Desalination 297 (2012) 8796

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Desalination
journal homepage: www.elsevier.com/locate/desal

Reactive dyes rejection and textile efuent treatment study using ultraltration and
nanoltration processes
A. Aouni a, 1, C. Fersi a, c,, B. Cuartas-Uribe b, 2, A. Bes-Pa b, 2, M.I. Alcaina-Miranda b, 2, M. Dhahbi a, 1
a
Water and Membrane Technologies Laboratory, CERTE, BP 273, Soliman 8020 Tunisia
b
Department of Chemical and Nuclear Engineering, Polytechnic University of Valencia, Camino de Vera s/n, 46022 Valencia, Spain
c
Method and Technical Analysis Laboratory, INRAP, Sidi Thabet 2020, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: Ultraltration and nanoltration processes were used to treat synthetic reactive dyes aqueous solutions and a
Received 30 November 2011 raw textile efuent supplied from rinsing baths of Spanish textile industry. The inuence of the reactive dyes
Received in revised form 18 April 2012 molecular weights and the effect of the used membranes types and cut-offs were investigated with regard to
Accepted 22 April 2012
the permeate ux at different transmembrane pressures (27 bar for UF and 415 bar for NF). The extent of
Available online 14 May 2012
colour retention, COD and conductivity was determined in order to monitor the membrane's separation ef-
Keywords:
ciencies aiming at waste water treatment, water reuse and chemical usage minimisation. High COD reten-
Ultraltration tions (80100%) were achieved using UF and NF processes. Good conductivity rates (80%) and high COD
Nanoltration and colour retention rates (> 90%) were obtained for both NF 200 and NF 270 membranes for all studied
Reactive dyes dyes solutions. An improvement of the rinsing wastewater quality was obtained using UF and NF processes.
Rinsing wastewater 2012 Elsevier B.V. All rights reserved.

1. Introduction Many dyes are difcult to decolourise due to their complex struc-
ture and synthetic origin.
The characteristics of wastewater from textile processing opera- There are many structural varieties, such as, azo, diazo, anthroquinone,
tions are comprehensively reviewed. The categorisation of wastewa- triphenylmethane, phetalocyanine, stilbene, and metal complex dyes.
ters proceeds through a consideration of the nature of the various Decolouration of textile dye efuent does not occur when treated aerobi-
industrial processes employed by the industry and the chemicals as- cally by municipal sewerage systems [8].
sociated with these operations. Chemical pollutants arise both from The conventional method of textile wastewater treatment consists
the raw material itself and a broad range of additives used to produce of chemical coagulation (using ferrous, lime and polyelectrolytes), bi-
the nished product. The industrial categories considered include ological treatment followed by activated carbon adsorption. The con-
sizing and weaving, scouring, bleaching, mercerising, carbonising, dye- ventional coagulation process generates huge volume of hazardous
ing and nishing. Pollutants of concern range from non-biodegradable sludge and poses a problem of sludge disposal. In order to meet the
highly-coloured organic dyes to pesticides from special nishes such legal requirements for the discharge of textile wastewater, researchers
as insect-proong [1]. are attempting a combination of two or more treatment methods for
Textile industries consume large volumes of water and chemicals the complete and successful removal. Combination of electrochemical
for wet processing of textiles. The chemical reagents used are very di- treatment and chemical coagulation [9], combined chemical coagu-
verse in chemical composition, ranging from inorganic compounds to lation, electrochemical oxidation, and activated sludge process [10],
polymers and organic products [2,3]. Chitin and chitosan were used in and combination of electrochemical method, chemical coagulation,
lobster shell wastes for colour removal from aqueous solutions [4]. and ion exchange [11] were reported for textile efuent treatment
The presence of very low concentrations of dyes in efuent is highly to comply with the legal requirements or for reuse standards. Each
visible and undesirable [5]. Due to their chemical structure, dyes are treatment method has its own advantages and disadvantages, and
resistant to fading on exposure to light, water and many chemicals the selection of the method mainly depends on the treatment target
[6,7]. to be achieved.
The uctuating compound concentrations and ow rates make the
conventional processes quite insufcient for the treatment of textile
wastewaters, especially for colour removal [12,13].
Corresponding author at: Method and Technical Analysis Laboratory, INRAP, Sidi The discharge regulations are becoming more stringent, and there is
Thabet 2020, Tunisia. Tel.: + 216 71 537 666; fax: + 216 71 537 767.
E-mail address: cheimafersi@yahoo.fr (C. Fersi).
a growing tendency and interest in the advanced treatment methods
1
Tel.: + 216 79 325 798; fax: + 216 79 325 802. like ozonation, photo catalysis, and membrane processes for a better
2
Tel.: + 34 96 3879633; fax: + 34 96 3877639. treatment of the textile wastewaters [14].

0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.04.022
88 A. Aouni et al. / Desalination 297 (2012) 8796

NaO3SOCH2CH2O2S SO2CH2CH2OSO3Na

OH H2N
N N
N N

NaO3S SO3Na

Fig. 1. Chemical structure of Everzol Black (MBlack = 991 g mol 1).

The recovery and reuse of textile wastewaters have been studied into a tank of 25 L. Then, an amount of 12.5 g of NaCl was added and
extensively by membrane researchers [1524]. Membrane tech- supplemented with ultrapure water up to the mark.
niques hold great promise in this eld, as they have the potential to Just after, pH was adjusted to 10 with 5 M sodium hydroxide solu-
either remove the dyes stuffs or allow reuse of the auxiliary chemicals tion and the solutions prepared were homogenised by simple mag-
used for dyeing or to concentrate the dyestuffs and auxiliaries and netic stirrer. The dye concentration and NaCl concentration are
produce puried water. equal to 600 mg L 1 and 500 mg L 1 respectively.
In fact, membrane processes can be used for the purication of these The choice of pH value is in relation with the simulation of dies
complex wastewater streams [2125]. There have been many investiga- solutions to a real textile wastewater.
tions on the treatment of the dye house efuents using microltration In fact, the real textile wastewater is highly alkaline (pH 10.012.5)
[26,27], ultraltration [26,2832], nanoltration [26,3339], and reverse and is characterised by strong colour and high pH. The textile industry
osmosis membranes [26,4044]. plant consists mainly of printing and dying processes. In these process-
Several applications of the ultraltration process (UF) have been es, the use of substances such as NaCl and Na2CO3 is required to improve
reported for the separation of certain dyes, such as indigo, direct, the aggregation of dye ions on the ber to x the dyestuffs.
disperse and reactive dyes [2530]. A special attention was given to The molecular structures and weights of the three dyes are pres-
the application of membrane processes; especially the nanoltration ented in Figs. 1, 2 and 3.
(NF), on the rejection of reactive dyes, whose xation rates on the The main characteristics of these solutions are shown in Table 1.
fabric is one of the lowest (6090%) [3133].
In this work, different UF and NF membranes were used to treat 2.2. Textile wastewater characteristics
three synthetic reactive dyes aqueous solutions (using black, blue and
red EVERZOL dyes). The effect the of dye molecular weight (MW), the The study was conducted with a textile wastewater sample sup-
cut-off and the type of used membranes were investigated with regard plied from the rinsing baths of COLORTEX textile industry, Spain.
to the permeate ux and separation efciency. The main characteristics of this sample are given in Table 2.
These processes were also used to treat a rinsing textile efuent
supplied from rinsing baths of Spanish textile industry. The extent 2.3. Analytical methods
of colour retention, COD and conductivity were determined in order
to monitor the membrane's separation efciencies aiming at waste pH values were determined by means of a GLP 22 pH-meter
treatment, water reuse and chemical usage minimisation. (Crison). The conductivities were measured by a Crison (GLP 32) in-
strument type conductivitymeter. Both conductivity and pH sensors
2. Materials and methods used for these analyses allowed automatic and continuous correction
of the values by taking into account the sample temperature. Turbid-
2.1. Synthetic model solutions ity was measured with a DINKO D-112 turbidimeter according to the
ISO 7027:1999. Turbidity and conductivity were measured with accu-
Experiments were conducted using three reactive azo dyes (Everzol racies of 2 NTU and 1.0%, respectively. The COD concentrations
Black, Everzol Blue and Everzol Red) which are known to contain anion- were obtained using a Spectroquant Nova 60 from MERCK (Germany)
ic sulphonate groups to various degrees. type COD-meter, whereas SAC (spectral absorption coefcient) values
Three synthetic model solutions were prepared using reactive azo were obtained by UVvis absorption using a HP 8453 spectrophotom-
dyes and chloride sodium. The three synthetic solutions of azo reac- eter (1 cm cell width) after samples ltration with a 0.45 m lter,
tive dyes were prepared by dissolving 15 g of Everzol dye powder in according to the ISO 7887:1994 method [45].
a ask containing two liters of ultrapure water. This mixture was COD analyses were carried out in a cell tests from MERCK (den-
heated for 30 min at a temperature of 80 C to ensure complete disso- ominated kits). These tubes contain the required reagents for the
lution of the dye. After cooling, the contents of the ask were poured oxidation (potassium dichromate, sulphuric acid and silver sulphate).

O NH2

SO3Na
Cl

N H HO N N SO3Na

N N

N SO3Na O HN
Ph N

Me

NaO3S SO2CH2CH2OSO3Na

Fig. 2. Chemical structure of Everzol Red (MRed = 788 g mol 1). Fig. 3. Chemical structure of Everzol Blue (MBlue = 626 g mol 1).
 A. Aouni et al. / Desalination 297 (2012) 8796 89

Table 1 Table 3 provides the specication of these membranes as given by

Synthetic model solutions characteristics. the manufacturers. The effective surface for all these membranes is
Parameter Everzol Black Everzol Blue Everzol Red equal to 90 cm 2. The water permeability was established for all used
solution solution solution membranes. Values are shown in Table 3.
MW of dye (g mol 1) 991 626 788 There are great differences between NF 200 and NF 270, especially in
pH 9.89 10.46 10.27 terms of pore diameter size and thickness. In fact, UF membranes have
Conductivity (S cm 1) 2490 1407 2240 the greater values (1100 nm as a pore size diameter and 150 10 3 nm
Colour 2.05 1.92 1.76
as a thickness) comparing with NF membranes (0.93 and 0.84 nm as a
COD (mg L 1) 566 450 470
[Dye] (mg L 1) 600 600 600 pore size diameter and 1.81 103 nm and 1.87 103 nm as a thickness).
[NaCl] (mg L 1) 500 500 500 These values conrm that UF membrane retains the larger molecules
that NF membrane cannot reject.

For the COD measurements, accuracies were depending on the COD 2.5. Membrane ltration units
range measured: 1.2 for 10150 mgCOD L 1 and 2.0 for 50
500 mgCOD L 1. Colour based on the spectral absorption coefcient Membrane experiments were performed in a pilot plant designed
(SAC) values at three different standard wavelengths in the visible in the Department of Chemical and Nuclear Engineering, at the Poly-
range (436, 525, and 620 nm) were measured. The colour intensity technic University of Valencia. This pilot plant is equipped with a
of dyes solutions and textile efuent were analysed by HEWLETT plane and at module.
PACKARD HP-84-53 type spectrophotometer, according to the stan- The feed rectangular tank (25 L) included a mixer model RZR-1
dard method EN ISO 7887:1994 (Section 3) [45] which measures (Heidolph) to homogenise the feed solution, and a level switch that
the sample absorbance at three wavelengths in the visible range, enables continuous operation of the pilot plant. Permeate and con-
and determined using Eq. (1). centrate streams were recycled and returned to the feed tank. Then,
it can be considered that the concentration of the feed solution was
A2436nm A2525nm A2620nm
Colour 1 kept constant for each experiment.
A436nm A525nm A620nm As temperature affects permeate ux, this variable was kept con-
stant by a cooling system at 22 C. A 10 m pre-lter was placed
where, A represents the absorbance values measured at the different upstream of a variable speed pump motor model 270 (cat pumps),
standard wavelengths (436 nm, 525 nm and 620 nm) [46]. in order to reduce the pass of particles into the system. Next to the
Colour retention and salt retention were calculated by the follow- feed pump exit there was a retentate security valve situated just
ing equation: before the owmeter model R-005 (Comaquinsa S.A.) which was
! used to regulate the transmembrane pressure and to limit the maxi-
Cp
R 100  1 2 mum operating pressure in the pilot plant. Two manometers at each
Cf side of the membrane module and a pressure tube of stainless steel
were used to measure the transmembrane pressure. A owmeter
Where Cp and Cf are respectively permeate and feed concentrations. was located in the retentate line to measure the retentate volumetric
The main ions (sodium, potassium, magnesium, calcium, sulphate, ow rate. The operating feed ow rate was xed to 400 L h 1 for all
and chloride) and the total dissolved solids were determined according experiments. The experimental set-up is illustrated in Fig. 4.
to the Standard Methods [45]. The particle size distribution (PSD) was The operating time was established according to the steady state
measured using Mastersizer 2000 from Malvern Instruments according conditions. It was about 120 min. Permeate uxes (JP) and retention
to the ISO 133201 [47]. rates (R) were measured every 120 min. Thus, a total recirculation
mode was used at the beginning of the experiment and a constant
2.4. Membranes permeate volume was extracted from the system when the steady
state was reached. The operating transmembrane pressure (P) was
Two nanoltration membranes (NF200 and NF270) provided by varied. In each series of experiments, three pressures were applied
Dow/Filmtec (USA) and two ultraltration membranes (10 kDa and (357 for UF membranes and 51015 for NF membranes).
1 kDa) purchased respectively from Rhodia Orelis and Synder Filtration After thoroughly cleaning the system several times using chemical
manufacturers were used in this work. Polyethersulfone membranes process and pure water, the membrane permeability was re-evaluated.
(PES) are widely used for UF applications because they have wide tem- The rst step of the chemical cleaning consists on circulating distilled
perature limits, wide pH tolerances, fairly good chlorine resistance and water in the system for 40 min and then applying basic cleaning using a
wide range of pore sizes. sodium hydroxide solution (5 mol L 1) at pH=11during 20 min. The
second step of the procedure consists in rinsing again with distilled
water for 40 min and then applying acidic cleaning using a chlorhydric
Table 2 acid solution at pH =3 for 20 min. Finally, a rinsing step with distilled
Textile wastewater characteristics. water was applied for 40 min.
Parameter Value
The steps of membrane cleaning procedure were followed with-
out applying any pressure and increasing the feed ow rate in order
pH 7.11
to eliminate the organic and inorganic substances that clogged the
Conductivity (S cm 1) 3840
Turbidity (NTU) 4.02 membrane. After that, the membrane permeability was re-evaluated
COD (mg L 1) 708 in order to check the membrane fouling state.
Particle size distribution (m) 0.768
TDS (mg L 1) 3137
3. Results and discussions
Colour 0.12
Cl 1
(mg L ) >125
SO42 (mg L 1) 28 3.1. Reactive dyes rejection using ultraltration
Ca2+ (mg L 1) 42
Mg2+ (mg L 1) 18.6 Synthetic model solutions were prepared at xed dye and NaCl
Na+ (mg L 1) 1008
salt concentrations which were respectively 600 and 500 mg L 1 as
90 A. Aouni et al. / Desalination 297 (2012) 8796

Table 3
Membrane specications.

Membrane UF 10 kDa UF 1 kDa NF 200 NF 270

Manufacturer Rhodia orelis Synder ltration Dow/Filmtec Dow/Filmtec

Material Polyethersulfone Polyethersulfone Polyamide Polyamide
Surface charge (pH 7) Neutral Neutral Negative [51] Negative [51]
Maximum operating pressure (bar) 7 8 41 41
Maximum operating temperature (C) 50 50 45 45
pH range 314 211 310 310
Cut-off (Da) 10,000 1000 200300 200300
Contact angle () 56 38 [52] 56 38 [52] 30.3 [53] 51.4 [56]
Isoelectric point N.D. N.D. 4.3 3.3 [57]
Roughness (nm) 12.7 1.3A [52] 12.7 1.3A [52] 5.19 [53] 19.80 [57]
Pore diameter size (nm) 1100 [58] 1100 [58] 0.93a 0.84 [55]
Thickness (nm) 150 103 [58] 150 103 [58] 1.81 103a 1.87 103 [59]

N.D: Not Dened.

a
By authors.

given in Table 1. The transmembrane pressure was varied from 3 to and hydrophobic adhesion determines the outcomes of membrane
7 bar during each experiment. Permeate uxes of Everzol dyes solu- fouling, as well as the efciency of chemical cleaning.
tions versus transmembrane pressure using UF 10 kDa and UF 1 kDa Dye molecules can be adsorbed on membrane surface, which affects
membranes are presented in Fig. 2. The equations of linear parts of the permeate ux due to physicochemical interactions, i.e. hydrophobic
obtained plots are shown in corresponding gures. It is evident that interactions (dispersion forces), polar interactions (dipole forces) and
membrane uxes were lower than for the corresponding pure water charge transfer (hydrogen bonding). The nature of the membrane ma-
ux. This is a phenomenon that can be related to the presence of or- terial, the type of solute, the solute concentration, crossow velocity
ganic and inorganic solutes, which can be retained at the membrane and pH are the most important parameters that can determine the
surface causing concentration polarisation [34]. extent of dye adsorption [34].
However, fouling due to dissolved inorganic and organic com- Organic adsorption was reported to cause the greatest synergistic
pounds specically is more problematic to nanoltration [48]. Mem- effect due to the ability to reduce repulsive interaction between
brane fouling can lower the permeate ux and might inuence the foulants (organic and inorganic colloidal foulants) and the membrane
retention of organic compounds [49]. The factors that affect membrane as well as that among foulants. After the adsorption taken place, the
fouling can be classied into three categories: membrane properties, dye aggregates will build multiple sublayer and nally the bulk con-
operating parameters and rinsing wastewater itself [50]. centration of dye will increase after the compacted sublayer had
Membrane fouling is a complicated phenomenon of which causes been developed.
of fouling are multiple and poorly understood. The core of the issue is During the permeation of dye solutions, the adsorption of dye
interactions between fouling materials and membrane, and between molecules at the membrane surface and inside the pores contributes
fouling materials themselves. It has been recognised that electrostatic to the decrease of the membrane pore sizes and as a consequence
interaction and hydrophobic/hydrophilic interaction between mem- to the alteration of the pure water permeability coefcient, Lp.
branes and fouling materials have a signicant bearing on membrane Dye molecules have amino, sulphonic and hydroxyl groups as sub-
fouling. This is particularly true to more difcult fouling problems cau- stituents bound to the aromatic rings. Those functional groups could
sed by adsorption of natural organic matters and biopolymers on the interact with the membrane that has also functional groups as car-
membrane. The balance between the forces of electrostatic repulsion boxyl, amide and amino.

Fig. 4. Membrane ltration experimental set-up.

 A. Aouni et al. / Desalination 297 (2012) 8796 91

The nature of the membrane material, the type and concentration A 100
of solute, cross-ow velocity and pH are the parameters that can af-
fect the dye adsorption in dye and NaCl mixtures. In each case, differ- 90
ent electrostatic interactions take place between dye, NaCl and the 80
membrane.
70
Fig. 5A. shows that permeate uxes plots were not linear for a

RBlack (%)
transmembrane pressure higher than 3 bar. An important decline of 60
permeate uxes were observed for all Everzol dyes solutions at high 50 COD(Black)
transmembrane pressures using UF 10 kDa membrane. However, in
40 Colour(Black)
the case of UF 1 kDa membrane, all plots were linear for the studied
30 Conductivity(Black)
transmembrane range as shown in Fig. 5B. This result demonstrates
that an important concentration polarisation occurs using the rst 20
UF membrane for transmembrane pressure higher than 3 bar.
10
Fig. 5 illustrates that Everzol Blue solution presented the higher
permeate uxes and Everzol Black solution presented the lowest per- 0
0 1 2 3 4 5 6 7 8
meate uxes for the whole transmembrane range. This is related to
P (bar)
the difference between molecular weights of studied dyes as given
in Table 1. B 100
Fig. 6 shows the evolution of colour, COD and conductivity reten-
tion rates with transmembrane pressure in the case of Everzol Black 90
solution using respectively UF 10 kDa and UF 1 kDa membranes. The
80
same experiment conditions were used for Everzol Blue and Everzol
Red solutions as shown in Figs. 7 and 8. High COD retention rates 70

RBlack (%)
(>80%) were obtained for all dyes solutions using both UF 10 kDa 60
and UF 1 kDa membranes. 50
40
30
COD(Black)
A 20 Colour(Black)
J0 (Water) = 62.8 P 10 Conductivity(Black)
390
Jp (Black) = 46.4 P - 1.6
360 0
Jp (Blue) = 55.8 P - 0.1 0 1 2 3 4 5 6 7 8
330
300
Jp (Red) = 49.2 P - 0.03 P (bar)
270
Jp (L h-1 m-2)

Fig. 6. Retention rates as a function of transmembrane pressure after Everzol Black so-
240 lution treatment using UF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1).
210 A) UF 10 kDa; B) UF 1 kDa.
180
150 It can be observed that transmembrane pressure affects especially
120 salt retention. In fact, an increase of the conductivity rate was ob-
90 served by increasing transmembrane pressure from 3 to 7 bar for all
60 dyes solutions.
30 When UF membrane was placed in contact with an ionic solution
0 (Everzol solution or textile efuent), the association and dissociation
0 2 4 6 8 of functional group on the surface of UF membrane leads to the for-
P (bar) mation of charges. Thus, the charge generated can be related to the
ionisation of functional group existing on the surface of the mem-
B brane, which strongly depends on pH, thereby resulting in acid and
30
J0 (Water) = 3.7 P base dissociation. At pH = 10, if the charge generated is negative, a re-
Jp (Black) = 1.5 P - 0.2 pulsion strength with negative ions appears and leads to a decrease of
25
Jp (Blue) = 1.9 P - 0.4 the conductivity value.
Jp (Red) = 1.5 P - 0.3 Other possible interpretation can also be taken into consideration:
20
Na + has a strong afnity for sulfonate groups to complex with anionic
Jp (L h-1 m-2)

dye molecules and partially neutralises their negative charge. Due to

15 the opposite charge of solutes (cationic salt particles and anionic
dye), the electrostatic interactions prevent the formation of high-
10 molecular-weight complexes between dye molecules and salt parti-
cles. This can affect the solution conductivity.
5
Due to its higher molecular weight cutoff, UF 10 kDa membrane
presented retention rate values lower than those obtained with UF
1 kDa membrane in terms of conductivity, colour and COD. As an ex-
0
ample, Fig. 7 shows that conductivity rates for Everzol Blue solution
0 2 4 6 8
didn't exceed 40% using UF 10 kDa membrane. However, these rates
P (bar)
increased to 80% in the case of UF 1 kDa membrane as shown in
Fig. 5. Permeate ux of Everzol dyes solutions versus transmembrane pressure using UF Fig. 7B. This result can be related to the size of the complex formed
membranes ([Dye] = 600 mg L 1; [NaCl]= 500 mg L 1). A) UF 10 kDa; B) UF 1 kDa. and the pore sizes of the membranes.
92 A. Aouni et al. / Desalination 297 (2012) 8796

A pressure using NF 200 and NF 270 membranes are presented in Fig. 9.

100 The equations of obtained plots are shown in the corresponding gure
90 for pure water and studied dyes solutions.
We notice that permeate ux increases proportionally with the
80
pressure drop within the pressure range studied in all cases, which
70 indicates that the operation is in the pressure- controlled region.
Permeate uxes using dye solutions were lower than the
RBlue (%)

60
COD(Blue)
50
corresponding pure water uxes for both NF 200 and NF 270. In the
Colour(Blue)
case of nanoltration processes, this phenomenon can be related,
40 Conductivity(Blue)
not only, to the concentration polarisation but also to the presence
30 of an important osmotic pressure near the membrane-efuent inter-
20 face which leads to a decrease in the effective driving force [32]. In
fact, the retention of the ionic species results in an osmotic pressure
10
build-up across the membrane. The osmotic pressure causes ux to
0 decline, but this is due to reduced driving force rather than an in-
0 1 2 3 4 5 6 7 8 crease in the resistance to mass transfer.
P (bar) It can be also observed that the initial deviation of the permeate
ux depends on the molecular weight of used dyes. In fact, Everzol
B Blue which characterised by the smaller molecular weight presented
100
the lower intercept as shown in Fig. 9 (1.5 L h 1 m 2 for NF 200
90
membrane and 1.1 L h 1 m 2 for NF 270 membrane). This result
80 proves that osmotic pressure occurs progressively in the case of
70 Everzol Blue solution. Nevertheless, this solution presented the lower
permeability (the lower slope which was about 10.3 L h 1 m 2 bar 1
RBlue (%)

60
in the case of NF 200 and 9.3 L h 1 m 2 bar 1 in the case of NF 270).
50 This observation is related to pore plugging with Everzol Blue molecules
40 which can be increased at high transmembrane pressure.
COD(Blue)
30
Colour(Blue)
20
Conductivity(Blue)
A
100
10
90
0
0 1 2 3 4 5 6 7 8 80
P (bar) 70
COD(Red)
RRed (%)

60
Fig. 7. Retention rates as a function of transmembrane pressure after Everzol Blue so- Colour(Red)
lution treatment using UF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1). 50
Conductivity(Red)
A) UF 10 kDa; B) UF 1 kDa.
40
30
Although Everzol Black dye presents the higher molecular weight
comparing to Everzol Blue and Everzol Red, its corresponding colour 20
retention rates were the lowest ones. In fact, Fig. 6 shows that black 10
retention rates didn't exceed 15% in the case of UF 10 kDa membrane
0
and 80% in the case of UF 1 kDa membrane even at high transmem- 0 1 2 3 4 5 6 7 8
brane pressure. A total decolourisation was observed for blue and P (bar)
red dyes using UF 1 kDa membrane. This result could be related to
the spatial conguration of the Everzol black dye. B
100
In fact, the chemical structure (shape, number of active groups,
stability of a negative charge) of the dye could give the difference in 90
the afnity of these reactive dyes toward surface membrane. 80
Comparing the performances of the used ultraltration mem-
70
branes (UF 10 kDa and UF 1 kDa) in the treatment of the studied re-
active dyes solutions, we can conclude that ultraltration seems to
RRed (%)

60
be an appropriate technology for the COD decrease. In addition, ultra- 50
ltration using UF 1 kDa membrane could be used as pretreatment
40
step especially for highly charged efuent. This membrane process
could be followed by nanoltration or reverse osmosis processes 30 COD(Red)

depending on the efuent characteristics and the treatment objective. 20 Colour(Red)

Conductivity(Red)
10
3.2. Reactive dyes rejection using nanoltration
0
0 1 2 3 4 5 6 7 8
The same reactive dyes solutions using Everzol Black, Blue and Red
P (bar)
dyes and NaCl were treated using two nanoltration membranes (NF
200 and NF 270) which are described in Table 3. The transmembrane Fig. 8. Retention rates as a function of transmembrane pressure after Everzol Red solu-
pressure was varied from 3 to 12 bar during each experiment. The var- tion treatment using UF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1).
iation of permeate uxes of Everzol dyes solutions with transmembrane A) UF 10 kDa; B) UF 1 kDa.
 A. Aouni et al. / Desalination 297 (2012) 8796 93

A can be concluded that permeate ux, contact angle and roughness

240 J0 (Water) = 12.6 P values conrmed the fouling tendency showed by the NF 270 mem-
Jp (Black) = 12.3 P - 16.8 brane in the laboratory tests. This conrms that the NF 270 mem-
210
Jp (Blue) = 10.3 P - 1.5 brane is more sensitive to fouling phenomenon.
180 Jp (Red) = 12.6 P - 3.1
Fig. 10 shows the retention rates for colour, COD and conductivity
in the case of Everzol Black solution using respectively NF 200 and NF
Jp (L h-1 m-2)

150
270 membranes. The some experiment conditions were used for
120 Everzol Blue and Everzol Red solutions as shown in Figs. 11 and 12.
Comparing nanoltration membrane performances, similar results
90 were obtained: high COD and colour retention rates (>90%) were
obtained for both NF 200 and NF 270 membranes even using Everzol
60
Black dye as shown in Fig. 10. Conductivity retention rate exceeded
30 85%.
In fact, negatively charged membranes increase electrostatic repul-
0
sion of anionic compounds. The studied reactive dyes are characterised
0 2 4 6 8 10 12 14 16 18
by sulfonate groups which highly interact with the negative charge
P (bar)
membrane. This phenomenon justies the high colour retention and
B the improvement of chloride retention which affects the conductivity
240 J0 (Water) = 15.6 P
retention rates.
Jp (Black) = 11.3 P - 10.8
These results are very interesting in terms of environment, econo-
210
Jp (Blue) = 9.3 P - 1.1
my and industrial management using nanoltration process. This pre-
liminary study using synthetic dye and salt mixtures is interesting for
180 Jp (Red) = 11.4 P - 7.4
predicting nanoltration performances in the treatment of industrial
Jp (L h-1 m-2)

150 efuents using similar experimental conditions.

120

90

60
A
30 100
0
0 2 4 6 8 10 12 14 16 18
P (bar)
90
RBlack (%)

Fig. 9. Permeate ux of Everzol dyes solutions versus transmembrane pressure using

NF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1). A) NF 200; B) NF 270.

It can be also observed that all dyes solutions presented a decrease 80

of the permeate ux comparing to the pure water ux for both NF 200 COD(Black)

and NF 270 as shown in Fig. 9. This decrease was more important in Colour(Black)

the case of NF 270 (from 27 to 40%) than NF 200 (from 0 to 18%) 10 Conductivity(Black)
for all used reactive dyes solutions and for all applied transmembrane
0
pressure. This demonstrates that NF 270 membrane is more sensitive 0 2 4 6 8 10 12 14 16
to fouling phenomena. P (bar)
Contact angle is a semi-quantitative index associated to the hydro-
philicity/hydrophobicity of the membrane surface. The lower contact B
angle, the higher hydrophilicity and fouling tendency decreases [54]. 100
In addition, the contact angle of the membrane 270 NF (51.4) is
higher than that of NF 200 (30.3), so the surface hydrophobicity of
the NF 270 membrane is greater, generating a hooking of particles
more accentuated on the surface of the membrane. 90
RBlack (%)

In this way, it seems that NF 200 membrane presented a larger

resistance to fouling because of its low contact angle value (30.3).
On the contrary, NF 270 membrane has the highest value (51.4)
and therefore the major ux ratio reduction and maximum fouling. 80 COD(Black)

Other parameter to be considered is the surface roughness. This Colour(Black)

parameter is a physical property that denes the surface morphology Conductivity(Black)

which is also connected with the fouling tendency. In fact, the rough- 10
ness of the NF 270 membrane is equal to 19.80 nm and it is greater
than that of the NF 200 membrane which is equal to 5.9 nm. 0
0 2 4 6 8 10 12 14 16
Particularly, the NF 270 membrane presented the maximum ux
P (bar)
decrease and the highest roughness value (19.80 nm). On the con-
trary, NF200 membrane showed the minimum ux decrease and
Fig. 10. Retention rates as a function of transmembrane pressure after Everzol Black so-
the smoothest surface (5.9 nm). This small roughness value allows lution treatment using NF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1).
conrming the lack and the difculty for linking foulants. Thus, it A) NF 200; B) NF 270.
94 A. Aouni et al. / Desalination 297 (2012) 8796

A A
100 100

90 90

RRed (%)
RBlue (%)

80 80
COD(Red)
COD(Blue)
Colour(Red)
Colour(Black)
10 Conductivity(Red)
10 Conductivity(Black)

0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
P (bar) P (bar)

B B
100 100

90 90

RRed (%)
RBlue (%)

80 80
COD(Red)
COD(Blue)
Colour(Red)
Colour(Blue)
Conductivity(Red)
Conductivity(Blue) 10
10

0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
P (bar) P (bar)

Fig. 11. Retention rates as a function of transmembrane pressure after Everzol Blue Fig. 12. Retention rates as a function of transmembrane pressure after Everzol Red
solution treatment using NF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1). solution treatment using NF membranes ([Dye] = 600 mg L 1; [NaCl] = 500 mg L 1).
A) NF 200; B) NF 270. A) NF 200; B) NF 270.

3.3. Application of membrane processes in textile efuent treatment water produced is called dye bath water and after washing the waste
water generated is called wash water. Dye Bath contains higher solids
3.3.1. Application of ultraltration in textile efuent treatment in the range 45% whereas wash water contains only 0.51% solids.
Ultraltration process using UF 1 kDa membrane was used in the The main characteristics of this sample were given previously in
treatment of an industrial wastewater supplied from the rinsing Table 2. It can be observed that this efuent presents particularly high
baths of a Spanish textile industry. conductivity (l4 mS cm 1) and high COD (708 mg L 1) which
The textile industry plant of the study mainly consists of printing causes environmental problems and makes impossible its reuse.
and dying processes. In these processes, the use of substances such
as NaCl and Na2CO3 is required to favour the aggregation of dye 30
ions on the bre to x the dyestuffs.
About 10% of the total wastewater comes from the dying and print-
25
ing residual baths whereas 85% comes from rinsing. Hence, water J0 (Water) = 3.7 P
recycling in rinse process is the key point for saving fresh water in this Jp (Rinsing) = 2.0 P - 0.5
20
industry.
Jp (L h-1 m-2)

Rinsing efuents were considered for on-site treatment and reuse

in the same or in other production processes, being characterised by a 15
large volume but low concentration of contaminants. Their direct
reuse is not suggested for the wide quality variability in con contrast 10
to the standard quality required in the processes, which cannot be as-
sured without a proper treatment of the raw efuents. 5
Textile dyeing industries need huge quantity of water for textile
dyeing, which they normally pump out repeatedly from the ground
0
or natural water sources resulting in depletion of ground water level.
0 1 2 3 4 5 6 7 8
In the dyeing process textile industries generate huge quantity of
P (bar)
toxic efuent containing colours, sodium sulphate, sodium chloride,
sodium hydroxide and traces of other salts. These are generated after Fig. 13. Rinsing wastewater permeate ux versus transmembrane pressure using UF
dyeing and after washing of garments/fabrics. After dyeing the waste 1 kDa membrane.
 A. Aouni et al. / Desalination 297 (2012) 8796 95

100 100
90 90
80 80
70 70
RRinsing (%)

RRinsing (%)
60 COD 60
50 Colour 50
Conductivity
40 40
30 30 COD
20 20 Colour
Conductivity
10 10
0 0
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
P (bar) P (bar)

Fig. 14. Retention rates as a function of transmembrane pressure after rinsing waste- Fig. 16. Retention rates as a function of transmembrane pressure after rinsing waste-
water treatment using UF 1 kDa membrane. water treatment using NF 270 membrane.

The variation of water and permeate uxes with the transmem- COD, colour and conductivity retention rates of the rinsing waste-
brane pressure is presented in Fig. 13. Similar results were observed water after nanoltration process are shown in Fig. 16. More than 95%
comparing to Everzol Blue solution using the same ultraltration of COD retention and more than 98% of colour retention were ob-
membrane. served for all transmembrane pressure range using NF 270 mem-
Fig. 14 illustrates COD, colour and conductivity retention rates of brane. It can be also observed that an important improvement was
the rinsing wastewater after ultraltration process. More than 90% occurred for conductivity retention rates. In fact, this parameter in-
of colour was retained by UF 1 kDa membrane for a transmembrane creases with the transmembrane pressure and reaches 71% at
pressure varied from 3 to 7 bar. Good COD retention was also 15 bar. These results demonstrate that nanoltration highly improves
obtained (70% at 3 bar and more than 80% at 7 bar). the rinsing wastewater quality.
The same gure demonstrates that ultraltration didn't highly im-
prove the quality of the studied textile efuent in terms of conductiv- 4. Conclusions
ity. In fact, conductivity retention rates didn't exceed 30% even at high
transmembrane pressure. In this study, membrane separation efciencies were evaluated by
These results conrm the efciency of ultraltration process in determining three parameters retentions (colour, COD and conduc-
COD reduction and offer the possibility of using this process as pre- tivity) for treating textile model dyes solutions and real rinsing efu-
treatment to improve the waste water quality. ents. Addition of chemicals was not required, to favorise better
permeate quality. A step forward in water treatment is to obtain an
efuent quality suitable to produce reusable water.
3.3.2. Application of nanoltration in textile efuent treatment The following conclusions are made based on this experimental
The same industrial efuent was treated using NF 270 membrane. study:
Fig. 15 illustrates the variation of water and permeate uxes with the
High COD retention rates (>80%) were obtained for all dyes solu-
transmembrane pressure. Comparing to results obtained previously in
tions using both UF 10 kDa and UF 1 kDa membranes.
Fig. 9B, it can be observed that the initial deviation of the permeate
A total decolourisation was observed for blue and red dyes using UF
ux was more important in the case of the industrial efuent sample
1 kDa membrane.
than using the Everzol dyes solutions. This result conrms the com-
Good conductivity rates (80%) and high COD and colour retention
plexity of the wastewater matrix which leads to a rapid pore plugging.
rates (>90%) were obtained for both NF 200 and NF 270 mem-
branes for all studied dyes solutions.
200 An improvement of the rinsing wastewater quality was obtained
180 using UF 1 kDa in terms of COD and colour.
J0 (Water) = 9.7 P NF process was chosen as an appropriate and an efcient process for
160
Jp (Rinsing) = 6.0 P - 15.8 reducing conductivity, COD and colour in industrial efuent, to assure
140 constant good water quality demanded by textile nishing processes.
Jp (L h-1 m-2)

120
References
100
[1] V.M. Correia, T. Stephenson, S.J. Judd, Characterisation of textile watsewatersa
80
review, Environ. Technol. 15 (1994) 917929.
60 [2] G. Mishra, M. Tripathy, A critical review of the treatments for decolourization of
textile efuent, Colourage 40 (1993) 3538.
40 [3] I.M. Banat, P. Nigam, D. Singh, R. Marchant, Microbial decolorization of textile-
dyecontaining efuents: a review, Bioresour. Technol. 58 (1996) 217227.
20 [4] R.S. Juang, R.L. Tseng, F.C. Wu, S.J. Lin, Use of chitin and chitosan in lobster shell
wastes for colour removal from aqueous solutions, J. Environ. Sci. Health 31
0
(1996) 325338.
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
[5] P. Nigam, G. Armour, I.M. Banat, D. Singh, R. Marchant, Physical removal of textile
P (bar) dyes and solid state fermentation of dye-adsorbed agricultural residues, Bioresour.
Technol. 72 (2000) 219226.
Fig. 15. Rinsing wastewater permeate ux versus transmembrane pressure using NF [6] V.J.P. Poots, J.J. Mckay, The removal of acid dye from efuent using natural adsor-
270 membrane. bents, Water Res. 10 (1976) 10611066.
96 A. Aouni et al. / Desalination 297 (2012) 8796

[7] G. Mckay, Waste colour removal from textile efuents, Am. Dyest Rep. 68 (1979) [35] I. Koyuncu, Inuence of dyes, salts and auxiliary chemicals on nanoltration of
2936. reactive dye baths: experimental observations and model verication, Desalination
[8] N. Willmott, J. Guthrie, G. Nelson, The biotechnology approach to colour removal 154 (1) (2003) 7988.
from textile efuent, JSDC 14 (1998) 3841. [36] A.D. Dhale, V.V. Mahajani, Studies in treatment of disperse dye waste:
[9] S.H. Lin, C.F. Peng, Treatment of textile wastewater by electrochemical method, membrane-wet oxidation process, Waste Manage. 20 (2000) 8592.
Water Res. 28 (1994) 277282. [37] K.M. Pastagia, S. Chakraborty, S. DasGupta, J.K. Basu, S. De, Prediction of permeate
[10] S.H. Lin, C.F. Peng, Continuous treatment of textile wastewater by combined coag- ux and concentration of two-component dye mixture in batch nanoltration,
ulation, electrochemical oxidation and activated sludge, Water Res. 30 (1996) J. Membr. Sci. 218 (2003) 195210.
587592. [38] A. Akbari, S. Desclaux, J.C. Rouch, P. Aptel, J.C. Remigy, New UV-photografted
[11] S.H. Lin, M.L. Chen, Treatment of textile wastewater by chemical methods for nanoltration membranes for the treatment of colored textile dye efuents,
reuse, Water Res. 31 (1997) 868876. J. Membr. Sci. 286 (2006) 342350.
[12] H. Shu, C. Huang, Degradation of commercial azo dyes in water using ozonation [39] I. Koyuncu, D. Topacik, M.R. Wiesner, Factors inuencing ux decline during
and UV enhanced ozonation process, Chemosphere 31 (1995) 38133825. nanoltration of solutions containing dyes and salts, Water Res. 38 (2004) 432440.
[13] H. Abdul Aziz, S. Alias, M.N. Adlan, A.H. Faridah, M. Asaari, Shahrir Zahari, Colour re- [40] S.K. Nataraj, K.M. Hosamani, T.M. Aminabhavi, Nanoltration and reverse osmosis
moval from landll leachate by coagulation and occulation processes, Bioresour. thin lm composite membrane module for the removal of dye and salts from the
Technol. 98 (2007) 218220. simulated mixtures, Desalination 249 (2009) 1217.
[14] C. Tang, V. Chen, Nanoltration of textile wastewater for water reuse, Des 143 [41] C. Allegre, P. Moulin, M. Maisseu, F. Charbit, Savings and re-use of salts and water
(2002) 1120. present in dye house efuents, Desalination 162 (2004) 1322.
[15] A. Aouni, C. Fersi, M. Ben Sik Ali, M. Dhahbi, Treatment of textile wastewater by a [42] A. Bdalo-Santoyo, J.L. Gmez-Carrasco, E. Gmez-Gmez, F. Mximo-Martn, A.M.
hybrid electrocoagulation/nanoltration process, J. Hazard. Mater. 168 (2009) Hidalgo-Montesinos, Application of reverse osmosis to reduce pollutants present
868874. in industrial wastewater, Desalination 155 (2003) 101108.
[16] C. Fersi, L. Gzara, M. Dhahbi, Flux decline study for textile wastewater treatment [43] I. Kim, K. Lee, Dyeing process wastewater treatment using fouling resistant
by membrane processes, Des 244 (2009) 321332. nanoltration and reverse osmosis membranes, Desalination 192 (2006) 246251.
[17] C. Fersi, M. Dhahbi, Treatment of textile plant efuent by ultraltration and/or [44] A. Aouni, C. Fersi, B. Cuartas-Uribe, A. Bes-pi, M. Isabel Alcaina-Miranda, M. Dhahbi,
nanoltration for water reuse, Des 222 (2008) 263271. Study of membrane fouling using synthetic model solutions in UF and NF processes,
[18] C. Fersi, L. Gzara, M. Dhahbi, Treatment of textile efuents by membrane technol- Chem. Eng. J. 175 (2011) 192200.
ogies, Des 185 (2005) 18251835. [45] American Public Health Association, American WaterWorksAssociation, Water
[19] A. Bes-Pi, A. Iborra-Clar, C. Garca-Figueruelo, S. Barredo-Damas, M.I. Alcaina- Pollution Control Federation, in: S.A. Daz Santos (Ed.), Standard Methods of Ex-
Miranda, J.A. Mendoza-Roca, M.I. Iborra-Clar, Comparison of three NF membranes amination of Water and Wastewater, APHA/AWWA/WPCF, Madrid, Espana,
for the reuse of secondary textile efuents, Des 241 (2009) 17. 1992.
[20] A. Bes-Pi, M.I. Iborra-Clar, A. Iborra-Clar, J.A. Mendoza-Roca, B. Cuartas-Uribe, [46] B. Cuartas-Uribe, M.C. Vincent-Vela, S. Alvarez-Blanco, M.I. Alcaina-Miranda,
M.I. Alcaina-Miranda, Nanoltration of textile industry wastewater using a phys- E. Soriano-Costa, Nanoltration of sweet whey and prediction of lactose retention as
icochemical process as a pre-treatment, Des 178 (2005) 343349. a function of permeate ux using the KedemSpiegler and Donnan Steric Partioning
[21] J.M. Gozlvez-Zafrilla, D. Sanz-Escribano, J. Lora-Garca, M.C. Len Hidalgo, models, Sep. Purif. Technol. 56 (2007) 3846.
Nanoltration of secondary efuent for wastewater reuse in the textile industry, [47] International Organization for Standardization, Particle Size AnalysisLaser
Des 222 (2008) 272279. Diffraction MethodsPart 1: General Principles, ISO 133201:1999, 2009.
[22] M. Brik, P. Schoeberl, B. Chamam, R. Braun, W. Fuchs, Advanced treatment of tex- [48] B. Van der Bruggen, M. Manttari, M. Nystrom, Drawbacks of applying nanoltration
tile wastewater towards reuse using a membrane bioreactor, Process. Biochem. and how to avoid them: a review, Sep. Purif. Technol. 63 (2008) 251263.
41 (2006) 17511757. [49] L. Braeken, B. Van der Bruggen, C. Vandecasteele, Flux decline in nanoriltration
[23] H. Yen, S. Kang, Mu-Hoe, Separation of textile efuents by polyamide membrane due to adsorption of dissolved organic compounds: model prediction of time
for reuse, Polym. Test. 21 (2002) 539543. dependency, J. Phys. Chem. B 110 (2006) 29572962.
[24] C. Suksaroj, M. Hran, C. Allgre, F. Persin, Treatment of textile plant efuent by [50] M. Cheryan, Ultraltration and Microltration Handbook, Technomic Publishing
nanoltration and/or reverse osmosis for water reuse, Des 178 (2005) 333341. Company, Inc., Lancaster-Basel, 1998.
[25] N. Zaghbani, A. Haane, M. Dhahbi, Removal of Eriochrome Blue Black R from [51] Yi-Li Lin, Pen-Chi Chiang, E.-E. Chang, Removal of small trihalomethane precur-
wastewater using micellar-enhanced ultraltration, J. Hazard. Mater. 168 sors from aqueous solution by nanoltration, J. Hazard. Mater. 146 (2007) 2029.
(2009) 14171421. [52] J. Pieracci, J.V. Crivello, G. Belfort, Photochemical modication of 10 kDa poly-
[26] N. Zaghbani, A. Haane, M. Dhahbi, Removal of Safranin T from wastewater using ethersulfone ultraltration membranes for reduction of biofouling, J. Membr.
micellar enhanced ultraltration, Des 222 (2008) 348356. Sci. 156 (1999) 223240.
[27] N. Zaghbani, A. Haane, M. Dhahbi, Separation of methylene blue from aqueous [53] C. Bellona, J.E. Drewes, The role of membrane surface charge and solute physico-
solution by micellar enhanced ultraltration, Sep. Purif. Technol. 55 (2007) chemical properties in the rejection of organic acids by NF, J. Membr. Sci. 249
117124. (2005) 227234.
[28] K. Majewska-Nowak, The effect of a polyelectrolyte on the efciency of dye- [54] D. Norberg, S. Hong, J. Taylor, Y. Zhao, Surface characterization and performance
surfactant solution treatment by ultraltration, Des 221 (2008) 395404. evaluation of commercial fouling resistant low-pressure RO membranes, Desali-
[29] J.J. Porter, R.S. Porter, Filtration studies of selected anionic dyes using asymmetric nation 202 (2007) 4552.
titanium dioxide membranes on porous stainless-steel tubes, J. Membr. Sci. 101 [55] L.D. Nghiem, P.J. Coleman, NF/RO ltration of the hydrophobic ionogenic com-
(1995) 6781. pound triclosan: transport mechanisms and the inuence of membrane fouling,
[30] A.L. Ahmad, S.W. Puasa, Reactive dyes decolourization from an aqueous solution Sep. Purif. Technol. 62 (2008) 711718.
by combined coagulation/micellar-enhanced ultraltration process, Chem. Eng. [56] J. Tanninen, S. Platt, A. Weis, M. Nystrom, Long-term acid resistance and selectiv-
J. 132 (2007) 257265. ity of NF membranes in very acidic conditions, J. Membr. Sci. 240 (2006) 1118.
[31] Y. He, G. Li, H. Wang, Z. Jiang, J. Zhao, H. Su, Q. Huang, Experimental study on the [57] N. Park, B. Kwon, I.S. Kim, J. Cho, Biofouling potential of various NF membranes
rejection of salt and dye with cellulose acetate nanoltration membrane, J. Taiwan with respect to bacteria and their soluble microbial products (SMP): character-
Inst. Chem. Eng. 40 (2009) 289295. izations, ux decline, and transport parameters, J. Membr. Sci. 258 (2005)
[32] I. Petrini, N.P.R. Andersen, S. ostar-Turk, A.M. Le Marechal, The removal of reactive 4354.
dye printing compounds using nanoltration, Dyes Pigm. 74 (2007) 512518. [58] M. Takht Ravanchi, T. Kaghazchi, A. Kargari, Application of membrane separation
[33] A. Akbari, S. Desclaux, J.C. Rouch, J.C. Remigy, Application of nanoltration hollow processes in petrochemical industry: a review, Desalination 235 (2009) 199244.
bre membranes, developed by photografting, to treatment of anionic dye solu- [59] Amparo Bes-Pi, Beatriz Cuartas-Uribe, Jose-Antonio Mendoza-Roca, Maria Isabel
tions, J. Membr. Sci. 297 (2007) 243252. Alcaina-Miranda, Study of the behaviour of different NF membranes for the reclama-
[34] B. Van der Bruggen, L. Braeken, C. Vandecasteele, Flux decline in nanoltration tion of a secondary textile efuent in rinsing processes, J. Hazard. Mater. 178 (2010)
due to adsorption of organic compounds, Sep. Purif. Technol. 29 (2002) 2331. 341348.