Chemical Engineering and Processing 41 (2002) 601– 609

www.elsevier.com/locate/cep

Treatment of textile dye effluent using a polyamide-based

nanofiltration membrane
A. Akbari a,*, J.C. Remigy b, P. Aptel b
a
Uni6ersity of Kashan, Kashan, Iran
b
Laboratoire de Génie Chimique (CNRS UMR 5503), Uni6ersité Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, Cedex, France

Received 6 August 2001; received in revised form 10 October 2001; accepted 12 October 2001

Abstract

Experiments were run with seven dyes and a Desal 5DK membrane (cut-off, 150– 300 g/mole). The effects of concentration, pH
and salt on flux and retention were studied. The cut-off of the membrane explains that the retention of the relative high molecular
weight dyes (as direct red 80 or direct yellow 8) is always almost 100%. For anionic dyes as acid orange 10 or acid red 4, the
amphoteric nature of polyamide explains the lower retention at pH 3 than 6. This effect is more pronounced and reversed for basic
blue 3, a cationic dye. The membrane is sensitive to fouling since most of the dyes are used for polyamide textile dying. Moreover,
the presence of salt leads to a further decrease in flux. © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Nanofiltration; Textile dyes; Fouling; Polyamide

1. Introduction waste constituents (specifically dyes). In the last few

It is well-established fact that dye effluents dis-
charged without appropriate treatment bring about a
number of undesirable changes in the recipient stream.
Increased colour concentrations not only make the
water unfit for domestic or industrial uses, but they also
reduce light transmittance, thus limiting aquatic plant
growth and self-purification processes. In addition, dyes
exert an adverse effect on fish life.
Colour removal by conventional treatment methods
(e.g. ozonation, bleaching, hydrogen peroxide/UV, elec-
trochemical techniques) was found to be inadequate [1]
because most textile dyes have complex aromatic
molecular structures that resist degradation. They are
stable to light, oxidising agents and aerobic digestion.
The need for more efficient treatment processes has
attracted the attention of environmental scientists and
engineers towards pressure-driven membrane tech-
niques. The application of membrane filtration pro-
cesses not only enables high removal efficiencies, but
also allows reuse of water and some of the valuable
* Corresponding author. Tel.: +33-561-55-7615; fax: + 33-561-55-
6139.
E-mail address: akbari@chimie.ups-tlse.fr (A. Akbari).
years, technical and economical improvements [2–7]
have made the treatment of industrial wastewater by
membrane systems even more advantageous.
Ultrafiltration has been successfully applied for recy-
cling high molecular weight and insoluble dyes (e.g.
indigo, disperse), auxiliary chemicals (polyvinyl alco-
hol) and water [8,9]. However, ultrafiltration does not
remove low molecular weight and soluble dyes (acid,
direct, reactive, basic, etc.) [10] but efficient colour
removal has been achieved by nanofiltration and re-
verse osmosis [11 –18].
As for all membrane processes, the major problem is
the decline of permeate flux due to the accumulation of
molecules on the membrane surface. This accumula-
tion, known as concentration polarisation, leads to an
increase of membrane fouling. Several approaches have
been proposed to limit fouling for the treatment of
textile wastewater. Buckley has proposed the use of
microfiltration to remove colloidal species from the
exhausted dye bath before nanofiltration [11,12].
Noël et al. have evaluated the performance of two
types of membrane (NF45 and BQ01) for a direct dye
solution [13]. They applied an electric field to eliminate
fouling problems. Electro-nanofiltration performance
was quantified for different potentials and concentra-

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602 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609

tions. An electric field was found to be efficient in
reducing fouling for both membranes studied. They
also noticed that direct dye solution-fouling changes the
NF45 membrane into a reverse osmosis membrane,
while the permeability of the second membrane was
enhanced.
Ratana et al. have studied three nanofiltration mem-
branes for the treatment of effluents containing salt and
reactive dye [14]. The membranes were ES20, NTR-
729HF and LES90. ES20 and LES90 are negatively
charged membranes and NTR-729HF, a substituted
polyvinyl alcohol membrane, is neutral. It was observed
that the ES20 and LES90 membranes can effectively
retain colour, producing a permeate suitable for reuse.
They also noted that for feed containing salt and dye,
the transmembrane osmotic pressure difference is en-
hanced, resulting in a substantial flux decline. The
presence of dye in the effluent significantly affects the
salt removal effectiveness of ES20 and LES90.
The dye molecule can be considered to be structured
from two components the dye chromophore and the
dye auxochrome [20]. The chromophore includes dou-
ble bonds (CC) and is responsible for the colour of the
dye. When the molecule is exposed to light, the struc-
ture of chromophore oscillates, light is absorbed and
colour is visible. There are several chemical classes of
chromophore groups, which include the azo, an-
thraquinone, triphenylmethane, indigo, sulphur groups,
etc. The second portion of the molecule is responsible
for the bond between the fibre and the dye. These
groups include the carboxyl, sulphonic, hydroxyl,
amino groups, etc.
The dye is bound to the fibre through covalent and
ionic bonding, Van der Waals forces and impregnation
of colloidal dye particles into the fibre. Practically,
textile dyes are classified into acid, basic, direct, dis-
perse, reactive, sulphur or vat (Table 1) [21].
The acid dyes were so named because of the presence
in their molecules of one or more sulphonic acid or
other acidic groups. Acid dyes are water-soluble anionic
dyes that are applied to nitrogenous fibres such as
wool, silk, polyamide (nylon) and modified acrylic
fibres from acid or neutral baths. Attachment to the
fibre is attributed at least partly to salt formation
between anionic groups in the dyes and cationic groups
in the fibre.
Basic dyes, which are water soluble in aqueous solu-
tion, yield coloured cations. In the late 1930s a few
basic dyes were developed for acetate and to a lesser
extent for nylon. A number of these dyes were later to
become more important for application to acrylic
fibres.
The conventional definition [22] of direct dyes is,
‘anionic dyes substantive to cellulose when applied
from an aqueous bath containing an electrolyte’. They
provide the simplest means of colouring cellulose mate-
rials since they are normally applied from a neutral or
slightly alkaline bath, at or near the boil, to which
sodium chloride or sulphate is added in such quantities
and at such intervals of time appropriate to the dyeing

Table 1
Dye classification

Dye class Characteristics Application Dye-fibre Dyeing method

attachment
mechanism

Acid Anionic, water soluble Nylon, wool Ionic bond, Van Fibre placed in acidified aqueous
der Waals media pH 2.5–7 dye added and
temperature 100–110 °C
Basic Cationic, water soluble Acrylic, nylon, silk cotton, Ionic bond Fibre placed in acidified aqueous
wool dye bath at pH 5–6.5 and
temperature 105 °C
Direct Anionic, water soluble Cotton H-bond Fibre placed in dye bath slightly
alkaline and electrolyte at
temperature 100 °C
Disperse Colloidal dispersion, very low water Polyester, nylon, acetate, Solid solution Fibre placed in acidified dye bath
solubility cellulose, acrylic formation pH 5.5 temperature 130–210 °C
Sulphur Colloidal, insoluble Cotton Dye precipitated Fibre placed in dye bath dye
fibre dissolved in alkaline sodium
sulphur, dye displaced to fibre with
electrolyte, dye precipitate in situ
with air or peroxide
Reactive Anionic, water soluble Cotton, silk, nylon, wool Covalent bond Fibre placed in dye bath add salt
to displace dye to fibre add alkali
to cause reaction between dye and
fibre
Vat As sulphur dye Cotton As sulphur dye As sulphur dye
 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609 603

Table 2
Characteristics of the dyes tested [21]

Dye (C.I…) M.W (g/mole) Structure Compact formula Charge

Acid red 4 (Aldrich) 402.36 Monoazo C17H13N2NaO5S −1

Acid orange 10 (Aldrich) 496.38 Monoazo C16H10N2Na2O7S2 −2
Basic blue 3 359.90 Oxazine C20H26N3OCl +1
Direct yellow 8 (Aldrich) 540.55 Monoazo C23H19N4NaO5S2 −1
Direct red 80 (Ciba) 1372.55 Polyazo C45H26N10Na6O21S6 −6
Disperse blue 56 (Ciba 305.7 Antraquinone C14H10N2O4Cl 0
Reactive orange 16 (Aldrich) 661.54 Monoazo C20H17N3Na2O11S3 −1

properties of individual dyes. The majority of direct
dyes belong to the dis-, tris-, and polyazo classes, the
remainder being monoazo, stilbene, oxazine, thiazole
and phthalocyanine compounds. Some direct dyes have
extensive uses other than on cellulose fibres, many
being of outstanding importance for use on paper,
leather, wool, silk and nylon.
The disperse dyes are defined as ‘substantially water
insoluble dyes, behaving substantively for one or more
hydrophobic fibre, for example cellulose acetate, and
usually applied from fine aqueous dispersion’. Although
substantially insoluble, these dyes are slightly soluble in
water and uptake by the fibres is believed to take place
from this aqueous phase. The solubility of the dye and
hence its uptake equilibrium and dyeing rate may be
modified by the dispersing agent employed.
The reactive dyes include molecules with active
groups such as mono-, dichlorotriazinyl, di-,
trichlorophrimidinyl, chloroethylsulphonyl. They form
a bond with fibre, and it has been suggested that
self-condensation or the elimination of soluble groups
fix some of them. A range of reactive procinyl dyes for
nylon was introduced by ICI in 1959. They are applied
in weakly acid conditions, under which reaction with
the fibre does not occur. Dyeing is then readily ob-
tained on treatment with alkali, a reaction with the
fibre takes place and the resulting dyeing is very fast to
wet treatments. Free amino groups in the nylon fibre
provide reactive sites, but there is some evidence sug-
gesting that reactions may also occur with amide
groups.
Thus, the textile dyes are reactive towards the chemi-
cal functions present at the fibre surface. These same
chemical functions are found in the polymer surface
used for the preparation of membranes. For example,
most nonofiltration membranes are composite mem-
branes, the active surface of which is polyamide.
Polyamide fibres can be dyed by most classes of dyes.
Acid, disperse, direct and reactive dyes are classic ex-
amples but basic dye can also be used by changing pH.
Thus, it is reasonable to think that nanofiltration of
textile dyes with polyamide membranes will be prob-
lematic, heavy fouling is very probable because the dyes
will be fixed to the fibres by chemical bonds; and it is
highly probable that this fouling will be irreversible.
The following equations show the reaction schemes
between the polyamide fibres and the textile dyes.
Below the isoelectric point (4.2) polyamides have a
positive charge and can react with anionic dyes (acid,
direct, etc.).
H3N+ − Polyamide− COOH + DyeSO−
3
“ DyeSO− +
3 H3N − Polyamide−COOH
Ionic bond
Above the isoelectric point, polyamides have a nega-
tive charge and can react with cationic dyes.
H2N− Polyamide− COO− + Dye+
“ H2N− Polyamide− COO−Dye+
Ionic bond
In all cases, the exhaustion is dependent on pH,
concentration, temperature, class of dye and electrolyte
as NaCl or Na2SO4.
There are two types of reactive dye, which can form
a covalent bond with polyamide:
H2N− Polyamide− COOH +Dye −Cl
“ Dye − HN − Polyamide− COOH
Covalent bond
H2N− Polyamide− COOH + Dye − x−CH2CH2 −y
“ Dye − x− CH2CH2 − HN − Polyamide −COOH
Covalent bond
(x=O, SO2, … ,y= Cl, SO3H, …)
This study primarily concerned the influence of the
interactions between a polyamide membrane (Desal
5DK) and seven dyes, on the transport properties in
nanofiltration. The effects of such significant parame-
ters as pH, solution concentration and salt effects on
two fundamental characteristics of nanofiltration (flux
and retention) will be presented.
2. Material and methods
The Desal 5DK membrane, manufactured by Os-
monics, was selected for study. It is a hydrophilic
membrane with a nominal molecular weight cut-off of
150–300 g/mole. This membrane is a thin-film com-
posite with an active layer made of polyamide [19].
604 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609
The supplier, the chemical structure, the molecular
weight and the number of charges of the dyes tested
are given in Table 2 and Fig. 1. Model dye solutions
were prepared by dissolving dyes (as supplied) in dis-
tilled water at a concentration of 1 g/l without adding
any auxiliary compounds. Addition of NaOH and
H2SO4 to the solution was used to set the pH.
All the nanofiltration experiments were performed in
a cylindrical stirred cell (300 cm3) with an active mem-
brane area of 36.3 cm2. Tests were first run using
distilled water under 20 bar in order to compact the
membrane. The filtration was then carried out at a
pressure of 10 bar with or without stirring. The stir-
ring rate was measured by a stroboscope. After 10 min
filtration, the permeate sample was collected for 10
min and weighted. During the nanofiltration operation
with dye solutions, the permeate samples were sent
back to the cell to ensure a constant concentration of
Fig. 1. Chemical structure of tested dyes.
the feed solution. After the measurements, the mem-
brane was rinsed with distilled water and the fouled
membrane permeability was measured with distilled
water. A new membrane was used for each experi-
ment.
The concentrations are determined either by visible-
UV spectrophotometry for the dye solution at the
maximum absorption wavelength or by conductivity
for the Na2SO4 solution.
Adsorption tests were performed in a small cylindri-
cal filtration cell (active membrane surface area of 13.2
cm2). A clean wet sample of membrane was installed
and 100 cm3 of the dye solution was poured into the
cell. Adsorption was followed versus time by measur-
ing the decrease in absorbance of the solution. The
increase in dry weight of the exposed membrane was
estimated by weighting another membrane sample of
the same surface area.
 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609 605

3. Definitions Table 3
Flux and retention of dye solutions with or without stirring (DP=10
bar, temperature 25 °C, concentration 1 g/l and pH 6)
The distilled water flux is proportional to the applied
pressure and distilled water permeability, Lp (l/h m2 Dye (C.I…) Flux (l/h m2) Retention (%)
bar) is defined as [19]:
Re=0 Re= 4100 Re=0 Re=4100
Jw
Lp = (1)
DP Direct red 80 27.1 41.1 99 100
Disperse blue 56 28.3 41.3 99.4 100
where, Jw is the permeate flux (1/h m2) and DP the Acid red 4 13.3 21.7 83 96.5
Basic blue 3 13.1 18.6 21.2 41
applied pressure (bar or 105Pa). Taking account the
osmotic pressure, Noel et al. applied Eq. (2) for salt
solution permeability Ls (1/h m2 bar):
Js
Ls = with DPe =DP −D^ and 4.2. Effect of hydraulic conditions on membrane
DPe
properties
D^ = ^(Cm)− ^(Cp) (2)

where, Js is the permeate flux (1/h m2), DPe the effective
pressure (bar),  the osmotic pressure (bar). Cm and Cp
are the concentration of the concentrated boundary and
of the permeate, respectively.
The osmotic pressure can be calculated according to
Van’t Hoff’s equation [13,18]:
^=% i · R · T · C
where, i is the number of ions per molecule of solute, R
the perfect gas constant, T the temperature (°K) and C
the concentration (mole/1).
When concentration polarisation is limited by stir-
ring, (Cm) is close to (Cb) thus D^ = ^(Cb)−
^(Cp) ((Cb): concentration of bulk).
The retention of dye solution is defined as:
Ab −Ap
R% = 100
Ab
Ab and Ap are the absorbance of the bulk and
permeate solutions, respectively.
The experiments were carried out at ambient temper-
ature (q). Fluxes are given at 25 °C after correction of
the influence of the water viscosity [23]:
Table 3 shows the effect of stirring on the flux and
the retention of four dye solutions.
The measurements were performed after 20 min of
filtration. As shown by these data, stirring of the bulk
solution at a velocity corresponding to a Reynolds
number of 4100 (turbulent regime) improved the dye
solution permeability and the retention. It should be
pointed out that for higher velocities, the fluxes de-
(3)
creased while the retention remained constant. This is
due to the formation of a vortex, which limits the
membrane surface area. For maximum stirring velocity,
the unfavourable concentration polarisation effect was
practically eliminated. All the following experiments
were conducted in these conditions.
4.3. Fouling
Fig. 2 shows the evolution of the permeability ratio
(4) and the retention as a function of time. The initial and
final distilled water permeability are also shown at
time= 0 and 140 min, respectively.

J25 = Jq exp(0.0239(25−q)) (5)

The viscosity of the solutions is assumed to be equal

to the water viscosity at the same temperature.

4. Results

4.1. Initial water permeability

The membrane samples did not all have exactly the

same initial permeability, Lp varied from 3.6 to 4.5 l/h. Fig. 2. Permeability ratio (a) and retention (b) vs. time (DP=10 bar,
m2. bar. temperature 25 °C, concentration 1 g/l, Re= 4100 and pH 6).
606 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609

Fig. 3. Dye exhaustion by the membrane (concentration 1 g/l, temper-

ature 25 °C).

A flux decrease is observed for all solutions (Fig. 2a)

which was not stabilised after 2 h of operation. This
decrease is attributed to the fouling of the membrane.
After rinsing with water, it is surprising to observe that
the water permeability was higher than the initial value
for the anionic dyes (direct red 80 and acid red 4).
On the other hand, the retention was stable, except
for the basic dye (Fig. 2b). The sharp drop in retention
for the basic blue 3 can be correlated to the adsorption
of this dye onto the active polyamide surface of the
membrane as shown in Fig. 3. Adsorption equilibrium
was reached in 2 h.
Fig. 4. Influence of concentration on the permeability ratio (a) and
retention (b) of dye solutions (DP= 10 bar, temperature 25 °C and
Re=4100).
As previously observed, for all except the cationic
dye, there was a net decrease in flux versus time, while
retention remained constant.
4.5. Influence of the concentration

4.4. Effect of pH on the permeability and retention of
dye solutions
Table 4 shows the effect of pH on the retention and
permeability of 6 dye solutions. It can be seen that the
Desal 5DK membrane retained direct red 80 and direct
yellow 8 completely at pH values of 3 and 6. For these
dyes, the pH also had no influence on the permeability
ratio. The results were slightly different for the 2 other
anionic dyes (acid red 4 and acid orange 10), the
permeability ratio and; to a lesser degree, the retention
improved when the pH increased from pH 3 to 6. The
last anionic dye was only studied at pH 6, and as for
the other anionic dyes, the retention was high.
The behaviour was quite the opposite for the cationic
dye (basic blue), both permeability ratio and retention
decreased as the pH was increased from pH 3 to 6.
Since the purpose of nanofiltration is to concentrate
the effluent, it was important to have an idea of the
influence of concentration on the performance. In
nanofiltration membrane separation, concentration
plays a significant role. In general, the higher the con-
centration, the higher the osmotic pressure and conse-
quently the lower the permeate flux. For the solutions
of direct red 80, acid red 4 and disperse blue 56, it can
be seen in Fig. 4 that the permeate flux decreased with
the concentration increase and the flux was always
higher at lower solution concentration.
4.6. Influence of the addition of sodium sulphate
Preliminary studies were done to determine the per-
formance of the membrane in the treatment of solu-
tions composed of sodium sulphate and dyes. A direct

Table 4
Influence of pH on the permeability ratio and retention of dye solutions (DP= 10 bar, temperature 25 °C, Re=4100, concentration 1 g/l)

Dye (C.I…) Ls/Lp Retention (%)

pH 3 pH 6 pH 3 pH=6

t= 1 h t= 2 h t= 1 h t= 2 h t= 1 h t =2 h t =1 h t=2 h

Direct red 80 0.73 0.66 0.72 0.64 100 100 100 100
Direct yellow 8 0.51 0.44 0.66 0.49 99.3 100 100 100
Basic blue 3 0.52 0.38 0.21 0.18 97.3 96 91 75
Acid red 4 0.47 0.40 0.73 0.65 96.3 95.5 96.1 95.9
Acid orange 10 0.74 0.64 0.90 0.83 95.2 94.3 98.1 97.9
Reactive orange 16 – – 0.94 0.86 – – 95.6 95.8
 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609 607

dye and a reactive dye were chosen since they are
widely used to colour cellulose fibres and the process
requires large amount of salt and causes serious envi-
ronmental problems. The dye concentration was 1 g/l
and the sodium sulphate concentration was 10 g/l. The
applied pressure was 10 bars for the all experiments and
the Reynolds number was 4100. The results are pre-
sented in Table 5. Dye retention was 100% in all cases
for the direct dye while the retention of reactive dye
was lower (96% or less). The retention of salt was
noticeably affected by the presence of the dye. The
more the dye was retained, the less the salt was
retained.
5. Discussion
In nanofiltration, there are two principal mechanisms
of separation:
transport of uncharged solutes takes place by convec-
tion due to a pressure difference and by diffusion due
to a concentration gradient across the membrane. A
sieving mechanism is responsible for the retention.
For charged components electrostatic interactions
take place between the components and the mem-
brane charges. The transport of ions across the mem-
brane can be described in terms of diffusion and
migration, as a result of concentration and electrical
potential gradients, as well as convection caused by
transmembrane pressure.
As mentioned in the introduction, the polyamide
membrane has a cut-off around 150– 300 and carries
negative charges (COO−) at pH 6 and positive charges
at pH 3 (NH+ 3 ). Based on that and on the schematic
dyeing mechanisms briefly recalled in the introduction,
most of the data obtained in this paper can be qualita-
tively explained.
1. For high molecular weight (1373 g/mole) direct red
80, retention was 100% in all cases whatever the
conditions, the size of the molecule is larger than the
pore size of the membrane and it cannot enter into
the membrane; retention is controlled by a sieving
mechanism. However, strong interactions (ionic and
Hbonding) take place at the surface of the mem-
brane at both values of pH, this explains the de-
crease in permeability versus time (Fig. 2a and
Table 4).
2. For the three other anionic dyes (acid orange 10,
acid red 4 and direct yellow 8) their MW is lower
and the sieving mechanism was slightly less impor-
tant than for the direct red 80. The pH effect begins
to be noticeable (Table 4), when the membrane
carries the same charge as the dye (pH 6) repulsion
between the membrane and the solute explains the
slightly better performance in terms of permeability
and retention.
3. For the cationic dye (basic blue 3) ionic interactions
play a major role in the transport properties as
shown in Fig. 2 and Table 4. At pH 6 there is a
strong ionic interaction between the membrane and
the solute (Fig. 3). The initial retention of 100% can
be explained by the binding of the dye to the
membrane. With a progressive saturation of COO−
groups, retention began to decrease to reach 75%
after 2 h, which corresponds to the time needed to
reach adsorption equilibrium (Fig. 3). On the con-
trary, at pH 3, there is a repulsion between the
membrane charges and the cationic dye, retention
increased from 75% at pH 6 to 96% at pH 3, while
the flux doubled (Table 4).
4. In the presence of salt an interesting result was the
decrease in rejection (Table 5) for the salt and the
dye when they were mixed compared with the rejec-
tion observed when they were alone (excepted for
the high molecular weight direct red 80, always
totally retained by a sieving mechanism). The reason
for this decrease is that, in the presence of a high
salt concentration, Donnan exclusion becomes less
effective and the anionic species are repelled less.
5. A notable result concerns the apparent increase in
permeability after nanofiltration of anionic dyes
(Fig. 2a, values at 140 min and Table 5, last line).

Table 5
Permeability ratio and retention of the membrane with the solution containing dye and Na2SO4 (DP= 10 bar, temperature 25 °C, Re=4100 and
pH 6)

Solution Ls/Lp %R (Na2SO4) %R (Dye) D^ (bar)

t= 1 h t =2 h t =1 h t= 2 h t= 1 h t=2 h t=1 h

Distilled water before NF 1.00 – – – – – –

10 g/l Na2SO4 0.88 0.70 96.8 96.1 – – 4.67
1 g/l Direct red 80 0.85 0.76 – – 100 100 0.13
1 g/l Direct red 80+10 g/l Na2SO4 0.79 0.65 78.6 72.8 100 100 2.91
1 g/l Reactive orange 16 0.86 0.78 – – 95.6 95.8 0.11
1 g/l Reactive orange 16+10 g/l Na2SO4 0.79 0.69 88.2 87.2 86.6 83.0 3.47
Distilled water after NF 1.10 – – – – – –
608 A. Akbari et al. / Chemical Engineering and Processing 41 (2002) 601–609
We may assume that this is due to the charges of the
dyes adsorbed at the membrane surface, this proba-
bly increases the hydrophilicity of the skin layer of
the membrane. However, this effect is not perma-
nent and after a longer cleaning in water, the initial
permeability is restored.
6. A more general comment concerns the fouling prob-
lem and the performance in terms of flux. Although
the experiments were run in a turbulent flow regime
(low concentration polarisation), fouling was heavy
and the values of the permeability ratio, after 2 h of
operation, were often between 0.6 and 0.8 which
corresponds to a permeate flux of only 25– 35 l/h
per m2 under a pressure of 10 bar. These values will
certainly be lower in the long term and full-scale
operation with conventionally spiral wound mod-
ules. The fouling is more or less reversible as a
function of the class of the dye and of the molecular
weight. Qualitatively, it could be expected that the
reversibility decreases in the following order, direct
rouge 80Bdirect yellow 8Bacid red 4B acid or-
ange 10Bdisperse blue 56B reactive orange 16
basic blue 3. Since the fouling is mainly due to the
amphoteric nature of the polyamide skin layer, the
development of less fouling-sensitive nanofiltration
membranes will be necessary to improve the eco-
nomics of the process.
6. Conclusions
The present work investigates the performance of a
polyamide nanofiltration membrane in treating
coloured textile effluent. For anionic dyes (acid red 4,
acid orange 10, direct red 80, direct yellow 8, and
reactive orange 16), the membrane generally showed
acceptable rejection due mainly to its relatively low
cut-off and the cationic dyes were more than 95%
retained whatever the range of pH and concentration
used. In particular, direct red 80 and direct yellow 8
were 100% retained and produced a permeate suitable
for reuse. However, the membrane suffered from flux
decline due to its sensitivity to fouling. In the presence
of salt, the osmotic pressure resulted in a further de-
crease in flux.
For the cationic dye tested (basic blue 3), the influ-
ence of the Donnan exclusion phenomena was clearly
observed and the membrane was not suitable for such
an application.
With these conclusions in mind, we now intend to
develop a membrane that is less sensitive to fouling.
Acknowledgements
This study has been financially supported by a doc-
toral grant from the government of Iran and Société
Française d’Exporatation des Ressources Educatives
(SFERE).
Appendix A. Nomenclature
Ab absorbance of the bulk solution
Ap absorbance of the permeate
C concentration (mole/l)
Cb concentration of bulk (mole/l)
Cm concentration at the membrane surface (mole/l)
Cp concentration of the permeate (mole/l)
i number of ions per molecule of solute
Js permeate flux of salt and dye solutions (l/h m2)
Jw permeate flux of distilled water (l/h m2)
Lp distilled water permeability (l/h m2 bar)
Ls permeability of salt and dye solutions (l/h m2
bar)
Pe effective pressure (bar or 105 Pa)
R perfect gas constant
T temperature (°K)
Greek letters
D Difference
 osmotic pressure
q temperature (°C)
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