‫ﺑﺳﻢ ﷲ اﻠﺮﺣﻣﻦ اﻠﺮﺣﻴﻢ‬

MINISTRY OF HIGH EDUCATION AND SCIENTIFIC

RESERCH
AL-QADISIYAH UNIVERSITY
COLLEGE OF ENGINEERING
CHEMICAL ENGINEERING DEPARTMENT

PRODUCTION OF NAPHTHALENE
A Project Submitted to the College Of Engineering Al-Qadisiya

University in Partial Fulfillment of the Requirement for The Degree Of

Bachelor of Science in Chemical Engineering .

BY

Mohsin Abdul Ellah

Mustafa Farhan Shamran

Mohammed Basim Kadhim

Supervisor

Ass. Prof. Husham . M. Majid

Lec. Ahmed. A. Ubaid
 ‫اﻻھداء‬

‫ﺑﺎﺳم اﷲ اﻟﺧﺎﻟق اﻟذي اﺿﺎء اﻟﻛون ﺑﻧورﻩ اﻟﺑﻬﻲ وﺣدﻩ اﻋﺑد وﻟﻪ وﺣدﻩ اﺳﺟد ﺧﺎﺷﻌﺎ ﺷﺎﻛ ار‬
‫ﻟﻧﻌﻣﺗﻪ وﻓﺿﻠﻪ ﻋﻠﻲ ﻓﻲ اﺗﻣﺎم ﻫذا اﻟﺟﻬد‬
‫اﻟﻰ‪...‬‬
‫ﻣن ﺳﻬر اﻟﻠﯾﺎﻟﻲ ‪ ...‬وﻧﺳﻲ اﻟﻐواﻟﻲ ‪ ...‬وظل ﺳﻧدي اﻟﻣواﻟﻲ ‪ ...‬وﺣﻣل ﻫﻣﻲ ﻏﯾر ﻣﺑﺎﻟﻲ‬
‫ﺑدر اﻟﺗﻣﺎم اﻟﻰ روح واﻟدي اﻟﻐﺎﻟﻲ‬
‫اﻟﻰ … ﻣن اﺛﻘﻠت اﻟﺟﻔون ﺳﻬرا ‪ ...‬وﺣﻣﻠت اﻟﻔؤاد ﻫﻣﺎ ‪ ...‬وﺟﺎﻫدت اﻻﯾﺎم ﺻﺑ ار ‪...‬‬
‫وﺷﻐﻠت اﻟﺑﺎل ﻓﻛ ار ‪ ...‬ورﻓﻌت اﻻﯾﺎدي دﻋﺎءاَ ‪ ...‬واﯾﻘﻧت ﺑﺎﷲ اﻣﻼ اﻏﻠﻰ اﻟﻐواﻟﻲ واﺣب‬
‫اﻻﺣﺑﺎب ‪ ...‬اﻣﻲ اﻟﻌزﯾزة اﻟﻐﺎﻟﯾﺔ‬
‫اﻟﻰ ‪ ...‬ورود اﻟﻣﺣﺑﺔ ‪ ...‬وﯾﻧﺎﺑﯾﻊ اﻟوﻓﺎء ‪ ...‬اﻟﻰ ﻣن راﻓﻘوﻧﻲ ﻓﻲ اﻟﺳراء واﻟﺿراء اﻟﻰ‬
‫اﺻدق اﻻﺻﺣﺎب ‪ ...‬اﺧوﺗﻲ واﺧواﺗﻲ‬
‫اﻟﻰ‪ ...‬اﻟﻘﻠﻌﺔ اﻟﺣﺻﯾﻧﺔ اﻟﺗﻲ اﻟﺟﺄ اﻟﯾﻬﺎ ﻋﻧد ﺷدﺗﻲ اﺻدﻗﺎﺋﻲ اﻻﻋزاء‬
‫اﻟﻰ… ﻣن ﻗﺿﯾﻧﺎ ﺳﻧﯾن اﻟدراﺳﺔ ﺑﻔﯾض دﻣﺎﺋﻬم …اﻟﻰ ﻋزﻧﺎ و ﻓﺧرﻧﺎ …اﻟﻰ ﺷﻬداﺋﻧﺎ ﻣن‬
‫اﻟﺟﯾش و اﻟﺣﺷد اﻟﺷﻌﺑﻲ ‪.‬‬
 INTRODUCTION

Naphthalene, C10H8, is an aromatic hydrocarbon with two, ortho-condensed,

benzene rings. It is first member of the series of condensed-ring aromatic
compound. It forms easily sublimable colorless leaflets or monoclinic crystals.
It has a characteristic odor in grades of technical quality due in large measure
to contain impurities; very pure, sulfur free material has a milder and more
pleasant odor. It burns in air with the formation of much soot.
Garden first recorded finding it as a solid in distillate from coal tar in 1820.
Kidd who isolated the material in purer form from pyrolyzed coal tar gave it
the name “Naphthalene” in 1821. E. Erlenmeyer in 1866 showed it to be a
hydrocarbon with two benzene nuclei condensed in the ortho position and C.
Graebe in 1869 established the accepted structural formula by its oxidation to
o-phthalic acid.
Naphthalene and its lower alkyl derivatives occur in commercial
concentration in, and are commercially recovered from, high-temperature
coal tar and from aromatized petroleum oil fraction. Naphthalene also occurs
naturally in some essential oils.
In India naphthalene is obtained from coal tar. In developed countries like U.
S. with newer technologies naphthalene is obtained from petroleum also.
This report presents a detailed design of naphthalene distillation column with
its overhead condenser. Process design requires thermo physical property
data, most of which are generated using contribution methods.
 PROPERTIES AND USES

CHEMICAL AND PHYSICAL PROPERTIES OF NAPHTHALENE:

PROPERTY VALUE

Molecular Weight 1228

0
Melting point, C 80.29
0
Normal Boiling point (at 101.3kpa),0C 217.993
Triple point (ttp), 0C 80.28
0
Critical temperature (tc), C 475.2
Critical pressure (pc),kpa 4051
0
Flash point (closed cup), C 79
Ignition temperature, 0C 526
Flammable limits, Vol% Upper 5.9
Lowe 0.9
r
Heat of Vaporisation, KJ/mol 43.5
Heat of fusion at triple point, KJ/mol 18.97
9
Heat of combustion(15.50C, 101.3kpa), KJ/mol -5158.41
Heat capacity (at 15.50C, 101.3kpa), KJ/mol0C 159.2
8
Heat of formation (at 250C), KJ/mol
Soli 78.53
d 150.5
Gas 8
Density (at 250C), g/cm3 1.175
Density (at900C), g/cm3 0.97021
VAPOR PRESSURE TEMPERATURE RELATIONSHIP FOR
NAPHTHALENE:

TEMPRATURE,0 PRESSURE, KPa

C

0 0.0008
10 0.003
20 0.007
40 0.043
87.6 1.33
119.1 5.33
166.3 26.66
191.3 53.33
214.3 93.33
218.0 101.33
230.5 133.32
250.6 199.98

VISCOSITY-TEMPERATURE RELATIONSHIP FOR LIQUID

NAPHTHALENE:

TEMPERATURE VISCOSITY,
,0C mPa.s
80.3 0.960
90 0.846
100 0.754
110 0.678
120 0.616
150 0.482
180 0.394
220 0.320
NAPHTHALENE AZEOTROPES:
Naphthalene forms azeotropes (constant-boiling mixtures) with various
compounds. Some of them are listed below.

COMPOUND BOILING NAPHTHALE

POINT NE
AT 760,0C WEIGHT%
Benzoic acid 217.7 95
1,2-benzenedion 216.3 98.8
(catechol)
4-chlorophenol 216.3 63.5
2-nitrophenol 215.75 40
1,3,5-triethylbenzene 215.0 15
Benzyl acetate 214.65 28
Benzyl alcohol 204.1 40
m-cresol 202.08 97.2
Acetamide 199.55 72.8
Ethylene glycol 183.9 49

Naphthalene is only slightly soluble in water (0.019g/l at 00C and 0.030g/l at

1000C) but is soluble in many organic compounds. The best solvent is
tetrahydronaphthalene, which of are solvents has the greatest
configurationally similarity to naphthalene. Naphthalene is soluble in liquid
sulfur dioxide, giving it a greenish yellow color, in phenols, ethers and
acetic acid, and in fats and volatile oils. Naphthalene is a good solvent for
many compounds including such inorganic substances as phosphorus,
iodine, sulfur and several metal sulfides.
Naphthalene derivatives are important intermediates in dyes,
pharmaceuticals, agriculture chemical, surface-active agents, etc. the
reaction of naphthalene are of three distinct types:
1) Substitution, 2) Addition, and 3) Rupture of one or both rings
 Substitution:
The industrially important substituents in naphthalene are the nitro, hydroxy,
sulfonic, amino and alkyl groups, and chlorine. Reactants at lower
temperature tend towards alpha- or 1-position substitution; at higher
temperatures, toward beta- or 2- position substitution.
The four alpha (1,4,5 or 8) and the four beta (2,3,6 or 7) position are
equivalent. There are therefore two possible isomers when there is
substituent, ten isomers when naphthalene is di-substituted with the same
group or fourteen when the two substituents are different.

Addition Reaction:
The important addition products or naphthalene are made by the addition to it
of hydrogen or the halogens. Addition and substitution may occur in the same
naphthalene molecule.

Ring Rupture:
Oxidation of naphthalene under normal condition conditions lead to
naphthaquinone, but if the oxidation is continued beyond naphthaquinone,
one ring of naphthalene ruptures with further oxidation of two carbons to
carbon dioxide. The two remaining carbons, ortho to each other on the
remaining ring, form carboxy groups to yield o-phthalic acid, which dehydride
is the largest use for naphthalene.

Uses:
The largest-volume use of naphthalene is for the manufacture of phthalic
anhydride. Insecticides (q.v.) now from the second largest outlet for
naphthalene. At one time naphthalene itself, in flake, ball or cake form, found
extensive use against cloths moths.
 MATERIAL BALANCE

Feed contains toluene, naphthalene, dimethylnaphthalene, hexadecene. The naphthalene

produced is usually better than 99 % pure and low in sulfur content. 95% feed made up of
aromatic.

BASIS: 100 Kg feed.

So feed composition
20 –30% toluene
10 – 15% naphthalene
50 – 60% methylnaphthalene

COMPONENT WEIGHT PERCENT

Toluene 20 –30%
Naphthalene 10 – 15%
Methylnaphthalene 50 – 60%
Hexadecene 5%

Let the feed composition

COMPONENT WEIGHT PERCENT MOLECULAR WT.
Toluene 25 92
Naphthalene 15 128
Methylnaphthalene 55 156
Hexadecene 5 226
Number of Moles =(Weight \ Molecular wt)
Mole of toluene = 0.2717
Mole of naphthalene =0.1171
Mole of methylnaphthalene =0.3525
Mole of hexadecene =0.02212
Total mole of feed =0.76342
Mole fraction = (mole\ total mole)
 COMPONENT MOLE PERCENT
Toluene 35.58
Naphthalene 15.33
Methylnaphthalene 46.17
Hexadecene 2.877

Avg. molecular wt of feed = (92 x 0.355 + 128 x 0.1534 + 156 x0.4617 + 226 x0.0289)
=130.951 kg\ kmole

Production capacity = 450,000 Tpy

Assume in year plant working 330 day and in a day plant working 20 hours.
Plant capacity =(450,000,000)\ (330 x20)
= 68181.82 kg\ hr
Let composition of product :
COMPONENT WEIGHT PERCENT MOLE FRACTION
Toluene 0.2 2.78 x 10-3
Naphthalene 99 0.9911
Methylnaphthalene 0.8 6.572 x10-3
Hexadecene 0 0

Moles of naphthalene in product

(6181.82 8x0.99)\ 128
= 527.34 Kmole\hr
Moles of dimethylnaphthalene in product
=(68181.82 x0.008)\ 156
= 3.49 Kmole\hr
Moles of toluene in product
(6181.82 x0.002)\226
=1.4822 Kmole\hr
 Total moles of product =532.3122 Kmole\hr

Dimethylation reaction
C10H6 (CH3) 2 (g) +2H2 (g)) C10H8 ((g) + 2CH4 (g)
(70% -100% conversion efficiency)
Naphthalene in 1 mole feed
= (Moles present in feed +moles by conversion)
= (0.15338 +0.92 x0.46517)
= 0.5782 mole of naphthalene
When 0.5782 mole naphthalene then product = 527.34 Kmole\hr
One mole naphthalene then product = (527.34)\(0. 5782)
FD = 911.936 Kmole\hr
Toluene in feed = 324.54 Kmole\hr

TOLUENE TOWER:
Let composition in stream T
COMPONENT MOLE PERCENT
Toluene 99.00
Naphthalene 1.00
Over all toluene balance
T = (Kmole\hr of toluene in feed – that in product)
= (324.54 –1.4822)
= 326.331 Kmole\hr
Naphthalene in stream T = 0.01 x 326.33
= 3.263 Kmole\hr
Hexadecane in feed = 911.934 x 0.02893
= 26.420 Kmole\hr
Naphthalene produced by reactor is:
= 527.34 –(911.934 x 0.1534)
= 390.71 Kmole\hr
Mole fraction is = (390.71\911.396)
 = 0.4284
Corrected overall conversion = 92.796%
Dimethylnaphthalene in stream H:
= 421.040 - 3.49 – 390.71
= 27.38 Kmole\hr
Total moles in H stream:
Moles of (C16H34) + (mole of Dimethylnaphthalene)
= 26.420 +27.38
= 53.8 Kmole\hr
Composition of H stream
COMPONENT MOLEPERCENT
Dimethylnaphthalene 50.89
C16H34 49.11

NAPHTHALENE TOWER:
Here we assume the composition of stream F
Mole %
Toluene (x1F) 0.0012
Naphthalene(x2F) 0.60
Dimethylnaphthalene(x3F) 0.3988
Hexadecane (x4F) 0
Over all toluene balance
0.0012F = 1.4822
F = 1235.166
Over all balance
F=P+D
D = 1235.166 –532.312
= 703.046 Kmole\hr
Overall Naphthalene balance
0.6(1235.166) = 527.43 +X2DD
X2D = 0.3040
 X1D = X4D = 0

X2D+ X3D =1
X3D = 0.6959
MATERIAL MOLE PERCENT

Toluene 0
Naphthalene 0.3040
Dimethylnaphthalene 0.6959
Hexadecane 0

TOWER (II) & (III):

Let mole fraction of naphthalene in stream F2 = 0.69
Let mole fraction of naphthalene in stream F3 = 0.1
Since the reaction does not change the totel mole of liquid and gases (H2 + CH4)
Which are immiscible with liquid which are removed in the separator .
Feed in ii tower F2 = FD + D + R – T
= R +1288.651 Kmole\hr
Naphthalene balance around tower ii ;
(R +1288.651) x 0.69 = (1235.166) x 0.89 +R +53.8)
R = 365.271Kmole\hr
F3 = R +H
= 419.071 Kmole\hr
F2 =1653.92 Kmole\hr
Let Toluene mole fraction in stream F2 = 0.0008
Let Toluene mole fraction in stream F3 = 0
Let Dimethylnaphthalene mole fraction in stream F2 = 0.275

Dimethylnaphthalene balance around tower ii :

F2( 0.275 ) = F3 X3F3 +F(0.1088)
X3F3 =0.7646
TOWER I :
F1 = F2 +T
= 1980.251 Kmole\hr
Toluene balance around tower i
1980.251X1 = 0.99 x 326.331 +0.0008 x 1653.92
X1 = 0.1638
Naphthalene balance around tower i
1980.251 X2 = 0.1 x 326.331 + 0.69 x 1653.93
X2 = 0.5927
Dimethylnaphthalene balance around tower I
1980.251X3 = 1653.93 x0.275
X3 = 0.2296
Hexadecane balance
X4 = 1-(X1 + X2 + X3)
X4 = 0.0139

BALANCE AROUND JUNCTION J1 :

FDD = FD +R
= 1276.670 Kmole\hr
Toluene balance
FD x 0.3 5589 = FDD x X1
911.33 x 0.35589 = 1276.607
X1 = 0.254
Naphthalene balance
1276.607 X2 = 911.336 x0.1534 + 365.271x 0.1167
X2 = 0.1423
Dimethylnaphthalene balance
1276.607 X3 =911. 336 x 0.4617 +365.271 x 0.8022
X3 = 0.5591
Hexadecane balance
X4 = 1-(X1 + X2 + X3)
 X4 = 0.0445
H2 : Naphthalene =5 :1
Kmole of Dimethylnaphthalene in FDD stream
= 1276.607 x 0.5591
= 713.750 Kmole\hr
So that H2 = 5 x 713.750
= 3568.75 Kmole\hr
= 7137.5097 Kg
Here H2 is goes into the reactor
In put in reactor = FDD + H2
= 1276.60 + 3568.75
= 4845.35 Kmole\hr

BALANCE AROUND JUNCTION J2:

Over all balance
Toluene balance
LX1 = 1980.245 x0.1688
X1 = 0.2539
Naphthalene balance
1277.205 x X2 = 1980.251 x 0.5927-703.046x0.8137
X2 = 0.471
Dimethylnaphthalene balance
1980.251 x X3 = 1277.205 X3 + 703.046 x0.1862
X3= 0.2534
Hexadecane balance
X4 = 1-(X1 + X2 + X3)
X4 = 0.02155

REACTOR BALANCE
Dimethylnaphthalene input to reactor = 4845.38 Kmole\hr
Dimethylnaphthalene input to reactor =1276.607x 0.5591
 = 713.750
Kmole\hr Dimethylnaphthalene output from reactor
=
1277.205 x0.2534
= 323.6437 Kmole\hr
Dimethylnaphthalene converted = 713.75 - 323.6437
= 390.106
Kmole\hr Per pass conversion in reactor =
(390.106\713.75 ) x100
= 54.65%
Mathen gas produced in the reactor
= Moles of Dimethylnaphthalene reacted

= 390.106 Kmole\hr
H2 un reacted = 3568.75 – 390.106
= 3178.64
Kmole\hr Balance around
separator
Over
all
balanc
C=L+G

G =3568.75
Kmole\hr H2
balance
H2 in feed =3568.75
H2 un reacted =3178.644
% Of H2 in stream G = 3178.64\3568.75 =0.890
CH4 in stream G =11%
 ENERGY BALANCE

BASIS : 1 Hr of operation
Reference temperature =250C

Balance around naphthalene tower

Enthalpy of feed stream at 231.670C
Assume feed is binary mixture
Feed is saturated liquid
HF =F {XNF Cpl (231.67-25) + XDF Cpl (231.67-25)}
= 1235.16 {0.6 x 226.1 x(231.67 –25) +0.3988 x240 x(231.67 –25)}
= 61107677.49 KJ\hr
Enthalpy of bottom stream at 2450C
HD=D{XND Cpl (245-25) + XDD Cpl (245-25)}
=703.046 {0.3010 x 228.1 x (245 –25) +0.6959 x240 x(245 –25)}
= 38893781.45 KJ\hr
Enthalpy of at top stream at 218.330C
HP =P{XNP Cpl (218.33-25) + XDP Cpl (218.33-25)}
=532.312 {0.9911 x 220.1 x(218.33–25) +6.56 x10-3 x234 x(218.33 –
25)}
= 22608196.13 KJ\hr
Condenser load
QC =12539255.76 KJ\hr
QB = HP + H' - HF+ QC
QB =12933556.03 KJ\hr

Balance around tower 1st

At=1600C
HF1 =F1{XNF1 Cpl (160-25) + XDF1 Cpl (160-25) +XTF1 Cpl (160-
25) }
=1980.25 {0.5927 x 160 x(160 -25) +0.2227 x180x(160–25)
+ 0.1638 x 110(160-25)}
= 41241761.83KJ\hr
HF2 =F2{XNF2 Cpl (230.6 -25) + XDF2 Cpl (230.6-25) +XTF2 Cpl
(230.6-25) }
=1653.92 {0.69 x 230 x(230.6-25) +0.275 x240x(230.6–25)
+ 0.0008x 180 x(230.6 -25)}
= 76457292.03 KJ\hr
similarly at top at 1120C
HT =2849976.605 KJ\hr
condenser load
QC =m ç
=( 0.9911 x92 + 0.01 x128 ) x326.31 x 295.2
= 8896735.12 KJ\hr
QB = 46962241.93 KJ\hr

Balance around tower 2

HF2 =76457292.03 KJ\hr
HF = 61107677.44 KJ\hr
HF3 at 2590C
HF3 =419.071{ 230 x 0.1 x 234 +240 x0.7646 x234}
=0322.04 KJ\hr 2025
QC =m ç
= 4910707.45 KJ\hr
QB = 4910707.45 KJ\hr

Balance around column 3

HF3 =61107677.44 KJ\hr
HH = 53.8{0.5081(276.15 –25) x240 + 0.4911 x230 (276.15 –25)}
= 3173897.72 KJ\hr
HR = 365.271{0.1147(256-25) +0.8028x240(256 – 25)}
= 18483122.12 KJ\hr
QC =m ç
= 365.271 x0.142 x 338.2
= 18948618.41 KJ\hr

Balance around cooler at 2380C

Q = D{ X2D Cp(238 –159.2) + X3D Cp ( 238 –159.2)}
= 703.046 { 0.3040 x190 x78.8 + 0.6960 x 200 x 78.8}
= 10911523.07 KJ\hr

Balance around heater feed stream entering

Let feed temperature is 1050C
HF1 =911.93 { 0.3558 x(105-25)x93 +0.1536 x130 ( 105 –25)
+ 0.4617 x159.12 (105 –25) }
= 9230477.86 KJ\hr
heat added in heater to heat the feed to 256.430C
= 911.93{ 0.3558 x 170.2 x(256.43-105) +0.1535 x200 (256.43 –105)
+ 0.4617x240 (256.43 –105)}
= 27904079.28 KJ\hr
HF2 = HF1 + HFQ
= 37134557.08 KJ\hr
Balance around reactor

heat of reaction = -82920 KJ\kmole

total heat produced by reaction
= 82920 x 390.71
= 32397673.2 KJ\hr

Balance around J1
FDD = FDD1 + HD
= 55617681.2 KJ\hr

Balance around junction J2

HL = HF1 + HR1
= 18948618.41

balance around separator

HG = 3658.75{ 0.89 x 30 x(160 –25) +0.11 x 85.34( 160 - 25)

= 17821044.4 KJ\hr
Hc = HL + HG
= 36769662.81 KJ\hr

balance around H2 gas heater

Q = H2 x Cp (700 –25)
= 3658.75 x 30 ( 700 –25)
= 74049187.5 KJ\hr