarbons, such as
hexane, octane, are readily biodegradable while complex or large molecular hydrocarbons,
such as dodecane, are considered low- or non-biodegradable.
Examples of biodegradable organic compounds include common aliphatic alcohols,
aliphatic aldehydes, phenols, and aliphatic esters. Surfactants, such as alkyl benzene
sulfonates and glycols, are biodegradable. These surfactants/co-surfactants are main residual
pollutants in effluent from physical and physico-chemical treatment of oil wastewater. So it is
feasible to treat these effluent by biological processes.
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Examples of substances generally resistant to biological degradation includes some

hydrocarbons, esp. long chain aliphatic and aromatics, ethers, tertiary aliphatic alcohols, and
tertiary aliphatic sulfonates.
However, biodegradability also depends on reactor design and cultures (or species)
of microorganisms. Moderate biodegradable substances may be treated if the reactor is
properly design, e.g. the solid residence time (or sludge age) is long enough. Some special
cultivated bacteria can decompose oil effectively. For example, commercial mixture
containing certain emulsifier and microorganisms are used to treat sea oil spill.
On the other hand, hydrocarbons, mainly in the form of free oil, are considered to be
biotoxic substances for microorganisms. Free oils can cover the surfaces of floc and water,
thus disturb the oxygen transfer. Emulsified oil cause much less problem and usually
biodegradable. Presence of some hydrocarbons at some concentration can cause adverse effect
on the performance of the biological treatment process. Biodegradability and biotoxicity of
certain substance are presented in table 11.2.1-2. EC50% means effective concentration of the
corresponding substances that, if present in the wastewater, reduces the performance of the
process to 50% of the maximum or nominal value. Nitorsomonas and heterotrophs represent
the species of bacteria for nitrification (nitrogen removal) and generally organic oxidation
(BOD removal), respectively.
It should be noted that biodegradability, shown in the table, is expressed in the form
of ratio of BOD/TOD. TOD means total oxygen demand. This parameter can be conveniently
measured by automatic sensor. So it is widely used in process control because it can be
measured in real-time mode. TOD value includes non-organic oxygen demand such as
ammonium. Thus it is usually higher than BOD. In laboratory, some researches, including
GPIs, presented the oxygen demand in the form of TOD. When relation between BOD and
TOD is known (table 11.2.1-2), it can be used to convert TOD, shown in the researches, to
BOD for biological process design.
Some toxic substances, esp. heavy metals, may present in oil products. API recommended
the toxic threshold of some metals for biological system as shown in table 11.2.1-3.
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Table 11.2.1-2 Biodegradability and biotoxicity data [51]
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Table 11.2.1-2 Biodegradability and biotoxicity data [51] (Cont.)
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Table 11.2.1-2 Biodegradability and biotoxicity data [51] (Cont.)
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Table 11.2.1-3 Concentration of certain metals affecting biological systems [45]

Conc. (mg/l)
Chromium (6)
Copper
Nickel
Zinc
Threshold
10
1.0-2.5
5.0-10.0
Harmful
500
75
50-200
160
11.2.2
Design consideration and significant finding on biological treatment for oily

wastewater from GPIs researches
GPIs lab had also studied on feasibility of biological process for treatment of
residual pollutants from oil/water separation processes, discussed in the previous chapters
[11]. Design consideration and some significant findings on biological treatment of oily
wastewater are summarized below,
1.
Maximum inlet concentration of oil and expected effluent concentration
It may not be possible to designate the exact values of maximum inlet oil
concentration and expected effluent concentration since there are many parameters involved,
such as type of oil, reactor design, etc. Furthermore, biological process is noted for its
versatility. If the reactor is properly acclimated, the microorganisms can adapt to use the
existing pollutants as their main substrate. So even hydrocarbons may be treated. Apart from
the data in section 11.2.1.2, some case studies are summarized from many sources to provide
some ideas about the performance of biological treatment of oily waster, as shown in table.
11.2.2-1.
Table 11.2.2-1 Case studies on biological treatment of oily wastewater [66]
Process
Inlet oil concentration (mg/l)
Effluent oil (mg/l)
Activated sludge (AS)
5-100
5-40
Aerated lagoon
5-100
5-40
Stabilization pond
5-100
5-50
Chemical treatment + DAF +AS
5-100
2-20
Using data from several AS plants for petroleum refineries, API [45] reported
that BOD and COD removal efficiency is around 50-87% and 60-70%, respectively. MLSS
ranged from 1200 to 5000 mg/l. Retention time varied from 2.8 - 29 h. Eckenfelder [51]
showed that the biological processes were used effectively in petroleum refinery wastewater
treatments. He reported that, with BODin = 138-575 mg/l and CODin = 275-981 mg/l, effluent
COD is around 42-106 mg/l and rate coefficient are 1.11-1.7 d-1 and 2.74-7.97 d-1, based on
BOD and COD respectively. It shows that, with properly designed reactor, biological process
can be used to treat the oily wastewater to meet effluent standard.
2.
Treatment of surfactants/co-surfactants
For the treatment of surfactant/co-surfactants, which is the main residual

pollutant in permeate of membrane process and other separation processes, WANICHKUL
[11] had performed the biodegradability test of the permeate from UF of cutting oil emulsion
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(TOD > 3600 mg/l). The result showed that, after 4 days acclamation period, total organic
carbon (TOC) removal from 5-hour biodegradation test is 82-90% at the fifth and the sixth
day. Thus it can be concluded that biological process is feasible to treat the surfactants-rich
effluent from oil/water separation.
3.
General design consideration
General design consideration on biological treatment design for oily

wastewater, summarized from many literatures, include.
11.3
For industrial wastewater, since oily wastewater is usually only one portion
of the whole wastewater, it is recommended, if possible, to treat the oily
wastewater separately by physical or physico-chemical process. After that
the effluent from those process may be sent to mix with relatively
biodegradable wastewater, e.g. canteen wastewater, before sending to
biological treatment. This will prevent adverse effect on the biological
process by the presence of oil. It also helps saving the energy required for
aeration system to cover high oxygen demand of oil. Furthermore, these
domestic wastes can provide nutrient (e.g. nitrogen and phosphorus)
required for biological treatment, which are usually not present in oily
wastewater from industrial processes. General ratio of BOD to nutrients
is BOD: N: P = 100: 5: 1. If nutrient quantities in the wastewater are not
sufficient, they must be added in the form of chemicals, e.g. urea,
anhydrous ammonia and phosphate.
Since hydrocarbons or oils have very high oxygen demand. Their presence
must be taken into account for aeration or oxygenation system in aerobic
process, otherwise it may cause some shortage in oxygen level in the
reactor, resulting in low performance or, even, plant failure.
Adsorption
Adsorption process is referred to the process that uses special material that is capable
to adsorb molecules or colloids into its surface. This special material is called adsorbent.
The molecules or colloids adsorbed are called adsorbate. For its ability to remove dissolved
matters and molecules that somehow remain in the effluent of main treatment processes, the
adsorption process is usually used as a tertiary treatment or polishing process, which is the
last process before the effluent being discharged. It also used in recycled water treatment
system.
Adsorption phenomenon is caused by non-equilibrium of surface force field of the
adsorbent. Thus it tends to adsorb the molecules or colloids into itself in order to gain selfequilibrium. Attractive forces between adsorbent and adsorbate are Van Der Waal force and
chemical bonds.
Major characteristic of adsorbent is its high surface area, which is the result from its
highly porous structure. This characteristic is indicated by a parameter called specific
surface area, normally on m2/g. Adsorbates are actually adsorbed to the surface of the
material, both external surface and pore surfaces. When the adsorbent is saturated by
adsorbates, it loses its adsorptive capacity. Some adsorbents can be regenerated, normally by
heat, to recover its adsorptive capacity by removing of the adsorbates from its pores and
surfaces.
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re
Po
r
ate
W
fil
ion
fus
dif
lm
Fi
n
sio
u
ff
di
Adsorption to
surface
Fig. 11.3-1 Schematic diagram of adsorption

Adsorbents can be divided into 3 major types, i.e.,
11.3.1
Natural adsorbents, such as natural clays, bone char, activated silica. Important
limitation of these adsorbents is that they can adsorb only some kinds of
molecules.
Synthetic adsorbents, such as ion exchange resins. Thy have moderate specific
surface area (300-500 m2/g). Its main advantage is that it can be regenerated
relatively easily and less expensive, such as regeneration by NaCl.
Activated carbon (AC). AC can be classified as synthetic adsorbents. But, from

its very high specific surface area (600-1100 m2/g), it is widely used. So it is
classified as its own class. Adsorption process, described in this chapter and
many literatures, is usually referred to activated carbon adsorption process.
Activated carbon (AC)
Activated carbon can be made of various materials, such as coconut shells, coals,
bones, etc. These materials will be subjected to dehydration process (at low heat) then
carbonization (heat at 400-600 oC), following by activation (heat at 750-950 oC) to eliminate
tar in its pore. AC can be divided into 2 type, i.e., powder activated carbon (PAC) and
granular activated carbon (GAC). AC is the most popular adsorbent for its adsorption
efficiency and very specific surface area. Examples of PAC and GAC properties are as shown
in table 11.3.1-1. From the table, Iodine number is the parameter that indicates performance of
AC on adsorption of small molecules. The higher the number, the better the performance.
Table 11.3.1-1 Examples of PAC and GAC properties
Property
GAC
PAC
Specific surface area (m2/g)
600-1100
600-1100
0.55-1.0 mm
100 325 mesh (< 0.15 mm)
Apparent density
430-600 kg/m3
520-650 kg/m3
Specific gravity
1.30-1.55
1.4-1.5
Iodine number
850-1050
700-900
Particle size
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AC is capable to adsorb many kinds of substances, including heavy metals, phenol,

surfactants and hydrocarbons. Thus it is widely used as adsorbent material for polishing
process of industrial effluents. Absorption capacities of some hydrocarbons are listed in table
11.3.1-2. However, AC cannot absorb very small molecules (atoms of C < 3), such as small
molecular of organic acid and some alcohol. Anyway, they are readily biodegradable
substances, which can be easily eliminated by biological process.
For oily wastewater treatment polishing process, AC is usually used in the form of
GAC filter. Its hydraulic working principle is similar to that of sand filter or granular bed
coalescer, described in chapter 5. Thus, in this chapter, only this application will be described.
11.3.2
Basic knowledge
11.3.2.1 Isotherm diagram

The adsorptive capacity (q) at a specific temperature is normally presented in the
form of graph, called isotherm diagram (fig. 11.3.2-1). The graph is normally obtained by
experiment. In the experiment, the water to be treated (initial concentration = Co) and the
adsorbents are put in contact in a constant stirred reactor for a sufficient time to approach
equilibrium. Concentration will decrease from Co to equilibrium concentration (Ce).
1.
Freundlich model, as shown in eq. 11.3.1

q = k C e(1 / n )
Where
2.
{11.3.1}
= Adsorptive capacity (amount of adsorbates adsorbed per

unit weight of adsorbent) (M/M)
k,n = Empirical constants
Ce = Equilibrium concentration (ML-3)
Langmuir model, as shown in eq. 11.3.2

q=
Where
ab C e
1 + bC e
{11.3.2}
a, b = Empirical constants
It is recommended to fit the empirical isotherm with the both models and use
the one that give more accurate correlation.
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Table 11.3.1-2 Adsorptive capacity of AC for some hydrocarbons [65]
300
Adsorptive capacity (q), mg/g
250
200
150
100
50
0
0
1000
2000
3000
4000
5000
6000
Equillibrium concentration (Ce), mg/l
Fig. 11.3.2-1 Examples of adsorption isotherm diagrams

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11.3.2.2 Process analysis for GAC filter

In GAC filter (or contactor), as wastewater passes through the bed at a design rate,
the pollutant will be adsorbed and its concentration will be reduced as shown in fig. 11.3.2-2.
The height of the bed in which adsorption occurs is called the mass transfer zone (MTZ).
After of MTZ, the pollutant is practically eliminated, so there is no adsorption in the lower
bed under MTZ. Upper portion of bed is exposed to the pollutant first so this portion is the
first to be saturated. After it is saturated, it no longer has adsorptive capacity. The adsorption
will occur at the lower portion of bed instead. Thus it seems that the MTZ moves along the
depth of the bed as shown in fig. 11.3.2-1. When it move to the bottommost of the bed, it
signifies that the bed is expired. Pollutant concentration no longer meets the required value.
Thus the bed should be replaced.
Feed
C
Ha
GAC bed.
HT
Ce
Co
Satured
zone
Co
MTZ
Ce
Ce
Co
C = Ce
Co
Ha
Ha
H Outlet
Bed needs to
H be replaced.
< t3
t1
< t2
Outlet C does not

H meet requirement.
< t4
Fig. 11.3.2-2 Evolution of pollutant concentration along the bed depth

MTZ is obtained from experiment. The wastewater will be fed to a GAC bed at a
constant rate. Effluent concentration and feed quantity of wastewater is collected and plotted
as shown in fig. 11.3.2-3. Then, the bed height of MTZ (or adsorption height (Ha)) can be
calculated by eq. 11.3.3, which is derived based upon the symmetry between C/V curve and
C/H curve.
Co
Co
Qa
Qa
Ce
Ce
H
Vc
Ha
Vb
Va
Ve
Fig. 11.3.2-3 C/V curve and C/H curve

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Ha =
Where
H cV a
(V e Vc )
{11.3.3}
Hc = Bed height corresponding to the concentration C (L)

Vc = Accumulated feed volume corresponding to the concentration C
(L3)
Ve = Accumulated feed volume at equilibrium (L3)
Va = Accumulated feed volume required to saturate the MTZ (L3)
From fig.11.3.2-2, when the MTZ moves to the bottommost of the bed, it does not
mean that the whole bed is saturated. Only the portion above the MTZ is saturated. The bed
is the MTZ is partially saturated otherwise the effluent concentration will not meet the design
value. This means the bed in the MTZ cannot be fully utilized up to it capacity. If the MTZ is
large, this means partially utilized zone is large too. The available capacity left form
utilization in the MTZ, represented by a toned area in fig. 11.3.2-3, can be calculated eq.
11.3.4.
Ve
Qa = (C 0 C )dVc
{11.3.4a}
Vb
qa =
Where
Qa
Co
qa
ma
=
=
=
=
1
ma
Ve
(C
C ) dVc
{11.3.4b}
Vb
Total available (or left) capacity of absorbent in MTZ (M)

Initial concentration (ML-3)
Available adsorption of MTZ (M/M)
Mass of absorbent in MTZ (M)
C/V curve and C/H curve vary with empty bed velocity (or flowrate per unit area of
bed), as shown in fig. 11.3.2-4. It means that the value of Ha and Qa also vary with empty bed
velocity (v). If wastewater flowrate and empty bed velocity (v) are specified and the C/H or
C/V at that v and isotherm diagram are known from experiments, total bed height (HT)at
any given total operating period (tT) before the adsorbent needs to be replaced can be
calculated from basic mass balance equation, as shown in eq. 11.3.5.
Where
Vo (C o C e ) = AH T b q Q a
{11.3.5a}
Vo = Q t T = v A t T
{11.3.5b}
V0 = Total accumulated feed volume before the bed needs to be replaced

(L3)
tT = Total operating time before bed replacement ( or regeneration)
(ML-3)
A = Cross section area of GAC bed (L2)
HT = Total Bed depth (L)
b = Bulk (or apparent) density of bed (ML-3)
v = Empty bed velocity (LT-1)
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The value of q is obtained from isotherm diagram while the value of Qa is calculated
by eq. 11.3.4 from C/V relation obtained from experiments. Empty bed velocity can be
chosen arbitrarily but it will affect the value of Qa as described on the previous paragraph.
Recommended value of v is around 2.5 m/h per every 0.30 m of bed height (e.g. v = 7.5 m/h
for bed height of 0.90 m.). Total operating time (tT) can be chosen to match main
manufacturing process plant shutdown, in case of industrial wastewater, such as 1 year, etc.
Recommended retention time is not less than 5 min.
Since the bed is not totally saturated, effective saturation of bed (E) can be
calculated by eq. 11.3.6a and b. The value of E is normally between 0.5 0.95 (average 0.75).
E (%) = 100 (1 (1 e)
e =1
Ha
)
H
Qa
C oV a
{11.3.6a}
{11.3.6b}
From the concept of E, eq. 11.3.5a can be rewritten in the form of E, as shown in eq.
11.3.6c
V o (C o C e ) = EAHT b q
{11.3.6c}

Important parameters that affect the performance in adsorption process include,
1.
Types of adsorbate: Adsorptive capacities of AC for each molecule are

different. If possible, isotherm test on the pollutants to be removed should be
performed.
2.
Specification of carbon: Adsorptive capacity depends mainly on surface area of

AC. The higher the surface, the better the capacity.
3.
Temperature: Since the process is exothermal, adsorptive capacity will

decrease with increase of temperature.
4.
pH: pH affects ionization of molecules. Thus it may affect the ionization of the
molecule to be adsorbed.
5.
Turbulence: Adsorption also depends on mass transfer of adsorbates to the

surface. So turbulence of reactor affects the performance. In GAC filter, film
diffusion is usually rate determining step. Design parameters such as empty
bed velocity can be optimized in lab-scale test to obtain good performance.
Generally, recommended design criteria is proven to provide good result.
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11.3.3
Design calculation
11.3.3.1 GAC filter sizing

To calculate the size of GAC filter, the following procedure is recommended,
1.
Find the reference about isotherm and relation between Qa and V at various
values of v. ZHU recommended these relation for some common cosurfactants, usually found in effluent of cutting oil emulsion after physical or
physico-chemical processes, as shown in table 11.3.3-1.
2.
Select design empty bed velocity (v) and total operating time (tT)
3.
From required wastewater flowrate (Q), calculate cross section area of GAC
filter (A) from
A=Q/v
4.
{11.3.7}
Calculate q and Qa at the selected value of v, if the relation q VS. v and Qa VS.
v are known from item 1.
Table 11.3.3-1 Adsorption isotherm and MTZ data of some co-surfactants [21]
Co-surfactants
Relation
Benzylic alcohol
Adsorption isotherm [Lungmuir model], in mg/g (Ce in mg/l)
q=
Height of mass transfer zone, in cm (v in m/h)
H a = 6.26 10 0.112v
Available capacity of the bed in MTZ (by volume)
Qa = 3.83 10 0.078v A
2.19Ce
1 + 8.77 10 3 Ce
Butyldiglycol
Adsorption isotherm [Lungmuir model], in mg/g (Ce in mg/l)
q=
1.39C e
1 + 4.16 10 3 C e
Note: q in mg/g, Ha in cm, Qa in cm3, A in cm2, C in mg/l
5.
Calculate Vo and HT from eq. 11.3.5.
6.
When relation between Qa and v or Ha and v are not available. It can be

assumed that Qa = 0, replace q in eq. 11.3.5 with q/ S.F, then use procedure in
step 2 to step 5 to calculate HT. The value of safety factor is between 1.3 to 2.
However, it is recommended to perform lab-scale to obtain the data about Qa
and Ha.
7.
In case that the isotherm data is not available, it is strongly recommended to

perform lab-scale test. The data of other substances of the same kind can be
used to estimate the size of the filter, but for preliminary evaluation only.
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11.3.3.2 Headloss
Headloss of the filter can be calculated in the same manner as that of sand filter or
granular coalescer. The size of GAC is around 0.5-1.0 mm, about identical to that of coalescer
bed. Thus headloss of GAC bed should be calculated using the equation (Koseny-Carman)
and other data of the coalescer bed, e.g. porosity data, described in chapter 5.
11.3.3.3 Filter construction and accessories
GAC filter construction and accessories are relatively identical to those of sand
filter. So feed pumps, piping, underdrain and backwash system can be designed in the same
way as for sand filter. However specific gravity of GAC is around that of anthracite (1.3
1.5), which is lower than sands. Thus recommended backwash rate is around 20 50 m/h.
Bed expansion is about 50%. It should be noted that wet GAC is corrosive. Rubber liner or
equivalent anti-corrosion material must be used.
a) Granular activated carbon
c) AC plant (Source: Carbonel)
b) Powder activated carbon
d) Example of GAC filter (Source: NFS)
Fig.11.3.3-1 Examples of AC and GAC filter
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Chapter 12 Guideline for treatment process selection and examples
Chapter 12 Guideline for treatment process selection and examples of

treatment processes for certain oily wastewaters
12.1
Guideline for treatment process selection
From detail of each process, described before in the previous chapters, it is clearly
shown that each process has its own limitation and can be effectively used on some range of
oily wastewater. In this case, the treatment system will consist of several processes connecting
together as a process train. On the other hand, for some ranges of oily wastewater, there is
more than one process that can be applied to treat them. To design practical wastewater
treatment system, designers should understand the nature and limitation of each process, both
from technical and economic points of view.
It must be noted that treatment process selection and design is a state-of-art. It is
very difficult to decide that which one is the most suitable one. Normally, engineers base their
design on their experience. In some situation, it is still difficult to choose the best process train
because there are more than one applicable process. In this case, to select the most suitable
process, advantages, disadvantages and economic constraints and theoretical comparison of
removal efficiency between each feasible process shall be taken into account. Concept of least
cost method can be used, as described previously in chapter 2.
In previous chapters, many researches, covering almost all of the possible range of
oily wastewater and their treatment processes, have been reviewed. These researches can be
summarized to formulate a guideline for process selection and to develop a computer program
for design and simulation of oily wastewater treatment process.
The guideline, categorized by the types of oily wastewater, can be summarized as
shown in table 12.1-1 and section 12.1.1 to 12.1.4.
12.1.1
Oil film
The oil film is the simplest form of oily wastewater. Technically, the oil in this case
is already separated from the water and presents in the form of 2 separate layers of oil and
water, rather than homogeneous mixture of oil and water. This type of oily wastewater might
be raw wastewater from the source or the result from other treatment processes, such as
decanted oil from decanter or destabilized oil retentate from UF process.
Oil layer can be removed or skimmed from water surface in several ways. The
simplest form of skimmer is overflow device, such as weir, bell mouth pipe. GPI lab has
developed oil disk skimmer and oil drum skimmer based on surface chemistry concept, as
described in chapter 3. These types of skimmers have good selectivity for they recover
relatively water-free oil.
To select the skimmer, one should consider:
Usage of skimmed oil: If the water-free skimmed oil is required, the skimmers
with good oil-water selectivity, such as drum skimmer or disk skimmer, may be
required to assure efficient separation.
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Table 12.1-1 Guideline for oily wastewater process selection (based on GPIs researches)
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12.1.2
Geometry or size of the decanter or oil retaining vessel: If the size of the tank
is not so large. Simple hydraulic device, such as bell mouth, can work
effectively. To enhance its oil-water selectivity, the thickness of oil layer can be
increased to avoid carry-over of water with the skimmed oil. In case of small
tank, this can be done because the open surface of tank is small. So loss of
volatile oil in this case is quite acceptable. However, it may not be practical for
large tanks.
Economic point of view: investment and operating cost of skimmer and

recovered benefit from usage of skimmed oil and other related cost and benefit
(if any) should be taken into account.
Primary emulsion
For primary emulsion, the oil droplets in the wastewater are relatively big and can be
separated by natural or non-accelerated process, i.e. decanter However, besides the oil droplet
size, presence of suspended solids in the wastewater is an important factor that has to be taken
into account. Guideline for treatment process selection in this case, categorized by presence of
suspended solids, will be as described below.
Primary emulsion without presence of suspended solids: Examples of this

case are condensate and process waters from industries. In this case, both simple
decanter and lamella decanter are applicable. Without presence of suspended
solids, there is no risk of clogging. So, compact decanter or closely inserted
lamella decanter, such as Spiraloil, can be used.
Primary emulsion containing coarse suspended solids: Example of this case is

wastewater from general washing, etc. In order to consider if the suspended
solids are classified as coarse suspended solids, the rising velocity of droplet and
the settling velocity of the solids will be compared. If the settling velocity of
solids is greater than the rising velocity, the suspended solids, then, tend to settle
within the oil separator. In this case, the suspended solids are considered as
coarse suspended solids. For API tank, design cut size of oil droplet is around
150 microns, then the suspended solids that can be classified as coarse will be
around 50 microns in diameter. For this type of wastewater, API tank, inclining
tube settler or lamella decanter with large spacing between plate are
recommended for they can serve 2 purposes, i.e., solids and oil separation.
Closely inserted decanter is not recommended for risk of clogging. Dissolved Air
Flotation is also a good choice in this case.
Primary emulsion containing fine suspended solids: Example of this case is

stormwater. If these solids are fine, it will not settle in the oil separator. In this
case, theoretically, it can be treated in the same way as condensates. However,
the solid separation process should be provided. DAF is recommended in this
case because it can separate both oil and solids alike.
Among these 3 categories, the second or combination between the second and the
third categories are more common. Other accelerated processes, such as hydrocyclone, are
also applicable. But it requires further treatment process, such as coalescer, to treat the
separated oil. Thus it may not be economical choice when simple process can do the job as
well. In effect, when the land is not the restricting condition, the process with relatively low
loading rate, such as decanter or DAF, may be useful. Because they can serve as both solid
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and oil separation, as stated above. Their voluminous size can be used to dampen any
transient conditions occurring. And they can always be upgraded or changed to other
processes that require smaller footprint in the future. Membrane process and thermal process
are applicable but not recommended for economic reason. After oil separation, the wastewater
may need finishing processes (e.g. biological treatment and carbon adsorption), depending on
amount of residual pollutants.
12.1.3
Secondary emulsion
For secondary emulsion, the oil droplet sizes in the wastewater are between 5 to 100
microns. However, since lower limitations of some treatment processes are around 20
microns, it is reasonable to divide the emulsion into 2 groups, i.e. (1) droplet size between 20100 microns and (2) droplet size from 5-20 microns. In both groups, the treatment processes
are still affected by presence of suspended solids. Guideline for treatment process selection,
categorized by presence of suspended solids, will be as described below.
12.1.3.1 Droplet size between 20-100 microns
Emulsion without presence of suspended solids: Examples of this case are

condensate and oil-contaminated process waters from industries. In this case,
decanter alone is unable or uneconomical to completely treat this emulsion.
However, lamella decanter and spiraloil may be used as preliminary treatment
(but not necessary) since it can handle the upper range of oil droplets in the
emulsion. Lamella decanter is the better choice between the two because it is
more voluminous so it can handle some strayed solids, if any, or equalize some
shock load better than spiraloil. Every type of coalescers and hydrocyclones can
treat this group of emulsion effectively. However, for hydrocyclone, it always
requires further process to treat the separated oil. Combination of hydrocyclone/
coaleser is recommended. Hydrocyclone can reduce the amount of wastewater
to be treated. Then the concentrated wastewater is sent to a small coalescer since
it handles only small portion of wastewater.
Emulsion containing coarse suspended solids: Example of this case is

wastewater from general washing, etc. In this case, Upflow granular bed
coalescer is not recommended since it can be clogged and its cleaning is very
difficult. Downflow granular bed coalescer, fibrous bed coalescer (only brush
type) and hydrocyclones are applicable. Solids can be separated by API tank or
lamella separator, which can be used as preliminary treatment process otherwise
specific solid separation process must be provided. DAF is recommended for its
solid and oil separation capability.
Emulsion containing fine suspended solids: Example of this case is

stormwater. In this case, theoretically, it can be treated in the same way as
condensates. However, the solid separation process should be provided. DAF
is recommended in this case because it can separate both oil and solids alike.
12.1.3.2 Droplet size between 5 - 20 microns

In this range of droplet size, these two processes are not applicable. Fibrous bed
coalescer or hydrocyclone alone still cannot treat this emulsion. Recommended process is
DAF or combination of coalscer/ hydrocyclone/ coalescer. For the latter case, the first
coalscer will partially coalesce the oil droplets to bigger sizes (around 10-20 microns), which
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are sufficient to separate by the hydrocyclone. Concentrated wastewater from the

hydrocyclone will be treated by the downstream coalescer. In case that SS is present, solids
separation process must be provided
Membrane process and thermal process are applicable but not recommended for
economic reason. After oil separation, the wastewater may need finishing processes (e.g.
biological treatment and carbon adsorption), depending on amount of residual pollutants. It is
possible that surfactants may be present in this type of wastewater.
Effect of surfactants on the performance of each process is provided in the previous
chapters. When the efficiency equation includes the interfacial tension, efficiency of process
with presence of surfactants can be readily calculated. If not, its effect can be compensate by
applying some safety factors.
12.1.4
Macroemulsion and microemulsion
For macro- and microemulsion, the oil droplet sizes in the wastewater are between
0.1 to 5 microns and 10 60 nm, respectively. At these ranges of dropets, Brownian motion is
predominant. Furthermore the droplets are stabilized by surfactants so they cannot coalesce.
STOKEs law-based process without destabilization of emulsion are completely not
applicable. Recommended treatment processes are divided into 3 groups, i.e.,
12.1.5
Chemical destabilization process and decanter or DAF: Major step of this

process train is destabilization of the emulsion. Detail of this process is described
in chapter 10. After destabilization, the droplets can coalesce or flocculate, then
be separated by decanter of DAF. The use of coalescer and hydrocyclone may
not provide further advantage since the interfacial after destabilization is still low
which is unfavorable for these two processes. Precaution for this process train is
the residual pollutants, depending on characteristic of wastewater and
destabilization chemicals. Finishing process is normally required.
Membrane process: Membrane processes, esp. UF, are capable of treating these
emulsions. However, residual pollutant, esp. co-surfactants, concentration are
always high. Permeate from UF of emulsion treatment can be sent to RO to
remove these soluble pollutants. Anyway, RO effluent still contains relatively
high residual pollutants and needs further polishing treatment, such as biological
treatment or carbon adsorption.
Thermal process: the emulsion can also be treated by classic distillation.

However energy cost will be high. Again, dissolved residual pollutant can be
found in the distillate. So it needs polishing process.
Concentrated oily wastewater or refinery slops
Concentrated oily wastewater in this case refers mainly to retentate from membrane
process of stabilized emulsion treatment, such as cutting oil treatment. Refinery slops refers to
residue from refinery process in the form of viscous, concentrated oily wastewater, Slops
usually compose of 40-80% of water, 20-50% of hydrocarbon and 1-10% of suspended solids.
Because of their high concentration and viscous characteristic, they cannot be treated
effectively by normal physical processes. To treat these wastes, GPI lab recommends the use
of heteroazeotropic distillation (chapter 9). The process provide the opportunity to recycle the
oil, esp. in case of slops, since the separated oil is relatively water-free and ready to be sent
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back to refinery process. In case of retentate, the separated oil, also water-free, can be
disposed of as used oil or reused in fuel for incinerator.
12.2
Examples of treatment processes for certain oily wastewaters
Apart from detailed studies on each process, GPI lab also conducted feasibility
studies on treatment process trains of certain oily wastewaters, i.e. non-stabilized emulsion
and cutting oil emulsion. Recommended processes trains for the two wastewaters, based on
GPIs researches, are summarized as follows,
12.2.1
Treatment of cutting oil emulsion
Cutting oil emulsion is one of the most difficult-to-treat wastewater. From it

components, it contains relatively high concentration of oil and surfactants. Concentrate of
macroemulsion contains around 80 % of oil and 15 % of surfactants/co-surfactants. For
microemulsion, it contains 20-30 % of oil, 40-50 % of surfactants/co-surfactants and 5-10%
of water. Generally, the concentrates are mixed with water at 2-6 % by volume of to prepare
cutting oil emulsion. Oil and surfactants/co-surfactants contribute to very high concentration
of oxygen demand. Oil droplets are very small and very stable. Thus they cannot be treated by
STOKEs law-based processes alone.
WANICHKUL [11] had compared the performance of many possible process trains,
e.g. combination of various membrane processes, thermal processes and biological processes.
The result showed that the feasible treatment process train, as shown in fig. 12.2.1-1, should
consist of the following processes, i.e.,
1.
Ultrafiltration: UF is used to treat wasted cutting oil emulsions from sources.

It is recommended to perform lab-scale or pilot-scale test to find the optimum
type of membrane and operating condition before design the real system.
Operation at mid- or lower side of recommended pressure range might result in
less clogging and high average long-term flux. In case of macroemulsion,
partially destabilization by addition of salt, as shown in section 8.2.3.2, may
enhance permeate flux. But a skimmer should be provided to remove
destabilized oil otherwise it will clog the membrane, resulting in lower flux.
Outlet oil concentration of 0-10 mg/l can be expected.
2.
Reverse osmosis: RO is used to remove major part of residual pollutants,

mainly dissolved co-surfactants, from UF permeate. At optimum operating
condition, which depends on types of emulsion and membrane, TOD removal
efficiency around 80-90% can be expected. However, since the inlet TOD is
very high, esp. in the case of microemulsion, RO permeate may still contain
high residual pollutants and need polishing treatment. Retentate from RO can
sent to treat together with the UF retentate.
3.
Heteroazeotropic distillation: It is used to treat the retentate from UF and

RO. With proper entrainer, residue from the distilltion will contain relatively
water-free oil, which is the base oil in cutting oil concentrate. The residue can
be disposed as oil, not waste, or can be recycled or used in an incinerator. The
distillate is 2 separate layers of entrainer, which can be recyled for the next
distillation cycle, and oil which somehow still contain some dissolved
pollutants. It is recommended to send this distillate to mix with the UF
permeate for treatment by RO.
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Retentate
Retentate
Inlet
wastewater
Po
Membrane
Pp
Po
Membrane
Pp
Effluent
dischared
(If possible)
Pi
Feed
Heat
exchanger
Feed
pump
Ultrafiltration
TI
Pi
Feed
Heat
exchanger
Feed
pump
RO Permeate
Wasted retentate
Storage
tank
Wasted retentate
Permeate
Reverse osmosis
Heat
exchanger
Effluent
X
Entrainer
Return sludge
Heater
Aeration tank
Distillate
Wasted
sludge
Clarifier
Fig. 12.2.1-1 Schematic diagram of cutting oil emulsion treatment system

4.
12.2.2
Biological treatment: Distillate and RO permeate are treated by biological

treatment before discharge to receiving water. WANICHKUL showed that the
biological treatment can use dissolved pollutants in RO as main substrate with
TOC removal efficiency more than 90%. So higher efficiency can be expected
if the permeate is mixed with the wastewater of more biodegradability, such as
domestic wastewater from office or canteen.
Treatment of non-stabilized secondary emulsion
This emulsion can be treated with very high efficiency by various methods. So the
efforts to enhance the performance are based mainly on minimization of process footprint.
Conventional oily wastewater treatment system is usually based on DAF, as shown in fig.
12.2.2-1, which is also effective when surfactant is present.
However, in case of non-stabilized wastewater, GPI lab proposes the compact
treatment process train for this emulsion (fig. 12.2.2-2), consisting of the following processes.
1.
Upstream in-line fibrous bed coalescer: The coalescer can partially coalesce
oil droplets of diameter into bigger oil droplets. The fibrous bed is used since it
is hardly clogged by suspended solids. Empty bed velocity of the coalsecer is
reported to be as high as 130 m/h or more [11].
2.
Hydrocyclone: The hydrocyclone will concentrate the partially coalesced oily

wastewater from the upstream coalescer. Since the oil droplets are partially
coalesced, thus bigger. The efficiency of cyclone is improved. The water can
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be discharged or sent to further treatment if some SS or other pollutants are

still present. Concentrated oil will be sent to downstream coalescer.
3.
Downstream fibrous bed coalescer: The coalescer receives the concentrated

or purged oily wastewater from the cyclone. Since the quantity of wastewater
is much reduced, the coalescer can be designed and operated at low loading
rate to ensure high efficiency without consuming unacceptable footprint. The
oil will be separated from the water and then reused or disposed of as oil. The
water can be discharged or sent to further treatment if SS or other pollutants
are still present.
Oil
Inlet
wastewater
Oil
Chemicals
M
Skimmer
To sludge
treatment
To sludge
treatment
Primary sedimentation tank
Chemical
treament
API tank
GAC filter
(if required)
Effluent
Oil
Skimmer
X
To
sludge
treatment
Return sludge
Aeration tank
DAF
Wasted
sludge
Saturator
Clarifier
Fig. 12.2.2-1 Schematic diagram of conventional oily wastewater treatment system
Oil
GAC filter
(if required)
Effluent
Oil
Inlet
wastewater
X
Return sludge
Aeration tank
Primary
Fibrous coalescer/
sedimentation
Hydrocyclone/
tank or API tank Fibrous coalescer
Wasted
sludge
Clarifier
Fig. 12.2.2-2 Schematic diagram of compact oily wastewater treatment system for
Non-stabilized secondary emulsion
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Part IV Computer program development
Contents
Page

Chapter 1
Program overview
1.1 Introduction
1.2 Conceptual design of the program
1.2.1 E-book mode
1.2.2 Recommendation mode
1.2.3 Design mode
1.2.4 Analysis mode
1.3 Development tools
1.3.1 Main development software package
1.3.2 Special graphic user interface (GUI) component
1.3.3 The third party software
1.4 Program architecture
1.4.1 Forms
1.4.2 Modules
1.4.3 Modules
1.4.4 Class modules
1.4.5 Add-in project
1.5 Program development
Chapter 2
IV-2
IV-2
IV-3
IV-5
IV-6
IV-7
IV-11
IV-11
IV-12
IV-12
IV-13
IV-13
IV-16
IV-16
IV-16
IV-16
IV-17
Program reference and user manual

2.1
2.2
2.3
2.4
2.5
2.6

2.1.1 Main program
2.1.2 Project window
2.1.3 E-books worksheet
2.1.4 Recommend worksheet
2.1.5 Design worksheet
2.1.6 Analysis mode
2.1.7 Warning dialog box
Program capability
Program limitation
System requirement
User instruction
2.5.1 Program Installation
2.5.2 Starting the program
2.5.3 Using E-book mode
2.5.4 Using Recommend mode
2.5.5 Using Design mode
2.5.6 Using Analysis mode
2.5.7 Printing and file operation
Upgrading procedure and recommendation for further
development
2.6.1 Upgrading procedure
2.6.2 Recommendation for further development
IV-15
IV-18
IV-20
IV-20
IV-21
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IV-24
IV-26
IV-26
IV-26
IV-28
IV-28
IV-28
IV-29
IV-29
IV-29
IV-31
IV-33
IV-36
IV-37
IV-37
IV-39
IV-i
Contents
Page
Chapter 3
Process references
1)
2)
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
16)
17)
18)
19)
20)
21)
22)
23)
24)
25)
26)
Drum skimmer
Disk skimmer
Simple decanter
Compact decanter
Customized decanter
Ultrafiltration
Reverse osmosis
Stripping
GAC filter
Inlet
Outlet
Flow merge
Flow split
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Table
Page
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
2.2-1
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1-2
2-1
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The processes included in the GPI program

Related parameters of drum skimmer
Influent parameters for drum skimmer
Related parameters of disk skimmer
Influent parameters for disk skimmer
Related parameters of simple decanter
Influent parameters for simple decanter
Related parameters of compact decanter
Influent parameters for compact decanter
Related parameters of customized decanter
Influent parameters for customized decanter
Related parameters of granular bed coalescer
Influent parameters of granular bed coalescer
Related parameters of brush type bed coalescer
Influent parameters of brush type bed coalescer
Related parameters of dynamic fibrous bed coalescer
Influent parameters of dynamic fibrous bed coalescer
Related parameters of metal wool bed coalescer
Influent parameters of metal wool bed coalescer
Related parameters of metal wool bed coalescer
Influent parameters of DAF
Related parameters of two-phase hydrocyclone
Influent parameters of two-phase hydrocyclone
Related parameters of three-phase hydrocyclone
Influent parameters of three-phase hydrocyclone
Related parameters of ultrafiltration
Influent parameters of three-phase hydrocyclone
Related parameters of RO
Related parameters of heteroazeotropic distillation
Related parameters of stripping
Related parameters of chemical destabilization
Related parameters of biological treatment
Related parameters of GAC filter
Related parameters of customized concentrator
Related parameters of simple decanter
Related parameters of chemical destabilization
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Figure
Page
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
1.2-1
1.2.1-1
1.2.2-1
1.2.3-1
1.2.4-1
1.2.4-2
1.2.4-3
1.4-1
1.4.1-1
1.4.1-2
1.4.1-3
2.1.1-1
2.1.3-1
2.1.4-1
2.1.4-2
2.1.4-3
2.1.5-1
2.1.6-1
2.1.7-1
2.5.3-1
2.5.4-1
2.5.4-2
2.5.5-1
2.5.5-2
2.5.5-3
2.5.5-4
2.5.6-1
2.5.6-2
2.5.6-3
2.5.6-4
2.6.1-1a
2.1.6-1b
2.1.6-2
Fig.
Fig.
Fig.
Fig.
1-2a
1-2b
2-1a
2-1b
Flow chart of the program under the scope of work of this thesis
Detailed flowchart of e-book mode
Detailed flowchart of recommendation mode
Detailed flowchart of design mode
Detailed flowchart of design mode: Data input operation
Detailed flowchart of design mode: Analysis and result display operation
Detailed flowchart of design mode: file management operation
Structure of the program
Main form (under construction)
Project form
Input data form
Graphic user interface of the main program
Graphic user interface of the E-book worksheet
Input screen ( a tabbed worksheet in project window)
Result screen. The program will put tick marks in the first column.
Flowchart of recommendation logic
User interfaces of design worksheet
User interface of analysis worksheet
Example of warning dialog box
Using E-book mode
Using recommend mode: Input data screen
Using recommend mode: Result window
Using Design mode: Step 1 Wastewater data input
Using Design mode: Step 2 Process selection
Using Design mode: Step 3 Process data input
Using Design mode: Step 4 Result
Using Analysis mode: Draw the schematic diagram
Using Analysis mode: Process data input
Using Analysis mode: Viewing result in the diagram
Using Analysis mode: Exporting the result to excel
Configuration of the database
Examples of existing database
Example on database upgrading. When new category is added in the
database (left), Related field in the program will be automatically
updated (right)
Icon of drum skimmer
Graphical diagram of drum skimmer
Icon of disk skimmer
Graphical diagram of disk skimmer
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Figure (Cont)
Page
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
3-1a
3-1b
4-1a
4-1b
5-1a
5-1b
6-1a
6-1b
7-1a
7-1b
8-1a
8-1b
9-1a
9-1b
10-1a
10-1b
11-1a
11-1b
12-1a
12-1b
13-1a
13-1b
14-1a
14-1b
15-1a
15-1b
16-1a
16-1b
17-1a
17-1b
18-1a
18-1b
19-1a
19-1b
20-1a
20-1b
21-1a
21-1b
Icon of simple decanter

Graphical diagram of simple decanter
Icon of compact decanter
Graphical diagram of compact decanter
Icon of customized decanter
Graphical diagram of customized decanter
Icon of granular bed coalescer
Graphical diagram of granular bed coalescer
Icon of brush type bed coalescer
Graphical diagram of brush type bed coalescer
Icon of dynamic fibrous bed coalescer
Graphical diagram of dynamic fibrous bed coalescer
Icon of metal wool bed coalescer
Graphical diagram of metal wool bed coalescer
Icon of DAF
Graphical diagram of DAF
Icon of 2-phase hydrocyclone
Graphical diagram of 2-phase hydrocyclone
Icon of 3-phase hydrocyclone
Graphical diagram of 3-phase hydrocyclone
Icon of ultrafiltration
Graphical diagram of ultrafiltration
Icon of RO
Graphical diagram of RO
Icon of heteroazeotropic distillation
Graphical diagram of heteroazeotropic distillation
Icon of stripping
Graphical diagram of stripping
Icon of chemical destabilization
Graphical diagram of chemical destabilization
Icon of biological treatment
Graphical diagram of biological treatment
Icon of GAC filter
Graphical diagram of GAC filter
Icon of customized concentrator
Graphical diagram of customized concentrator
Icon of customized separator
Graphical diagram of customized separator
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Figure (Cont)
Page
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
Fig.
22-1a
22-1b
23-1a
24-1a
25-1a
26-1a
26-1b
Icon of inline concentrator

Graphical diagram of inline concentrator
Icon of inlet
Icon of outlet
Icon of flow merge
Icon of flow split
Graphical diagram of flow split
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In this part, we will use the data reviewed and verified in Part 1 and Part 2 as well as
the text book composed in Part 3 as main theories to develop a computer program for design,
calculation and simulation of oily wastewater treatment processes.
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IV-1
Chapter 1 Program overview

1.1
Introduction
The final objective of this thesis is to develop a computer program for design,
calculation and simulation of oily wastewater treatment process or process train, which
includes every process reviewed in the previous three parts. The program is developed based
on 4 major aims, i.e.,
To provide background knowledge on oily wastewater treatment and working

principle, design formula and design consideration on each oily wastewater
treatment process.
To provide preliminary guideline on oily wastewater treatment process selection to

suit the wastewater to be treated.
To calculate or size the oily wastewater treatment process under the design
condition given by user, based on GPI researches under direction of Prof.
AURELLE reviewed in Part 1 to 3.
To simulate the oily wastewater treatment process train designed by user at any
operating condition.
In this chapter, development procedure and details of the program in development

stage are described. Details and user manual of the finished program will be described in
chapter 2.
To develop the software under the scope of work of this thesis, the following
procedure is used, i.e.,
1.
Conceptual design of the program
The outline of software is preliminary designed to fulfil the 4 aims described

above. Conceptual design of the program will be described section 1.2.
2.
Review of related data
Related data can be divided into 2 parts, i.e. data on oily wastewater treatment
and data relating to program development. The former is thoroughly reviewed in the first 3
part of this report. The latter will be described in section 1.3.
3.
Program development and debugging

Detail of each step is summarized as follows.
1.2
Conceptual design of the program

To fulfil the aims described above, the program is divided into 4 major modes, i.e.,
E-book mode: provides background knowledge and useful database about the oil
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Process recommendation mode: provides recommendation to narrow the range

of feasible processes for any input influent,
Design (or calculation) mode: used for sizing the process unit,
Analysis mode: allows users to integrate any separation processes, included in the
program database, to build their own treatment process train. And the program will
simulate the process train to forecast the efficiency of each unit.
Framework of the program is as shown in the flowchart in fig. 1.2-1. The program is
developed as a Windows-based program to make use of many standard and useful features of
Windows and to facilitate link to other common Windows-based program, such as MS Office
software package. It also operates in multi-tasking mode so users can toggle freely from one
mode to another and can work on more than one project (meaningly, can open more than 1
window) at a time.
Conceptual design and features of each mode are described in the following sections.
1.2.1
E-book mode
E-book mode is one part of the program that is designed to provide knowledge and
useful database about the oil pollution and the treatment processes. The program in this mode
is designed to provide the following features,
1.
Facilitate access or selection of the information. List of e-book files and their
brief description about the context of the file is provided. After access to the file,
detailed contents of each file are also provided to assure quick access to the
required information.
2.
E-book and help files are developed in general file formats, i.e. Acrobat and MS
office software package, to take advantage of useful features of these software,
such as browsing, word searching, printing, copy/paste capability, etc. Moreover,
users are usually familiar with these file formats so they can readily handle the
files.
3.
Facilitate upgrading of the program to cover more processes in the future. The
program is versatilely designed so it can be upgraded. List of e-book files is not
fixedly coded but linked to a database that can be easily added or editing. Once
that user adds new e-book file names, their short description text, and their
location (path and directory), the program will automatically include them in the
interface (screen) of e-book mode, ready to use.
The detailed flowchart of e-book mode is as shown in fig. 1.2.1-1.
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Acrobat
E-book
/Help
library
425
Print out
All mode
Yes
Display E-book
(Acrobat)
Select
E-book
Open E-book
window
No
Continue
Open MS Excel &

automatically
create workbook
No
Select
treatment
process
Open
Design
window
Display
calculation
result
Input
required data
Finish
Only for simulation
Print/Export
Recommend
applicable
processes
Input
wastewater
data
Open
Recommendation
window
Select mode
Start
Existing
Display
calculation
result
Program calculate
the performance
of processes
Input size
of each unit
process
Create or edit
process train
Open new
or selected
file
New (default)
Open file
Open Analysis
window
Fig. 1.2-1 Flow chart of the program under the scope of work of this thesis
Input
wastewater
characteristic
Select
saved
file
Process unit
library
Open file
management
window
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Start
To other
modes
Select mode
E-book
Select
E-book
tab
E-book
data in
srachu.mdb
Acrobat,
E-book
worksheet
activated
Select
E-book by
double-click
User can use all fuction

of the software, e.g
search, copy, print, etc.
E-book
files in
C:/../EBooks
Print
Print/Exit
Exit
Open the E-book file

by suitable software,
e.g. Acrobat
Print out by
the software
Close the software

and return to
E-book worksheet
Display E-book
(Acrobat)
Yes
Other E-book
No
Select other tab or
quit the program
Finish
Fig. 1.2.1-1 Detailed flowchart of e-book mode

1.2.2
Recommendation mode
Recommendation mode is one part of the program that is designed to provide

recommendation to narrow the range of feasible processes for any input influent. The program
in this mode is designed to provide the following features,
1.
Facilitate data input. Interface of this part is designed to be interactive to

prompt user to input all necessary data required for decision.
2.
Provide help to guide the user through each input step. It is usually that the
users do not know some required wastewater information, such as which
categories of oily wastewater they have. Thus the interface of recommendation
mode is provided with links to these data in e-book mode.
3.
Provide recommendation about the feasible processes in user friendly form as

a table with important precautions provided.
The detailed flowchart of recommendation mode is as shown in fig. 1.2.2-1.

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IV-5
Start
To other
modes
Select mode
Recommendation
Select
Recommend
tab
Click calculate
botton to start
calculation
Recommend
worksheet
activated
Required
parameters
data in
srachu.mdb
Program performs
logic calculation
New/Load/save file
subroutine
(fig. 1.2.4-3)
Input required data,
follow on-screen
instruction
Need help on
some parameters
Recommend parameter subroutine
Yes
E-book
files in
C:/../EBooks
Acrobat,
MS office
Display result
as new window
No
Continue
Print
Print/Exit
Exit
Click
recommend
parameter / reference
Print out by
the program Select other tab or
quit the program
Open the E-book file

by suitable software,
e.g. Acrobat, excel
New/Load/save file
subroutine
(fig. 1.2.4-3)
Finish
Display E-book
(acrobat, excel)
Print/Exit
Fig. 1.2.2-1 Detailed flowchart of recommendation mode

1.2.3
Design mode
Design mode is one part of the program that is designed for sizing the process unit.
The program in this mode is designed to provide the following features,
1.
Calculate any required parameters of considering unit process when the rest
data are provided. For example, users can provide the program with geometry of
the process to find the efficiency or vice versa.
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IV-6
2.
Provide help to guide the user through each input step in case that some data is
not known. So the interface of this mode also provides links to related data files.
3.
This mode is provided with printing capability so users can print out the data
and result as a hard copy. Moreover, the data can be saved for further use.
The detailed flowchart of design mode is as shown in fig. 1.2.3-1.

1.2.4
Analysis mode
Analysis of simulation mode is one part of the program that is designed to allow users
to integrate any separation processes, included in the program database, to build their own
treatment process train. And the program will simulate the process train to forecast the
efficiency of each unit process. The program in this mode is designed to provide the following
features,
1.
Allow users to freely integrate any unit processes into a process train in the
form of graphical schematic diagram.
2.
The program will provide with user-friendly graphic editing interface with all
common useful features, such as drag/drop, automatic snap-to-object connectors,
basic drawing and text tools. This kind of interface is a kind of common feature
in well-known software, such as MS PowerPoint, and other simulation software
(e.g. Superpro, etc.). So it can be readily handle by users.
3.
Provide help to guide the user through each input step in case that some data is
not known. So the interface of this mode also provides links to related data files.
4.
The program can calculate graded efficiency, total efficiency and other
necessary components of every process, reviewed in Part 3, e.g. pressure drops
for hydrocyclone, or saturator power requirement for DAF.
5.
This mode is provided with printing capability so users can print out the data
and result as a hard copy for further use.
6.
The data and result can also be exported to MS Excel to use its efficient and
useful features, such as formatting, chart building, etc., for advance display and
printing of the data and the result. It also helps saving the time for developing
these existing features.
7.
The data and result can be saved for further reviewing in the future.
The detailed flowcharts of analysis mode, categorized by groups of operations, are as

shown in fig. 1.2.4-1 to 1.2.4-3. They consist of,
Data input operation
Analysis and result display operation
File management operation
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IV-7

Start
To other
modes
Help can be
accessed at all
time
Select mode
Design
Need help on
some parameters
Select
Design
tab
Recommend
paremeter
subroutine
(see fig. 1.2.2-1)
Design
worksheet
activated
New/Load/save file
subroutine
(fig. 1.2.4-3)
Click calculate
botton/ step 4 tab
Select step
Required
parameters
data in
srachu.mdb
Step 1: WW
data input screen
activated
Program perform
calculation /send result
to Step 4 /
Input wastewater
data, follow onscreen instruction
Step 4 : Result
screen
activated
Yes
Edit
No
Step 2:select
process screen
activated
Built-in
process
data in
srachu.mdb
Yes
parameters
for result
in
srachu.mdb
select required
process by click
at category
and process
Display result
Edit/
Continue
Print/Exit
Yes
Print
Edit
Exit
No
Step 3:Input
process data
screen activated
Required
parameters
data in
srachu.mdb
Input required
Print out by
the program
Yes
No
Select other tab or

quit the program
New/Load/save file
subroutine
(fig. 1.2.4-3)
Edit
Finish
Fig. 1.2.3-1 Detailed flowchart of design mode

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Start
To other
modes
Select mode
Help can be
accessed at all
time
Analysis
Select
Analysis tab
Need help on
some parameters
Analysis
worksheet
activated
Recommend
paremeter
subroutine
(see fig. 1.2.2-1)
New/Load/save file
subroutine
(fig. 1.2.4-3)
select required
process by click
at process name
Program loads the

icon of the process
to the screen
Icons in
C:/../Unitp
rocess
Required
parameters
data in
srachu.mdb
Yes
More process
No
Select operation
To add
drawing object
To connect
the icons
To edit connector
or icon position
Click at
required
drawing tool
button
move the mouse over

the icon until the
hand cursor appears at
the required position
Click mouse, hold down,

move the mouse to another
required position
To enter/ edit data

of the process
Click mouse to
select the item
Double click
at the icon
Click at the position

on the connector to
be edited, hold down &
move to new location
Display input
data form
of the process
Click and hold down mouse

at require position to place
drawing object (line, text, circle, etc.)
Input required
Click OK to
close the form
Yes
Edit
No
To other operations
Fig. 1.2.4-1 Detailed flowchart of analysis mode: Data input operation
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From Input data

Fig. 1.2.4-1
Click calculate
button
Program validates
the process train
No
Pass
Yes
Result
parameters
from
srachu.mbd
Program calculates
the result
Formula in
UnitProcessLib
Program sends results

to result screen
Display warning
message
Select operation
To view result
in the program
To print by the program
To export
to Excel
Double click at icon

on the process train
Click print button

or Impremer
in Fichier menu
Click Exporter
in Donnee
Display input
data form
of the process
Display print form
Program open Excel and

export data and result
Click at result tab
Click Print
Display result form

of the process
Print out
Click OK to close
To edit data
Double click at
the icon
User can perform all

Excel operation, even
save the file in *.xls.
Operation does not
affect the program
Close excel or
click program
window to return
Click OK to close
Yes
Edit
No
To other operations
To data
input
fig. 1.2.4-1
Fig. 1.2.4-2 Detailed flowchart of analysis mode: Analysis and result display operation
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Start
Click Fichier
menu
Select operation
Select Nouveau
Select Ouvrir
Select
Enregistrer
Select Fermer
Select Supprimer
de ficher
Display file
management
form
Display file
management
form
Display file
management
form
Display file
management
form
Save
Select filename
Prompt to save
New file
No
No
Select filename
Yes
Yes
No
Program open
new project
Program open
the file
Select filename
Program perform
requested operation
To other operations
Fig. 1.2.4-3 Detailed flowchart of file management operation
1.3
Development tools
Related data for program development are reviewed. Tools and programming
techniques are evaluated and carefully selected to suit the objective of program development.
Evaluation criteria include,
Capability of development tools to fulfil program features described in section 1.2,
Developing time of each tool. Suitable tool should provide ready-to-use features
required without extra code writing,
Availability of the tools. The possible tools are firstly considered from the
development packages that are readily available without additional procurement.
Or they should be free-ware so it can be used without license problem.
From the criteria mentioned above, the program in this thesis is developed using the
following development tools, i.e.,
1.3.1
Main development software package
The program is developed using Microsoft Visual Basic programming language,

Version 6.0 (VB 6.0). The software is used under the permission of the software licensee,
Progress Technology Consultants Co., Ltd. (Thailand) (PTC). The software features readyto-use tools to create Windows-based application, such as builders of windows, forms and
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IV-11
other user interfaces, e.g. input boxes, buttons, database link engines, etc, which fulfil every
development requirement. It has event-driven feature, such as start working by mouse click or
after enter the data, that is suitable for development of interactive graphic user interface.
1.3.2
Special graphic user interface (GUI) component
Graphic user component in analysis mode is developed on a special GUI component,

FlowChartX version 3.2, the product of MindFusion limited. The component is actually an
ActiveX component that can be used as an add-on of MS VB 6.0. It features presenting and
producing of drag/drop graphic image, connectors, basic drawing tools and useful VB 6.0
compatible methods and properties. The software used in our program is free demo edition,
which, somehow, provides sufficient features for our scope of work.
1.3.3
The third party software
Apart from its own VB program file, the program in this scope of work makes use of
the third party software for their useful features, i.e.,
1.
Microsoft Excel
Microsoft Excel is one of the most famous spreadsheet software with a lot of
versatile and efficient features, e.g. calculation capability, chart builders, macro programming,
searching, editing, formatting and printing tools. Thus in our program, recommend
parameters, such as interfacial tension data, etc, are in excel file formats (*.xls) to facilitate
searching or copying the data to the program. In analysis mode, the result can be exported to
Excel to use its graph builder and formatting/printing facilities. Thus, to use the program of
this thesis, MS Excel is required otherwise some help file will not be available and some
results will not be exported. The program is compatible to MS excel 2000 or newer.
2.
Adobe Acrobat reader
As described in section 1.2, e-book files are in acrobat format (*.pdf) to make
use of its efficient searching and categorizing features. Other useful features are that it can
operate in any platforms, e.g. Windows, Macintosh, etc., and it eliminates the problem about
the font so the file is always readable on every computer. Acrobat reader is free ware so
everybody can have a copy without purchasing. The e-book files are created by Adobe
Acrobat professional version 7.0, under the permission of the software licensee, Progress
Technology Consultants Co., Ltd. (Thailand) (PTC). To use the program of this thesis,
Acrobat reader is required otherwise some e-book files will not be available. It is
recommended to use Acrobat reader 6.0 or newer. The older version may be used but there
may be a problem about using index and fonts, which makes some letters unreadable.
3.
Microsoft Access
MS Access is used as open data source connectivity (ODBC). It allows the main
program to connect to MS Access database file format (*.mdb), which is used as principle
database of the program. To use the program, it requires only MS Access driver, which is
usually provided with Windows OS. The program will automatically acquire the driver from
the Windows in setup procedure of the program. However, if users want to change the
database, such as addition of more process, or e-book files, they will need full MS Access
program. The database is compatible to MS Access 2000 or newer.
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1.4
Program architecture
In this section, program architecture will be described to provide the idea about how
the program is developed and relation between components of the program. This information
is also helpful for further program development in the future.
Major program file is a Visual Basic program group named prjThesis
(prjThesis.vbp). To fulfil the conceptual design described in section 1.2, program architecture
of prjThesis, based on VB 6.0, is divided into following components, i.e. (see fig 1.4-1).
Fig. 1.4-1 Structure of the program

1.4.1
Forms
Forms are practically the graphic interface of the program. They will consists of many
controls (such as buttons, menu, etc.), which, in turns, consists of many source codes to
handle activity or event happening to the interface, such as button clicking. The program is
divided into 3 major forms, i.e.,
1.4.1.1 Main form
Main form (frmain.frm) is the major form of the program that includes a workspace of
the program as well as command button and the menu that control basis operation and file
management operation. It is the first form that is open when the program is run. The interface
of the form is as shown in fig. 1.4.1-1.
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Fig. 1.4.1-1 Main form (as seen in source code)

1.4.1.2 Project form
Project form (frDesigngrid.frm) is the form that is used as a workspace for operation
of the program in every mode (recommendation, design, anlysis and e-book.) for one project.
It is divided into 4 tabbed worksheets that represent 4 modes of operation. Users can freely
toggle between sheets to work in each mode. The data keyed in one worksheet still remains
while working in other worksheets. Data in each field in this form will be saved as encrypted
data in the preset database file of the program. Each tabbed worksheet will contain controls
and corresponding source code required for operation in each mode, as shown in fig. 1.4.1-2.
The texts display in each fields are linked to a database file (srachu.mdb)
1.4.1.3 Input data form
Input data form (frInputdata.frm) is the form that is used for data input in analysis
mode. Unlike the first two forms, it is normally not shown on the screen. The form will appear
when a new unit process is inserted to the schematic diagram in the analysis mode or by
double click at the process icon in the diagram. It is also used to display the result of each
process in the analysis mode after the calculation is finished.
However, Other miscellaneous forms are also developed to fulfil purposes other than
process calculation, such as frPrintMain.frm for printing task, frOpenDialog.frm for Open
file task, etc.
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Fig. 1.4.1-2 Project form
Fig. 1.4.1-3 Input data form

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1.4.2
Modules
Modules are the source codes that govern the overall operation of the program, which
is not linked to events. The major module is Main module (modMain.bas). It governs basic
tasks of the program, such as starting the program, file path setting, etc.
There are also other supplementary modules, i.e. modDatefunctions.bas,
modDBManager.bas and modUtil.bas. These modules are the customized source codes that
govern basic file operations (such as open and save file, link to database) which are written by
AWS Co., Ltd. (Thailand), system service provider of PTC. These modules are used under
the permission of the company. The use of the modules allows us to save the time to develop
the codes for these fundamental tasks.
1.4.3
User controls
User controls are special or add-in components besides standard components that
come with standard VB development packages. In our case, one user control component
called ctlGrid, is added to use in various input and output form in our program.
1.4.4
Class modules
Class module is special module which can be developed to have its own customized
properties, e.g., in our case, .isdroplet (used to check if the process has its droplet data or
not), etc. It greatly facilitates program development. In our program, class modules are used to
control link of each type of data, i.e. process category name, unit process name and variables,
etc., between the database file and the corresponding fields in the forms. For examples, it will
link the file names and short descriptions of e-books file to display in grid table in the e-book
form. Lists of class modules are shown in fig.1.4-1.
1.4.5
Add-in project
To facilitate upgrading of the program and versatile operation of the program, the subprograms used for calculation of each unit process are separated as another Visual Basic
project, namely UnitProcessLib (UnitProcessLib.vbp). It consists of module and class
modules, i.e.,
1.4.5.1 Module
There is two modules in this add-in project. The first module is called
ModUNPFunction (modUNPFunction.bas). It is used to manage operation in the analysis
workspace, such as load the picture of selected unit process and run the tag number for each
unit process. It can handle more addition unit process without any modification, in case that
more processes are added in the future.
The second module is ModExcelFunction(ModExcelFunction.bas). It is used to
control excel operation, such as calculation of some processes, import & export data between
excel and our program.
1.4.5.2 Class modules
There are a lot of class modules in the add-in project. Each class module devotes to
each unit process (see fig. 1.4-1). Thus, if more processes are to be added, all that have to do
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about coding is add the corresponding modules for those processes and add their variables
and corresponding help or e-book file data in the database file srachu.mdb. The rest of
the program needs no modification.
To develop new class modules for new processes, one of the old class modules can be
used as a prototype. Developers just change the equation and solving procedure (such as
iteration, etc.) to suit the new process and then add them into the add-in project. Details and
equations used in calculation of each process are described in chapter 2.
1.5
Program development
After the conceptual design is set, all components and source codes of the program are
developed in accordance with the flowcharts aforementioned.
When all components described above are completely developed, the program then
undergoes debugging process to iron out any syntax errors and error from wrong coding.
After that, the Visual Basic source codes are complied to make a ready-to-use or
executable file and setup file, using VB compiler and the third party VB setup file builder,
called Wise Installation system. User will not see the components or source codes described
above. They will see only a group of executable files and supplementary files. Details and
user manual of the compiled program will be described in chapter 2.
The setup file, as well as the source code, of the program is submitted to Prof.
AURELLE, thesis director. So it may be available upon request. For more information,
please contact Prof. AURELLE or gpi_program@yahoo.com.
The copyright of the program, as well as the textbook shown in Part 3 of this thesis
and as e-book files in the program, is registered with the Copyright office, Department of
Intellectual Properties, Thailand and under international agreement on copyright (TRIPs).
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Chapter 2 Program reference and user manual

2.1
The program developed under the scope of work of this thesis is the computer program
that can calculate the size of processes and simulate or analyze the performance of process
train, defined by users, without limitation on the number and configurations of the process.
The program is intended to be upgradable to cover more process in the future. However, in
this scope of work, the program covers only wastewater treatment processes, based on GPIs
researches under the supervision of Prof. AURELLE. Thus, it is named GPI program.
GPI program is developed in accordance with the conceptual design described in the
previous chapter. Thus, GPI program can be divided into 4 main modes, i.e.,
E-book mode: provides background knowledge and useful database about the oil

of feasible processes for any input influent,
Design (or calculation) mode: used for sizing the process unit,
Analysis mode: allows users to integrate any separation processes, included in the
program database, to build their own treatment process train. And the program will
simulate the process train to forecast the efficiency of each unit.
However, from the user point of view, it is more convenient to describe each mode of
program by the screens or graphic user interfaces (GUI). From this, the program can be
divided into 2 major parts, i.e. main program and project window. Their relations can
compare to those of the main Excel program and its workbook (which contains many
worksheets). Details of each part of completely developed program are shown in section 2.1.1
to 2.1.4. They will describe the features of each part and show that how the conceptual design
is transformed into real working program.
2.1.1
Main program
Main program is the main graphic user interface (see fig. 2.1.1-1) including main
menu and a blank area that are used as workspaces for project window(s). The main program
is developed from the common tasks of each mode, i.e.
File management operation (open, save, close, etc.) of every mode,
Basic edit tool (such as cut, copy, paste) for certain components,
Print and export operation of every mode,
Access to E-books and help that can be commonly accessed by any modes of
program at any time.
Main components of this GUI is menu and tool bars. The menu, written in French
language, provides common basic functions for all modes, i.e.,
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1.
Fichier (File) menu: consists of the following functions or operations, i.e.,
Nouveau (New): open new (blank) project window. User can use more than 1
project window independently at the same time. Change active project
window from one to another can be done by click at any area on the new
active window, like standard Windows-based softwares.
Ouvrir (Open): open existing project, which can be save as encrypted data in
database of the program.
Fermer (Close): close active project.
Enregistrer (Save): save active project as encrypted data in database of the

program.
Supprimmer de fichier (Delete file): delete unwanted project from the

database.
Imprimer (Print): print selected screen to printer in built-in preset format.

User cannot alter the format. However, data in analysis mode can be
exported (see menu donne) to Excel for advance presentation or report
formatting.
Quitter: exit the program.
2.
Edition (Edit) menu: consists of the standard edit functions, i.e., resto (undo),
redo (redo), couper (cut), coupier (copy) and coller (paste) for some applicable
fields.
3.
Donne (Data) menu: consists of data transfer functions, i.e.,
4.
Exporter dimage (Export picture): export active process train diagram (only
in Analysis mode) as a bitmap file, compatible with presentation or graphic
editing software, such as PowerPoint, or PhotoShop.
Exporter (Export): export active input data and result to MS Excel.
Aide (Help) menu: consists of help and information functions, i.e.,
Utilisation du programme (help contents and index): open program help file,
which is exactly brought from the context of section 2.2 in this chapter.
Documentation lectronique (E-book): open E-book mode. Clicking at Ebook tab in a project window also gives the same operation.
A propos de (About): open program information (names, version, etc.) dialog

box.
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Main menu
Tool bar
Project window
Main program
Fig. 2.1.1-1 Graphic user interface of the main program

2.1.2
Project window
Project window is the window containing tabbed worksheets that contribute to each
mode of program, i.e., recommend, design, analysis and e-book. User can open more than 1
project window at a time (see fig. 2.1.1-1). These windows operate separately. This part of
program are combination of the 4 modes of the program as described in the flowcharts in
section 1.2, except the parts that are separated to be a main program.
2.1.3
E-books worksheet
E-books worksheet is one of the tabbed worksheets in a project window. It is actually

customized open file window that can show the list of built-in e-books or help files with
their short description or synopsis of the files to inform the users about the content of each
file. Double clicking at the file name or clicking at open button after file name selection will
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open the selected e-book (see fig. 2.1.3-1). E-book worksheet is developed under the
conceptual design, shown in fig. 1.2.1-1.
The help or e-book file names and short descriptions are stored in a database, namely
srachu.mdb. If there are more help files or e-books to be added into the program. Users can
simply input the filenames and their short description (as normal text data) into the database
file, using MS Access, and copy the new help file or e-books into the existing Ebooks
directory.
Overview of oily wastewater treatment

Decanter
STOKEs law, Interfacial tension, Capillary

API, PPI, Spiraloil,
Fig. 2.1.3-1 Graphic user interface of the E-book worksheet

2.1.4
Recommend worksheet
Recommend worksheet is one of the tabbed worksheets in project window (fig. 2.1.41). It can provide recommendation about possible or potential processes (based on guideline
summarized from GPIs researches in Part 3, chapter12), corresponding to input wastewater
data. Recommend worksheet is developed under the conceptual design shown in fig. 1.2.2-1.
Users just answer the preset questions to provide the closest description to the
wastewater to be treated. The questions start at the topmost frame, while the rest frames are
still disabled to avoid confusion. The frame corresponding to the previous answer will be
shown next. Fig. 2.1.4-2 is the retouched screen to show all frames at the same time. After
clicking calculation button, the program will display the result screen (fig. 2.1.4-2) and put
tick mark (3) in the first column to indicate the categories of the wastewater to be treated.
This mode of operation is designed for oily wastewater treatment process only since
decision logic is relatively complex so it needs fixed source code. The logic used to
recommend feasible processes is as shown in flowchart (fig. 2.1.4-3).
Thus, to upgrade the program to cover other process categories (such as air pollution
treatments) in the future, it can be done by addition of checklists in the form of help files or ebooks in e-book worksheet instead. It may not be interactive but it would be equally
effective.
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Fig. 2.1.4-1 Input screen ( one of tabbed worksheets in project window)
Fig. 2.1.4-2 Result screen. The program will put tick marks in the first column.
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Start
Just show
the guideline
Categories
Known
categories
Select
categories
Oil/HC, sheared by pump
Oil lyer + Primary +

secondary emulsion.
Storm water/
condensate

secondary emulsion.
Wash water w/
surfactants
Primary +
secondary emulsion.
Oily WW
w/o surfactants

secondary emulsion.
Slop/ retentate/
conc. oily WW
Slop/ retentate/
conc. oily WW
By source/
granulometry
Source /
granulometry
By source
By granulometry
D=1-100
Oil layer
D<1
d>100
WW contains
oil layer.
WW contains
secondary emulsion.
WW contains
primary emulsion.
WW contains
macro/micro emulsion.
Cutting oil/
stabilized
emulsion
Display result
as new window
Macro/micro
emulsion
Program puts tick

mark in
corresponding cells
Finish
Fig. 2.1.4-3 Flowchart of recommendation logic

2.1.5
Design worksheet
Design worksheet is one of the tabbed worksheets in project window. It is used to

calculate any parameter providing that the remaining parameters are given, e.g. find efficiency
from the given size of process at the given wastewater data. Thus its operation can compare to
programmable calculator. Design mode, in this thesis, is developed for oily wastewater
treatment processes and can be expandable to cover other types of processes in the future (by
others). Design mode worksheet is also divided into 4 tabbed worksheets, devoting to each
design step, i.e.,
1.
Step 1: input wastewater properties. (fig. 2.1.5-1a) Required data includes

influent parameters on oily wastewater treatment process, i.e, oil concentration,
physical properties, such as densities and viscosities of oil and water, as well as
size distribution data (granulometry). In case that some parameters are not
known, user can consult built-in parameter database, by clicking recommend
parameters button. The database is in MS Excel format, to facilitate additional,
editting and cut/paste operation. The files are stored in directory RefFiles.
2.
Step 2: select the process to be calculated (fig. 2.1.5-1b). Oily wastewater

treatment processes included in the program are based on every process
reviewed and described in Part 3, i.e.,
Membrane processes
Skimmers
Decanters
Chemical process
Coalescers
(Destabilization)
Hydrocyclones
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Equations and guide on data input are described in chapter 3. The program is
versatilely designed so it can be upgraded to include more process categories,
such as air pollution treatments, various biological treatments, etc., in the future.
Details will be described in chapter 3.
3.
Step 3: specify the parameter to be calculated and input the rest parameters (fig.
2.1.5-1c).
4.
Step 4: display the result (fig. 2.1.5-1d). The result will be displayed after user
clicks at the calculate button. If the data is changed, the result will be cleared
to avoid confusion or using the wrong set of result.
If the design worksheet is activated (tab design is clicked), the data and the result
can be printed in the preset format by selecting Imprimer in Fichier menu. Recommend
worksheet is developed under the conceptual design shown in fig. 1.2.3-1.
Step 1 Wastewater data input
Step 2 Process selection
Step 3 Process data input
Step 4 Result
Fig. 2.1.5-1 User interfaces of design worksheet

2.1.6
Analysis mode
Analysis mode is one of the tabbed worksheets in project window. It provides users
with capability to analysis the performance of process trains of any combinations of unit
processes. The process train will be represented by graphical schematic diagram as shown in
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fig. 2.1.6-1. User can select the process category in the top left list box. Then, the program
will display list of available process in that category in the lower list box. In this thesis, there
is only one category available, namely oily wastewater treatment.
User can insert required process by double clicking at the name of the process. Then,
the program will insert the icon (picture) of the process into the graphic-editing screen. The
icons can be move freely by normal drag/drop method. Each icon will be automatically
labeled by a code, indicating its type of process and number, such as SD-01 for simple
decanter no. 1. These tag numbers are useful for calculation of the program.
The program is equipped with automatic connector capability that can connect the
processes just by mouse clicking and dragging. Basic graphic tools, such as text box, line,
rectangular, circle, are provided. Users can add/edit these items into the diagram without
affect on calculation of the program.
Sizing of each process is specified by double clicking at the icon. Data input screen
will be displayed. After the schematic diagram and data input are ready, user can start
calculation by clicking at calculation button or calcul menu. The program will validate
the data and prompt for correction in case of error until it is cleared. Then it will analyze the
process to find efficiency of the process as well as other important parameters of each process,
such as pressure drop for hydrocyclone, etc. The details will be described in chapter 3. The
result will be displayed within the program or exported to Excel. User instructions on drawing
the diagram, calculation, etc. are described in section 2.5.
Calculation button
Basic drawing tool bar
Category selection
Input and result screen

(displayed when double clicking at the icon)
Process selection
Graphic editing area
Fig. 2.1.6-1 User interface of analysis worksheet
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2.1.7
Warning dialog box
Warning dialog box is the text box that is displayed when the program finds some
error, e.g. in data typing, or wants to prompt users on some events or information, e.g. SD-01:
specified droplets are beyond limit of the process. Example of warning dialog box is as shown
in fig. 2.1.7-1. It can be closed by clicking OK or close (X) button at its corner.
Fig. 2.1.7-1 Example of warning dialog box
2.2
Program capability
Capability of program, from the point of view of process calculation, can be divided
into 2 parts, in accordance with 2 main modes of the program, i.e. design and analysis mode.
The processes included in the program are mainly the treatment processes that are
reviewed in Part 3. However, there are some additional processes that are included as logical
module in the analysis mode, e.g. inlet module and outlet module, or to represent a
customized process that is not included in those of Part 3. All processes included in design
and analysis mode are summarized in table 2.2-1. Equations and related parameters, as well as
guideline for data input, for each process are described in chapter 3 Program references.
2.3
Program limitation
Since the program is newly developed, it has some limitations, based on programming
techniques, limitation from scope of work of the thesis, as well as attempts to generalize the
program to support upgrading in the future. General limitation of the program are as
summarized below.
1)
In this scope of work, GPI program includes only oily wastewater treatment
process.
2)
The unit of every parameter (e.g. kg, m. second, etc.) is fixed to lessen the
complication of the program.
3)
The program includes only calculation of oil separation. Other pollutants, such as
suspended solids, are not taken into account. However, from its open
architecture, it can be upgraded to cover other treatment or other type of process
in the future.
4)
The process train in the program can contain only 1 outlet since it is an important
logical module, used in program loop. In case that there is more than 1 outlet in
the real process train, user can combine those outlets, using flow merge module,
into 1 outlet. However, to do so, it does not affect calculation result.
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Table 2.2-1 The processes included in the GPI program

Name
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Skimmer
Drum skimmer
Disk skimmer
Decanter
Simple decanter
Compact decanter
Customized decanter
Coalescer
Hydrocyclone
Membrane processes
Ultrafiltration
Reverse osmosis
Thermal processes
Stripping
Chemical process
Chemical destabilization
Finishing processes
Biological process
GAC filter
Customized process
Customized oil concentrator
Inline oil concentrator
Logical module
Inlet
Outlet
Flow merge
Flow split
Design mode
Analysis mode
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
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2.4
5)
Some influent parameters can not be interpreted in the form of equation, such as
tortousity of bed in coalescer process, thus can not be accounted in calculation.
However, effect of these parameters can be compensated by the use of correction
factor (CF).
6)
The program requires third party program to operate, such as MS excel, Acrobat.
Some of these programs are not free-ware and may cause some expense if they
are not readily available.
7)
From the limitation of VB 6.0, its control components, such as text box, menu,
table, etc., support only one font, which is Windows (English version) default
font (as seen in the windows explorer and menu of every program in the
Windows). So we cannot use symbols, Greek letters or the letters with accent,
such as , , , etc. in the program.
System requirement
To use the program, these hardware and software, based mainly on the requirement of
Windows, VB and Excel, are needed.
Hardware
1.
2.
3.
4.
5.
Computer and processor: PC with 300 megahertz or higher processor clock

speed recommended; 233 MHz minimum required (single or dual processor
system);* Intel Pentium/Celeron family, or AMD K6/Athlon/Duron family, or
compatible processor recommended.
Memory: 128 MB of RAM or greater (minimum of 256 MB is recommended.)
Hard disk: 50 MB of available hard-disk space
Display: Super VGA (800x600) or higher resolution
CD-ROM or DVD drive
Software
1.
2.
3.
4.
2.5
Windows 2000 with service pack 3 (SP3), Windows XP or higher

Adobe Acrobat reader 6.0 or higher
Microsoft Excel 2000 or higher
Microsoft Access 2000 or higher (Optional for database editing)
User instruction
GPI program is Windows-based program so it features familiar graphic user interface

and basic Windows function, e.g. drag/drop, etc. Thus it is quite ready to use for Windows
users. In this section, instructions for using customized features of the program are described
2.5.1
Program Installation
Setup files of the GPI program are contained in a CD. To install program;
1.
Insert CD into a drive
2.
The program will run setup program automatically. If auto run is not operated,
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2.1
Use any browsing programs, such as window explorer, to browse the

contents on the CD and then <double click> at Setup.exe.
2.2 <Click> Windowss Start button, <Click> Run Then type <your CDROM drive>:setup, such as d:setup
2.5.2
2.5.3
3.
Follow on-screen instruction.
4.
Set program will install GPI program to the computer and automatically create
an icon on the desktop and add the program into the Programs menu of the
Windows.
Starting the program

1.
<click> Windowss Start button, then <click> Programs and <Click> the
program name.
2.
Or <double click> at the shortcut
3.
Or <click> Windowss Start button, then <click> Programs and <Click> the
program name.
4.
The Main form and a new project window will appear on the screen. The
program is ready to use.
on the desktop (created by user).
Using E-book mode
2, 4
Fig 2.5.3-1 Using E-book mode
2.5.4
1.
<Click> E-book tab or documentation lectronique in Aide menu.
2.
<Click> at the name of an e-book to be open
3.
<Click> Open button
4.
Or <Double click> at the name
5.
The program will open Acrobat and display the selected file.
Using Recommend mode

1.
<Click> Recommend tab
2.
<Click> a radio button to select the suitable answer for your wastewater in the
topmost frame
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5
Fig. 2.5.4-1 Using recommend mode: Input data screen
Fig. 2.5.4-2 Using recommend mode: Result window

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2.5.5
3.
The frame corresponding to your first answer will be displayed. <Click> another
radio button. Other frames will be disabled to avoid confusion.
4.
<Click> suitable list box. You can select more than one box.
5.
When data input is sufficient, Calculate button will be enabled. <Click> the
button to start calculation and display the result.
6.
Result window (fig.2.5.4-2) is shown. Your wastewater is indicated by tick

marks. <Click> X button to close the result. To start over, go back to step 1.
Using Design mode

1.
<Click> Design tab
2.
<Click> Step 1 tab. Wastewater data input screen is shown.
3.
Input the data in input fields (text boxes and table) by <Click> at the selected
field, then type your data
4.
To move to next field, user arrow keys (<>,<>) or <enter> or <click> at the
next field
5.
When data in step 1 is complete, <Click> Step 2 tab or <click> next button.
Process selection data is shown.
1
2
3
Fig. 2.5.5-1 Using Design mode: Step 1 Wastewater data input

6.
<Click> at required category name and process name. The text boxes on the left
hand will display short description of the selected category and process. In this
thesis, these are only 1 category, i.e. oily wastewater treatment.
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Fig. 2.5.5-2 Using Design mode: Step 2 Process selection
Fig. 2.5.5-3 Using Design mode: Step 3 Process data input
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7.
When selection is done, <click> Next button or Step 3 tab. Process data
input screen is shown.
8.
Input the data in input fields (text boxes and table) by <Click> at the selected
field, then type your data. To move to next field, user arrow keys (<>,<>) or
<enter> or <click> at the next field. The field that we want to find the answer
must be left blank. <Click> Recommend parameters or Reference for more
information on the value of each parameter and related equations and limitation
of each process.
9.
When data in step 3 is complete, <Click> Calculate button. The program will
calculate the result and put it in the result screen Step 4. If the data is not
sufficient or redundant, the program will not calculate and will display a
warning.
10.
After calculation, the result screen (step 4) will be automatically shown.
11.
To edit some data in each step, <click> the required tab or <click> Back and
Next button. When the data is edited, the result is cleared to avoid confusion.
10
11
Fig. 2.5.5-4 Using Design mode: Step 4 Result

2.5.6
Using Analysis mode

1.
<Click> Analysis tab
2.
<Click> at require category name in the upper left box. List of processes in that
category will be shown in the lower left box. In this thesis, there is only 1
category, i.e. oily wastewater treatment.
454
IV-33
5
5
"
Drag and drop to move

<Double click> to insert
Fig. 2.5.6-1 Using Analysis mode: Draw the schematic diagram

3.
Input your process train by drawing the schematic diagram, using the unit
processes provided in the lower left box on the screen. To insert an icon or
graphic representative of the process, <Double click> at the process name. The
corresponding icon is shown in the graphic editing area.
4.
To move the icon to proper location, move the cursor over the icon until it turns
into a 4-direction arrow ( ) sign. Then <click> and hold the mouse button to
drag and release the button to drop the icon at new location.
5.
Insert other processes using step 3 and 4 until all required processes are inserted.
To connect the processes together, move the cursor over the icon until it turns
into a hand (") sign. Connecting points of the process will be shown as small
red squares. Move the hand to the required connecting point, <click> the
mouse, hold the button to a required connecting point of another process to be
connected and release the mouse. The program will draw the connecting line
automatically. Users will actually see the line while they hold and move the
mouse. User can add non-active graphic, e.g. text box, line, etc. into the diagram,
using drawing tools.
6.
After connecting the processes, User must input the size of each process. To
input or edit the data of a process, <double click> at its icon. Process data input/
result screen is shown. However, the result tab will be disabled unless the
calculation is completed. The process train must contain only 1 outlet module.
But there can be several inlet modules. See chapter 3 for details and restriction of
each module.
455
IV-34
10
Fig. 2.5.6-2 Using Analysis mode: Process data input

7.
After data input procedure is completed. <Click> Calculate button or Calcul

Now in Calcul menu to start caluculation. The program will validate the data
and display warning to prompt users to correct the errors. After the errors are
cleared, the program will calculate the result of each process. In analysis mode,
the program can calculate process performance (e.g. graded efficiency, outlet
concentration of oil, etc.) only. It can not be used for sizing the process, as in the
design mode.
8.
To view the result, <Double click> at required process icon. The data input/
result will be displayed. After calculation in step 8, the Result tab is enabled.
<Click> the tab to view the result of the process. The result tab is just the same
as that of design mode, shown in fig. 2.5.5.4.
9.
Total outlet concentration of each process will also be shown as a text box under
each icon for evaluation of the performance at-a-gaze (fig. 2.5.6-3)
10.
To display result in more complex format, it must be exported to Excel. To do

so, <Click> Exporter in Donne menu. The program will open Excel and
automatically create a workbook. Each worksheet in the workbook devotes to
result of each process (fig 2.5.6-4). User can also save this excel file. User can
formulate their own formats of result such as building graph showing graded
efficiency of every process, etc., in Excel. The diagram can also be exported to
any Windows-compatible software, such as PowerPoint, PhotoShop, etc., by
<click> at Exporter dimage in Donne menu.
456
IV-35
Fig. 2.5.6-3 Using Analysis mode: Viewing result in the diagram
Fig. 2.5.6-4 Using Analysis mode: Exporting the result to excel

2.5.7
Printing and file operation

1.
Every screen in the program can be printed in pre-set format. To print, <click>
Imprimer in Fichier menu. Print dialog box will be shown. User can select
the mode(s) that they want to prink, then click OK.
2.
Data and result of design and analysis can be saved in the database. To conduct
file operation (new, open, save, delete, close), <click> required operation in
Fichier menu. File operation dialog box will be shown.
457
IV-36
2.6
Upgrading procedure and recommendation for further development
As described in previous section that the program is designed to facilitate upgrading in

the future, in this section, upgrading procedure and recommendation for further development
are described.
2.6.1
Upgrading procedure
Upgrading procedure can be divided into 2 major parts, i.e. upgrading of database and
source code upgrading.
2.6.1.1 Upgrading of the database
Every data related to process calculation, as listed below, is linked to the database,
namely srach.mdb, which is automatically installed in setup procedure.
1.
Process categories (see fig. 2.5.5-2, and 2.5.6-1)
2.
Unit processes of each process category, as shown in table 2.2-1 and sub-routine
names (called class as described the previous chapter)
3.
Wastewater input data for each process category (see fig. 2.5.5-1 and 2.5.6-2)
4.
Input data for each unit process, as well as its icon file and help file (see fig.
2.5.5-3 and 2.5.6-2)
5.
Output data for each process (see fig. 2.5.4-4 and chapter 3)
6.
E-book (see fig. 2.5.3-1)
These data are in the form of tables in the database file, as shown in fig. 2.6.1-1. If
users want to add new process or process categories, it can be easily done by add related data
into the tables. The additional data will be automatically displayed in the related screens of the
program without any additional coding, as shown in fig. 2.6.1-2. This procedure does not
require Visual Basic development package.
Standard result
(such as Cout, etc. :
Standard result for

that category
Unit process:
Input data for other

wastewater
category :
Table name:
tbStdResult
Process category:
Unit process:
Table name:
tbProcessCategory
Table name:
tbUnitProcess
Ebook file:
Input/output data
for oily wastewater
category :
Table name:
tbEBook
Table name:
tbVariableDef
For future upgrading
Existing
Fig. 2.6.1-1a Configuration of the database
458
IV-37
Fig. 2.1.6-1b Examples of existing database
CAT000001
CAT000002
Air pollution treatment
Air pollution treatment
Fig. 2.1.6-2 Example on database upgrading. When new category is added in the database
(left), Related field in the program will be automatically updated (right)
2.6.1.2 Source code updating
Even though the programs interfaces can be easily upgraded by updating the database
file. To add sub-routines (or classes) of new processes into the program, the new classes have
to be written in Visual Basic. The simplest way to write a new class is to copy one of the old
class and change the formula or equation to suit the new process. To do so, Visual basic
development package and the original source code of any process is required. Developers can
define their own variable easily in the database file. So, in their new classes, they can use
these variables in the new equations.
459
IV-38
After writing the new classes in VB, the classes need to be recompiled into executable
file. Then, the file will be copied to replace the old compiled class file without reinstallation
of the whole program.
The reason that we developed the program in the manner that it requires source code
for updating is that we can control the development of the program to proper developers. The
source code of the program is submitted to thesis director, Prof. AURELLE.
2.6.2
Recommendation for further development
Since this program in newly developed so it have some limitations as discussed in

section 2.3. However it may have prospect for further development, at least, in the following
approach.
1.
To upgrade to include more process categories,
2.
To add a subroutine for unit conversion (metric, US customary, etc.), which

would be very useful in case that some users may be familiar with different kind
of unit.
3.
To develop or include some advanced components, which may be present in the

newer version of VB, to enhance the performance of the program or make it
operate in stand-alone mode without requiring third-party software (such as
Excel). It is also useful to enhance its text display capability so it will be able to
display Greek letter, subscript, or superscript.
4.
Recommend mode should be enhanced by replacing the fixed-coded source

codes with sub-program written with logical programming language, such as
Prolog.
460
IV-39
Chapter 3 Process references

Process references, which include the parameter to be calculated, equations used and
specific constraints of each process, are described in the following sections. This information
is included in the help file of the program, (<Click> Utilisation du program in Aide
menu), or (<Click> Reference button in any input forms or user interfaces).
Common parameters
Common parameters or variables that are used for every process module are
summarized as follows,
Variable name in Unit used in the
the program
program
Parameter
Description
Cod
Granulometry or oil droplet size

distribution : graded concentration
(concentration of oil at each droplet size)
Concentration of inlet oil in the form of
oil layer or film
Total oil inlet concentration
Granulometry or oil droplet size
distribution : droplet size
Wastewater flowrate
Temperature
Dynamic (or absolute) viscosity of
continuous phase, which is water, for oily
wastewater
Density of dispersed phase, in this case, oil
wastewater
Dynamic (Absolute) viscosity of
dispersed phase, in this case, oil
Co
d
Q
T
c
d
C
d
ow
Cind
mg/l
Cinlayer
mg/l
Co
din
mg/l
micron
Qin
temp
Denc
m3/h
Celcius
Kg/m3
Dend
Muc
Kg/m3
N.s/m2
(= 1000 cp)
Mud
N.s/m2
(= 1000 cp)
gow
kg/s2 or N/m
(= 1000 dyne/cm)
Values of these parameters will be given by user via inlet module (See section 23).
They will be used to calculate the results, which are usually divided into 2 streams, i.e., water
outlet and oil (or concentrated oily wastewater outlet. Generally, the result will contain the
parameters mentioned above. But the values will be changed in accordance with
corresponding model or equations of each process. Then they will be sent as input data for
downstream process until the end of process train (outlet module).
General remarks and precautions of the program
General remarks and precautions of the program are as shown below,
The program is valid only when the oil is lighter than water.
461
IV-40
The processes available in the program generally consists of 1 inlet port and 2
outlet ports, i.e., outlet port of treated water, called water outlet port, and outlet
port of separated pure oil or concentrated oily water, called Oil outlet port.
Graded concentration is specified as quantity of oil (mg) per volume of wastewater

(= volume of oil+water).
Graded efficiency (d) in the program is based solely oil mass removal, regardless
of flow splitting effect. To calculate outlet concentration, flow splitting between
oil outlet port and water outlet port of each process will be taken in to account.
Thus, in some processes, outlet oil concentration is not exactly equal to (1-d)Cod.
Total efficiency (t) in the program can be generally used to calculate total inlet
concentration. Total outlet oil concentration is equal to (1-t)Co in some processes.
However, there may be some exceptions in certain processes. See reference of
each process for more information.
The pictures or icons of processes in analysis mode generally contain 3

connections or hot spots (there may be only 1 or 2 spots in some processes.) The
black connection represents inlet point of the process. The red one represents oil
outlet port and the blue one represents treated water outlet port.
In E-book mode, the e-book files are designed for a fixed directory, named
c:/SR/E-book.
The
directory
contains
an
Acrobat
index
file
E_book_oily_wastewater. This index facilitates users to search for any words or
topics in all e-book files in the directory. However, it is developed by Acrobat 7.0,
it may not be run on some old versions of Acrobat reader. In this case, it is
recommend to set option of the option All PDF documents in in Acrobats
search window to the e-book directory. It can substitute the use of the index file.
The program is linked to MS Excel for parameter recommendation, calculation of

some processes and for result display. In case that, Excel security is set to high
level, it will happen that the program is not allowed to link to Excel. To solve or
avoid this problem, you can choose one of these options,
Set security of Excel to medium or low. (in Menu Tools>Options>Security).
If high or highest security level is needed, try setting the macro in the file
Process_calculation.xls
as
a
trusted
source
(in
Menu
Tools>Options>Security). Consult your corresponding Excels help file for
more information.
462
IV-41
1)
Drum skimmer
1.
Process abbreviation: DRM
2.
Process description : Oleophilic oil drum skimmer
3.
Reference : Part 3, chapter 3
4.
List of outputs and related equations

4.1
Graded efficiency: 100% for oil film or layer and 0% for droplet.
4.2
Total efficiency: 100% for oil film or layer and 0% for droplet.
4.3
Graded outlet oil concentration in water outlet flow: This parameter is not
valid for this process.
4.4
Total outlet oil concentration in water outlet flow: This parameter is not
valid for this process.
4.5
Graded outlet oil concentration in oil outlet flow: the outlet oil in the oil
outlet flow is in pure condition (100% oil).
4.6
Total outlet oil concentration in oil outlet flow: the outlet oil in the oil
4.7
Inlet flow: the process is valid only for separated oil flow from upstream
process.
4.8
Water outlet flow: This process does not have this property.
4.9 Oil outlet flow: flowrate or oil productivity (m3/h) is governed by the
following equation.
0.486
3.035D1.541 N1.541 o
L
P = CF
0.514
g
5.
{1.1}
Related parameters: Related parameters are as summarized in the following

table.
Table .1-1 Related parameters of drum skimmer
Parameter
Variable name in
the program
Description
CF
Efficiency correction factor, CF 1
D
g
L
N
P
Diameter of skimmer
Length of the skimmer

Rotational speed of the skimmer
Oil productivity of the skimmer
Kinematics viscosity of oil
CF
D
Constant = 9.81
L
N
Prod
go
(used /)
463
Unit used in the

program
M
m/s2
M
Rev/s
m3/h
kg/s2 or N/m
(= 1000 dyne/cm)
m2/s
IV-42
6.
Related graphics: Icon in analysis mode and graphic diagram for input screen for
this process are as shown below.
Scrapper
Drum Skimmer (DRM-??)

D
Oil layer
Fig. 1-1a Icon of drum skimmer
7.
Fig .1-1b Graphical diagram of drum skimmer
Constraints and limitations

7.1 Superficial tension of oil is in the range of 27 34 dynes/cm, which
practically covers all common oil.
7.2 Capillary number (Ca = o V/o) is in the range of 0.2 1.0.
7.3 Oil density is around 790 830 kg/m3. Oil dynamic viscosity () tested is
7.4 Peripheral or tip velocity should not be greater than 0.8 m/s. To avoid
water entraining, velocity of 0.44 m/s or less is recommended.
7.5 Recommended minimum immersion depth is 1.0-2.0 cm.
7.6 Drum skimmer surface used for model development is polypropylene. But
it is proven to be valid for SS, PVC, and PTFE.
7.7 Skimmer can only be connected to pure oil outlet flow of upstream process.
Influent parameters: Effects of certain parameters, when they are increased, on
the oil removal performance of the process are summarized as follows. For more
details, see chapter 3, Part 3.
8.
Table 1-2 Influent parameters for drum skimmer

Effect on process performance if
the parameter is increased
Parameter
Length of drum
+ is
Diameter of skimmer
+ is
Oil viscosity
Velocity
Present of surfactants
Note:
+ means increases performance, - means decreases performance, means

have both positive and adverse affects, is means effect is insignificant.
464
IV-43
2)
Disk skimmer
1.
Process abbreviation: DSK
2.
Process description : Oleophilic oil disk skimmer
3.
4.

4.1 Graded efficiency: 100% for oil film or layer and 0% for droplet.
4.2 Total efficiency: 100% for oil film or layer and 0% for droplet.
4.3 Graded outlet oil concentration in water outlet flow (Cd): This parameter is
not valid for this process.
4.4 Total outlet oil concentration in water outlet flow (C): This parameter is
not valid for this process.
4.5 Graded outlet oil concentration in oil outlet flow (Coild): The outlet oil in
the oil outlet flow is in pure condition (100% oil).
4.6 Total outlet oil concentration in oil outlet flow(Coil): The outlet oil in the oil
4.7 Inlet flow: the process is valid only for separated oil flow from upstream
process.
4.8 Water outlet flow: This process does not have this property.
4.9 Oil outlet flow: flowrate or oil productivity (m3/h) is governed by the
following equation.
P = CF n
5.
1.328D1.258 N1.212 o
g 0.332
0.452 1.17
I
{2.1}
Related parameters: Related parameters are as summarized in the following table.

Table 2-1 Related parameters of disk skimmer
Parameter

the program
program
Description
CF
Efficiency correction factor, CF 1
CF
Diameter of skimmer
Constant = 9.81
m/s2
Immersion depth of the skimmer, I D/2.
The number of disk
Rotational speed of the skimmer
Oil productivity of two sides of the

skimmer
Kinematics viscosity of oil
num
465
Rev/s
Prod
m3/h
go
kg/s2 or N/m
(= 1000 dyne/cm)
(used /)
m2/s
IV-44
6.
Disk Skimmer (DSK-??)
k
Dis
Scrapper
Fig. 2-1a Icon of disk skimmer
7.
Fig. 2-1b Graphical diagram of disk skimmer
Constraints and limitations.

7.1 Superficial tension of oil is in the range of 27 34 dynes/cm, which
practically covers all common oil.
7.2 Capillary number (Ca = o V/o) is in the range of 0.04 3.6.
7.3 Oil density is around 790 830 kg/m3. Oil dynamic viscosity () tested is
7.4 Peripheral or tip velocity should not be greater than 1.13 m/s. To avoid
water entraining, velocity of 0.5 m/s or less is recommended.
7.5 Disc skimmer surface used for model development is PVC. But it is proven
to be valid for SS, PP, and PTFE.
7.6 Skimmer can only be connected to pure oil outlet flow of the upstream
process.
8.

Table 2-2 Influent parameters for disk skimmer
Parameter
Immersion depth
Diameter of skimmer
+ is
Oil viscosity
Velocity
Present of surfactants
Note:

466
IV-45
3)
Simple decanter
1.
Process abbreviation: SD
2.
Process description: API tank or any decanter that does not have any oil
interceptors installed in the tank so the rising distance of oil drops is equal to the
water depth.
3.
4.

4.1 Graded efficiency (d): Graded efficiency of the process is governed by the
following equation.
d = CF 100%
{3.1}

d = CF
{3.2a}
Ud
100 %
U dc
For oil droplet size, d 20 microns

{3.2b}
d = 0%
Rising velocity (U), m/s, of the droplet d or of the cut size dc is

calculated from the following equations.
Ud =
g (d 10 6 ) 2
{3.3}
18 c
Q
U dc =
3600 S
{3.4}
Cut size is calculated by the following equation.

18Q c
d c =
g S .3600
1/ 2
10 6 micron
{3.5}
4.2 Total efficiency (t):

d max
t =
C od
d min
Co
{3.6}
100 %
4.3 Graded outlet oil concentration in water outlet flow (Cd):

Cd =
4.4
Q
C od (1 d )
Q out
mg/l
{3.7}
Total outlet oil concentration in water outlet flow (C ):

C =
d max
C mg/l
{3.8}
d min
4.5
Graded outlet oil concentration in oil outlet flow (Coild): The outlet oil in
467
IV-46
4.6 Total outlet oil concentration in oil outlet flow (Coil): The outlet oil in the
oil outlet flow is in pure condition (100% oil).
4.7 Inlet flow (Q): Inlet flow of the process is equal to the outlet flow of the
upstream process.
4.8 Water outlet flow (Qout):
Q out = Q (1 ( C o C ) / oil / 1000 )
4.9
m3/h
{3.9}
Oil outlet flow(Qoil):

Q oil = Q Q out
m3/h
{3.10}
4.10 Customized output:

4.10.1 Theoretical cut size (dc): cut size is calculated by eq. 3.5.
5.
Related parameters: Related parameters are as summarized in the following table

Table 3-1 Related parameters of simple decanter
the program
program
Parameter
Description
dc
S
Ud
Udc

Difference between density of dispersed
phase and continuous phase
Density of continuous phase, in this case,
water
wastewater
c
C
d
6.
dc
S
Ud
Udc
Denc-Dend
micron
m2
m/s
m/s
Kg/m3
Denc
Kg/m3
Muc
N.s/m2
(= 1000 cp)
Dend
Kg/m3
L
Influent
Separated
oil layer
Q
Ud
d > cut size
V
d = cut size
d < cut size
Oil droplets
Simple decanter (SD-??)

Fig. 3-1a Icon of simple decanter
Fig. 3-1b Graphical diagram of simple decanter

468
IV-47
7.

7.1 Reynolds number of droplet, Re, is between 10-4 to 1, which is the range
Re =
c U d d
c
{3.11}
7.2 The oil droplets are uniformly distributed across the cross section area of
8.
7.3
d of oil layer is 100%.
7.4
7.5

7.6
Oil outlet point of the process can only be connected to the skimmers only.

Table 3-2 Influent parameters for simple decanter
Parameter
Hydraulic loading rate
Droplet diameter
Note:

469
IV-48
4)
Compact decanter
1.
Process abbreviation: CD
2.
Process description: Parallel plate interceptor, lamella separator, or other types of

plate insertion decanter that the rising distance of the droplets is equally divided
and can be clearly specified.
3.
4.

following equation.
d = CF 100%
{4.1}

d = CF
{4.2a}
Ud
100 %
U dc

{4.2b}
d = 0%
Rising velocity (U) of the droplet d or of the cut size dc is calculated

from the following equations.
Ud =
g (d 10 6 ) 2
18 c
Q
U dc =
3600 S d
m/s
{4.3}

Q
m/s
=
3600 S p ( N + 1) cos
{4.4}
Cut size (micron) is calculated by the following equation.

1/ 2
18Q c
d c =
3600 gS P ( N + 1) cos
10 6 micron
{4.5}

d max
t =
C od
d min
Co
{4.6}
100 %

Cd =
Q
C od (1 d )
Q out
mg/l
{4.7}
4.4 Total outlet oil concentration in water outlet flow (C ):

C =
d max
C mg/l
{4.8}
d min
4.5
Graded outlet oil concentration in oil outlet flow (Coild): The outlet oil in the
470
IV-49
4.6
Total outlet oil concentration in oil outlet flow (Coil): The outlet oil in the oil
4.7
Inlet flow (Q): Inlet flow of the process is equal to the outlet flow of the
upstream process.
4.8
Water outlet flow (Qout):

3
Q out = Q (1 ( C o C ) / oil / 1000 ) m
/h
{4.9}
4.9 Oil outlet flow(Qoil):

Q oil = Q Q out
m3/h
{4.10}

4.10.2 Foot print area of the decanter (S): It is assumed to be identical to
Sp.
5.

Table 4-1 Related parameters of compact decanter
Parameter

the program
program
Description
dc
dc
The number of plates
Sp
Area of one inserted plate (only 1 side and

measured perpendicularly to the plate
surface.)
Sp
m2
Ud
Ud
m/s
Udc
Udc
m/s
Inclination of plate from horizontal axis (090 degree)
incl
degree

Denc-Dend
Kg/m3

water
Denc
Kg/m3

wastewater
Muc
N.s/m2
(= 1000 cp)
Dend
Kg/m3
6.
micron
471
IV-50
Sp
Influent
Q
H
Com
t
p ac
Compact decanter (CD-??)

Inserted plates
(No. of plates = N)
Fig. 4-1a Icon of compact decanter
7.
Fig. 4-1b Graphical diagram of compact decanter

7.1
Reynolds number of droplet, Re, is between 10-4 to 1, which is the range

Re =
c U d d
c
{4.11}
7.2 The oil droplets are uniformly distributed across the cross section area of
8.
7.3
The oil droplet is spherical, which is normally true. d of oil layer is 100%.
7.4

7.5

Table 4-2 Influent parameters for compact decanter
Parameter
Droplet diameter
Inclination of plates (0o = horizontal axis)

Note:
- but helps draining the sludge from

the plate surfaces

472
IV-51
5)
Customized decanter
1.
Process abbreviation: CTD
2.
Process description: Decanter that decanting area or oil interception area is

specified. Decanting area is the area of every surface that can intercept oil
droplets, regardless of rising distance of oil droplets. However, majority of rising
paths should be identical. An example of the decanters is closely inserted plate
interceptor, e.g. Spiraloil.
3.
4.

following equation.
d = CF 100%
{5.1}

d = CF
{5.2a}
Ud
100 %
U dc

{5.2b}
d = 0%
Rising velocity (U) of the droplet d or of the cut size dc is calculated

from the following equations.
Ud =
g (d 10 6 ) 2
18 c
Q
U dc =
3600 S d
m/s
m/s
{5.3}
{5.4}
Cut size is calculated by the following equation.

18Q c
d c =
3600 gS d
4.2
1/ 2
10 6 micron
{5.5}
Total efficiency (t):

d max
t =
C od
d min
Co
{5.6}
100 %

Cd =
Q
C od (1 d )
Q out
mg/l
{5.7}

C =
d max
C mg/l
{5.8}
d min
473
IV-52
4.6
Total outlet oil concentration in oil outlet flow (Coil): The outlet oil in the
4.7
upstream process.
4.8

3
Q out = Q (1 ( C o C ) / oil / 1000 ) m
4.9
/h
{5.9}
Oil outlet flow(Qoil):

Q oil = Q Q out
m3/h
{5.10}

5.

Table 5-1 Related parameters of customized decanter
Parameter
Description
dc
Sd
Cut size
Decanting area ( the area of all surfaces in the
decanter that can intercept oil droplets)
Rising velocity of the droplet at cut size
Difference between density of dispersed phase
and continuous phase
water
Dynamic (or absolute) viscosity of continuous
phase, which is water
Ud
Udc
c
C
d
6.
Variable name in
the program
Unit used in the

program
dc
Sd
micron
m2
Ud
Udc
Denc-Dend
m/s
m/s
Kg/m3
Denc
Kg/m3
Muc
N.s/m2
(= 1000 cp)
Kg/m3
Dend
Sd
Influent
to
Cus
Customized decanter (CTD-??)

Fig. 5-1a Icon of customized decanter
Fig. 5-1b Graphical diagram of customized decanter

474
IV-53
7.

7.1
Reynolds number of droplet, Re, is between 10-4 to 1, which is the range

Re =
8.
c U d d
c
{5.11}
7.2
7.3
7.4
7.5

7.6
7.7
Loading rate of the decanter can be as high as 14.1-54 m/h.
7.8
Calculated efficiencies of closely inserted plate interceptor are usually

lower than observed values. Prediction of cut size is relatively accurate so
the difference of 20% can be expected.

Table 5-2 Influent parameters for customized decanter
Parameter
Effect on process performance if the parameter

is increased
Droplet diameter
Inclination of plates (0o = horizontal axis)
- but helps draining the sludge from the plate

surfaces
Decanting area
Rising distance of oil
+
- but too small distance may cause clogging.
Note:
- for closely inserted plate interceptor

475
IV-54
6)
1.
Process abbreviation: GCC
2.
Process description: Granular bed coalescer in this program is based on upflow

pattern. However, it can be applied to downflow coalescer since the rising
velocity of droplet are usually small, compared to flow velocity. So relative
velocity between oil droplets and bed can be safely assumed to equal flow
velocity.
3.
4.

4.1
Graded efficiency (d): Graded efficiency of the process is governed by the

following equation.
d 10 6 0.2 H 0.12 c dpV 0.08 d 0.09 0.09

d = CF 0.58(
) ( ) (
)
( ) ( ) 100%
dp
dp
ow
c
c
And d 100%
{6.1}
{6.2}

d max
t =
C od
{6.3}
100 %
d min
Co

Cd =
Q
C od (1 d )
Q out
mg/l
{6.4}

C =
d max
C mg/l
{6.5}
d min
upstream process.
Q out = Q (1 ( C o C ) / oil / 1000 )
m3/h
{6.6}

Q oil = Q Q out
m3/h
{6.7}

4.10.1 Theoretical cut size (dc): Cut size is calculated from eq. 6.1 by
assuming that the graded efficiency is 100%.
476
IV-55
4.10.2 Range of pressure drop (P): Pressure drop is calculated from

Kozeny-Carman equation, as shown in eq. 6.8. Recommended
minimum and maximum value of porosity are 0.13 and 0.23,
respectively.
P=
5.
180 HcV (1 ) 2
m
c g dp 2 3
{6.8}

Table 6-1 Related parameters of granular bed coalescer
Parameter

the program
program
Description
dc
dp
Cut size
Diameter of collector or bed material
dc
dpc
micron
m
Bed height (height of granular bed)
Pressure drop across the bed
Pdropmin,
Pdropmax
Flow velocity or empty bed velocity
m/s
Porosity or void ratio of the bed (= void

volume / total volume)
Constant 0.13 and

0.23
gow
kg/s2 or N/m
(= 1000 dyne/cm)

Denc-Dend
Kg/m3

water
Denc
Kg/m3

wastewater
Muc
N.s/m2
(= 1000 cp)

dispersed phase, which is oil, for oily
wastewater
Mud
N.s/m2
(= 1000 cp)
Density of dispersed phase, in this case,

oil
Dend
Kg/m3
ow
6.
477
IV-56
Oil outlet
Cross section area

=A
Bed height
=H
Collector
size = dp
Void ratio =
Granular bed
coalescer
(GCC-??)
Fig. 6-1a Icon of granular bed coalescer
7.
Velocity = V
=Q/A
Effluent
Influent
Flow = Q
Fig. 6-1b Graphical diagram of granular bed

coalescer

7.1
Coalescer bed shall be oleophilic and relatively spherical in shape.
7.2
Tested size of bed media (dp) is between 0.20 1.0 mm. The larger the
media size, the lower the efficiency.
7.3
Tested range of bed height (H) of the model is between 1 to 10 cm.

However, bed height as low as 1 cm is not recommended. The greater the
bed height, the safer the coalescer operation. However, it also results in
higher pressure drop.
7.4
The velocity (V) should be in the range of 0.09 to 0.54 cm/s or 3.2 to
19.4 m/h.
7.5
Tested interfacial tension (ow) is between 11 to 42 dyne/cm or 0.011 to

0.042 N/m. (i.e. T.I.O.A, Heptane, Anisole, Toluene and Kerosene)
7.6
Different density between dispersed phase (oil) and continuous phase

(water) () is between 80 to 315 kg/m3 (approx.).
7.7
The equation is valid for droplet size (d) of 10 microns or bigger. For
smaller droplets, result from the equation may not be accurate because it
is beyond the data range that has been used to verify the model.
7.8
The model is valid for inlet concentration between 100 to 1,000 mg/l. At
higher concentration, mousse or jet formation may occur, resulting in
unpredictable decreasing of the efficiency.
7.9
7.10
Within the valid range of model, error in efficiency prediction is less than
10%.
7.11
Oil outlet point of the process can only be connected to the skimmers
only.
478
IV-57
7.12
8.
Recommended minimum and maximum value of porosity are 0.13 and

0.23, respectively. For pressure drop calculation, since wastewater is
rather diluted, it is assumed that density and viscosity of water is used in
the equation.

Table 6-2 Influent parameters of granular bed coalescer
Parameter
Empty bed velocity
Droplet diameter
Collector or bed material diameter
Hydrophilicity of bed
Surface roughness of bed
Bed height
Ratio of oil to water
Temperature
Note:

479
IV-58
7)
1.
Process abbreviation: BCC
2.
Process description: Brush type bed coalescer refers to the coalescer whose
fibrous elements are in aligned neatly in radial direction, like bottlebrush.
3.
4.

4.1

following equation.
d = CF 104.5(
cVD 0.77 d 10 6 0.18 d F 0.18

(1 )0.35 ( H )0.694 100% {7.1}
)
(
) ( )
D
D
D
c
And d 100%
{7.2}

d max
t =
C od
{7.3}
100 %
d min
Co

Cd =
Q
C od (1 d )
Q out
mg/l
{7.4}

C =
d max
C mg/l
{7.5}
d min
upstream process.
Q out = Q (1 ( C o C ) / oil / 1000 )
m3/h
{7.6}

Q oil = Q Q out
m3/h
{7.7}

4.10.1
4.10.2
Theoretical cut size (dc): Cut size is calculated from eq. 7.1 by
Pressure drop (P): Pressure drop is calculated from Hazen
William equation, using equivalent length of the coaleser. The
equivalent length is assumed to be 5 times of the actual length of
coalescer column.
480
IV-59
V
P = 6.82
CHW
5.
1.85
1.167
5H
m {7.8}

Table 7-1 Related parameters of brush type bed coalescer
Variable name in
the program
Parameter
Description
CHW
Hazen Williams C, depanding on material. C

of 130 is recommended for steel column.
Unit used in the

program
Constant = 130
dc
Cut size
dc
micron
Diameter of coalescer column or of brush,

which should be relatively closed.
Dcc
dF
Diameter of fiber element
dF
Pdrop
By calculation
m/s

volume / total volume) (must be < 1)
Void
Density of continuous phase, in this case, water
Denc
Kg/m3

phase, which is water, for oily wastewater
Muc
N.s/m2
(= 1000 cp)
Dend
Kg/m3
6.
Oil outlet
Cross section area

=A
Bed height
=H
Fiber element
size = dF
Void ratio =
Brush type bed

coalescer
(BCC-??)
Fig. 7-1a Icon of brush type bed coalescer
Velocity = V
=Q/A
Effluent
Influent
Flow = Q
Fig. 7-1b Graphical diagram of brush type bed

coalescer
481
IV-60
7.
8.

7.1
48 < Re < 1100. Re is the term (cVD/c) in the equation. 1 < H/D < 10.
7.2
Diameter of coalescer bed (D) tested is around 5.0 cm. Using bigger
coalescer diameter may cause deflection at the tips of fibers because of
longer overhung length, which may cause channeling of untreated
wastewater and error in efficiency calculation.
7.3
The model is valid for droplet size (d) of 1 micron and greater.
7.4
Empty bed velocity (V) is between 0.5 to 5.0 cm/s (1.8 to 180 m/h).
However available raw data used to verify the model is between 0.5 to
2.0 cm/s. Using velocity > 2.0 cm/s may cause unpredictable error on
7.5
Fiber size (dF) is between 40 to 200 microns. However available raw data
used to verify the model is between 100 to 200 microns. Using fiber size
< 100 microns may cause unpredictable error on calculated efficiency.
7.6
Void ratio of the bed () is around 0.845 to 0.96.
7.7
7.8
The model is verified at inlet oil concentration up to 1000 mg/l. Applying

the model to the concentration > 1000 mg/l will cause underestimation of
predicted efficiency.
7.9
The beds used in these researches vary from bottle brush type, simple
spiral type and combination of internal bed of simple spiral and
concentric coil springlike external bed with the tip of the fibers
pointed to the centerline. However, they are all oleophilic. There is some
difference in efficiency between each type, but there is too few data to
make a conclusion. However, because of its rigidity, the simple spiral in
coil springlike bed tends to operate more stable without decreasing in
efficiency with time, while others tend to be deflected by weight of
accumulated oil drops.
7.10
7.11
20%.
7.12
only.

482
IV-61
Table 7-2 Influent parameters of brush type bed coalescer

Parameter
Empty bed velocity
Droplet diameter
Coalescer diameter
Porosity
Bed height
Tortousity of bed
Temperature
Note:

483
IV-62
8)
1.
Process abbreviation: DCC
2.
Process description: Dynamic fibrous bed coalescer is actually the brush type
bed coalescer whose bed is rotated by outside prime mover.
3.
4.

4.1

following equation.
d = CF 1.76(
cVD 0.21 d 0.58 d F 0.58

(1 )0.35 ( H ) 0.35 ( D N ) 0.53 100% {8.1}
)
( ) ( )
c
D
D
D
V
And d 100%
{8.2}

d max
t =
C od
{8.3}
100 %
d min
Co

Cd =
Q
C od (1 d )
Q out
mg/l
{8.4}

C =
d max
C mg/l
{8.5}
d min
upstream process.
3
Q out = Q (1 ( C o C ) / oil / 1000 ) m
/h
{8.6}

Q oil = Q Q out
m3/h
{8.7}

4.10.1
4.10.2
484
IV-63

coalescer column.
V
P = 6.82
CHW
5.
1.85
1.167
5H
{8.8}

Table 8-1 Related parameters of dynamic fibrous bed coalescer
Variable name in
the program
Parameter
Description
CHW
Hazen Williams C, depanding on material. C

of 130 is recommended for steel column.
Unit used in the

program
Constant = 130
dc
Cut size
dc
micron
Diameter of coalescer column or of brush,

Rotating speed of bed
volume / total volume)
Density of continuous phase, in this case, water
Dcc
dF
H
N
Pdrop
By calculation
void
m
m
Rev/s
m
m/s
Denc
Muc
Kg/m3
N.s/m2
(= 1000 cp)
Kg/m3
dF
H
N
P
V
c
C
d
6.
Dend
Oil outlet
Cross section area

=A
N rev/s
Bed height
=H
Fiber element
size = dF
Void ratio =
Dynamic bed
coalescer
(DCC-??)
Fig. 8-1a Icon of dynamic fibrous bed

coalescer
Velocity = V
=Q/A
Effluent
Influent
Influent
Flow = Q
Fig. 8-1b Graphical diagram of dynamic fibrous

bed coalescer
485
IV-64
7.

7.1
7.2 1 < H/D < 2. Using H/D > 2 in the model can be also applied for
comparison purpose only. However, the maximum H/D is 6.
7.3 Rotating speed of the bed (N) is between 0.167 to 3.33 rps (10 to 200 rpm).
Please note that N is in the form of revolution per unit time, not radian per
unit time). Recommended minimum rotating speed is 75 rpm. Using lower
speed may not provide any additional benefit over simple fibrous bed
coalescer because the effect of rotating on interception probability may be
cancelled out by the shear effect, which causes fragmentation of oil drops.
7.4 Empty bed velocity (V) is between 0.1 to 1.1 cm/s (3.6 to 39.6 m/h).
7.5 Diameter of fiber (dF) is around 100 to 300 microns
7.6 Diameter of coalescer bed (D) is not greater than 11.5 cm. Using bigger
diameter may cause deflection at the end of fibers from longer overhung
lengths, which may cause channeling of untreated wastewater and error in
calculation.
7.7 It is recommended to use the model only for the droplet size (d) of 10
microns or greater. For smaller droplet, the model can also be applied, but
for comparison purpose only.
7.8 The beds, used in the experiment, are bottle brush types, made of
oleophilic polyamide or polypropylene with stainless steel shaft. The area
of shaft should not be greater than 30% of cross section area of the bed
otherwise it will affect the efficiency.
7.9 Void ratio of the bed () is around 0.845 to 0.96
7.10 d of oil layer is 100%.
7.11 Within the valid range of model, error in efficiency prediction is less than
10%.
7.12 Oil outlet point of the process can only be connected to the skimmers only.
8.

486
IV-65
Table 8-2 Influent parameters of dynamic fibrous bed coalescer

Parameter
Empty bed velocity
Droplet diameter
Coalescer diameter
Rotating speed
+ within the upper limit
Porosity
Bed height
Tortousity of bed
Temperature
Note:

487
IV-66
9)
1.
Process abbreviation: WCC
2.
Process description: Metal wool bed coalescer is one of fibrous bed coalescer
that uses disorderly (random) or woven fiber material, like steel wool for kitchen
use, as a bed. The bed is actually not necessary to be of metal. It is just named to
refer to general appearance of bed.
3.
4.

4.1

following equation.
d = CF 3.35(
cVD 0.23 d 0.03 d F 0..03 H 0.36

)
( ) ( )
( ) 100%
c
D
D
D
And d 100%
4.2
{9.1}
{9.2}

d max
t =
C od
{9.3}
100 %
d min
Co

Cd =
Q
C od (1 d )
Q out
mg/l
{9.4}

C =
d max
C mg/l
{9.5}
d min
upstream process.
Q out = Q (1 ( C o C ) / oil / 1000 )
m3/h
{9.6}

Q oil = Q Q out
m3/h
{9.7}

4.10.1
488
IV-67
4.10.2

coalescer column.
V
P = 6.82
CHW
5.
1.85
1.167
5H
{9.8}

Table 9-1 Related parameters of metal wool bed coalescer
Parameter
CHW
dc
D

the program
program
Description
Hazen Williams C, depanding on

material. C of 130 is recommended for
steel column.
Cut size
Diameter of coalescer column or of bed,
Constant = 130
dc
Dcc
micron
m
dF
dF
Pdrop
By calculation
m/s

water
Denc
Kg/m3

wastewater
Muc
N.s/m2
(= 1000 cp)
Dend
Kg/m3
6.
489
IV-68
Oil outlet
Cross section area
=A
Bed height
=H
Collector
size = dp
Void ratio =
Metal wool bed

coalescer
(WCC-??)
Fig. 9-1a Icon of metal wool bed coalescer

7.
8.
Velocity = V
=Q/A
Effluent
Influent
Flow = Q
Fig. 9-1b Graphical diagram of metal wool bed

coalescer

7.1
The beds used in the experiment are highly disorderly bulk of stainless
steel fiber, dF = 75 microns, and steel wool, dF = 40 microns (see fig.
5.4.1-4). However, only the latter case, which raw experimental data is
available, is used to develop the model. The minimum size of oil droplet
tested is 1 micron.
7.2
Tested Reynolds number is between 840 to 2470.
7.3
Porosity of the bed () is around 0.95. But there is not sufficient data to
include it into the model.
7.4
Diameter of the coalescer (D) = 5 cm. However, according to rigidity

and, controversially, density uniformity of this type of bed, the diameter
in the model should be scaled up or down without causing serious error.
7.5
Height of the coalescer bed (H) is between 0.07 to 0.21 m.
7.6
Velocity (V) is between 1 to 2.5 cm/s or 36 to 90 m/h.
7.7
7.8
7.9
10%.
7.10
only.

490
IV-69
Table 9-2 Influent parameters of metal wool bed coalescer

Parameter

is increased
Empty bed velocity
Droplet diameter
Coalescer diameter
Porosity
not sufficient data to verify but should be -
Bed height
Tortousity of bed
+ but can cause clogging
Temperature
Note:

491
IV-70
10)
1.
Process abbreviation: DAF
2.
Process description: Dissolved air flotation (DAF) in this case does not include
the coagulation/flocculation process, which is separated into another module.
3.
4.

4.1 Graded efficiency (d): Graded efficiency of the process is governed by
SIEMs model (INSA thesis 1983) and its scale-up procedure, derived in
the scope of work of this program.
SIEMs model
d ,ref = CF (1 e
3
H
( exp ) )
2 AV
db
) 100%
( exp ) = 0.009005( theo ) 0.5919
{10.1}
{10.2}

3 d 10 6 2
)
2
db
{10.3}
g (d 10 6 ) 2
18 cVr
{10.4}
Int = (
sed =
Diff = 0.9(
Vr = U b =
K (T + 273) 2 / 3
)
c dVr d b
air / water gd b2
18 c
And d 100%
{10.5}
{10.6}
{10.7}
The model is valid only when /AV = 0.0516. However H can vary.
Scale-up from SIEMs condition by population balance method
1)
Calculate the reference efficiency (d,ref) of the model at required

height (Hreq), average bubble diameter (db) and droplet sizes (d) using
eq. 10.1 to eq.10.7. Use /AV = 0.0516 in order that the operating
condition of SIEM still holds.
2)
Scale up the area from 0.01767 m2 (Amodel) to required area (Areq). At

this step, SIEMs operating condition still holds. So efficiency from
above equations remains the same. This required area could be
approximated from recommended hydraulic loading rate (Vreq) and
ratio of pressurized water to wastewater ((Qpw/Q)req). Refer to
reference for more detail.
Areq
Q req 1 + ( pw ) req
Q
=
V req
492
{10.8}
IV-71
3)
Find ref, corresponding to the area Areq, by following equation,

ref =
4)
Areq
Amod el
mod el =
4.2 10 7 Areq
0.01767
m3/s
{10.9}
Find ref, corresponding to the height Hreq, by following equation,

ref =
H req
H mod el
mod el =
1
0.00046 3600
H req
Hour
{2.610.10}
Change and from SIEMs condition by population balance model

5)
From population balance method, calculate 2,ref corresponding to

Areq, Hreq, ref and ref from the reference efficiency (from item 1)) by
the following equations. Please note that, at this point, SIEMs
condition still holds. 2,req has to be calculated separately for each
droplet diameter.
ln(1 d , ref )
{10.11}
2, ref =
ref ref
Or
(
)
{10.12}
d ,ref = 1 e
2 , ref
6)
ref ref
Find req from required ratio of pressurized water to wastewater (see

reference for the recommended value) by following equations.
V
V
Q m3/s
{10.13a}
= air Q pw = air R
V pw
3600
V pw
Then, from Henrys law

= y ( P Patm ) (T + 273 ) ( 0 . 082 10 3 m 3 /( mol K )) H R Q
{10.13b}
For air, y = 1. H is Henrys constant as molair/(m water.atm). Henrys

constant of air can be calculated from the following equation.
{10.14}
H = ( 0 . 00002 T 3 + 0 . 0039 T 2 0 . 2745 T + 12 . 472 ) 10 1
7)
Choose req from recommended criteria (see reference).
8)
To change and from SIEMs, the following procedure is

recommended and precautions should be noted.
In this case, 2 is assumed to remain the same and be equal to

2,ref. req and ref are used. The efficiency can be estimated by eq.
10.15a.
(
)
{10.15a}
d = 1 e
2 , ref
req ref
The calculated efficiency will be lower than the real value.
In this case, 2 = 2,ref. req and req are used. The efficiency can
be calculated by eq. 10.15b. The calculated efficiency will be
(
)
{10.15b}
d = 1 e
2 , ref
req req
493
IV-72
Like the former case, the efficiency can be calculated by eq.

10.15b.
This case is not feasible because it means that we have to

decrease wastewater flowrate and increase pressurized water
flowrate.
There is no obvious limit for the 4 adaptations, shown above.
However it is recommended to use the values of each parameter
(d, db, C, etc.) within general range (see reference).
It must be noted that the graded efficiency in this case is independent of
source of water that is used as pressurized water.
4.2 Total efficiency (t): The value depends on the source of water that is used
as pressurized water. In the program, it is assumed that DAF effluent is
used to prepare pressurized water.
(C o C )
100 %
Co
t =
{10.16a}
4.3 Graded outlet oil concentration in water outlet flow (Cd): In the program, it
is assumed that DAF effluent is used to prepare pressurized water. Thus
residual oil in the effluent is recycled. So oil of certain droplet sizes may
accumulate in the system, depending on their d.
Cd =
Q
(1 d ) C od , dil
Q out
C od , dil =
((
mg/l
{10.17}
R
(1 d )) r max 1 1 )
C Q
1+R
od
R
Qt
(1 d ) 1
1+R
mg/l
{10.18}
The rmax is an assumed number of loop, which effluent is recycled until the
concentration reaches steady stage. Ideally, rmax must approach infinity.
However, the value of rmax in the program is set at 30, which is generally
sufficient to make the equation reach steady stage (esp. when d > 20%). If
the value of Cod,dil from r = 30 differs from Cod, dil at r = 29 more than 10%,
the program will display the warning box, showing that the oil may
accumulate in the system.
C =
d max
C mg/l
{10.19}
d min
upstream process.
494
IV-73

Q out = Q (1 ( C o C ) / oil / 1000 )
m3/h
{10.20}

3
Q oil = Q Q oil m /h
{10.21}

4.10.1
Ratio of air/oil (W/W)

air 3600
W air
= req
1000
W oil
Q C0
4.10.2
kg air / kg oil
{10.22}
Theoretical energy (watt) required for air compressor:

R (T + 273 )
Power = air
comp 0 . 4
1 . 4 1
(
)
1 .4
Conc ( air )
P
Q pw
Patm
( MW ( air ) / 1000 )
{10.23}
Rair = universal gas constant (8.314)

Conc .( air ) =
4.10.3
y P MW ( air ) H
1000
mg/l
{10.24}
Theoretical energy required for pressurized water pump:

Power =
Q pw ( P Patm )
3600 pump
R Q c g ( P Patm ) 10
3600 pump
watt {10.25}
P is measured in atm.
4.10.4

V =
4.10.5
m/h
{10.25}
Retention time (based on total flow (Q+Qpressurized water):

=
5.
Q (1 + R )
A
H
60
V
min
{10.25}

Table 10-1 Related parameters of DAF
Parameter
Description
Variable name in
the program
Unit used in the

program
Cross section area of DAF column
m2
db
Diameter of bubble
db
Column height
DAFH
Absolute pressure of saturator
DAFP
atm
Recycled ratio (R = Q pressurized water/Q)
comp, pump
Note:
Efficiency of air compressor and pressurized

water pump (always < 100%, 60-70% is
recommended)
R
Constant = 70%
Other parameters are internally used. Users do not need to input. For list of others
parameters, see reference.
495
IV-74
6.
Area = A
Oil outlet
Influent
Effluent

(DAF-??)
Pressurized water
flow = Qpw
Fig. 10-1a Icon of DAF

7.
Fig. 10-1b Graphical diagram of DAF

7.1 Inlet oil concentration should not be greater than 1,200 mg/l (before
dilution) or 435 mg/l (after dilution). Using the model with higher oil
concentration will result in underestimating of efficiency.
7.2 SIEMs model is tested at the following operating condition;
/AV = 0.0516. Only this value must be used in the equations. As

long as this value is fixed, SIEMs operating condition still holds and
the model is still valid.
Retention time, based on total flowrate (Qt), is around 25 minutes.
Diameter of air bubbles (db) varies from 15 to 130 microns. Tested
average bubble diameter is 70 microns, which is used to verify the
model, and standard deviation of bubble diameters is 34.5 microns. The
range of bubble sizes is common for commercial pressurized water
system or saturator. The pressure of the test system is 4 atm (absolute).
Tested air flowrate () is 0.42 cm3/s (4.2e-7 m3/s).
Tested wastewater flowrate (Q) is 3.9 cm3/s (3.9e-6 m3/s)
Tested water depth (H) is 0.70 m. H can be freely changed as long as
(/AV) is fixed. Anyway, H around 1.8 to 2.7 is recommended by API.
Diameter of flotation column is 0.15 m Cross section area of column
(A) is 0.01767 m2.
Ratio of number of bubble/ oil droplet tested is around 1.4 oil droplet/ 1
air bubble.
Hydraulic loading rate or flow velocity (V), based on Qt, is 1.6 m/h
7.3 Within the valid range of model, error in efficiency prediction is less than
20%. If SIEMs condition does not holds and procedure described in item
8) is used, error in efficiency prediction depends on difference between
496
IV-75
SIEMs and actual condition. However, the predicted efficiency is usually

lower than actual value.
7.4 d of oil layer is 100%.
7.6 It is assumed that DAF is operated at Patm. Thus Equations and some
constants, e.g. air density, are fixed and valid for Patm only.
8.

Table 10-2 Influent parameters of DAF
Parameter

is increased
Retention time
Droplet diameter
Diameter of bubble
Air flowrate
Column height
+
see reference
Presence of transfer compound

Turbulence in column
see reference
Note:

497
IV-76
11)
1.
Process abbreviation: 2CY
2.
Process description: The process is based on THEW type, liquid-liquid

hydrocyclone.
3.
4.

following equation.
For d dc, = 100%
{11.1}
For d < dc,

D
(0.186 n ) 2
2
=
100%
d
Dn 2
D
((
) (0.186 n ) 2
2
2
(R
{11.2}
Rd (Radial distance from axial axis to entry position of droplet d

(Z=0))can be calculated from the following equations. If Rd in eq. 11.3a is
equal to Dn/2, the corresponding d will be equal to dc.
R
d dR L dZ
=
U 0W
R
zvv
U=
{11.3a}
(d 10- 6 ) 2 V 2 m/s
18
R
V=(
{11.3b}
Q D n 0.65 m/s
)(
)
D 2 R
i
{11.3c}
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
Wz =
(0.5D n Z tan( )) 2
R
+ 1.19
Rz
m/s
{11.3d}
{11.3e}
Rz =
L=
Dn
Z tan( ) m
2
2
{11.3f}
0.25( Dn )
{11.3g}
tan(1.5 o / 2)
For THEWs type hydrocyclone, when Z = L:

{11.3f}
RVZZ = 0.186( D n / 2)
4.2

t =
1
Co
d max
d C od
(1 R
d min
{11.4}
100 %
498
IV-77

Cd =
(1 d ) C od
(1 R f )
mg/l
{11.5}

C =
d max
C mg/l
{11.6}
d min
4.5 Graded outlet oil concentration in oil outlet flow (Coild): Unlike other true
separation process, hydrocyclone only concentrates oil. Thus concentrated
oily wastewater, not pure oil, is obtained at oil outlet (overflow) port.
C oild = C d ,overflow =
d C od mg/l
{11.7}
Rf
4.6 Total outlet oil concentration in oil outlet flow (Coil):

C oil =
d max
oild
mg/l
{11.8}
d min
upstream process.
Q out = Q (1 R f )
m3/h
{11.9}

Q oil = Q R f
m3/h
{11.10}

4.10.1
4.10.2
Theoretical cut size (dc): Cut size is calculated from item 4.1.
Pressure drop (P): Pressure drops across inlet/overflow (Po) and
inlet/underflow (Pu) ports of 2-phase hydrocyclone are governed
by the following equations.
(Q / 3600) 2.3
Po = 16
4
Dn
Pu = 4.6
5.
2.6
(1 R )
f
(Q / 3600) 2.2 bar

4
Dn
0.1611
bar {11.11a}
{11.11b}
499
IV-78
Table 11-1 Related parameters of two-phase hydrocyclone

Parameter
dc
Dn
Rf
Note:
Variable name Unit used in the

in the program
program
Description
Cut size
Nominal diameter of hydrocyclone
dc
Dn
micron
m
Rf
Split ratio (Qoverflow/Q), Rf < 1.

Recommended value of Qoil is 1.8 to 2
times of inlet oil flowrate.
6.
L1
L
Oil out
Do
2-phase
hydrocyclone
(2CY-??)
Di
L3
Ds
Dn
Water out
Water in
Dn/D=0.5, Ds/D=0.25, Do/D<0.05, L1/D=1, L3/D=15-20 ,

=1.50o, =20o,Di/D=0.25 for 1 inlet and 0.175 for 2 inlet ports,
total length/D =45 (approx.)
Fig. 11-1a Icon of 2-phase

hydrocyclone
7.
Fig. 11-1b Graphical diagram of 2-phase hydrocyclone

7.1
The model is valid for THEW hydrocyclone or other cyclones with

relative identical geometry.
7.2

comparison only. In analysis mode and design mode when Find
efficiency is selected, efficiencies of droplets smaller than 20 microns
are assumed to be 0%. d of oil is 100%.
7.3
The equations are valid for the hydrocyclone with 2 inlet ports only.
7.4
Overflow quantity (Qoveflow) is usually small, not greater than 10%. Its
effect on velocity profiles and efficiency is small, thus, negligible.
Recommended Qoveflow is 1.8 to 2 times of inlet oil flowrate.
7.5
The model tends to predict lower efficiency when d < d80% and higher
efficiency when d > d80%. Error of cut size prediction is around 10-20%,
500
IV-79
e.g. if predicted cut size is 50 microns, observed cut size should be

around 40 45 microns. For more details, see reference.
7.6
8.
Graded efficiency (d) in this case is based on ratio between outlet oil
quantity at water outlet port to that of inlet wastewater. Effect of split
flow is not yet taken into account.

Table 11-2 Influent parameters of two-phase hydrocyclone
Parameter
Flowrate
Droplet diameter
Split ratio
is
Inlet oil concentration
is
Pressure drop
Temperature
Note: + means increases performance, - means decreases performance, means

501
IV-80
12)
1.
Process abbreviation: 3CY
2.
Process description: The process is based on 3-phase hydrocyclone, initiated by

MA and AURELLE. Geometry of liquid-liquid separation of the hydrocyclone is
based on Thew type. For solid-liquid, it is based on Rietema type. It can be used
for simultaneous separation of oil and suspended solids from wastewater.
Calculation procedure and equation are relatively identical to that of 2-phase
cyclone with only little modification. Solid removal efficiency is not included in
this program.
3.
4.

following equations. Dn in this case is equal to Do and L is equal to L5 (See
graphical diagram).
For d dc, = 100%
{12.1}
For d < dc,

D
(0.186 n ) 2
2
=
100%
d
Dn 2
D
((
) (0.186 n ) 2
2
2
(R
{12.2}
Rd (Radial distance from axial axis to entry position of droplet d

(Z=0))can be calculated from the following equations. If Rd in eq. 12.3a is
equal to Dn/2, the corresponding d will be equal to dc.
R
d dR L dZ
=
U 0W
R
zvv
{12.3a}
(d 10- 6 ) 2 V 2
18
R
{12.3b}
(Q/2) D
( n ) 0.65
V = 0.676
D2 R
4 i
{12.3c}
U=
R
W
R
= 3.33 + 12
8.63
Wz
Rz
Rz
Wz =
Rz =
L=
R
+ 1.19
Rz
Q
(0.5D n Z tan( /2)) 2
Dn
Z tan( )
2
2
{12.3d}
{12.3e}
{12.3f}
0.25( Dn )
tan(1.5 o / 2)
{12.3g}
502
IV-81
For THEWs part hydrocyclone, when Z = L:

{12.3f}
RVZZ = 0.186( Dn / 2)

1
Co
t =
d max
d C od
d min
(1 R
{12.4}
100 %

Cd =
(1 d ) C od
(1 R f )
mg/l
{12.5}

C =
d max
C mg/l
12.6}
d min
4.5
Graded outlet oil concentration in oil outlet flow (Coild): Unlike other true
separation process, hydrocyclone only concentrate oil. Thus concentrated
oily wastewater, not pure oil, is obtained at oil outlet (overflow) port.
C oild =
4.6
d C od mg/l
{12.7}
Rf
Total outlet oil concentration in oil outlet flow (Coil):

C oil =
d max
oild
mg/l
{12.8}
d min
4.7
upstream process.
4.8

Q out = Q (1 R f R SS )
m3/h
{12.9}

Q oil = Q R f
m3/h
{12.10}

4.10.1
4.10.2
4.10.3
Theoretical cut size (dc): Cut size is calculated from item 4.1.
Purged flow for SS removal:
{12.11}
Q ss = Q R SS
Pressure drop (P): Pressure drops across inlet/overflow (Po) and
inlet/underflow (Pu) ports of 2-phase hydrocyclone are governed
by the following equations.
Pwater = 49.8
Pss = 21
(Q/3600) 2.12 bar

D4
{12.12a}
(Q/3600) 2.34 bar

D4
{12.12b}
(Q/3600) 2.03 bar

D4
{12.12c}
P = 55
oil
503
IV-82
Please not that RSS is not included in the model so the pressure drop for SS
port and water port are estimated value only. But for oil port, Rf is usually
small so Poil is relatively accurate and hardly affected by Rf.
5.

Table 12-1 Related parameters of three-phase hydrocyclone
Parameter
dc

in the program
program
Description
Cut size
Diameter of the biggest cylinder of

hydrocyclone (refer to related graphic)
Rf
Split ratio (Qoil /Q), Rf < 1.

Recommended value of Qoil is 1.8 to 2
times of inlet oil flowrate.
RSS
Split ratio (QSS/Q). Recommended value

is 0.2.
Note:
dc
micron
D3cy
1. Other parameters are internally used. Users do not need to input. For list of others
2. Rss is calculated by Yoshioka and Hotta relation [30]: 1-Rf=0.95/((Du/Ds)4+1).
6.
Solid-liquid part

Di
Du
D Do
Dp
Ds
L4
L3
3-phase
hydrocyclone
(3CY-??)
L1
L5
L3
Note: Di/D=0.25 for 1- inlet and 0.175 for 2- inlet,

Do/D=0.43,Ds/D=0.28, Du/D=0.19, Dp/D=0.034,
L1/D=0.4,L2/D=5, L3/D=15, L4/D=0.3, Solid-liquid part cone
angle=12o, for liquid-liquid part=1.5o
Fig. 12-1a Icon of 3-phase

hydrocyclone
7.
Fig. 12-1b Graphical diagram of 3-phase hydrocyclone

7.1
The model is valid for THEW hydrocyclone or other cyclones with relative
identical geometry.
504
IV-83
7.2

comparison only. In analysis mode and design mode when Find
efficiency is selected, efficiencies of droplets smaller than 20 microns are
assumed to be 0%. d of oil is 100%.
7.3 The equations are valid for the hydrocyclone with 2 inlet ports only.
Purged quantity at oil outlet port (Qoil) is usually small, not greater than
10%. Its effect on velocity profiles and efficiency is small, thus, negligible.
7.4
7.5 The model tends to predict lower efficiency when d < d80% and higher
efficiency when d > d80%. Error of cut size prediction is around 10-20%,
e.g. if predicted cut size is 50 microns, observed cut size should be around
40 45 microns. For more details, see reference.
7.6
SS removal coefficient is not calculated since it is not major scope of work

of this thesis so it cannot connect to other model. Only purged flow of SS
port is calculated
7.7
RSS is not included in the model so the pressure drop for SS port and water
port are estimated value only. But for oil port, Rf is usually small so Poil is
relatively accurate and hardly affected by Rf.
7.8 Graded efficiency (d) in this case is based on ratio between outlet oil
quantity at water outlet port to that of inlet wastewater. Effect of split flow
is not yet taken into account.
8.

Table 12-2 Influent parameters of three-phase hydrocyclone

Parameter
Flowrate
Droplet diameter
Split ratio (Rf)
is
Inlet oil concentration
is
Pressure drop
Temperature
Note:

505
IV-84
13)
Ultrafiltration
1.
Process abbreviation: UF
2.
Process description: Flux calculation of UF in the program is based on film

model and resistance model. Flux prediction is available in DESIGN mode only.
3.
4.

4.1 Graded efficiency (d): For stabilized emulsion wastewater, oil removal
efficiency of UF can be safely assume to be 100%. The program will use
the value of CF.100%.
{13.1a}
d = CF 100 %
For wastewater containing free oil or non -stabilized emulsion, the

efficiency is lower but, somehow, unpredictable. Anyway, for such
wastewater, the use of UF is not necessary. However the program will,
nonetheless, assume that the efficiency is CF.100%.
4.2
Total efficiency (t): Total efficiency falls into the same case as that of
hydrocyclone. For UF, users normally set their final volume of filtrated
wastewater or retentate (Volretentate), which will be used for total efficiency
calculation. UF calculation in the program is based on batch system
without additional feed during operation period. So the concentration
depends on initial wastewater volume (Volo) and feed duration (tf)
t =
1
Co
d max
d min
(1 d ) C od
1
100 % =
Vol retentate
C
o
(1
)
Vol o
d max
d min
(1 d ) C od
100 %
1
(1 )
F
{13.1b}
F is factor of concentration, which is specified by user.

Cd =
(1 d ) C od
Vol retentate
(1
)
Vol o
mg/l
{13.2}

C =
d max
C mg/l
{13.3}
d min
4.5 Graded outlet oil concentration in oil outlet flow (Coild): Unlike other true
separation process, UF only concentrate oil. Thus concentrated oily
wastewater, not pure oil, is obtained as retentate. Granulometries of the
retentate were not studied. Coalescence and partial destabilization, which
leads to formation of oil film, were reported. However, to be on the safe
side, the program will assume that there is no coalesce occurring.
C oild =
d C od
= d C od F
(Vol retentate / Vol o )
506
mg/l
{13.4}
IV-85
4.6
Total outlet oil concentration in oil outlet flow (Coil):

C oil =
d max
oild
mg/l
{13.5}
d min
upstream process.
4.8 Water outlet flow (Qout): Actual water outlet flow from the membrane is the
product of permeate flux, which varies with time, and membrane area.
However, since the process is usually designed as batch system, outlet flow
can be chosen freely, providing that permeate storage tank is big enough.
User can freely specify permeate discharge time (td). To imitate a
continuous process, it can be assumes that default permeate discharge
duration (td) is equal to wastewater inlet duration.
Q out =
( Q t f Vol retentate )
= Q t f (1
td
1 m3/h
)
F
{13.6}
4.9 Oil outlet flow (Qoil): Like water outlet flow, oil outlet flow or retantate
flow depends on its discharge duration (tdoil). This duration should be equal
to that of tf and td to fully imitate continuous process.
Q oil = Vol retentate / t doil =
Q tf
F t doil
m3/h
{13.7}

4.10.1 Permeate flux and volume evolution: Flux varies with time since
concentration of the feed (actually, retentate) increases from
continuous loss of its permeate. The program can calculate the
flux under the assumption that there is no fouling, which is
practically proven in case that suitable pretreament is provided.
Flux will be calculated using 2 models, i.e. Film model and
Resistance model, and the related equations,
J = kV ln(
J=
Cg
C
Pt
) l/(m -h)
R' m + V Pt
l/(m2-h)
J AoC = J B oC e ( 0.0239 ( B A))
{13.8}
{13.9}
{13.10}
The values of K, Cg, etc. for certain wastewaters are provided in

help file.
If two types of wastewater with different values of k, Cg,
etc.(such as microemulsion mixes with macroemulsion.) are
encountered, the flux will be calculated using weight average
method (eq. 13.11). This calculation exists only in design mode.
J mix =
+C
J
J
oil,mic mic,Coil,mix {13.11}
C
oil,mix
Evolution of permeate flux and volume is governed by the

following equation.
{13.12}
dVol = J(c) Adt
507
IV-86
Integration of eq. 13.11 is carried out using step method by

dividing total permeate volume (eq. 3.12) into 100 parts.
4.10.2
5.
Time required to complete one batch for a specified amount of

wastewater: It is also governed by eq. 13.12. It must be noted that
the program can calculate the flux/time evolution under the
condition that there is no additional inlet wastewater during UF
operation.
Table 13-1 Related parameters of ultrafiltration

Parameter
Variable name in
the program
Description
Unit used in the

program
Membrane area
AreaUF
m2
Gel concentration for low range of
Cg1low, Cg2low % oil volume/total
concentration (if any) of 1st and 2nd emulsion
volume
st
nd
Cg, Cg2
Real gel concentration of 1 and 2 emulsion
Cg1High,
% by volume of oil
(see reference)
Cg2High
Cref1, Cref2
Reference concentration of 1st and 2nd emulsion
Cref1, Cref2
% by volume of oil
(conc. that is used to acquire the value of
model constants)
Co1/(Co1+Co2 Oil concentration ratio of wastewater no.1 to
Rofoil1
in the unit of bar,
)
total oil concentration[2], always < 1
(m/s) and l/h-m2
k1, k2
Constant for film model for low range of oil
Kreflow1,
in the unit of bar,
concentration of 1st and 2nd emulsion
kreflow2
(m/s) and l/h-m2
k1, k2
Constant for film model for high range of oil
Krefhigh1,
in the unit of bar,
st
nd
concentration of 1 and 2 emulsion
krefhigh2
(m/s) and l/h-m2
Pt
Transmembrane pressure
UFP
bar
Q
Flowrate of inlet wastewater
Q
m3/s
Rm (or Rm) Modified membrane resistance (= membrane
Rm
in the unit of bar,
resistance + fouling resistance (if any))
(m/s) and l/h-m2
td
h
td
Duration for discharge the permeate (after UF
operation is finished), recommended to be
equal to tf.
tdoil
Duration for discharge the retentate (after UF
tdoil
h
equal to tf.
tf
h
tf
Duration to fill the storage tank by inlet
wastewater before the wastewater is stopped
and UF operation starts.
V
Recirculation velocity
UFV
m/s
F
Concentration factor (Volo /Volretentate)
ConcF
Constant for resistance model of 1st and 2nd
alpharef1,
in the unit of bar,
1, 2
emulsion
alpharef2
(m/s) and l/h-m2
Constant for film model of 1st and 2nd emulsion
bref1, bref2
in the unit of bar,
1, 2
(m/s) and l/h-m2
st
nd
Constant for film model of 1 and 2 emulsion Phiref1,Phiref2
in the unit of bar,
1,2
(m/s) and l/h-m2
A
Cg, Cg2
Note:
508
IV-87
6.
No influent added during filtration process
Retentate
Po
V
Storage
tank
UF
Ultrafiltration
(UF-??)
Pi
Feed
Fig. 13-1a Icon of ultrafiltration
8.
Permeate
Pt = ((Pi+Po)/2)-Pp
Feed
pump
7.
Membrane
Pp
Heat
exchanger
Fig. 13-1b Graphical diagram of ultrafiltration

7.1
Flux calculation of mixed wastewater exists only in design mode.
7.2
The process can be used for microfiltration and nanofiltration if they can be
represented by film model and resistance model.
7.3
The program can calculate only batch operation.
7.4
Accuracy of the models are governed by that of constants used, and

deviation of real operation from their assumption, thus unpredictable. If
possible, it is recommended to perform UF test, using real wastewater.

Table 13-2 Influent parameters of ultrafiltration

Parameter
Viscosity of feed
Temperature
Membrane properties
Reaction between feed and membrane
Note:

509
IV-88
14)
Reverse osmosis
1.
Process abbreviation: RO
2.
Process description: RO in this case is used as a finishing treatment process to

treat the effluent of UF or distillation only. Its main purpose is to remove soluble
pollutants, normally surfactants/co-surfactants, left after oil separation.
Furthermore, process calculation is based mainly on specific data from
manufacturer. Thus, the module exists only in ANALYSIS mode.
3.
4.

4.1 Graded efficiency (d): It is assumed to be 100%. CF is not allowed in this
process.
4.2 Total efficiency (t): It is assumed to be 100%.
Cd = 0 mg/l
C = 0 mg/l
4.5
Graded outlet oil concentration in oil outlet flow (Coild): Unlike other true
separation process, RO only concentrate oil. Thus concentrated oily
wastewater, not pure oil, is obtained as retentate. The program will assume
that droplet sized and numbers are not changed.
C oild =
d C od
= d C od F
(Vol retentate / Vol o )
mg/l
{14.1}

C oil =
d max
oild
mg/l
{14.2}
d min
upstream process.
4.8
Water outlet flow (Qout): Actual water oultet flow from the membrane is the
product of permeate flux, which varies with time, and membrane area.
However, since the process is usually designed as batch system, outlet flow
can be chosen freely, providing that permeate storage tank is big enough.
User can freely specify permeate discharge time (td). To imitate a
continuous process, it can be assumes that default permeate discharge
duration (td) is equal to wastewater inlet duration.
Q out =
( Q t f Vol retentate )
td
Q tf
td
(1
1 m3/h
)
F
{14.3}
4.9 Oil outlet flow (Qoil): Like water outlet flow, oil outlet flow or retantate
flow depends on its discharge duration (tdoil). This duration should be equal
to that of tf and td to fully imitate continuous process.
Q oil = Vol retentate / t doil =
Q tf
F t doil
m3/h
510
{14.4}
IV-89

4.10.1
TOD of water outlet flow (TODwater): Since characteristic of inlet

wastewater for RO varies only slightly. TOD removal efficiency
(TOD) is within the certain range around 70-90% (see reference).
So the program will calculate the TOD from TODo and the
efficiency, using the following equation.
TODwater = (TODo Co (
4.10.2
mgTOD
1
)) (1 TOD )
(1 1 / F )
mg oil
TOD of oil outlet flow (TODoil):

TODoil = (TODo TODwater (1
5.
{14.5}
1
)) F
F
{14.6}
Table 14-1 Related parameters of RO

Parameter
mgTOD/
mgoil

in the program
program
Description
Unit TOD of oil. For more information, see

reference
unitTOD
td
Duration for discharge the permeate (after UF

equal to tf.
td
tdoil
Duration for discharge the retentate (after UF

equal to tf.
tdoil
tf
Duration to fill the storage tank by inlet

wastewater before the wastewater is stopped
and UF operation starts.
tf
TOD of the inlet wastewater
TODin
mg/l
Concentration factor (Volo /Volretentate)
ConcF
TODo
F
TOD
Note:
1.
6.
TOD removal efficiency. It includes only

soluble TOD. TOD from oil is not included.
effTOD
511
IV-90
No influent added during filtration process

Retentate
Po
RO
Storage
tank
Permeate
Pt = ((Pi+Po)/2)-Pp
Pi
Feed
Reverse osmosis
(RO-??)
Feed
pump
Fig. 14-1a Icon of RO

7.
Membrane
Pp
Heat
exchanger
Fig. 14-1b Graphical diagram of RO

7.1 The process is included in the program to fulfil the entire process train of
oily wastewater treatment only. Thus, its calculation is based on data from
researches, rather than mathematical model.
7.2
The process should be connected only to the water outlet port of UF or

distillation since it can used only with oil-free water or water with only
trace of oil. If connected to other unit, the program will display warning.
7.3
The program can calculate only batch operation.
7.4
Calculated TOD is an internal result of the model. It cannot be exported to

other process because of programming limitation.
7.5
This module is available only in ANALYSIS mode.
512
IV-91
15)
1.
Process abbreviation: HD
2.
Process description: Heteroazeotropic distillation is an enhanced distillation

process by addition of certain chemical, usually hydrocarbons, as an entrainer to
lower the boiling point of the system and extract the water from the waste to be
treated. The process can be used to treat slop or UF retentate from cutting oil
treatment or concentrated oily wastewater.
3.
4.

process.
4.4
Cd = 0 mg/l
C = 0 mg/l
Graded outlet oil concentration in oil outlet flow (Coild): Outlet oil is in the
form of water-free oil (100% oil).
4.6 Total outlet oil concentration in oil outlet flow (Coil): Outlet oil is in the
form of water-free oil (100% oil).
upstream process.
4.8 Water outlet flow (Qout): Water outlet flow is equal to water content of inlet
wastewater under the assumption that size of the process is sufficient to
handle inlet flowrate on real time basis.
4.5
m3/h
{15.1}
Oil outlet flow (Qoil): Oil outlet flow is equal to oil content of inlet
wastewater.
Q out = Q (1 ( C o C ) / oil / 1000 )
4.9
m3/h
{15.2}
Q oil = Q Q out
4.10.1
Required quantity of entrainer: Quantity of entrainer depends on

the type of entrainer and the quantity of water to be removed,
which can be calculated by the following equation.
Qentrainer = Qout
(1 y H ) m3/h
yH
{15.3}
The values of yH (azeotropic composition) of certain entrainers

are provided in the help file.
5.
513
IV-92
Table 15-1 Related parameters of heteroazeotropic distillation

in the program
program
Parameter
Description
yH
Azeotropic composition (Ratio of volume of

water in ditillate to total distillate volume)
Note:
Vol/vol
Azeotropic
6.
yH
Temperature
2 ph.vapor
Boiling point
of hydrocarbon
TH
Dew curves
Boiling point
of water
1 ph.vapor +
1 ph. liquid
Bubble curve
Azeotrope (H)
2 ph. liquid
Pure
hydrocarbon
yH
x,y Pure H2O
Heterozeotropic
distillation (HD-??)
Fig. 15-1a Icon of heteroazeotropic

distillation
7.
Fig. 15-1b Graphical diagram of heteroazeotropic

distillation

7.1
Calculation is based on theoretical equation, regardless of distillation

column design.
7.2
There is some TOD present in the distillate, caused by volatile pollutants,

which depends on wastewater characteristic. Thus it can not be accurately
predicted. Distillate TOD of 2000 3000 mg/l is recommended for
distillation of UF retentate from cutting oil treatment.
7.3
Entrainer can be continuously reused.
7.4 If possible, pilot-test should be conducted to verify the value of yH and

observe other problems that may be present, such as release of hydrogen
sulfide.
514
IV-93
16)
Stripping
1.
Process abbreviation: ST
2.
Process description: Stripping is reversed version of heteroazeotropic distillation.

It is an enhanced distillation process by addition of water, as an entrainer to
lower the boiling point of the system and extract the hydrocarbon from the waste
to be treated. The process can be used to treat water with trace volatile
hydrocarbons.
3.
4.

process.
Cd = 0 mg/l
C = 0 mg/l
Graded outlet oil concentration in oil outlet flow (Coild): Outlet oil is in the
form of water-free oil.
4.6 Total outlet oil concentration in oil outlet flow (Coil): Outlet oil is in the
form of water-free oil.
upstream process.
4.8 Water outlet flow (Qout): Water outlet flow is equal to water content of inlet
wastewater under the assumption that size of the process is sufficient to
handle inlet flowrate on real time basis.
4.5
m3/h
{16.1}
4.9 Oil outlet flow (Qoil): Oil outlet flow is equal to oil content of inlet
wastewater.
Q out = Q (1 ( C o C ) / oil / 1000 )
m3/h
{16.2}
4.10.1 Required quantity of entrainer: Quantity of entrainer, in this case,
water, depends on the type and the qauntity of hydrocarbon to be
removed, which can be calculated by the following equation.
Q oil = Q Q out
Qsteam = Qoil
yH
m3/h
(1 y H )
{16.3}
The values of yH (azeotropic composition)

hydrocarbons are provided in the help file.
5.
of
certain
515
IV-94
Table 16-1 Related parameters of stripping

in the program
program
Parameter
Description
yH
Azeotropic composition (Ratio of volume of

water in ditillate to total distillate volume).
The value for various hydrocarbons are
recommended in the help file.
Vol/vol
1.
6.
Temperature
2 ph.vapor
Boiling point
of hydrocarbon
Stripping
Note:
yH
TH
Dew curves
Boiling point
of water
1 ph.vapor +
1 ph. liquid
Bubble curve
Azeotrope (H)
2 ph. liquid
Pure
hydrocarbon
yH
x,y Pure H2O
Stripping (ST-??)
Fig. 16-1a Icon of stripping

7.
Fig. 16-1b Graphical diagram of stripping

7.1 Calculation is based on theoretical equation, regardless of distillation
column design.
7.2 The quantity of steam calculated by the program is not included the steam
for heating requirement.
7.3
Entrainer ( water) can be continuously reused.
7.4
If possible, pilot-test should be conducted to verify the value of yH and

other problems that may be present.
516
IV-95
17)
1.
Process abbreviation: CH
2.
Process description: Calculation is based on reactor design, which can be applied

to any type of chemical or coagulant. Mixing is provided by mean of mechanical
mixers. The process is classified as inline concentrator and consists of 1 mixing
tank and 3 flocculation tanks. Droplets smaller than 200 microns are assumed to
successfully coalesce to form droplets of 200 micros. For bigger oil droplets,
they are assumed to remain the same.
3.
4.

4.1 Graded efficiency (d): This parameter is actually not valid since no oil is
removed from the wastewater. However, the term d in this case represents
removal efficiency due to coalesce. From this definition, the value of d are
as follows,
For d < 200 microns, d = CF.100%
For d = or > 200 microns, d = 0%
However, for d=200 microns, its concentration (if already existed) will
increase since coalesced droplets are assumed to be of this size.
4.2
Total efficiency (t): This parameter is not valid since no oil is removed.
4.3 Graded outlet oil concentration in water outlet flow (Cd): It is assumed that
all oil droplets are coalesced or flocculated to form big oil drop of 200
microns in diameter. Thus
Cd = Co for d > 200 microns and Cd = 0 for other values of d.
For d= 200 microns, its Cd is summation of its initial concentration and the
sum of concentration of droplets smaller than 200 microns.
C = Co mg/l
4.5 Graded outlet oil concentration in oil outlet flow (Coild): This parameter is
not valid since no oil is removed.
4.6
Total outlet oil concentration in oil outlet flow (Coil): This parameter is not
valid since no oil is removed.
4.7
upstream process.
4.8
Water outlet flow (Qout): Outlet flow of the process is equal to the inlet
flow.
4.9
Oil outlet flow (Qoil): This parameter is not valid since no oil is removed.

4.10.1
Retention time:
=
V
60 min
Q
{17.1}
517
IV-96
4.10.2
Product between G and
4.10.3
Power required (P) or Velocity gradient (G) of each tank: G and

P of each tank can be calculated by the following equations,
depending which value is specified by users.
P
G =
V
0. 5
{17.2}
For turbine mixer,

{17.3a}
P = N p n3 D5
The program features built-in Np for pitched blade turbine mixer
and propeller mixer.
For paddle mixer,
{17.3b}
P = Cd N A c (v) 3
If turbine mixer option is selected, the program will calculate both
pitch blade and propeller type.
5.
Table 17-1 Related parameters of chemical destabilization

Parameter

in the program
program
Description
Area of one paddle blade (single side)
Cd
Drag coefficient of paddle blade
Diameter of impeller of mixer
Velocity gradient
Rotating speed of mixer
Number of blades
Np
Power coefficient for turbine mixer
Power required for mixer1 of mixing tank and

mixer 2,3,4 of flocculation tanks
AreaPaddle
m2
Constant = 0.6
DMixer
Grapid,
Gfloc1,2,3
Sec-1
RPS1-4
Rev/s
NumBlade
Built-in
Prepid,
Pfloc1,2,3
Watt
Tip speed of paddle (= 2n (D/2))
VolRapid,
VolFloc1,2,3
m3
Volume of mixing tank and flocculation tanks
VolRapid,
VolFloc1,2,3
m3
Density of continuos phase, in this case,

water
Denc
Kg/m3
Note:
6.
518
IV-97
Destabilization
chemicals
Influent
M
Chemical
destabilizaion
(CH-??)
G = 50 s-1
G = 30 s-1
G = 20 s-1
Effluent
M
G = 100-300 s-1
Rapid mixing
Flocculator
The values of G in the figure are general values.
Fig. 17-1a Icon of chemical

destabilization
7.
Fig. 17-1b Graphical diagram of chemical destabilization

7.1 The program assumes that destabilization is successful and the oil droplets
coalesce to form bigger drops that can be decanted within 20 min. to 1
hour. So the final droplet size of 200 microns is proposed, Users can
change this value in the input screen.
7.2 Dosage of chemical varies with wastewater characteristic, type of
chemicals used. Thus it cannot be calculated and must be confirmed by jar
test.
7.3
For ANALYSIS mode, The configuration of the process is fixed, i.e. 1

mixing tank and 3 flocculation tanks, all with mechanical mixers.
7.4
For DESIGN mode, the program can be used for sizing 2 types of mixers,
i.e. turbine and paddle mixers. Turbine mixers are also divided into 2 cases,
i.e. pitched blade turbine and propeller. However, they will be calculated
simultaneously by the program.
519
IV-98
18)
1.
Process abbreviation: Bio
2.
Process description: Biological process in this case is used as a finishing

treatment process to treat the effluent of other process. It is included in the
program to fulfil the entire process train of oily wastewater treatment. The
process is not intended to refer to any specific type of biological system. Its
calculation is based on user-specified total TOD and oil removal.
3.
4.

4.1
Graded efficiency (d): This parameter is equal to total efficiency.
4.2
Total efficiency (t): This parameter is specified by user.
4.3
Graded outlet oil concentration in water outlet flow (Cd):

C d = (1 d ) C od
4.4
mg/l
{18.1}

C =
d max
C mg/l
{18.2}
d min
4.5
Graded outlet oil concentration in oil outlet flow (Coild): This parameter is
not valid since oil is not removed but destroyed or transform into other
forms.
4.6
valid since oil is not removed but destroyed or transform into other forms.
4.7
upstream process.
4.8
flow.
4.9

4.10.1 TOD of water outlet flow (TOD): It can be calculated by the
following equation. TODo, unit TOD and TOD are given by users.
TOD = (TODo (1 t )Co (
5.
mg TOD
)) (1 TOD ) mg/l
mg oil
{18.1}
520
IV-99
Table 18-1 Related parameters of biological treatment

in the program
program
Parameter
Description
mgTOD
/mgoil
Unit TOD of oil. For more information, see

reference file
TODo
TOD of the inlet wastewater
TODin
mg/l
Total oil removal efficiency.
efft
effTOD
TOD
Note:
6.
TOD removal efficiency. It includes only

soluble TOD. TOD from oil is not included.
unitTOD
Biological reactor
Influent
Clarifier
(if any)
Effluent
Biological
treatment
(Bio_??)
Wasted biomass
(if any)
Fig. 18-1a Icon of biological treatment Fig. 18-1b Graphical diagram of biological treatment
7.

7.1 The process is included in the program to fulfil the entire process train of
oily wastewater treatment only. Thus, its calculation is based on data from
researches, rather than mathematical model.
7.2
The module is available only in ANALYSIS mode.
7.3
Flowrate of wasted sludge is assumed to be negligible. Thus outlet flow is

equal to inlet flow.
7.4
It is assumed that there is no coalescence taking place within the process.
7.5
Calculated TOD is an internal result of the model. It cannot be exported to

other process because of programming limitation.
521
IV-100
19)
GAC filter
1.
Process abbreviation: GAC
2.
Process description: GAC filter in this case is used as a finishing treatment

process to treat the effluent of other process. It is included in the program to
fulfil the entire process train of oily wastewater treatment. Its calculation is based
on user-specified TOD removal. For oil removal, the efficiency is assumed to be
100%. Since its main objective is removal of residual pollutant, its inlet oil
concentration should be not greater than 50 mg/l. If the inlet wastewater contains
higher oil concentration, the program will display warning.
3.
4.

4.1 Graded efficiency (d): It is assumed to be 100%.
Cd = 0 mg/l
C = 0 mg/l
4.5 Graded outlet oil concentration in oil outlet flow (Coild): This parameter is
not valid since oil adsorbed into the bed.
4.6 Total outlet oil concentration in oil outlet flow (Coil): This parameter is not
valid since oil is adsorbed into the bed.
upstream process.
4.8 Water outlet flow (Qout): Outlet flow of the process is equal to the inlet
flow.
4.9 Oil outlet flow (Qoil): This parameter is not valid.
4.10.1
Adsorptive capacity (q): The program can predict adsorptive

capacity, using 2 well-known Isotherm models, i.e.,
aC po
Lungmuirs model: q =
(1 / n )
Frendlichs model: q = k C po
mg/g
1 + bC po
mg/g
{19.1a}
{19.1b}
A, b, k and n are numerical constant, acquired from experiment.

User can select the model from on-screen option button.
4.10.2
Bed life span or total operation time before bed replacement (tT):
When isotherm (q VS. Cp relation) and mass transfer zone data
(Qa, Ha or E as the functions of Cp) are available;
522
IV-101
tT =
HA b q Q a
Q (C po C p )
{19.2a}
Or,
tT =
E HA b q
Q (C po C p )
E =1
{19.2b}
1
c 10 d ( Q / A)
H 100
{19.3}
E is effective saturation of bed. The recommended valued is

around 50-95% (average 75%). In the program, eq. 19.2b is used.
H and V are in m and m/h, respectively.
4.10.3
Hydraulic loading rate:

Q
m/h
A
V=
4.10.4
Retention time ():

=
4.10.5
H
60 min
(Q / A)
{19.5}
Headloss (P): Head loss of the bed can be calculated from

Kozeny-Carmans equation. Built-in minimum and maximum
void ration is 0.18 to 0.25, respectively.
P=
5.
{19.4}
180 Hc (V / 60)(1 ) 2
g dp 2 3
{19.3}
523
IV-102
Table 19-1 Related parameters of GAC filter

Parameter

the program
program
Description
m2
Required outlet pollutant concentration
Polout
mg/l
Cpo
Inlet concentration of pollutant
Polin
mg/l
dp
GAC particle size
Dpc
Effective saturation of bed, E < 100%
GACE
Bed height
GACH
Pressure drop
Pdropmin,
Pdropmax
Isotherm data (mass of adsorbate/ mass of

adsorbent)
GACq
mg/g
Empty bed velocity or hydraulic loading rate
GACV
m/h
Cross section area of bed
Cp
a, b
Empirical constant for Lungmires model
Cpo in mg/l
m/h
k, n
Empirical constant for Freundlichs model
Cpo in mg/l
m/h
c, d
Empirical constant for mass transfer zone data
Cpo in mg/l
m/h
Bed porosity or void ratio, recommended value is

0.18 0.25.
Void
Density of continuous phase
Denc
kg/m3
Bulk density of bed (430 600 kg/m3)
DenGAC
kg/m3
Note:
6.
Influent
Ha
GAC bed.
GAC filter
(GAC-??)
Effluent
t=0
Fig. 19-1a Icon of GAC filter
HT
Ce
Satured
zone
Co
MTZ
Ce
Co
Velocity=V
Ha
Bed needs to
be replaced.
t = tT
Fig. 19-1b Graphical diagram of GAC filter

524
IV-103
7.

7.1
Calculation is based on research data, given by users.
7.2
If possible, it is recommended to conduct is lab test, using real wastewater,

to find the exact data about isotherm adsorptive capacity (a, b, k, n), and
mass transfer zone (c and d) data of GAC bed.
525
IV-104
20)
1.
Process abbreviation: CC
2.
Process description: The process works as an oil concentrator, e.g. hydrocyclone.

But users are allowed to specify graded efficiency of the process.
3.
Reference : None
4.

4.1 Graded efficiency (d): User-defined in the form of a table. Graded
efficiency of the droplet size that falls between 2 specified values will be
obtained by interpolation or extrapolation.
4.2

t =
1
Co
(1 d ) C od
100 %
(1 R f )
d max
d min
{20.1}

Cd =
(1 d ) C od
(1 R f )
mg/l
{20.2}

C =
d max
C mg/l
{20.3}
d min
4.5 Graded outlet oil concentration in oil outlet flow (Coild):

C oild =
d C od mg/l
{20.4}
Rf

C oil =
{20.5}
d max
oild
d min
upstream process.
4.8

Q out = Q (1 R f )
m3/h
{20.6}

Q oil = Q R f
m3/h
{20.7}
4.10 Customized output: None

5.
526
IV-105
Table 20-1 Related parameters of customized concentrator

Parameter
Rf

the program
program
Description
Split ratio (Qoil/Q)
d, d
6.
Rf
Specified droplet size and graded efficiency

of the process
Customdin,
Customeffd
Micron, %
Effluent
Influent
Custom
concentrator
(CC-??)
Oil outlet
Fig. 20-1a Icon of customized

concentrator
Fig. 20-1b Graphical diagram of customized

concentrator
527
IV-106
21)
1.
Process abbreviation: CS
2.
Process description: the process works as an oil separator, e.g. decanter. But
users are allowed to specify graded efficiency of the process.
3.
Reference : None
4.

4.1 Graded efficiency (d): User-defined in the form of a table. Graded
efficiency of the droplet size that falls between 2 specified value will be
obtained by interpolation.
d max
t =
C od
{21.1}
100 %
d min
Co
4.3 Graded outlet oil concentration in water outlet flow(Cd):

Cd =
Q
C od (1 d )
Q out
mg/l
{21.2}

C =
C mg/l
{21.3}
d max
d min
upstream process.
3
Q out = Q (1 ( C o C ) / oil / 1000 ) m
/h
{21.4}

Q oil = Q Q out
m3/h
{21.5}

5.
528
IV-107
Table 21-1 Related parameters of customized separator

the program
program
Parameter
Description
d, d

of the process
6.
Customdin,
Customeffd
Micron, %
Influent
Effluent
Custom separator
(CS-??)
Oil outlet
Fig. 21-1a Icon of customized separator

7.
Fig. 21-1b Graphical diagram of customized

separator

529
IV-108
22)
1.
Process abbreviation: IC
2.
Process description: the process work as an inline oil concentrator, e.g.

coagulation-flocculation, or inline coalescer. But users are allowed to specify
graded efficiency of the process.
3.
4.

4.1 Graded efficiency (d): This parameter is actually not valid since no oil is
removed from the wastewater. However, the term d in this case represents
removal efficiency due to coalesce, defined by user in the form of a table.
Graded efficiency of the droplet size that falls between 2 specified value
will be obtained by interpolation or extrapolation. However the
concentrated oil is not separated from the wastewater but assumed to
coalesce to form bigger oil drops of a specified size (dcoalesce). From this
definition, the value of d are as follows,
For d < dcoalesce, d is as specified by user. The rest of the droplets that are
not separated will partially coalesce to form bigger droplets at the size of
dcoalesce.
For d = or > dcoalesce, d is as specified by user.
However, for d = dcoalesce, its concentration (if already existed) will increase
since coalesced droplets are assumed to be of this size.
4.2
Total efficiency (t): This parameter is not valid since no oil is removed.
4.3
Graded outlet oil concentration in water outlet flow (Cd): It is assumed that
separated oil droplets coalesce to form big oil drop which is classified as
oil layer.
And as described above, it is assumed that there are partially coalesces of
the small oil droplets. These droplets will coalesce and form bigger oil
droplets dcoalesce. Or all droplets smaller than dcoalesce will coalesce to form
the droplet size dcoalesce.
Thus, for d < dcoalesce,
Cd = 0
mg/l
{22.1a}
For d = dcoalesce,
Cd =
d coalsce
(1 d )
mg/l
{22.1b}
d min
For d > dcoalesce,

C d = C od (1 d ) mg/l
{22.1c}
For oil layer,

C layer = C o ,layer +
C mg/l
{22.1d}
d max
d min
530
IV-109

C = Co mg/l
4.5
Graded outlet oil concentration in oil outlet flow (Coild): This parameter is
not valid since no oil is removed.
4.6
valid since no oil is removed.
4.7
upstream process.
4.8
flow.
4.9

5.
Related parameters: Related parameters are as summarized in the following

table
Table 22-1 Related parameters of customized inline concentrator

Parameter
dcoalesce
d, d
6.

the program
program
Description
Diameter of partially coalesced oil drop

from the process
of the process
customDcoalesce
micron
Customdin,
Customeffd
Micron, %
Effluent
Inline concentrator
(IC-??)
Fig. 22-1a Icon of inline concentrator
Influent
Fig. 22-1b Graphical diagram of inline concentrator
531
IV-110
23)
Inlet
1.
Process abbreviation: IN
2.
Process description: This module is used to input the wastewater into a process
train. There can be more than one input module in a process train.
3.
Reference : None
4.
Input parameters
Parameter
Description
Cod
Granulometry or oil droplet size distribution :

graded concentration (concentration of oil at
each droplet size)
Concentration of inlet oil in the form of oil
layer or film
Total oil inlet concentration
Granulometry or oil droplet size distribution :
droplet size
Wastewater flowrate
Temperature
Co
d
Q
T
c
d
C
Variable name in
the program
Unit used in the

program
Cind
mg/l
Cinlayer
mg/l
Co
din
mg/l
micron
Qin
temp
Denc
m3/h
Celcius
Kg/m3
Dend
Muc
Kg/m3
N.s/m2
(= 1000 cp)
N.s/m2
(= 1000 cp)
kg/s2 or N/m
(= 1000 dyne/cm)
Dynamic (Absolute) viscosity of dispersed

phase, in this case, oil
Mud
ow
gow
5.
Related graphics: Icon in analysis mode for this process are as shown below.
Inlet
Inlet
Inlet
(IN-??)
Fig. 23-1a Icon of inlet

6.

6.1 There can be more than one inlet module in a process train.
6.2 Graded concentration is specified as quantity of oil (mg) per volume of
wastewater (= volume of oil+water).
532
IV-111
24)
Outlet
1.
Process abbreviation: -
2.
Process description: This module is used to specify the outlet point of the process
train. It is also used as a logical checkpoint of the program to perform
calculation. Thus there can be only one outlet in a process train.
3.
Reference : None
4.
Outlet
Outlet
Outlet
Fig. 24-1a Icon of outlet

5.

5.1 There can be only one outlet in a process train.
5.2 Location of the outlet in the process train does not need to be an actual
location. However, it is recommended to place it at the end of main process
stream for faster calculation.
533
IV-112
25)
Flow merge
1.
Process abbreviation: FM
2.
Process description: This module is used to combine or merge any 2 streams of

wastewater together.
3.
Reference : None
4.
Output parameters:
4.1 Wastewater flowrate (Q): It is calculated from the summation of the
flowrate of the two streams.
4.2 Granulometry or size distribution of oil droplets in the wastewater: It is
calculated from weight average value, as shown in the following equation.
Cd =
C d ,1Q1 + C d , 2 Q 2
Q1 + Q 2
{25.1}
4.3 Total oil concentration (C):

d max
C =
{25.2}
d min
4.4 Oil density (d): as kg/m3. It is assumed to be equal to the weight average
value, as shown in the following equation.
d =
d ,1C 1Q1 + d , 2 C 2 Q 2
{25.3}
C 1Q1 + C 2 Q 2
4.5 Water density (c):

c =
c 1 Q1 + c 2 Q 2
{25.4}
Q1 + Q 2
4.6 Oil viscosity (d): as N.s/m2. It is assumed to be equal to the weight

average value, as shown in the following equation.
d =
d ,1C 1Q1 + d , 2 C 2 Q 2
{25.5}
C 1Q1 + C 2 Q 2
4.7 Water viscosity (c):

c =
c 1Q 1 + c 2 Q 2
{25.6}
Q1 + Q 2
4.8 Temperature (T):

T =
T1Q1 + T 2 Q 2
Q1 + Q 2
Celcius
{25.7}
4.9 Interfacial tension (ow): It is assumed to be equal to the weight average

ow =
5.
ow ,1C 1Q1 + ow , 2 C 2 Q 2
{25.8}
C 1Q1 + C 2 Q 2
Related graphics: Icon in analysis mode for this process are as shown below.
534
IV-113
2
Flow merge
(FM-??)
Fig. 25-1a Icon of flow merge
535
IV-114
26)
Flow split
1.
Process abbreviation: FS
2.
Process description: This module is used to divide or split a stream of wastewater

into 2 streams.
3.
Reference : None
4.
Output parameters:
4.1 Wastewater flowrate (Q1 and Q2):
Q1 = R f Q
{26.1a}
Q2 = 1 R f Q
{26.1b}
4.2 Granulometry or size distribution of oil droplets in the wastewater:

{26.2}
C d ,1 = C d , 2 = C od
4.3 Total oil concentration (C):

{26.3}
C1 = C 2 = C o
4.4 Oil density (oil):

{26.4}
oil ,1 = oil , 2 = oil
4.5 Temperature (T):

{26.5}
T1 = T 2 = T
4.6 Interfacial tension (ow): It is assumed to be equal to the weight average

{26.6}
ow ,1 = ow , 2 = ow
5.
1
1
2
Influent
2
Flow split
(FS-??)
Fig. 26-1a Icon of flow split
Q1 = RfQ
Q2 = 1- RfQ
Fig. 26-1b Graphical diagram of flow

split
536
IV-115
Part V General conclusion
General conclusion
General conclusion
One of the main objectives of this thesis is to review all of the researches on various
oily wastewater treatment processes, directed by Prof. AURELLE and summarize and
establish general theory or mathematical models that govern the performance and design of
such processes.
This objective is accomplished in Part 1 to Part 3 of this thesis. Every unit processes
for oil separation, studied in GPI lab, had been revised and their corresponding mathematical
models as well as design limitation and influent parameters had been found. These processes
revised under the scope of work of this thesis include,
1.
Oil skimmer
This equipment is developed to selectively remove oil layer from the water
surface without carrying over the water with it. It is found that the key to achieve good oil
selectivity depends on the surface energy or critical surface tension of skimmer material. The
material with low critical surface tension is suitable to use as skimmer material. Mathematical
models of 2 types of skimmer, i.e. drum skimmer and disk skimmer are verified.
2.
Decanter
Its underlining theory, namely STOKEs law, is quoted. General mathematical

models for 3 different varieties of the processes, i.e. simple decanter (e.g. API tank), parallel
plate interceptor (e.g. PPI and lamella separator), and compact decantor (e.g. Spiraloil) are
proposed and verified.
3.
Coalescer
Theoretical model, proposed by AURELLE, based on filtration model, is

reviewed. The model provides clear ideas about influent parameters on coalescer
performance. Several initiative ideas for coalescer performance enhancemen, e.g. the use of
guide to increase oil loading of the coalescer and the use of mix bed material to treat mixture
of direct/inverse emulsion simultaneously are realised. Finally, the empirical models, which
are verified by relatively wide range of data, are proposed for 4 varieties of coalescer, i.e.
granular bed coalescer, brush type bed coalescer, dynamic fibrous bed (rotating brush)
coalescer, and disorderly fibrous bed (metal wool) coalescer. Headloss equations are also
proposed in this thesis.
4.
Mathematical model based on filtration concept, proposed by SIEM [12] is

reviewed. The model is useful for understanding effects of influent parameters on DAF
performance. Extension equations of SIEMs model, based on population balance theory, is
established within this thesis to extend the valid range of SIEMs model to cover the range of
oily wastewater frequently found. Equations for saturator or pressurized water system
design are also proposed and verified within this thesis.
5.
Hydrocyclone
Trajectory analysis model for 2-phase (liquid-liquid) hydrocyclone, the new

concept based on STOKEs law, is proposed and verified. The model can actually predict
537
V-1
General conclusion
graded oil removal efficiency of any sizes of oil droplet in the wastewater by theoretical based
equation, unlike other models which are based on curve fitting and similarity concepts. Thus
it is very useful to understand the effect of related parameters on hydrocyclone performance.
Models of three-phase hydrocyclone, GPI innovation for simultaneous removal of oil,
suspended solids amd water, are also established within the scope of work of this thesis. The
model is also based on trajectory analysis concept. Finally, headloss equations for 2- and 3phase hydrocyclone are established in this thesis.
6.
Membrane processes
Applications of membrane processes, i.e. microfiltration (MF), ultrafiltration

(UF), nanofiltration (NF) and reverse osmosis (RO) on oily wastewater treatment in GPI lab
had been reviewed. Several useful facts from those researches are realized and calculation
techniques are established in this thesis, i.e.,
7.
Flux enhancement for UF on cutting oil emulsion treatment by partial

destabilization. Additional of salt, in lower amount than that for total
destabilization, into the feed helps increasing permeate flux, thus saving on
energy consumption and membrane size. The downside of this technique,
concluded in this thesis, is that the destabilized oil can clog the membrane if
it is not properly partition or removed from recirculated feed stream.
Cleaning of UF membrane after treatment of cutting oil by cleaning

microemulsion. It can effectively wash accumulated oil or foulants from the
membrane. It can be reused for many times until it is saturated by oil.
Technique to extend the UF performance data at 1 condition to cover other

condition, based on combination of film model and resistance model. This
technique is proposed and verified in this thesis. It is useful when only
limited data on the wastewater is available. It allows us to estimate evolution
of flux and permeate volume with time, which is useful for process design.
Technique to predict flux of mixture of two different emulsion. This

technique is also proposed and verified in this thesis. It is useful when mixed
emulsion can be expected and its ratio is likely to vary.
Thermal process
The main interest of this type of process is heteroazeotropic distillation (HD).

Application of HD to remove water content from refinery slops and UF retentates from UF of
cutting oil emulsion is reviewed. The process is achieved by addition of certain chemical that
promotes azeotropic formation (called entrainer), usually hydrocarbons, into the wastewater.
It will lower the boiling temperatur of the system, thus save the energy. These applications
provide prospects on re-value these supposed-to-be-wastes. Its reverse application, namely
stream stripping (for removing volatile substance from water by addition of stream), is also
realized. Theoretical data to calculate required amount of entrainer are also proposed.
8.
Chemical process
Destabilization (or breaking or cracking) mechanism of emulsion by addition

of various chemicals, i.e. mono valence salt, bivalence salts, polyelectrolytes, acid and special
absorbates are reviewed. Equations for mixing tank and mixer designs are also reviewed and
included in the program.
538
V-2
General conclusion
9.
Finishing processes
Two widely used finishing processes, i.e., biological treatment and carbon
adsorption, is realized. Useful data on biological process, related to oily wastewater
treatment, and design equations of GAC filter, as well as absorptive capacity of certain
chemicals, are reviewed and included in the program.
To complete the first objective, guideline on oily wastewater treatment process
selection and recommended treatment processes for certain oily wastewater are proposed.
The final objective of the thesis is to develop the program for calculation, design and
simulation of wastewater treatment process train in order to value and make use of the knowhow and significant finding from the researches by presenting them in the form of userfriendly program. To fulfil this objective, the program, namely GPI program, is developed. It
is divided into 4 major modes, i.e.,
E-book mode: provides background knowledge and useful database about the
oil pollution and the treatment processes. Actually, the textbook in part 3 is
transformed into e-book files used in this mode,

of feasible processes for any input influent. Selection criteria are as proposed in
the guideline in Part 3, chapter 12.
Design (calculation) mode: used for sizing the unit process. The models used
for calculation are as summarized in Part 3.
Analysis (simulation) mode: allows users to integrate any separation processes,

included in the program database, to build their own treatment process train. And
the program will simulate the process train to forecast the efficiency of each unit.
The program is developed to be upgradable. Its architecture consists of the database in

the form of common text database file and sub-programs. To upgrade the program, it can be
done conveniently by adding the data, such as name of new process, its related parameter
needed for calculation, into the database. The program will link the new process into the
graphic user interface automatically. For sub-program for calculation of the new process, it
can be separately developed using Visual Basic programming language. The easiest way is to
copy the source code of an existing process and change the equation to suit the new process.
After compilation in to an executable file, it can be copied to replace the old GPI program file
without re-installation of the program. So the program could be further developed to cover
more researches and processes in the future.
539
V-3
Reference
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Cazal E.
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19
Toulgoat K.
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Matamoros H.
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26
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emulsionnes par coalescence sur resines oleophiles
Thse de doctorat, Universite Pual Sabatier de Toulouse, 1974
27
Tan Prapon
Theoritical study of Coalescer and its application to treatment of wastewater
for vegetable oil industry
Master degree thesis, Chulalongkorn University, Thailand, 1984
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Thew M.T.
Hydrocyclones for liquid-liquid separation
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Chebelin T.
Separation compacte: modilisation des hydrocyclones
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Bradley D.
The hydrocyclone
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M.a B., Aurelle Y., Seureau J.
Three phase hydrocyclone for simultaneous separation of solids from liquidliquid mixtures
Publication, source unknown
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32
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Modeling the global efficiency of dissolved air flotation
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Introduction to colloid and surface chemistry
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42
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43
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Viscous flow in multiparticle systems : slow motion of fluids relative to beds of
spherical particles
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Wastewater engineering: Treatment, disposal, reuse
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Wastewater treatment handbook
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62
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par distillation heteroazeotropique
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book, August 1981
64
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Potable water engineering
Book, 1st edition (Thai version), 1984
66
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Book, Que Corp., 1994
545
Annexe
Annex A.1.1 Comparison between calculated efficiency and experimental result

for simple spiral "Spiraloil" decanter
Ref. [4] pp.79
Case
Droplet
Empty
Calculated
Observed efficiency
Difference in
diameter
bed
removal
from experiment(by
calculated and
velcity
efficiency
droplet size)
observed efficiency
d observed
d
d
V
micron
m/s
%
%
1
1.8
0.4
1.04%
0.00%
-1.04%
2.3
0.4
1.71%
0.00%
-1.71%
2.95
0.4
2.81%
0.50%
-2.31%
3.7
0.4
4.42%
21.42%
17.00%
4.65
0.4
6.99%
51.80%
44.81%
5.9
0.4
11.25%
59.92%
48.67%
7.45
0.4
17.95%
68.96%
51.01%
9.45
0.4
28.57%
82.62%
54.05%
11.85
0.4
45.41%
93.20%
47.79%
14.95
0.4
72.29%
97.98%
25.69%
18.85
0.4
100.00%
99.35%
-0.65%
23.7
0.4
100.00%
100.00%
0.00%
29.85
0.4
100.00%
100.00%
0.00%
37.65
0.4
100.00%
100.00%
0.00%
47.5
0.4
100.00%
100.00%
0.00%
55.5
0.4
100.00%
100.00%
0.00%
2
1.8
0.8
0.52%
0.00%
-0.52%
2.3
0.8
0.85%
0.00%
-0.85%
2.95
0.8
1.40%
0.00%
-1.40%
3.7
0.8
2.21%
0.00%
-2.21%
4.65
0.8
3.49%
1.70%
-1.79%
5.9
0.8
5.62%
14.25%
8.63%
7.45
0.8
8.96%
48.01%
39.05%
9.45
0.8
14.26%
49.72%
35.46%
49.43%
11.85
0.8
22.67%
72.10%
14.95
0.8
36.09%
85.20%
49.11%
18.85
0.8
57.37%
94.00%
36.63%
23.7
0.8
90.70%
98.90%
8.20%
29.85
0.8
100.00%
100.00%
0.00%
37.65
0.8
100.00%
100.00%
0.00%
47.5
0.8
100.00%
100.00%
0.00%
55.5
0.8
100.00%
100.00%
0.00%
3
1.8
1.6
0.26%
0.00%
-0.26%
2.3
1.6
0.42%
0.00%
-0.42%
2.95
1.6
0.70%
0.00%
-0.70%
3.7
1.6
1.10%
0.00%
-1.10%
4.65
1.6
1.74%
0.00%
-1.74%
5.9
1.6
2.81%
0.00%
-2.81%
7.45
1.6
4.48%
0.00%
-4.48%
9.45
1.6
7.23%
0.00%
-7.23%
11.85
1.6
11.33%
5.40%
-5.93%
14.95
1.6
18.04%
26.20%
8.16%
18.85
1.6
28.35%
54.80%
26.45%
23.7
1.6
45.35%
80.20%
34.85%
29.85
1.6
71.94%
95.30%
23.36%
37.65
1.6
100.00%
98.80%
-1.20%
47.5
1.6
100.00%
99.90%
-0.10%
55.5
1.6
100.00%
100.00%
0.00%
546
Annex A1.2 Comparison between calculated efficiency and experimental result

for mixed spiral "Spiraloil" decanter
Ref. [4] pp.88
Case
Droplet
diameter
d
Empty
bed
velcity
V
Calculated
removal
efficiency
d
Observed efficiency
from experiment(by
droplet size)
d observed
micron
1.80
2.30
2.95
3.70
4.65
5.90
7.45
9.45
11.85
14.95
18.85
23.70
29.85
37.65
47.50
53.00
1.80
2.30
2.95
3.70
4.65
5.90
7.45
9.45
11.85
14.95
18.85
23.70
29.85
37.65
47.50
55.50
m/s
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
%
1.88%
3.08%
5.07%
7.97%
12.60%
20.29%
32.35%
51.50%
81.85%
100.00%
100.00%
100.00%
100.00%
100.00%
100.00%
%
52.22%
58.83%
67.54%
72.08%
79.89%
84.97%
89.00%
94.01%
97.02%
98.22%
99.40%
100.00%
100.00%
100.00%
100.00%
4.20%
6.76%
10.78%
17.17%
27.28%
43.18%
70.00%
100.00%
100.00%
100.00%
100.00%
43.18%
61.82%
67.27%
71.82%
75.45%
77.27%
84.54%
92.73%
100.00%
100.00%
100.00%
547
Difference in
calculated and
observed efficiency
50.34%
55.75%
62.47%
64.11%
67.29%
64.68%
56.65%
42.51%
15.17%
-1.78%
-0.60%
0.00%
0.00%
0.00%
0.00%
0.00%
38.98%
55.06%
56.49%
54.65%
48.17%
34.09%
14.54%
-7.27%
0.00%
0.00%
0.00%
Annex A2.1 Comparison between calculated efficiency and experimental result for granular bed coalescer
Ref. [3] pp.285 & 321, [9], pp.174
Case
Total
Droplet
Bed
Bed Dispersed Continuous Density Dynamic Dynamic
hydrocarbon diameter media height
phase
phase
difference viscosity viscosity of
concentration
diameter
density
density
of
continuous
dispersed
phase
phase
Co
dp
mg/l
kg/cu.m
kg/cu.m
kg/cu.m
1000
41.00
0.37
0.01
793.4
998
1000
41.00
0.37
0.03
793.4
998
Empty
bed
velcity
Interfacial
tension
o/w
Calculated
Observed
removal
efficiency
efficiency
from
from
experiment(by
DAMAK's droplet size)
model
d observed
204.6
(N.s)/m2 (N.s)/m2
m/s
N/m
(=1000cP (=0.1000cP)
(=1000dyn/cm
1.07E-03 1.08E-03 0.00351
4.20E-02
99.79%
95.00%
204.6
1.07E-03
100.00%
98.70%
1.08E-03
0.00351
4.20E-02
1000
41.00
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
41.00
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
32.65
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.99%
1000
32.65
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
32.65
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
25.90
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.00%
1000
25.90
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
25.90
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
20.57
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.18%
98.00%
1000
20.57
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
20.57
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
16.36
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
94.74%
96.00%
1000
16.36
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
16.36
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
12.99
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
90.47%
94.30%
1000
12.99
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
96.19%
99.70%
1000
12.99
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
10.30
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
86.37%
92.00%
1000
10.30
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
91.83%
98.70%
1000
10.30
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.79%
100.00%
1000
41.00
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
98.60%
1000
41.00
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
41.00
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.40%
1000
32.65
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.00%
1000
32.65
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
32.65
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.40%
1000
25.90
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
98.60%
1000
25.90
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
25.90
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.00%
1000
20.57
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.18%
97.00%
1000
20.57
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
20.57
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
98.60%
1000
16.36
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
94.74%
94.60%
1000
16.36
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
99.60%
1000
16.36
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
98.60%
1000
12.99
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
90.47%
92.60%
1000
12.99
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
96.19%
99.20%
1000
12.99
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
98.60%
1000
10.30
0.37
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
86.37%
88.80%
1000
10.30
0.37
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
91.83%
97.40%
1000
10.30
0.37
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.79%
98.20%
1000
41.00
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
93.83%
97.00%
1000
41.00
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.76%
99.00%
1000
41.00
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
100.00%
100.00%
1000
32.65
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
89.66%
93.00%
1000
32.65
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
95.32%
97.00%
548
Ref. [3] pp.285 & 321, [9], pp.174
Case
Total
Droplet
Bed
phase
phase
concentration
diameter
density
density
of
continuous
dispersed
phase
phase
Co
dp
mg/l
kg/cu.m
kg/cu.m
kg/cu.m
Empty
bed
velcity
Interfacial
tension
o/w
Calculated
Observed
removal
efficiency
efficiency
from
from
experiment(by
model
1000
32.65
0.60
0.1
793.4
998
204.6
(N.s)/m2 (N.s)/m2
m/s
N/m
%
(=1000cP (=0.1000cP)
(=1000dyn/cm
1.07E-03 1.08E-03 0.00351
4.20E-02
100.00%
1000
25.90
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
85.60%
d observed
%
100.00%
90.20%
1000
25.90
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
91.01%
96.40%
1000
25.90
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
98.90%
100.00%
1000
20.57
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
81.74%
83.20%
1000
20.57
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
86.91%
94.40%
1000
20.57
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
94.45%
99.40%
1000
16.36
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
78.08%
74.80%
1000
16.36
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
83.02%
91.20%
1000
16.36
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
90.22%
98.00%
1000
12.99
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
74.56%
61.00%
1000
12.99
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
79.28%
87.20%
1000
12.99
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
86.15%
96.60%
1000
10.30
0.60
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
71.18%
58.20%
1000
10.30
0.60
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
75.68%
84.00%
1000
10.30
0.60
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
82.25%
93.40%
1000
41.00
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
85.82%
89.60%
1000
41.00
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
91.25%
98.00%
1000
41.00
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
99.16%
100.00%
85.20%
1000
32.65
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
82.00%
1000
32.65
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
87.18%
93.20%
1000
32.65
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
94.75%
100.00%
1000
25.90
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
78.29%
75.80%
1000
25.90
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
83.24%
96.20%
1000
25.90
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
90.46%
99.60%
1000
20.57
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
74.76%
61.00%
1000
20.57
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
79.49%
95.40%
1000
20.57
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
86.38%
99.00%
1000
16.36
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
71.42%
56.00%
1000
16.36
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
75.93%
90.80%
1000
16.36
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
82.52%
96.60%
1000
12.99
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
68.20%
42.60%
1000
12.99
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
72.51%
83.20%
1000
12.99
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
78.80%
90.80%
1000
10.30
0.75
0.03
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
65.10%
24.60%
1000
10.30
0.75
0.05
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
69.22%
78.80%
1000
10.30
0.75
0.1
793.4
998
204.6
1.07E-03
1.08E-03
0.00351
4.20E-02
75.22%
84.20%
1000
10.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0009
1.10E-02
90.55%
95.00%
1000
14.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0009
1.10E-02
96.85%
96.50%
1000
20.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0009
1.10E-02
100.00%
98.00%
1000
28.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0009
1.10E-02
100.00%
99.00%
100.00%
1000
40.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0009
1.10E-02
100.00%
1000
10.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00136
1.10E-02
84.81%
91.00%
1000
14.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00136
1.10E-02
90.71%
94.00%
1000
20.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00136
1.10E-02
97.42%
97.00%
1000
28.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00136
1.10E-02
100.00%
99.00%
1000
40.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00136
1.10E-02
100.00%
100.00%
1000
10.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
75.99%
75.00%
549
Ref. [3] pp.285 & 321, [9], pp.174
Case
Total
Droplet
Bed
phase
phase
concentration
diameter
density
density
of
continuous
dispersed
phase
phase
Co
dp
mg/l
kg/cu.m
kg/cu.m
kg/cu.m
Empty
bed
velcity
Interfacial
tension
o/w
Calculated
Observed
removal
efficiency
efficiency
from
from
experiment(by
model
d observed
1000
14.00
0.36
0.02
914.5
998
83.5
(N.s)/m2 (N.s)/m2
m/s
N/m
(=1000cP (=0.1000cP)
(=1000dyn/cm
2.10E-03 1.07E-03
0.0027
1.10E-02
1000
20.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
81.28%
86.00%
87.29%
92.00%
1000
28.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
93.37%
97.00%
1000
40.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
99.00%
1000
10.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00406
1.10E-02
71.19%
67.00%
1000
14.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00406
1.10E-02
76.15%
79.00%
1000
20.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00406
1.10E-02
81.78%
84.00%
1000
28.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00406
1.10E-02
87.47%
92.00%
1000
40.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00406
1.10E-02
93.94%
94.00%
1000
10.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00541
1.10E-02
68.00%
61.00%
1000
14.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00541
1.10E-02
72.73%
65.00%
1000
20.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00541
1.10E-02
78.11%
71.50%
1000
28.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00541
1.10E-02
83.54%
85.50%
1000
40.00
0.36
0.02
914.5
998
83.5
2.10E-03
1.07E-03
0.00541
1.10E-02
89.72%
92.00%
1000
10.00
0.36
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
79.78%
85.00%
1000
14.00
0.36
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
85.34%
90.00%
1000
20.00
0.36
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
91.65%
94.50%
1000
28.00
0.36
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
98.03%
98.00%
1000
40.00
0.36
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
100.00%
1000
10.00
0.36
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
84.83%
89.00%
1000
14.00
0.36
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
90.73%
92.00%
1000
20.00
0.36
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
97.44%
96.00%
1000
28.00
0.36
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
99.00%
1000
40.00
0.36
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
100.00%
1000
10.00
0.36
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
92.18%
93.50%
1000
14.00
0.36
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
98.60%
95.00%
1000
20.00
0.36
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
99.00%
1000
28.00
0.36
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
100.00%
1000
40.00
0.36
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
100.00%
1000
10.00
0.56
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
66.86%
71.00%
1000
14.00
0.56
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
71.51%
76.00%
1000
20.00
0.56
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
76.80%
80.00%
1000
28.00
0.56
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
82.15%
85.00%
1000
40.00
0.56
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
88.22%
94.00%
1000
10.00
0.56
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
71.08%
78.00%
1000
14.00
0.56
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
76.03%
81.00%
1000
20.00
0.56
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
81.66%
85.00%
1000
28.00
0.56
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
87.34%
92.00%
1000
40.00
0.56
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
93.80%
98.00%
1000
10.00
0.56
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
77.25%
86.00%
1000
14.00
0.56
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
82.63%
90.00%
1000
20.00
0.56
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
88.74%
98.00%
1000
28.00
0.56
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
94.91%
98.00%
1000
40.00
0.56
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
100.00%
99.00%
1000
10.00
0.73
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
60.13%
60.00%
1000
14.00
0.73
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
64.32%
65.00%
1000
20.00
0.73
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
69.07%
70.00%
1000
28.00
0.73
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
73.88%
76.00%
550
Ref. [3] pp.285 & 321, [9], pp.174
Case
Total
Droplet
Bed
phase
phase
concentration
diameter
density
density
of
continuous
dispersed
phase
phase
Co
dp
mg/l
kg/cu.m
kg/cu.m
kg/cu.m
Empty
bed
velcity
Interfacial
tension
o/w
Calculated
Observed
removal
efficiency
efficiency
from
from
experiment(by
model
d observed
1000
40.00
0.73
0.03
914.5
998
83.5
(N.s)/m2 (N.s)/m2
m/s
N/m
(=1000cP (=0.1000cP)
(=1000dyn/cm
2.10E-03 1.07E-03
0.0027
1.10E-02
79.34%
91.00%
1000
10.00
0.73
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
63.93%
63.00%
1000
14.00
0.73
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
68.38%
69.00%
1000
20.00
0.73
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
73.44%
75.00%
1000
28.00
0.73
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
78.55%
81.00%
1000
40.00
0.73
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
84.36%
95.00%
1000
10.00
0.73
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
69.48%
71.00%
1000
14.00
0.73
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
74.31%
76.00%
1000
20.00
0.73
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
79.81%
84.00%
1000
28.00
0.73
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
85.36%
90.00%
1000
40.00
0.73
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
91.68%
98.00%
1000
10.00
0.94
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
54.35%
53.00%
1000
14.00
0.94
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
58.13%
58.00%
1000
20.00
0.94
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
62.43%
61.00%
1000
28.00
0.94
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
66.77%
66.00%
1000
40.00
0.94
0.03
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
71.71%
75.00%
1000
10.00
0.94
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
57.78%
57.00%
1000
14.00
0.94
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
61.81%
61.00%
1000
20.00
0.94
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
66.38%
65.00%
1000
28.00
0.94
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
71.00%
71.00%
1000
40.00
0.94
0.05
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
76.25%
82.00%
1000
10.00
0.94
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
62.79%
63.00%
1000
14.00
0.94
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
67.17%
67.00%
1000
20.00
0.94
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
72.13%
72.00%
1000
28.00
0.94
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
77.15%
78.00%
1000
40.00
0.94
0.1
914.5
998
83.5
2.10E-03
1.07E-03
0.0027
1.10E-02
82.86%
92.00%
1000
10.00
0.73
0.03
795
998
203
1.35E-03
1.07E-03
0.0027
4.20E-02
69.68%
68.00%
1000
14.00
0.73
0.03
795
998
203
1.35E-03
1.07E-03
0.0027
4.20E-02
74.53%
77.00%
1000
20.00
0.73
0.03
795
998
203
1.35E-03
1.07E-03
0.0027
4.20E-02
80.04%
84.50%
1000
28.00
0.73
0.03
795
998
203
1.35E-03
1.07E-03
0.0027
4.20E-02
85.61%
90.00%
1000
40.00
0.73
0.03
795
998
203
1.35E-03
1.07E-03
0.0027
4.20E-02
91.94%
92.00%
1000
10.00
0.73
0.03
994.1
998
3.9
1.09E-03
1.07E-03
0.0027
1.60E-02
44.33%
40.50%
1000
14.00
0.73
0.03
994.1
998
3.9
1.09E-03
1.07E-03
0.0027
1.60E-02
47.42%
45.50%
1000
20.00
0.73
0.03
994.1
998
3.9
1.09E-03
1.07E-03
0.0027
1.60E-02
50.93%
51.00%
1000
28.00
0.73
0.03
994.1
998
3.9
1.09E-03
1.07E-03
0.0027
1.60E-02
54.47%
56.00%
1000
40.00
0.73
0.03
994.1
998
3.9
1.09E-03
1.07E-03
0.0027
1.60E-02
58.50%
73.00%
1000
10.00
0.73
0.03
684
998
314
4.20E-04
1.07E-03
0.0027
3.62E-02
64.47%
62.00%
1000
14.00
0.73
0.03
684
998
314
4.20E-04
1.07E-03
0.0027
3.62E-02
68.96%
66.00%
1000
20.00
0.73
0.03
684
998
314
4.20E-04
1.07E-03
0.0027
3.62E-02
74.06%
72.10%
1000
28.00
0.73
0.03
684
998
314
4.20E-04
1.07E-03
0.0027
3.62E-02
79.21%
89.00%
1000
40.00
0.73
0.03
684
998
314
4.20E-04
1.07E-03
0.0027
3.62E-02
85.07%
90.00%
1000
10.00
0.73
0.03
860
998
138
7.16E-04
1.07E-03
0.0027
3.03E-02
61.93%
57.50%
1000
14.00
0.73
0.03
860
998
138
7.16E-04
1.07E-03
0.0027
3.03E-02
66.24%
64.50%
1000
20.00
0.73
0.03
860
998
138
7.16E-04
1.07E-03
0.0027
3.03E-02
71.14%
75.00%
1000
28.00
0.73
0.03
860
998
138
7.16E-04
1.07E-03
0.0027
3.03E-02
76.09%
83.00%
1000
40.00
0.73
0.03
860
998
138
7.16E-04
1.07E-03
0.0027
3.03E-02
81.71%
89.00%
551
Annex A2.2 Corresponding Kozeny-Carman's Porosity () for lower (critical) and upper part of bed and Porosity for single step caluculation
Ref. [3], pp.126,and [26], pp.49
Case Bed media
Bed
Dispersed Continuous Dynamic Dynamic Empty Interfacial tension Observed
Predicted Hc Corresponding Correcponding
corresponding
diameter
height
phase
phase viscosity of viscosity
bed
headloss
porosity for
porosity for H>Hc porosity for onedensity
density
dispersed
of
velcity
H<Hc
step calculation
phase
continuous
phase
d
c
o/w
d
c
V
dp
H
m
m
kg/cu.m
kg/cu.m
(N.s)/m2
(N.s)/m2
m/s
N/m
m
m
for H<Hc
for H>Hc
(=1000cP) (=1000cP)
(=1000dyn/cm)
1
6.50E-04
0.025
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
0.422
0.101
0.151
0.000
0.150
6.50E-04
0.05
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
0.654
0.101
0.162
0.000
0.162
6.50E-04
0.075
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.144
0.101
0.155
0.000
0.155
6.50E-04
0.1
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.539
0.101
0.155
0.000
0.155
6.50E-04
0.2
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.879
0.101
0.154
0.250
0.179
2
4.08E-04
0.025
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
0.545
0.062
0.184
0.000
0.184
4.08E-04
0.05
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.089
0.062
0.184
0.000
0.184
4.08E-04
0.075
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.607
0.062
0.177
0.265
0.185
4.08E-04
0.1
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.798
0.062
0.177
0.265
0.194
4.08E-04
0.2
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
2.315
0.062
0.177
0.265
0.220
3
2.20E-04
0.01
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.430
0.032
0.152
0.000
0.152
2.20E-04
0.025
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
4.358
0.032
0.143
0.000
0.143
2.20E-04
0.05
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
5.175
0.032
0.148
0.291
0.167
2.20E-04
0.075
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
5.992
0.032
0.148
0.291
0.180
2.20E-04
0.1
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
6.537
0.032
0.148
0.291
0.191
4
8.75E-05
0.01
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
8.171
0.010
0.141
0.000
0.157
8.75E-05
0.025
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
18.385
0.010
0.141
0.141
0.162
8.75E-05
0.05
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
60.263
0.010
0.141
0.141
0.139
8.75E-05
0.075
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
91.927
0.010
0.141
0.141
0.139
8.75E-05
0.1
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
127.676
0.010
0.141
0.141
0.137
5
6.50E-04
0.1
829
998
2.95E-03 1.08E-03 0.0017
2.20E-02
1.906
0.145
6
2.20E-04
0.02
829
998
2.95E-03 1.08E-03 0.0019
2.20E-02
3.541
0.147
7
3.00E-04
0.045
829
998
2.95E-03 1.08E-03
0.002
2.20E-02
1.226
0.211
8
3.00E-04
0.045
829
998
2.95E-03 1.08E-03
0.002
2.20E-02
0.286
0.318
9
3.00E-04
0.045
829
998
2.95E-03 1.08E-03
0.005
2.20E-02
8.171
0.162
10
3.00E-04
0.045
829
998
2.95E-03 1.08E-03
0.005
2.20E-02
5.447
0.183
11
0.00022
0.02
829
998
2.95E-03 1.08E-03 0.0025
2.20E-02
3.813
0.156
12
2.20E-04
0.02
829
998
2.95E-03 1.08E-03
0.02
2.20E-02
11.575
0.207
13
0.00065
0.02
829
998
2.95E-03 1.08E-03 0.0025
2.20E-02
0.817
0.130
14
6.50E-04
0.02
829
998
2.95E-03 1.08E-03
0.02
2.20E-02
2.043
0.183
552
Annex A2.3 Comparison between calculated efficiency and experimental result for brush-type bed coalescer (Based on Newly proposed SRIJAROONRAT's and TAPANEEYANGKUL's model)
Proposed SRIJAROONRAT's model
TAPANEEYANGKUL's model
-0.77
(dE/D)0.18 (dF/D)-0.18(H/D)0.694(1-)0.35
Eff(%) = 1.76 (c Vp D/c)-0.21 (dE/D)0.58 (dF/D)-0.58 (H/D)0.35 (1-)0.35 (DN/Vp)0.53
Eff(%) = 104.5(c Vp D/c)
Dynamic
Calculated
Droplet
Fiber
Bed
Porosity Bed height Dispersed Continu Density
Empty Interfaci
Case Ref. page Total
Dynamic
Observed
Assumed
Calculated
removal
ous
al
phase
bed
hydrocar diameter diameter diameter
efficiency
rotating speed
removal
of
efficiency from
phase
density
bon
continuous velcity tension
from
for
efficiency from
dispersed
Srijaroonrat's experiment(by Tapaneeyangkul Tapaneeyungkul
density
concentr
phase
phase
model
ation
droplet size)
model
's model
d
c
d
c
o/w
Co
dE
dF
D
Vp
Eff
Eff exp
N
Eff tapanee
Re
m/s
N/m
%
%
RPM
mg/l
m
m
m
m
kg/cu.m kg/cu.m kg/cu.m (N.s)/m2
(N.s)/m2
(=1000d
(=1000cP) (=0.1000cP)
yn/cm)
1
10 198
1000
1.8E-06 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
39.06%
39.66%
450
15.45%
2
10 198
1000
2.9E-06 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
42.51%
35.59%
450
20.29%
3
10 198
1000
1.6E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
58.01%
57.97%
450
55.26%
4
10 198
1000
2.4E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
62.49%
67.12%
450
70.21%
5
10 198
1000
4.8E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
70.60%
100.00%
450
100.00%
6
10 198
1000
6.4E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.02 3.30E-02 932.71
74.45%
100.00%
450
100.00%
7
10 198
1000 1.429E-06 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
63.99%
69.15%
450
22.67%
8
10 198
1000 1.786E-06 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
66.61%
68.14%
450
25.81%
9
10 198
1000 2.857E-06 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
72.49%
61.02%
450
33.89%
10 10 198
1000 1.214E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
94.06%
75.25%
450
78.44%
11 10 198
1000 1.607E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
98.93%
85.42%
450
92.29%
12 10 198
1000 2.429E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
100.00%
85.42%
450
100.00%
13 10 198
1000 3.214E-05 1.00E-04 5.00E-02
0.91
0.3
795
998
203
1.35E-03
1.07E-03
0.01 3.30E-02 466.36
100.00%
100.00%
450
100.00%
932.71
71.56%
19.46%
720
34.85%
14 16
67
520
5.00E-06 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
73.95%
57.30%
720
38.73%
15 16
67
520
6.00E-06 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
77.88%
71.35%
720
45.77%
16 16
67
520
8.00E-06 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
79.54%
81.08%
720
49.00%
17 16
67
520
9.00E-06 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
83.62%
90.81%
720
57.56%
18 16
67
520
1.19E-05 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
84.75%
94.05%
720
60.11%
19 16
67
520
1.28E-05 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
90.65%
97.30%
720
74.66%
20 16
67
520
1.86E-05 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
94.47%
99.46%
720
85.29%
21 16
67
520
2.34E-05 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
932.71
98.43%
100.00%
720
97.36%
22 16
67
520
2.94E-05 2.00E-04 5.00E-02 0.845
0.5
900
998
98
1.10E-03 1.07E-03
0.02
N/A
23
8
84
1000
8.00E-06 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
1.89%
450
100.00%
24
8
84
1000
9.00E-06 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
20.38%
450
100.00%
25
8
84
1000
1.20E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
24.91%
450
100.00%
26
8
84
1000
1.50E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
40.75%
450
100.00%
27
8
84
1000
1.90E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
46.79%
450
100.00%
28
8
84
1000
2.40E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
64.15%
450
100.00%
29
8
84
1000
3.00E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
77.74%
450
100.00%
30
8
84
1000
3.80E-05 1.00E-04 5.20E-02
0.96
0.2
795
998
203
1.35E-03 1.07E-03
0.001
0.042
48.50
100.00%
90.57%
450
100.00%
1.00E-06 1.00E-04 5.00E-02 0.91
0.1
795
998
203
1.35E-03 1.07E-03
0.02 4.20E-02 932.71
16.42%
52.00%
450
7.51%
31 11 229 1% V/V
32
11
229
1% V/V
33
11
229
1% V/V
34
11
229
1% V/V
35
11
229
1% V/V
36
11
229
1% V/V
37
11
229
1% V/V
2.00E-06
3.00E-06
8.00E-06
1.20E-05
1.60E-05
2.40E-05
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
18.60%
48.00%
450
11.23%
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
20.01%
55.00%
450
14.21%
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
23.87%
43.00%
450
25.10%
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
25.68%
34.00%
450
31.76%
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
27.04%
44.00%
450
37.52%
1.00E-04 5.00E-02
0.91
0.1
795
998
203
1.35E-03
1.07E-03
0.02
4.20E-02
932.71
29.09%
44.00%
450
47.47%
553
Annex A.3 DAF tested by SIEM
[12] pp.130
Description
Wastewater
Qin
flowrate
Pressurized
Qwater
water flowrate
Qin/Qwater
Total flow
Qtotal
Column cross
section area
Velocity based
on total flow
Air flowrate
degassed in
DAF column
Dissolved air
quantity in
pressurized
water
Effective
column height
Bubble diameter
Dispersed
phase density
Continuous
phase density
Air density
Dispersed
phase viscosity
Continuous
phase viscosity
Bolzman
constant
Temperature
cu.m/s
Value
3.9E-06
cu.m/s
4.2E-06
Ao
cu.m/s
l/hr
m2
0.92
8.14E-06
29.31
0.0177
Vo
m/s
4.60E-04
cu.m/s
4.20E-07
kg/cu.m
0.119
0.7
dB
d
m
kg/cu.m
7.00E-05
850
kg/cu.m
998
kg/cu.m
kg/m.s
1.201
0.0011
kg/m.s
0.00108
Kelvin
1.38E-23
293
K
T
554
Annex A.3 Comparison between observed efficiency and predicted efficiency for DAF
[12] pp.130
Item
1
2
3
4
5
6
7
8
9
10
11
12
13
Bubble
diameter
Droplet
diameter
dB
m
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
7.00E-05
dE
m
2.10E-06
2.60E-06
3.30E-06
4.10E-06
5.10E-06
6.50E-06
8.20E-06
1.03E-05
1.30E-05
1.64E-05
2.06E-05
2.59E-05
3.27E-05
Rising
Rising
velocity velocity of
of droplet
bubble
u
U
m/s
m/s
3.29E-07 2.46E-03
5.05E-07 2.46E-03
8.13E-07 2.46E-03
1.26E-06 2.46E-03
1.94E-06 2.46E-03
3.16E-06 2.46E-03
5.02E-06 2.46E-03
7.92E-06 2.46E-03
1.26E-05 2.46E-03
2.01E-05 2.46E-03
3.17E-05 2.46E-03
5.01E-05 2.46E-03
7.99E-05 2.46E-03
Relative Sedimentati Interception

velocity
on
efficiency
efficiency
S
I
U-u
m/s
2.46E-03 1.34E-04
1.35E-03
2.46E-03 2.05E-04
2.07E-03
2.46E-03 3.30E-04
3.33E-03
2.46E-03 5.10E-04
5.15E-03
2.46E-03 7.89E-04
7.96E-03
2.46E-03 1.28E-03
1.29E-02
2.46E-03 2.04E-03
2.06E-02
2.46E-03 3.23E-03
3.25E-02
2.45E-03 5.15E-03
5.17E-02
2.44E-03 8.22E-03
8.23E-02
2.43E-03 1.30E-02
1.30E-01
2.41E-03 2.07E-02
2.05E-01
2.38E-03 3.35E-02
3.27E-01
555
Diffusio Theoritica Predicted predicted Observed

n
l totla
(Co-Cs)/Co (Co-Cs)/Co
efficienc efficiency efficiency
D
t theo
exp
predicted
4.3E-04 1.91E-03 2.21E-04 15.75%
0.00%
3.7E-04 2.64E-03 2.68E-04 18.75%
16.01%
3.2E-04 3.98E-03 3.42E-04 23.24%
20.66%
2.7E-04 5.93E-03 4.33E-04 28.46%
26.79%
2.4E-04 8.99E-03 5.54E-04 34.84%
37.42%
2.0E-04 1.44E-02 7.32E-04 43.26%
50.42%
1.7E-04 2.28E-02 9.61E-04 52.44%
58.48%
1.5E-04 3.58E-02 1.26E-03 62.15%
67.49%
1.3E-04 5.70E-02 1.65E-03 72.16%
74.05%
1.1E-04 9.07E-02 2.17E-03 81.41%
79.93%
9.4E-05 1.43E-01 2.85E-03 88.96%
86.61%
8.1E-05 2.26E-01 3.74E-03 94.45%
93.94%
7.0E-05 3.61E-01 4.93E-03 97.79%
96.58%
Observed
total
efficiency
exp
observed
2.25E-04
2.99E-04
4.03E-04
6.06E-04
9.07E-04
1.14E-03
1.45E-03
1.74E-03
2.08E-03
2.60E-03
3.62E-03
4.36E-03
Annex A3.1 Two-Phases hydrocyclone tested by MA

Ref. [26] pp.105
Description
Value
Flowrate
Q
cu.m/s 5.40E-04
Diameter of upper
D
m
4.00E-02
cylindical part
Nominal diameter of
Dn
m
2.00E-02
hydrocyclone
Inlet diameter (2 ports)
Di
m
7.00E-03
Overflow diameter
Dover
m
2.00E-03
Dunder
m
1.00E-02
Underflow diameter
Angle of conical part
Rad
2.62E-02
Dispersed phase density

kg/cu.m 9.00E+02
d
Continuous phase
kg/cu.m 9.98E+02
c
Viscosity
Ns/m2 1.00E-03
c
Comparison between Observed efficiency and predicted efficiency from Ma's
and COLMAN's model for Two-Phases hydrocyclone

Ref. [26] pp.105, [16] pp.49
d75% for COLMAN model is based on [29] pp.15.

Efficienc Observed
Droplet
Droplet from
y
data
diameter
Ma's
from
predicted from Trajectory
[16], p105 COLMAN ([16]
method
eff%
dE
dE
dE
m
m
m
%
5%
8.49
10%
9.66
15%
10.89
20%
12.19
13.08
25%
13.58
30%
22
15.10
17.91
35%
16.70
40%
24
18.43
22.52
50%
25.6
22.36
26.63
60%
28.12
27.18
30.58
70%
30.75
33.39
34.12
75%
37.32
80%
34.7
42.12
37.26
90%
40
57.13
40.09
95%
72.05
99%
55.78
105.49
42.33
100%
156.93
42.54
556
Annex A3.2 Three-Phases hydrocyclone tested by MA

Ref. [16] pp.151
Description
Flowrate
Diameter of
upper
cylindical
Nominal
diameter of
inlet of oil
Inlet
diameter (2
Underflow
diameter for
SS
Underflow
diameter for
oil
Angle of
conical oil
Angle of
conical SS
part
Split ratio
Value
Q
D
cu.m/h
m
1.40E+00
4.00E-02
Do
1.40E-02
Di
5.60E-03
Du
6.00E-03
Dp
1.00E-03
1.5o
12o
2%
Comparison between Observed efficiency and predicted efficiency for
Three-Phases hydrocyclone
Ref. [16] pp.51
Efficiency
%
10
20
30
40
50
60
80
100
100
Droplet from Droplet from

predicted
observed
efficiency
efficiency
curve (micron) curve (micron)
5.07
8.5
9.00
9
12.46
15.81
10.5
18.82
12
21.73
14.25
26.83
20.5
31.02
42
50
557
Annex A5.1 Comparison between calculated flux and experimental result from resistance model of UF (reference temparature 20oC)
Item
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
Note
Gel resistance
Gel
Predicted
Concentratio Observed flux Membrane
Alpha
resistance
coefficient (Rg (exponent of concentration flux (J = Pt/
n (by volume
(Rm + Rg))
of oil, not
V)
= V Pt)
the
P or Pt
V
Co
Jobserved
Rm
Cg
Jpredicted
2
bar
m/s
%
%
l/(h.m2)
l/(h.m )
0
2.8
4
0
0.430
0.022
-1.500
16.200
0.00
0.1
2.8
4
14
0.430
0.022
-1.500
16.200
20.97
0.5
2.8
4
70.8
0.022
-1.500
16.200
0.430
75.21
1
2.8
4
114
0.022
-1.500
16.200
0.430
111.17
1.5
2.8
4
137.29
0.022
-1.500
16.200
0.430
132.24
2
2.8
4
150.8
0.022
-1.500
16.200
0.430
146.08
2.5
2.8
4
162.16
0.022
-1.500
16.200
0.430
155.87
3
2.8
4
165.4
0.022
-1.500
16.200
0.430
163.16
3.5
2.8
4
168.6
0.022
-1.500
16.200
0.430
168.80
0
2.1
4
0
0.022
-1.500
16.200
0.430
0.00
0.24
2.1
4
33.5
0.022
-1.500
16.200
0.430
39.77
0.5
2.1
4
60
0.022
-1.500
16.200
0.430
63.17
1
2.1
4
84.32
0.022
-1.500
16.200
0.430
86.74
1.5
2.1
4
97.3
0.022
-1.500
16.200
0.430
99.05
2
2.1
4
107.6
0.022
-1.500
16.200
0.430
106.62
2.5
2.1
4
110.8
0.022
-1.500
16.200
0.430
111.74
3
2.1
4
114
0.022
-1.500
16.200
0.430
115.44
0
1.4
4
0
0.022
-1.500
16.200
0.430
0.00
0.24
1.4
4
33.5
0.022
-1.500
16.200
0.430
32.05
0.5
1.4
4
45.4
0.022
-1.500
16.200
0.430
45.70
1
1.4
4
54
0.022
-1.500
16.200
0.430
56.88
1.5
1.4
4
59
0.022
-1.500
16.200
0.430
61.93
2
1.4
4
60
0.022
-1.500
16.200
0.430
64.80
2.5
1.4
4
62
0.022
-1.500
16.200
0.430
66.66
3
1.4
4
62.7
0.022
-1.500
16.200
0.430
67.96
3.5
1.4
4
63.24
0.022
-1.500
16.200
0.430
68.92
0
0.7
4
0
0.022
-1.500
16.200
0.430
0.00
0.1
0.7
4
14
0.022
-1.500
16.200
0.430
12.41
0.5
0.7
4
31.9
0.022
-1.500
16.200
0.430
21.66
1
0.7
4
33.5
0.022
-1.500
16.200
0.430
23.89
1.5
0.7
4
33.5
0.022
-1.500
16.200
0.430
24.73
2
0.7
4
33.5
0.022
-1.500
16.200
0.430
25.18
2.5
0.7
4
33.5
0.022
-1.500
16.200
0.430
25.46
3
0.7
4
33.5
0.022
-1.500
16.200
0.430
25.64
1.0
1.0
3.2
36.51
0.640
0.019
-1.401
16.200
40.07
0.019
-1.401
16.200
1.5
1.0
3.2
48.68
0.640
43.82
0.019
-1.401
16.200
2.0
1.0
3.2
48.68
0.640
45.96
0.019
-1.401
16.200
2.5
1.0
3.2
48.68
0.640
47.36
0.019
-1.401
16.200
3.0
1.0
3.2
48.68
0.640
48.33
0.019
-1.401
16.200
1.0
2.0
3.2
60.85
0.640
74.47
0.019
-1.401
16.200
1.5
2.0
3.2
93.31
0.640
88.53
0.019
-1.401
16.200
2.0
2.0
3.2
101.42
0.640
97.76
0.019
-1.401
16.200
2.5
2.0
3.2
109.54
0.640
104.29
0.019
-1.401
16.200
3.0
2.0
3.2
117.65
0.640
109.14
0.019
-1.401
16.200
1.0
2.8
3.2
97.37
0.640
92.70
0.019
-1.401
16.200
1.5
2.8
3.2
109.54
0.640
115.55
0.019
-1.401
16.200
2.0
2.8
3.2
133.88
0.640
131.79
0.019
-1.401
16.200
2.5
2.8
3.2
154.16
0.640
143.94
0.019
-1.401
16.200
3.0
2.8
3.2
170.39
0.640
153.35
1 Ref. [18] pp.86&88, Macroemulsion: Elf Seraft A, UF membrane: IRIS3042 (polyacrylic membrane), MWCO: 50 Kdalton (15 nm.)
2 Ref. [11] , Microemulsion: Elf G3EAB, UF membrane: IRIS3042 (polyacrylic membrane), MWCO: 50 Kdalton (15 nm.)
Transmembrane
pressure
Velocity
558
Ref.
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note1
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
see note2
Annex A5.2 Comparison between calculated flux and experimental result from film model of UF (reference temperature 20oC)
Item Velocity Transme Concentration Observed flux Constant Constant Constant Predicted flux J =
Ref.
mbrane (by volume of

k V ln (Cg/Co)
pressure
oil, not the
concentrate)
P or Pt
V
Co
Jobserved
k
Cg
Jpredicted
2
l/(h.m )
l/(h.m2)
m/s
bar
%
%
1
2.8
3.5
4
168.6
34.953 1.165
15.60
157.86
see note1
2.1
4
114
34.953 1.165
15.60
112.91
2
3.5
see note1
1.4
4
64
34.953 1.165
15.60
70.40
3
3.5
see note1
0.7
4
33.5
34.953 1.165
15.60
31.40
4
3.5
see note1
1.4
2
105.6
34.953 1.165
15.60
106.25
5
3.5
see note1
1.4
8
36
34.953 1.165
15.60
34.55
6
3.5
see note1
7
2.8
2
4
150.8
33.554 1.092
16.20
144.39
see note1
2.1
4
107.6
33.554 1.092
16.20
105.48
8
2
see note1
1.4
4
61.6
33.554 1.092
16.20
67.76
9
2
see note1
0.7
4
33.5
33.554
1.092
16.20
31.80
10
2
see note1
1.4
2
101.6
33.554 1.092
16.20
101.34
11
2
see note1
1.4
8
36
33.554 1.092
16.20
34.18
12
2
see note1
13
1.4
2
20
28.57
12.293 1.092 100.00
28.57
see note1
1.4
2
30
21.78
12.293 1.092 100.00
21.37
14
see note1
1.4
2
40
17.14
12.293 1.092 100.00
16.27
15
see note1
1.4
2
50
11.78
12.293 1.092 100.00
12.30
16
see note1
3
see note2
17
1
0.64
42.56
15.448 1.146 14.505
48.21
1.5
3
99.72
15.448 1.146 14.505
76.72
see note2
18
0.64
2
3
113.59
15.448 1.146 14.505
106.67
see note2
19
0.64
2.3
3
130.72
15.448
1.146
14.505
125.19
see note2
20
0.64
2.8
3
142.60
15.448 1.146 14.505
156.84
see note2
21
0.64
2.8
3
1.28
110.91
15.448 1.146 14.505
122.00
see note2
22
1
Ref.
[18]
pp.86&88,
Macroemulsion:
Elf
Seraft
A,
UF
membrane:
IRIS3042
(polyacrylic
membrane),
MWCO: 50 Kdalton (15 nm.)
Note
3 For item 13 to 16, Cg changes from 16.2% (of item 7-12) to 100%. So there is an inflection point in
flux vs. ln(Co) curve. In this case, the concentration at the inflection point is around 8.0%.
4 Data in tiem 1-6 and item 7 to 12 are observed from the same emulsion but at different pressure.
559
Annex A5.3 Comparison between calculated flux and experimental result from combination film and resistance model of UF (reference temperature 20oC)
Ref Gel
Refernce Reference
J at
J at C,V
J at
Alpha
Gel
Oil
Ref.
Item Transmembran Velocity Concentr Observed Membrane Ref Gel
Ref
Predicted
k
Beta
C,Vref
Cinf,V (exponent resistance flux (J = Pt/
concentration concentrat
e pressure
ation
flux
resistance resistance
Alpha
of V) at C coefficient (Rm + Rg))
ion
coefficient (exponent at inflection
(P=3.5
point
of V)
(Rg = V
(Rg = V
bar)
Pt)
Pt)
P or Pt
ref
ref
ref
at C
at C
V
Co
J
Rm
k ref
Cinf
Cg ref
J
bar
m/s
%
%
%
l/(h.m2)
l/(h.m2)
l/(h.m2)
l/(h.m2)
l/(h.m2)
1
0.2
1.400
2.0
27.2
0.430
0.022
-1.500
8.000
16.200
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
34.22
see note1
0.5
2.0
68.8
0.022
-1.500
8.000
16.200
2
1.400
0.430
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
61.27
see note1
1
2.0
86.4
0.022
-1.500
8.000
16.200
3
1.400
0.430
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
83.19
see note1
1.5
2.0
96
0.022
-1.500
8.000
16.200
4
1.400
0.430
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
94.45
see note1
2
2.0
101.6
0.022
-1.500
8.000
16.200
5
1.400
0.430
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
101.31
see note1
2.5
2.0
104.8
0.022
-1.500
8.000
16.200
6
1.400
0.430
33.540
1.092
101.314 101.313
34.172
-1.396
0.012
105.93
see note1
0.2
8.0
27.2
0.022
-1.500
8.000
16.200
7
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
20.57
see note1
0.5
8.0
34.8
0.022
-1.500
8.000
16.200
8
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
28.00
see note1
1
8.0
36
0.022
-1.500
8.000
16.200
9
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
31.84
see note1
1.5
8.0
36
0.022
-1.500
8.000
16.200
10
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
33.36
see note1
2
8.0
36
0.022
-1.500
8.000
16.200
11
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
34.18
see note1
2.5
8.0
36
0.022
-1.500
8.000
16.200
12
1.400
0.430
33.540
1.092
34.178
34.178
34.172
-1.179
0.040
34.69
see note1
1
2.800
1.28
63.38
0.64
0.015
-1.130
14.505
15.448
1.146
82.975
122.002
-1.463
0.027
80.24
13
see note 2
1.5
2.800
1.28
87.15
0.64
0.015
-1.130
14.505
15.448
1.146
82.975
122.002
-1.463
0.027
96.81
14
see note 2
2
2.800
1.28
99.03
0.64
0.015
-1.130
14.505
15.448
1.146
82.975
122.002
-1.463
0.027
107.95
15
see note 2
2.5
2.800
1.28
106.95
0.64
0.015
-1.130
14.505
15.448
1.146
82.975
122.002
-1.463
0.027
115.97
16
see note 2
3
2.800
1.28
110.91
0.64
0.015
-1.130
14.505
15.448
1.146
82.975
122.002
-1.463
0.027
122.00
17
see note 2
Note 1 Ref. [18] pp.86&88, Macroemulsion: Elf Seraft A, UF membrane: IRIS3042 (polyacrylic membrane), MWCO: 50 Kdalton (15 nm.)
3 For data in item 1 to 12, The velocity at required condition is the same as reference velocity (1.4 m/s). In this case, dummy condition at inflection point (C =8%) is introduced to show that the model can be used at any cond
(see Part2, section 6.1.3)
560
Annex A5.4 Comparison between calculated flux and experimental result of macro
.microemulsion mixture(reference temperature20 oC)
Item
Velocity
V
m/s
1.00
1.00
1.00
1.00
1.00
1.00
2.00
2.00
2.00
2.00
2.00
2.00
2.80
2.80
2.80
2.80
2.80
2.80
1.00
1.00
1.00
1.00
1.00
1.00
Flux of
Flux of
Predicted
Transmembra
%V of
%V of
% oil in
% oil in
% oil of Observed
macroemulsion microemulsion flux of the
ne pressure macroemulsi microemulsi macroemulsi microemulsio mixture
flux
mixture
at Coil,mix (2) at Coil,mix (2)
on
on
on
n concentrate
P or Pt
Cmac
Cmic
Roil,mac
Roil,mic
Coil,mix
J
Jmac:Coil,mix Jmic:Coil,mix
Jmix
2
bar
%
%
%
%
l/(h.m2)
l/(h.m2)
l/(h.m2)
l/(h.m )
0.00
0.00
0.00
0.0
4.0
1.0
80.0
32.0
0
3.52
46.12
20.01
43.75
1.0
4.0
1.0
80.0
32.0
27.73
3.52
49.39
20.90
46.80
1.5
4.0
1.0
80.0
32.0
27.73
3.52
51.20
21.38
48.49
2.0
4.0
1.0
80.0
32.0
35.65
3.52
52.35
21.67
49.56
2.5
4.0
1.0
80.0
32.0
43.57
3.52
53.15
21.88
50.31
3.0
4.0
1.0
80.0
32.0
43.57
3.52
0.00
0.00
0.00
0.0
4.0
1.0
80.0
32.0
0.00
3.52
88.40
40.11
84.01
1.0
4.0
1.0
80.0
32.0
63.38
3.52
101.23
43.87
96.01
1.5
4.0
1.0
80.0
32.0
71.30
3.52
109.14
46.02
103.41
2.0
4.0
1.0
80.0
32.0
87.15
3.52
114.52
47.42
108.42
2.5
4.0
1.0
80.0
32.0
95.07
3.52
118.41
48.40
112.04
3.0
4.0
1.0
80.0
32.0
99.03
3.52
0.00
0.00
0.00
0.0
4.0
1.0
80.0
32.0
0.00
3.52
117.71
54.59
111.97
1.0
4.0
1.0
80.0
32.0
91.11
3.52
141.61
61.78
134.35
1.5
4.0
1.0
80.0
32.0
110.91
3.52
157.60
66.14
149.28
2.0
4.0
1.0
80.0
32.0
126.76
3.52
169.06
69.06
159.97
2.5
4.0
1.0
80.0
32.0
142.60
3.52
177.67
71.16
167.98
3.0
4.0
1.0
80.0
32.0
146.56
3.52
0.00
0.00
0.00
0.00
0.0
4.0
2.0
80.0
32.0
3.84
29.09
43.74
18.88
39.60
1.0
4.0
2.0
80.0
32.0
3.84
29.09
46.67
19.67
42.17
1.5
4.0
2.0
80.0
32.0
3.84
2.0
4.0
2.0
80.0
32.0
37.40
48.28
20.09
43.58
3.84
2.5
4.0
2.0
80.0
32.0
41.55
49.31
20.35
44.48
3.84
3.0
4.0
2.0
80.0
32.0
45.71
50.01
20.53
45.10
3.84
0.0
4.0
2.0
80.0
32.0
0.00
0.00
0.00
0.00
3.84
1.0
4.0
2.0
80.0
32.0
45.71
84.27
38.05
76.57
3.84
1.5
4.0
2.0
80.0
32.0
62.33
95.85
41.41
86.78
3.84
2.0
4.0
2.0
80.0
32.0
70.64
102.92
43.32
92.99
3.84
2.5
4.0
2.0
80.0
32.0
74.79
107.69
44.56
97.17
3.84
3.0
4.0
2.0
80.0
32.0
74.79
111.12
45.42
100.17
3.84
0.0
4.0
2.0
80.0
32.0
0.00
0.00
0.00
0.00
3.84
1.0
4.0
2.0
80.0
32.0
78.95
112.63
51.98
102.52
3.84
1.5
4.0
2.0
80.0
32.0
91.41
134.31
58.46
121.67
3.84
2.0
4.0
2.0
80.0
32.0
103.88
148.62
62.35
134.24
3.84
2.5
4.0
2.0
80.0
32.0
103.88
158.76
64.94
143.12
3.84
3.0
4.0
2.0
80.0
32.0
108.03
166.33
66.79
149.74
3.84
0.0
4.0
4.0
80.0
32.0
0.00
0.00
0.00
0.00
4.48
1.0
4.0
4.0
80.0
32.0
23.77
37.51
16.85
31.60
4.48
1.5
4.0
4.0
80.0
32.0
27.73
39.64
17.47
33.31
4.48
2.0
4.0
4.0
80.0
32.0
31.69
40.80
17.80
34.23
4.48
2.5
4.0
4.0
80.0
32.0
31.69
41.53
18.01
34.81
4.48
3.0
4.0
4.0
80.0
32.0
35.65
42.03
18.15
35.20
4.48
0.0
4.0
4.0
80.0
32.0
0.00
0.00
0.00
0.00
4.48
1.0
4.0
4.0
80.0
32.0
39.61
73.27
34.28
62.13
4.48
1.5
4.0
4.0
80.0
32.0
55.46
81.87
36.99
69.04
4.48
2.0
4.0
4.0
80.0
32.0
67.34
86.97
38.50
73.12
4.48
2.5
4.0
4.0
80.0
32.0
67.34
90.35
39.48
75.81
4.48
3.0
4.0
4.0
80.0
32.0
71.30
92.75
40.15
77.72
4.48
0.0
4.0
4.0
80.0
32.0
0.00
0.00
0.00
0.00
4.48
1.0
4.0
4.0
80.0
32.0
63.38
98.88
47.16
84.10
4.48
1.5
4.0
4.0
80.0
32.0
83.18
115.21
52.44
97.28
4.48
2.0
4.0
4.0
80.0
32.0
91.11
125.58
55.54
105.57
4.48
2.5
4.0
4.0
80.0
32.0
99.03
132.75
57.59
111.27
4.48
3.0
4.0
4.0
80.0
32.0
99.03
138.00
59.04
115.44
4.48
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
2.00
25
2.00
26
2.00
27
2.00
28
2.00
29
2.00
30
2.80
31
2.80
32
2.80
33
2.80
34
2.80
35
2.80
36
1.00
37
1.00
38
1.00
39
1.00
40
1.00
41
1.00
42
2.00
43
2.00
44
2.00
45
2.00
46
2.00
47
2.00
48
2.80
49
2.80
50
2.80
51
2.80
52
2.80
53
2.80
54
Note 1 Use reference data of flux of microemulsion and macroemulsion from Annex A5.1 and 5.2 and culculate flux at any concentration by
combination model (as shown in Annex 5_3).
561

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THESE

CONTRIBUTION A LA MISE AU POINT DUN LOGICIEL DE

Soutenance prvue le 16 Dcembre 2005 devant la commission dexamen:

Professeur, IUT, Lorient

Professeur, UPS, Toulouse

Professeur, INSA, Toulouse

Professeur, INSA, Toulouse

Professeur Emrite, INSA, Toulouse

PDG, Progress Technology Consultants Co.,Ltd., Thalande

Professeur Emrite, INSA, Toulouse

Sommaire des procds de traitement des eaux rsiduaires huileuses

Les modles mathmatiques de deux types dcrmeur : le tambour et le disque

Pour le disque dshuileur,

(0.5 D )2.54 (0.5 D I ) 2.54 m3/s

P = Productivit en huile du tambour ou du disque (relative une

Tension superficielle tension de lhuile (kg/s2

Fig. 1-1 Tambour dhuileur

Fig. 1-2 Disque dhuileur (Par: Abanaki)

Les modles sont valides dans ces hypothses ;

Pour le tambour dshuileur, la vitesse priphrique ne devrait pas tre suprieure de

La vitesse ascensionnelle dune

La diamtre de coupure, cest--dire la plus petite taille de gouttelette dont lefficacit de

(A = aire ecoulement, Q = debit d c =

Pour un dcanteur compact qui

1re tape : La Transportation, qui se constitue de 3 phnomnes de transport

2me tape : LAdhsion-Coalescence. Lefficacit de cette tape dpend

3me tape : La Relargage de la phase disperse. Cette tape dpend de 4

Fig. 3-1 Schma dun coalesceur

Fig. 3-2 Schma des 3modes de transport de ltape 1

Les modles sont valides dans ces hypothses ;

La diemtre de collecteur (dp) = 0.36 - 0.94 mm.

Les modles sont valides dans ces hypothses ;

0.67d 0.58 (1 ) 0.35 H0.35 N0.53

Les modles sont valides dans ces hypothses,

cVD 0.23 d 0.03 d F 0.. 03 H 0.36

Les modles sont valides dans ces hypothses,

Re est entre 840 - 2470.

Les modles des pertes de charge sont aussi proposes ;

Pour les coalesceurs fibreux, lquation de Hazen-William est utilise,

Finalement, plusieurs ides initiatives pour amliorer la performance du coalesceur,

Fig. 4-1 Representation schmatique de vitesses at vitesse relative et schma de la

Vr= vitesse relative decoulement

Fig. 4-2 Schma des 3modes de transport

( exp ) = 0.009005( theo )

theo = sed + Int + diff

sed = oil / water

Viscosit de phase contenue (eau) (L2/T)

Temprature absolue (Kelvin)

Quant lquation de gnralisation du modle de SIEM, fonde sur le concept de

Les quations pour le design du pressurisateur ou du systme de leau pressuris

Le dbit du gas ou d air dgaz,

o H = constante de Henry (molair/(m3water-atm)) et y = fraction molaire du gaz

La consommation nergtique du pressurisateur au dbit Qpw,

O Rair = Constante universal du gaz. T = temprature absolue

(0.5D n Z tan( / 2)) 2

Pour le hydrocyclone de type THEW, quand Z = L:

Fig. 5-1 Trajectories of oil droplets and typical efficiency curve

Les modles sont valides dans ces conditions,

MA et AURELLE a galement invent une nouvelle type dhydrocyclone pour la