Chemical Engineering Journal 262 (2015) 156168

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Fouling of nanoltration membranes by dyes during brine recovery

from textile dye bath wastewater
T. Chidambaram a, Yoram Oren b, M. Noel a,
a
b

Water Research Laboratory, Water Institute, Karunya University, Tamil Nadu 641114, India
Department for Desalination and Water Treatment, Zuckerberg Institute for Water Research, Ben-Gurion University of the Negev, PO Box 653, Beer-Sheva 84106, Israel

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Electrostatic interactions between

charged dye molecules and NF

membrane during nanoltration are
reported.
 Strong sulfonic acid containing dye
molecules do not interact
electrostatically and hence do not foul
the membrane.
 Weak carboxylic acid strongly
interacts and fouls the membrane in
acidic pH.
 Weak bases and foul the membrane
in neutral and alkaline pH.
 Smaller dye molecules can also foul
the membrane by pore blocking.

a r t i c l e

i n f o

Article history:
Received 28 July 2014
Received in revised form 11 September
2014
Accepted 18 September 2014
Available online 28 September 2014
Keywords:
Nanoltration
Textile dye
Electrostatic interaction
Membrane fouling
Flux decline
Brine recovery

Corresponding author. Tel.: +91 422 2614422.

E-mail address: yemenoel1@gmail.com (M. Noel).
http://dx.doi.org/10.1016/j.cej.2014.09.062
1385-8947/ 2014 Elsevier B.V. All rights reserved.

a b s t r a c t
The present investigation aims at identifying the molecular properties of the dye which control
membrane fouling during nanoltration. Three negatively charged molecules, namely Acid red 87, Direct
blue 53 and Acid black 1 and three positively charged molecules, namely Azure A, Basic blue 9 and Basic
green 4 are investigated. Dye molecules of 50 mg/L dissolved in 2000 mg/L of NaCl were subjected to
nanoltration using NF 270 membrane (Dow Filmtec with an isoelectric point of 3.3) at pH-3, pH-7
and pH-10. The ux decline, salt rejection and dye rejection were measured using Sterlitech cross ow
cell (CF042) with an active membrane surface area of 14.6  104 m2. Flux decline due to membrane
fouling was also calculated by measuring pure water ux after washing the fouled membrane with water
at the same pH for 30 min. These results indicate electrostatic interactions between the charged dye
molecules and the membrane charge, which depend on the pH. Strong sulfonic acid containing dye
molecules (Direct blue 53 and Acid black 1) do not get adsorbed on the membrane surface. High ux rate
and dye rejection were noticed in all the three pH media investigated for these dyes. Weak carboxylic
acid (Acid red 87) shows strong ux decline and membrane fouling in acidic pH. Positively charged
dye molecules with relatively low molecular weights, exhibit strong fouling effect in neutral as well as
alkaline pH. The effects of molecular-membrane electrostatic interactions and acidbase interactions
on membrane fouling are highlighted in this work along with the molecular size effect.
2014 Elsevier B.V. All rights reserved.

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

1. Introduction

2. Materials and methods

Textile dyeing industry consumes large quantity of water.

Each kilogram of textile fabric consumes between 60 and
100 kg of water during dyeing and washing operations [1]. Dye
bath efuent, which constitutes approximately 10% of the total
water used, contains up to 75 g/L of inorganic salts such as NaCl
and Na2SO4 along with residual dye molecules [2]. Experiments
have established that up to 71% of the dissolved NaCl can be
recovered along with water as brine solution by commercially
available nanoltration membranes [3]. The commercial dyeing
units in and around Tiruppur town in Tamil Nadu, India also
employ available nanoltration membranes for brine recovery
[2]. However, membrane fouling remains a serious challenge
which limits its continuous and long term operation and hence
commercial viability. These dyeing units utilize a variety of dye
molecules based on color and shade requirements. A detailed
study to understand the inuence of molecular structure of dye
on NF membrane can throw further light on solving this problem
of membrane fouling.
Commercial NF membranes are essentially thin lm composites containing a polyamide layer over a more porous and hydrophobic polysulfone or poly ether sulfone support layer [4]. The
pore size of the surface layer is in the range of 0.61.3 nm which
determines the molecular weight cut off (MWCO) of each NF
membrane [5]. The dye molecules having molecular weights
close to or exceeding the MWCO of individual membranes would
be rejected by these membranes [6]. Nanoltration membranes
exhibits high and undisturbed ux rates in the presence of
organic acids [7], phenols [8], amines [9], drugs [10], pesticides
[11] and surfactants [12] near the IEP, due to the absence of
strong electrostatic interactions.
The origin of electrical charges on the polyamide membrane
surface containing COOH and NH2 group in pH regions below, at
and above the IEP values for different pH domains are given below
[13]:

2.1. Materials

157

Three anionic and three cationic dye molecules were selected

for the present experiments involving nanoltration (Table 3).
The dyes used for the experiments are Acid red 87 (AR 87; COO)
a carboxylate containing dye; Direct blue 53 (DR53, SO
3 ) and
Acid black 1 (AB 1, SO
3 ) dye molecules containing strong sulfonic
acid functional groups with molecular weights of 869 and 570 Da
respectively; Azure A (AZ A, N+/S+) and Basic blue 9 (BB 9; N+/S+)
heterocyclic dye molecules containing positive charges; Basic
green 4 (BG 4, N+) is a triaryl compound containing tertiary N
atoms. All the six dye molecules were supplied by Loba Chemi
Pvt. Ltd. India. Nanoltration of all the above mentioned molecules
was carried out with NF 270 (Dow Filmtec) in 2000 mg/L NaCl
solution maintained at three different pH values of 3, 7 and 10.
The pH was adjusted using HCl or NaOH, wherever necessary. Concentration of each dye molecule was kept constant at 50 mg/L and
the dye solutions prepared were subjected to nanoltration. The
solubility data for these molecules have been determined in the
different pH values mentioned above and are presented in Table 3.
The solubility varied from 10 g/L for AB 1 (SO
3 ) to 280 g/L for AR 87
(COO). Solubility was found to be pH sensitive for all the molecules, except for the highly soluble AR 87 (COO).
Potentiometric titrations were carried out for these dye solutions in order to determine the pKa values. The titration curves
for all the molecules exhibited similar trends with two distinct
pKa values. Values of pKa1 fall in the range of 4.3 and 4.8 and those
for pKa2 fall in the range of 8.0 and 8.5 (Table 4). The pH of the dye
solutions were selected so as to be below pKa1, between pKa1 and
pKa2 and above pKa2 of these dye molecules. The stability range
for the NF 270 membrane used in the present work is also found
to be in the range of pH 3 to10 [4]. The IEP value for this membrane
as reported by Aouni et al. is at pH 3.3 [4]. The molecular weight
cutoff (MWCO) for this membrane is 200300.

H3 N -COOH
H2 N-COOH
H2 N-COO
pH<IEP

pHIEP

pH>IEP

At pH values lower than that of the IEP of polyamide membrane, negatively charged organic molecules interact electrostatically with the membrane surface leading to organic adsorptive
blocking and ux decline [13]. Positively charged organic molecules [9,10] were found to exhibit similar blocking effect at pH
values higher than that of the IEP due to electrostatic interaction
with the negatively charged membrane. The IEP is thus an important parameter in determining the efcient functioning of newly
developed NF membranes [14,15] in the presence of organic molecules, particularly textile dyes. A few studies on the effect of pH
during the NF separation of positively and negatively charged dye
molecules are available [13,16]. One report indicates that acidic
dyes solutions exhibit maximum ux near the isoelectric point
[13]. The second report has compared the performance of cationic and anionic in pH 3 and 6 [16]. There is scope for further
studies on a wider pH range and also study the contributions
of concentration polarization towards membrane fouling. The
reversible and irreversible nature of membrane fouling by
charged molecules in different pH regions also needs to be
explored.
The present study investigates the effect of molecular charge
of different dyes and the pH of salt solution on water ux and
salt and dye rejections in the context of nanoltration used in
textile wastewater treatment for the recovery of both water
and salt. Efforts have also been made to measure and interpret
the ux decline due to fouling under each experimental
condition.

2.2. Experimental set-up and methods

A schematic diagram of the cross-ow at sheet membrane test
set-up used in this study is shown in Fig. 1. The NF 270 membrane
was supplied by M/s Sterlitech, USA. A at sheet membrane with
an effective area of 0.0042 m2 was installed in a cross ow cell
(Sterlitech CF042). High pressure pump (Hydra-cell) was used for
generating the required pressure and for circulating the solutions
in the membrane cell. The experiments were carried out at
10 bar constant operating pressure and at a constant temperature
of 25 1 C using heat exchanger on the feed tank ow line. Both
permeate and concentrate streams were constantly remixed and
circulated at the rate of 120 L/h through the feed vessel, after sampling roughly 0.25% of the total volume of the solution during the
experiments.
Initially the fresh membrane was kept in deionised water for
about 24 h followed by washing for 30 min duration in 30% isopropyl alcohol and 0.025% sodium dodecyl sulfate for removing
unwanted compounds like glycerol and grease. Then the membrane was installed in the cell and subjected to three times of
the operating pressure (30 bar) for about 4 h; simultaneously,
deionised water is circulated to ensure membrane compaction
and reproducibility. Subsequently, pure water ux and MgSO4
rejection were measured at the operating pressure of 10 bar to
verify reproducible membrane performance. Then the actual
experiments were carried out for about 2 h under identical experimental conditions. All the experiments were repeated three times.
The average values are reported with error bars. After measuring

158

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

Table 1
Real rejection corrections based on the concentration polarization values.
Samples

Jsd (m/s)

Re

Rep

Sc

Sh

km (105 m/s)

CP

R (%)

R0 (%)

NaCl at pH-3
NaCl at pH-7
NaCl at pH-10
AR 87 at pH-3
AR 87 at pH-7
AR 87 at pH-10
DB 53 at pH-3
DB 53 at pH-7
DB 53 at pH-10
AB 1 at pH-3
AB 1 at pH-7
AB 1 at pH-10
AZ A at pH-3
AZ A at pH-7
AZ A at pH-10
BB 9at pH-3
BB 9at pH-7
BB 9 at pH-10
MG 4 at pH-3
MG 4 at pH-7
MG 4 at pH-10

0.00002881
0.00003079
0.00003122
0.00001719
0.00003278
0.00003278
0.00002711
0.00003133
0.00002975
0.00002856
0.00003172
0.00003119
0.00003014
0.00002381
0.00001611
0.00002539
0.00001878
0.00001494
0.00002539
0.00002090
0.00001402

725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586
725.7586

0.065929
0.070468
0.071441
0.03935
0.075013
0.075013
0.062051
0.071708
0.068084
0.065351
0.072598
0.07139
0.068974
0.054486
0.036871
0.058104
0.042974
0.034201
0.058116
0.047824
0.032084

708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75
708.75

155.61
160.38
161.40
127.73
165.14
165.14
151.55
161.68
157.87
155.01
162.61
161.34
158.81
143.61
125.13
147.40
131.53
122.33
147.42
136.62
120.11

9.59
9.89
9.95
7.88
10.2
10.2
9.34
9.97
9.73
9.56
10.0
9.95
9.79
8.85
7.71
9.09
8.11
7.54
9.09
8.42
7.41

1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00

38.19
44.45
67.41
47.50
55.86
54.89
30.89
53.40
59.94
35.67
58.10
66.31
45.30
50.31
68.44
50.73
65.12
76.62
51.26
49.42
76.61

38.18
44.44
67.40
47.49
55.85
54.88
30.89
53.39
59.94
35.66
58.09
66.30
45.29
50.30
68.44
50.72
65.11
76.62
51.25
49.41
76.60

Table 2
Real rejection for the 2000 ppm of NaCl solution.
Flow rate (L/h)

Jsd (m/s)

Slope (1/k)

km (105m/s)

Intercept ln (1/R1)

CP

R (%)

R0 (%)

120

0.0000298

6083.8

0.1643

0.149

1.05

46.29

44.44

the total ux decline, the membranes were washed with water at

the same pH for 30 min to remove the dye molecules loosely held
on the membrane surface. The ux recovery value for the water
obtained after this washing process was used to estimate the ux
decline due to membrane fouling.
For studying the long term ux decline behavior and structure
of the membrane after the NF ltration process, experiments were
carried out for 10 h duration for selected dye molecules containing
strong acid (AB 1) at pH-7, weak acid (AR 87) at pH-3 and weak
base (BG 4) and BB 9 at pH-10. These membranes were washed
with water at the same pH values followed by drying in air and
thereafter characterized using ATR-FTIR spectroscopy (using Zn/
Se crystal NICOLET 380) and scanning electron microscopy (SEM,
JOEL-6390).

where Cb and Cp are the bulk and permeate concentration of the salt
solution.
The real rejection (R) was calculated by using the following
expression:

Cm  Cp
 100
Cm

where R is the real rejection, Cm the solute concentration on

membrane surface, Cp the solute concentration in the permeate.
The dye rejection is given as:

Rdye %

Ab  Ap
 100
Ab

where Ab and Ap are the bulk and permeate absorbance of the dye
molecules involved [19].

2.3. Data interpretation

2.3.1. Permeate ux and salt and dye rejection
The membrane productivity is expressed as the permeate ux
through the membrane. The pure water ux Jw (L m2 h1) is
dened as:

Jw

Qw
A  t

1
Concentration polarization CP

where Qw, A and t are the volume of permeate for pure water (Liter),
area of the membrane (m2), and permeate collection time (h)
respectively. The permeate ux in the presence of salt and dye, Jsd
(L m2 h1) is dened as:

J sd

Qs

A  t

where Qs is the volume of permeate for dye/salt mixtures.

The observed salt rejection (R0) is given by:

R0 %

Cb  Cp
 100
Cb

2.3.2. Determination of mass transfer coefcient and concentration

polarization
The experimentally determined rejection values were corrected
to account for the concentration polarization at the membranesolution interface to obtain the real rejections, using the following
approach adopted. [21]:

where the and mass transfer coefcient is:

km

Sh  Do
H

and Sherwood number is given by:

Sh A1 1 A2 ReA3 ScA4
3

 
Cm  Cp
J
exp sd
Cb  Cp
km

 A5
 1=3
H
H
Rep Re Sc
L
L

In Eqs. (7) and (8), H and L refer to the height and length of the
membrane channel (m) respectively, Do the diffusivity of salt in
solution (for NaCl, Do = 1.418  109 m2/s), A1 = 1.72, A2 = 1.25,

Table 3
Characteristics of the dye molecules used for this study.
S. No.

Dyes

Acid red 87 (AR 87)

Molecular formula/molecular weight (g/mol)

(C20H6Br4Na2O5)2Na+(645.88)

Solubility (g/L)

Absorbance (kmax)

pH-3

pH-7

pH-10

280

280

280

Molecular structure

515518

COOBr

Br
-

Br
2

Direct blue 53(DB 53)

(C34H24N6O14S4)4Na+ (869.81)

130

165

180

Br
SO3-

606611

SO3-

N
O

NH2 O
O3S

N
H

NH2

4Na+

SO33

Acid black 1(AB 1)

(C22H14N6O9S2)2 2Na+(570.49)

9.5

10

15

618624

SO3- Na+

Na O3S
N

N
OH

Azure A (AZ A)

(C14H14N3S) Cl (256.3)

15

10

14

NH2

NO2

625632

N
H3C

Basic blue 9 (BB 9)

(C16H18N3S)+Cl (284.3)

46

45

40

S+

N
CH3

Cl-

NH2

668669

N
S+

Basic green 4 (BG 4)

(C23H25N2)2 2C2HO4C2H2O4 (329.4)

46

50

39

616620

Cl-

O
HO

O
OH

OH

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

H
N

N+

OH

N+
159

160

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

inlet and up the average velocity of the permeate stream at

channel outlet (volume of the permeate [(m3/s)/cross section of
the membrane (42  104 m2)].
Cohen et al. have used Eqs. (6)(8) to calculate Re, Sc, Sh, km and
CP values for simple inorganic salt solutions of NaCl, CaCl2 and
Na2SO4. Since the system employed in the present experiments is
quite similar to the system employed by earlier workers, a similar
approach was adopted to calculate km and CP and R values. These
values were calculated for NaCl solutions as well as for NaCl solutions containing dye molecules in three different pH values. Typical
values of these parameters in 2000 mg/L NaCl solution with and
without AR 87 at pH values 3, 7 and 10 are given in Table 1. The
table highlights that km values differ marginally under different
experimental conditions. The km values calculated using
Eqs. (6)(8) is found to vary linearly with the experimentally

Table 4
pKa values of the textile dye molecules used for this study.
Dyes

pKa1

pKa2

AR 87
DB 53
AB 1
AZ A
BB 9
BG 4

4.3
4.8
4.5
4.5
4.6
4.3

7.95
8.5
8.3
8.3
8.0
8.0

A3 = 0.31, A4 = 0.50, A5 = 0.28, Sc-the uid Schmidt number

(go/Doqo), Re-the feed Reynolds number (Hu0qo/go), qo the
density (kg/m3), go the viscosity (kg/ms), Rep-the permeate
Reynolds number (Hupqo/go), u0 the average velocity at channel

11
10
1

9
6

8
7

3
Fig. 1. Schematic diagram of cross ow cell setup ((1) feed tank, (2) thermocouple with indicator, (3) high pressure, pumps, (4) pressure gauge, (5) NF membrane cell, (6)
permeate, (7) pressure gauge, (8) pressure gauge adjuster, (9) ow meter, (10) chiller, (11) heat exchanger).

Fig. 2. Mechanism of electrostatic interaction between membrane and dye molecules.

161

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

J sd
km


9

where R0 is the observed rejection, R the real rejection, Jsd the solution ux and km the mass transfer coefcient. This expression can be
modied to obtain the following equation:


ln




1
1
1
1
J sd ln
1
R0
km
R

10

Thus, if a linear behavior is obtained by expressing ln (R10  1) as

a function of jv, the mass transfer coefcient and real rejection can
be determined.
In this experiment, 2000 mg/L of NaCl at pH-7 was taken for
nding out the real rejection. Different applied pressures (5, 10,
15, 20, 25 bar) were used for nding out the corresponding Jsd
values. For achieving these pressures, the ow rate of the feed solution was manipulated between 120 and 200 L/h. The real rejection
and mass transfer coefcient values are presented in Table 2.
The real rejection value (R) was found to vary between 4% from
the observed rejection R0. This conrms that the concentration
polarization has little inuence on the ux rate under the present
experimental conditions. It appears for relatively low concentration of 2000 mg/L of NaCl; concentration polarization does not
practically inuence salt rejections. The real and observed rejection
values are given in Table 2.
2.3.3. Flux decline due to concentration polarization and fouling
During membrane ltration, the overall ux decline (Jw  Jsd) is
caused by concentration polarization (CP) as well as membrane
fouling. These two interdependent components can be obtained
from the experimental data using the procedure given below
[17,18].
The relative ux (RF) may be dened as:


RF


J sd
 100
Jw

11

3.1. Comparative behavior of dyes AR 87 (COO) and DB 53 (SO

3)
Fig. 3a shows the water ux through the membrane in the
presence of AR 87 and DB 53 dyes at pH-3, pH-7 and pH-10. The
carboxylate containing dye AR 87 exhibits strong blocking of NF
membrane leading to a ux decline at pH-3. For pH-7 and pH-10,
the ux rates are signicantly higher. The strong sulfonic acid containing DB 53 species exhibits a high ux in all the three pH media.
It appears that in acidic pH where the carboxylic groups are less
dissociated, hydrophobic interactions between the dye molecule
and the membrane surface dominate, leading to a signicant
adsorption of the dye and ux decline. With increasing pH, the
negative charge of the membrane surface goes on increasing and
the repulsion (Fig. 2) between negatively charged membrane and
the negatively charged COO dye molecule leads to less pore blocking, thus increasing the ux rate with pH for AR 87 (Fig. 3a). The
sulfonic acid based dye molecules DB 53 do not show such adsorptive blocking of NF membrane even in acidic pH due to its strong
acidic character and the resulting large electrostatic repulsions.

140
120
Flux rate (L/h/m2)

1  R0 1  R

 exp
R
R0

3. Results and discussion

 
Jf
 100
Jw

13

and the irreversible ux decline caused by fouling, FDF is given by:

FDF 100  FR

14

The reversible ux decline caused by CP alone, FDCP, may be estimated as:

FDCP FR  RF

80
60
40

0
pH-3

100
90
80
70
60
50
40
30
20
10
0

15

pH-7
Soluon pH

AR 87

(b)

pH-10

DB 53

pH-3

pH-7

pH-10

Soluon pH
100
90
80
70
60
50
40
30
20
10
0

AR 87

(c)

DB 53

Dye rejecon (%)

FR

DB 53

100

12

The dye molecules accumulated near the membrane surface,

primarily due to CP in the absence of strong interactions can be
washed away by circulating water with the same pH value
employed during the membrane ltration. The water ux obtained
after this washing process (Jf) may be used to calculate ux (FR)
recovery:

AR 87

20

and the total ux decline (FDT) may be obtained from RF using:

FDT 100  RF

(a)

Salt rejecon (%)

determined solution ux (Jsd). The concentration polarization is

almost unity for all the six dye molecules at pH-3, 7 and 10 as
represented in Table 1, implying that it does not signicantly
inuence the observed rejection values under the present
experimental conditions.
These results were substantiated by using the following
approach. Using the rejection fractions instead of concentrations,
the concentration polarization expression may be expressed as
[22]:

pH-3

pH-7
Soluon pH

pH-10

Fig. 3. Comparison of nanoltration performance for dye solution with 2000 ppm
of NaCl under constant operating condition: (a) ux rate for DB 53 and AR 87, (b)
salt rejection for DB 53 and AR 87, (c) dye rejection for DB 53 and AR 87.

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

ArCOO H

ArCOOH

16

In the alkaline pH, the electrostatic interactions between the

COO and the positively charged amide surface are likely to be
stronger than the SO3 group leading to higher fouling. This aspect
however deserves further investigation.
3.2. Comparative behavior of BB 9 (S+/N+) and BG 4 (N+)

140
120

(a)

BB 9

Flux (L/h/m2)

100
80
60
40
20
0
pH-3

100
90
80
70
60
50
40
30
20
10
0

pH-7
Soluon pH

BB 9

(b)

pH-3

pH-10

BG 4

pH-7

pH-10

Soluon pH
100
90
80
70
60
50
40
30
20
10
0

BB 9

(c)

pH-3

In general, basic dyes contain positive charge on the dye

molecule. The isoelectric point of NF 270 is reported to be around
3.3 [4]. Hence, with increasing pH, the negative charge of the membrane surface also increases, leading to enhanced electrostatic
interaction between the membrane charge and the positively
charged dye molecules (Fig. 2). The resulting adsorption of positively charged dye molecules on the membrane leads to signicant
ux decline with increasing pH. This trend (Fig. 4a) was noticed for
both BB 9 (S+/N+) and BG 4 (N+).
The salt rejection values are found to increase with increasing
pH for positive molecules as well (Fig. 4b). This trend is quite similar to the trend observed for negatively charged dye molecules.
The salt rejection is primarily controlled by the membrane surface
charge or Donnan effect [20]. However, strong electrostatic interaction between positively charged dye molecules and the negatively charged membrane, especially at high pH values, leads to
pore blocking. This factor also contributes to the enhanced salt
rejection. For negatively charged molecules, the salt rejection can
reach 60% at pH-10 (Fig. 4b). This value can go almost up to 75%
for positively charged dye molecules at the same pH (Fig. 4b).
Both positively charged dye molecules show lower (8291%)
dye rejection in acidic as well as neutral pH regions (Fig. 4c). At
pH-3, the membrane is closer to the IEP and hence the positively
charged dye molecules may not get adsorbed on the electrode surface. But the molecular weights of both these molecules (284 g/mol
for BB9 and 329 g/mol for BG 4) are closer to the MWCO of this
membrane. Hence, the dye molecules still pass through the membrane leading to lower dye rejection. Weak dye adsorption at pH-7
further enhances dye movement through the membrane leading to

BG 4

Salt rejecon (%)

In general, salt rejection increases with increasing pH, due to

enhanced negative charge on the membrane surface and the repulsive Donnan effect of Cl ions as well as anionic dye molecules
[19]. The salt rejection value for sulfonic acid based dye DB 53 at
pH-3 is indeed much lower as compared to the other pH values
given Fig. 3b. However, in case of carboxylic acid containing dye,
the neutral molecule adsorbed on the membrane also blocks salt
transport through the membrane. Hence, in this case, salt rejection
values are relatively higher (45%) in acidic pH (Fig. 3b). In neutral
and alkaline pH, the salt rejection values of AR 87 (COO) and DB
53 (SO
3 ) differ only slightly (5157%) as shown in Fig. 3b.
The carboxylic acid containing dye AR 87 also exhibit high dye
rejection in acidic pH (Fig. 3c). The dye rejection, however,
decreases signicantly with increasing pH for this molecule. The
sulfonic acid containing DB 53 exhibits high dye rejection in all
the three pH values (Fig. 3c). Since DB 53 (SO
3 ) does not electrosorb on NF membrane, it moves along with the reject solution
and do not adsorb and permeate through the membrane. On the
other hand, AR 87 (COO) tends to accumulate on the membrane
surface even in alkaline pH leading to higher membrane surface
concentration and permeation through the membrane leading to
lower dye rejection. The solubility of AR 87 (COO) does not
change with the pH of the medium (Table 3). Hence, in acidic pH,
pore blocking due to electrosorption of AR 87 (COO) appears to
be the main contributing factor for higher dye rejection. Since
the charge of the dye molecule is likely to be neutral in this pH
due to acid base interaction of this weak acid.

BG 4

Dye rejecon (%)

162

pH-7
Soluon pH

pH-10

Fig. 4. Comparison of nanoltration performance for dye solution with 2000 ppm
of NaCl under constant operating condition: (a) ux rate for BB 9 and BG 4, (b) salt
rejection for BB 9 and BG 4, (c) dye rejection for BB 9 and BG 4.

still lower dye rejection. In the alkaline pH, however, strong

adsorption leads to pore blocking and higher dye rejection
(Fig. 4c). For example, 95.5% dye rejection has been achieved for
the BG-4 at pH-10.
3.3. Comparison of electrostatic interaction and membrane
performance
The relative ux decline, salt rejection and dye rejection values
of all the six molecules were studied with three different pH values
using NF 270 membrane under identical conditions (Figs. 57). The
ndings are highlighted in the following paragraphs.
Electrostatic interaction between the membrane and charged
molecules is an important parameter which determines the ux
decline. The pH value of the efuents from the dyeing industry
generally lies between 7 and 12 [23]. In this pH range, the membranes generally possess negative charge. These negatively
charged dye molecules are not electrostatically attracted towards
the membrane (Fig. 2) and hence they do not signicantly reduce
the ux rate (Fig. 5b and c). Positively charged molecules accumulate near the membrane surface (Fig. 5b and c) and cause ux
decline. The ux decline also increases with increasing pH for these
molecules, since the electrostatic interaction leads to blocking of

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T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

140

Salt rejecon (%)

Flux (L/h/m2)

120

(a) pH-3

100
80
60
40
20

100
90
80
70
60
50
40
30
20
10
0
AR 87

0
AR 87

DB 53

AB 1

AZ A
Dyes

BB 9

BG 4

AB 1

(b) pH-7

100
80
60
40
20

100
90
80
70
60
50
40
30
20
10
0

AR 87
DB 53

AB 1

AZ A
Dyes

BB 9

BG 4

DB 53

AB 1

140
Salt rejecon (%)

Flux (L/h/m2)

120
100
80
60
40
20

BG 4

NaCl

AZ A

BB 9

BG 4

NaCl

BB 9

BG 4

NaCl

Dyes

NaCl

(c) pH-10

BB 9

(b) pH-7

0
AR 87

AZ A
Dyes

Salt rejecon (%)

Flux (L/h/m2)

DB 53

NaCl

140
120

(a) pH-3

100
90
80
70
60
50
40
30
20
10
0

(c) pH-10

AR 87

DB 53

AB 1

AZ A
Dyes

0
AR 87

DB 53

AB 1

AZ A
Dyes

BB 9

BG 4

NaCl

Fig. 6. Salt rejections for all the dye molecules (a) at pH-3 (b) at pH-7 (c) at pH-10.

Fig. 5. Permeate ux rate for all the dye molecules (a) at pH-3 (b) at pH-7 (c) at pH10.

the membrane pores due to concentration polarization and molecular adsorption.

In addition to electrostatic interaction, other types of interactions such as hydrophobic (between the aromatic rings of both
the dyes and membrane polyamide selective layer) or hydrogen
bonds can play an important role in membrane blocking, especially
under the conditions in which the acidic or basic groups in the dyes
are partially dissociated. Carboxylic acid group containing dyes
such as AR 87 shows strong ux decline in acidic pH, where the
carboxylic group is weakly dissociated. A similar situation is evident with all the three positively charged molecules that show
strong ux decline in the alkaline pH range.
Salt rejection has been shown to be more closely related to the
membrane charge [24]. With increasing pH, the passage of salt
anions (chloride in the present study) through the membrane is
more hindered, leading to higher salt rejection (Fig. 6). The salt
rejection range of the dye wastewater lies in the range of 2945%
in acidic pH, 4658% in neutral pH and 5374% in alkaline pH.
The salt rejection is also generally found to be higher for positively
charged molecules AZ A, BB 9 and BG 4 due to pore blocking caused
by electrostatic interaction (Fig. 6a and c). Even for a negatively

charged molecule like AR 87 (Fig. 6a), salt rejection increases at

lower pH due to adsorptive blocking.
The molecular weight cutoff for NF 270 is in the range of 200
300 Da. All the three negatively charged molecules have much
higher molecular weight (Table 3). The dye rejection values for
these are found to be close to 100% in acidic medium (Fig. 7a).
The carboxylate containing AR 87 is weakly adsorbed in neutral
and alkaline media. The dye rejection for this molecule is below
90% in the neutral as well as alkaline media. The molecular weights

of DB 53 (SO
3 , 869.8 g/mol) and AB 1 (SO3 , 570.5 g/mol) are significantly different though both are strong acids. Hence, their ux
rates (Fig. 5) as well as dye rejection values (Fig. 7) are quite similar
for all pH values.
All the three positively charged molecules selected in this study
have molecular weights in the range of 256 and 329 which is close
to the MWCO of NF 270 membrane. Hence, these molecules show
lower dye rejection even in the acidic pH region (Fig. 7a). The dye
rejection increases in the alkaline region (Fig. 7c) due to electrostatic interactions and adsorptive blocking.
The dye molecules selected for the present investigation show
different solubilities in 2000 mg/L NaCl solution, from 10 g/L for
AB 1 to 280 g/L for AR 87. For some molecules, the solubility also
depends on the pH of the medium (Table 3). However, at a low
concentration of 50 mg/L considered in the study, the dye

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

Dye rejecon (%)

164

100
90
80
70
60
50
40
30
20
10
0

(a) pH-3

AR 87

DB 53

AB 1

AZ A

BB 9

BG 4

Dye rejecon (%)

Dyes
100
90
80
70
60
50
40
30
20
10
0

(b) pH-7

3.5. Characterization of membrane fouling

Dye rejecon (%)

AR 87

100
90
80
70
60
50
40
30
20
10
0

also indicates signicant ux decline due to irreversible fouling. All

the other molecules containing both negative and positive charges
show relatively lower values of FDF.
The FDF values obtained for these molecules in neutral pH
media are compared in Fig. 8b. Negatively charged molecules of
AR 87 and DB 53 show marginal ux decline in neutral medium.
The total ux decline is found to be higher for all the positively
charged molecules. Positively charged molecules, AZ A and BB 9,
exhibited less fouling in acidic and neutral pH. The electrostatic
interaction between the negative membrane surface charge and
positive dye molecules are very strong in alkaline condition leading
to very high ux decline was very high (Fig. 8c). Flux decline for
positively charged molecules can reach up to 55% (Fig. 8c). Fouling
is the major consequence of ux decline in these cases.

DB 53

AB 1

DB 53

AB 1

Dyes

AZ A

BB 9

BG 4

AZ A

BB 9

BG 4

(c) pH-10

AR 87

Dyes

Fig. 7. Dye rejections for all the dye molecules (a) at pH-3 (b) at pH-7 (c) at pH-10.

solubility does not appear to be an important factor for the ux

decline. For example, among the negatively charged molecules,
AR 87 (COO) is much more water soluble than DB 53 (SO
3 ).
However, the weak acid containing molecules show stronger electrostatic interaction with the membrane, despite its higher solubility. The solubility factor may, however, become more important
when much higher concentrations of dye molecules are involved
in the nanoltration process.

3.4. Contribution of membrane fouling towards ux decline

The experimental ux values discussed so far correspond to the
overall ux values obtained for each dye under three different pH
conditions. From the ux values of solution, Jsd, the total ux
decline (FDT) was calculated using Eqs. (13) and (14). As discussed
in the experimental section, the ux recovery was obtained using
Eq. (15), after washing with water at the same pH without dye
molecules. The ux decline due to fouling (FDF) and concentration
polarization (FDCP) were then calculated using Eqs. (14) and (15)
respectively. The FDT, FDCP and FDF values obtained for all the three
pH values are presented in Fig. 8.
Flux decline data indicating FDT, FDCP and FDF values for all the
six dye molecules in the acidic pH range are presented in Fig. 8a for
comparison. In acidic medium, AR 87 exhibiting strong ux decline

For characterization of NF-270 membrane following long term

separation runs, negatively charged AR 87 and AB 1 and positively
charged BB 9 and BG 4 dyes were selected for acidic and basic conditions respectively. To establish the relative scale of ux decline,
the normalized ux decline dened as J/J0 in each case was plotted
against time (Fig. 9). As expected, the strong acid molecule AB 1
exhibits high steady ux rate and normalized ux for 10 h. The
weak carboxylic acid containing AR 87 exhibits much lower ux
rate (Fig. 3a), lower normalized ux and fouling (Fig. 9). The alkali
region of two positively charged molecules generally exhibits signicant ux decline and fouling. For BB 9, the normalized ux
decline remains steady throughout the experiment. BG 4, which
is a complex dye involving oxalate anions, exhibits signicant
decline in normalized ux with respect to time as shown in
Fig. 9. This aspect calls for further investigation.
After being subjected to long term separation with respect to all
the four dye molecules discussed (Fig. 9), the membranes were
washed for 30 min in the respective aqueous media without the
dye. These membranes were then air dried and analyzed using
SEM to identify the irreversible organic lm formation on the
membrane. The SEM image of NF 270 membrane, after subjecting
to membrane separation of 2000 mg/L of NaCl solution in the
absence of dye molecules, do not show any surface structural features (Fig. 10a). Sulfonic groups containing molecule AB 1 also does
not form any surface layer on the membrane (Fig. 10b). Other three
dye molecules showed lm formation on the NF 270 membrane
which could not be washed away by water (Fig. 10c and f). In acidic
pH, the carboxylic acid containing AR 87 forms a thin micro porous
layer on the NF 270 membrane (Fig. 10c). In alkaline conditions,
positively charged BB 9 forms a thin porous lm (Fig. 10d). However, BG 4 also containing a positive charge (N+) forms fairly thick
organic layer (Fig. 10e); the ribbon like polymeric foulant layer is
clearly visible at lower magnication (Fig. 10f).
ATR-FTIR analysis was conducted for the three membrane samples fouled by AR 87, BB 9 and BG 4 dye molecules. Typical FTIR
spectra of NF 270 membrane fouled by carboxylic acid containing
dye AR 87 (Fig. 11a) is compared with FTIR of AR 87 dye molecule
in solution (Fig. 11b) and pristine NF 270 membrane (Fig. 11c). The
fouled membrane exhibits strong signals in the region of 3500
4000 cm1 due to the dye molecule (Fig. 11a and b). Pure membrane however does not exhibit any signal in this region. Many
FTIR signals present in the low wave number region
(<1500 cm1) of the fouled membrane (Fig. 11a) also correspond
to the pure NF 270 membrane signals (Fig. 11c). In the wave number range of 15002000 cm1 (Fig. 11a) many signals of the dye
molecule can be identied with the specic functional groups of
the dye molecules. For example, the transmittance of peak at
1725 cm1 (Fig. 11a and b) may be attributed to the AC@O group.
The asymmetric stretching of the carboxylic acid (ACOO) group is

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

Fig. 8. Flux decline due to concentration polarization and fouling (a) at pH-3 (b) at pH-7 (c) at pH-10.

165

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T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

identied in the range of 14481466 cm1. The absorption noticed

at 1590 cm1in both Fig. 11a and b are due to CAN stretching of
the amide group.
In addition to this, the membranes fouled by AR 87 were also
compared with other membranes fouled by BB9 and BG 4 as shown
in Fig. 12. The same observation corresponding to the NF 270
membrane was noticed in all the three spectra. The signals corresponding to the dye molecules are observed in the region of
35004000 cm1. This is attributed to the amide (AN+A) present
in the dye molecules BB 9 and BG 4 (Table 3). For instance, signals
at 3910 cm1, 3755 cm1 and 3791 cm1 are noticed in this region.
The strong signals correspond to the dye molecules were observed
clearly for all the three fouled membranes. These observations further conrm irreversible molecular adsorption on the fouled membranes, whenever ux decline due to membrane fouling is
prevalent.

4. Conclusion and scope

Fig. 9. Normalized ux for long term studies of four dye molecules.

Some important conclusions drawn from the present work are

given below.

(a)

(b)

(c)

(d)

(e)

(f)

Fig. 10. SEM image for nanoltration membrane after dye waste separation (a) pure in 1500 (b) AB 1 at pH 7 in 1500 (c) AR 87 at pH-3 (d) BB 9 at pH-10 (e) BG 4 at pH-10
in 2000 magnication (f) BG 4 at pH-10 in 200 magnication.

T. Chidambaram et al. / Chemical Engineering Journal 262 (2015) 156168

Fig. 11. ATR-FTIR spectra for (a) AR 87 dye (b) pristine membrane (NF-270) (c)
fouled membrane by AR 87 dye separation.

Flux decline and fouling of NF 270 membranes by negatively

charged textile dye molecules at low pH values and positively
charged molecules at high pH values. The total ux decline was
found to be 48.42% for the negatively charged dye molecule AR
87 in acidic pH, and 51.17% for the positively charged molecule
Azure A at alkaline pH.
Dye molecules containing weak acidic and basic functional
groups exhibit high blocking and fouling effect in acidic and basic
regions respectively. AR 87 exhibits fouling in acidic condition
(Fig. 11c) and BG 4 exhibits high blocking and fouling in basic
medium (Fig. 11e and f). The acid base type interactions between
membrane and dye molecules always lead to membrane fouling.
Dye molecules with molecular weights lower or closer to the
MWCO of NF 270 membrane easily pass through the membrane
leading to low dye rejection. Dyes with low molecular weight such
as AZ A, BB 9 and BG 4, show low dye rejection for pH-3 and pH-7.
The present study indicates that electrostatic interactions
between the dye molecules and molecular weight of the dyes
appear to be the most important factors for efcient nanoltration.
Strong sulfonic acid containing molecules are likely to perform
well without membrane fouling. Since NF membranes generally
possess low IEP value in the range of 3 and 7 [9], high pH value
would lead to better performance for anionic dyes. Quite opposite
conditions (Low pH) would be required for the separation of basic
dyes. The solubility of the dye molecule in the medium would also
be a factor in membrane fouling, when dye concentrations are
closer to their solubility limits.

167

Fig. 12. ATR-FTIR spectra of fouled membranes by (a)AR 87 (b) BB 9 (c) BG 4.

Acknowledgement
The authors would like to thank Karunya University for providing nancial support for this project and Silver Jubilee Fellowship
to Chidambaram Thamaraiselvan to carry out this research. I
express my sincere thanks to Dr. E.J. James, Distinguished Professor, Water Institute, Karunya University for supported to do this
research and language check. We would also like to thank Mr.
Jayakumar Rayappan for his support in assembling the membrane
separation system.

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