Accepted Manuscript

Fouling of nanofiltration membranes by dyes during brine recovery from textile

dye bath wastewater
T. Chidambaram, Y. Oren, M. Noel
PII:
DOI:
Reference:

S1385-8947(14)01258-3
http://dx.doi.org/10.1016/j.cej.2014.09.062
CEJ 12680

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Chemical Engineering Journal

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28 July 2014
11 September 2014
18 September 2014

Please cite this article as: T. Chidambaram, Y. Oren, M. Noel, Fouling of nanofiltration membranes by dyes during
brine recovery from textile dye bath wastewater, Chemical Engineering Journal (2014), doi: http://dx.doi.org/
10.1016/j.cej.2014.09.062

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Fouling of nanofiltration membranes by dyes during brine recovery from textile dye bath
wastewater
T. Chidambaram a, Y. Orenb and M. Noela*
a
b

Water Research Laboratory, Water Institute, Karunya University, Tamilnadu-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.

*Corresponding author: Tel - +91 422 2614422, E-mail: yemenoel1@gmail.com

Fouling of nanofiltration membranes by dyes during brine recovery from textile dye bath
wastewater

ABSTRACT
The present investigation aims at identifying the molecular properties of the dye which
control membrane fouling during nanofiltration. 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 nanofiltration using NF 270 membrane (Dow-filmtec
with an isoelectric point of 3.3) at pH-3, pH-7 and pH-10. The flux decline, salt rejection and dye
rejection were measured using Sterilitech cross flow cell (CF042) with an active membrane
surface area of 14.610-4 m2. Flux decline due to membrane fouling was also calculated by
measuring pure water flux 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 flux rate
and dye rejection were noticed in all the three pH media investigated for these dyes. Weak
carboxylic acid (Acid red 87) shows strong flux 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 acid-base interactions on membrane fouling are highlighted in this work along
with the molecular size effect.
Keywords: Nanofiltration, Textile dye, Electrostatic interaction, Membrane fouling, Flux decline,
Brine recovery.

1. Introduction
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
effluent, 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 nanofiltration membranes [3]. The commercial dyeing
units in and around Tiruppur town in Tamilnadu, India also employ available nanofiltration
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 influence 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 film 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 0.6 to 1.3 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]. Nanofiltration membranes exhibits high and undisturbed flux 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]:
H3N+-COOH
pH<IEP

H 2N-COOH

H2N-COOpH>IEP

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
3

adsorptive blocking and flux 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 efficient 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 flux 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 flux and salt and dye rejections in the context of nanofiltration used in
textile wastewater treatment for the recovery of both water and salt. Efforts have also been made
to measure and interpret the flux decline due to fouling under each experimental condition.
2. Materials and methods
2.1 Materials
Three anionic and three cationic dye molecules were selected for the present experiments
involving nanofiltration (Table 3). The dyes used for the experiments are Acid red 87 (AR 87;
COO-) - a carboxylate containing dye; Direct blue 53 (DR53, SO3-) and Acid black 1 (AB 1,
SO3-) - 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. Nanofiltration 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
nanofiltration. 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

(SO3-) 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 Auoni et al. is at pH 3.3 [4]. The molecular weight cutoff
(MWCO) for this membrane is 200-300.
2.2. Experimental set-up and methods
A schematic diagram of the cross-flow flat sheet membrane test set-up used in this study
is shown in Fig. 1. The NF 270 membrane was supplied by M/s Sterilitec, USA. A flat sheet
membrane with an effective area of 0.0042 m2 was installed in a cross flow 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 251C using heat exchanger on the
feed tank flow 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 sulphate 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 flux 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 the total flux 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 flux recovery value
5

for the water obtained after this washing process was used to estimate the flux decline due to
membrane fouling.
For studying the long term flux decline behavior and structure of the membrane after the
NF filtration 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).
2.3 Data Interpretation
2.3.1 Permeate flux and salt and dye rejection
The membrane productivity is expressed as the permeate flux through the membrane. The
pure water flux Jw (L m -2 h-1) is defined as


Jw = ( )

(1)

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 flux in the presence of salt and dye,
Jsd (L m -2 h-1) is defined as
Jsd =

(2)

( )

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

The observed salt rejection (R0) is given by

R0 (%) =

100

(3)

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:
 

R =



100

(4)

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 (%) =

 


100

(5)

where Ab and Ap are the bulk and permeate absorbance of the dye molecules involved [19].
6

2.3.2 Determination of mass transfer coefficient and concentration polarization

The experimentally determined rejection values were corrected to account for the
concentration polarization at the membrane-solution interface to obtain the real rejections, using
the following approach adopted by Sutzkover et al., [22].
Concentration polarization (CP) =

 
 

= exp (  )

(6)

where the and mass transfer coefficient is

 =

.

(7)

and Sherwood number is given by



Sh = A1 (1+A2 ReA3 ScA4 (  )A5 Rep) (Re Sc (  )1/3

(8)

In equations (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 =1.41810-9 m2/s), A1 =
1.72, A2 = 1.25, A3 = -0.31, A4 = 0.50, A5 = -0.28, Sc-the fluid Schmidt number (o/ Doo), Rethe feed Reynolds number (Hu0o/o), o-the density (kg/m3), o-the viscosity (kg/ms), Rep-the
permeate Reynolds number (Hupo/o), u0-the average velocity at channel inlet and up- the
average velocity of the permeate stream at channel outlet (volume of the permeate [(m3/s)/cross
section of the membrane (4210-4 m2)].
Cohen et al. have used Eqs. (6) to (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) to (8) is found to vary linearly
with the experimentally determined solution flux (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 significantly influence 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]
 

. exp ( )

(9)

where R0 is the observed rejection, R the real rejection, Jsd the solution flux and km the mass
transfer coefficient. This expression can be modified to obtain the following equation;


ln ( -1) =  (!"# ) + ln ( -1)



(10)

Thus, if a linear behavior is obtained by expressing ln ( -1) as a function of !$ , the mass transfer


coefficient and real rejection can be determined.

In this experiment, 2000 mg/L of NaCl at pH-7 was taken for finding out the real
rejection. Different applied pressures (5, 10, 15, 20, 25 bar) were used for finding out the
corresponding Jsd values. For achieving these pressures, the flow rate of the feed solution was
manipulated between 120-200 L/h. The real rejection and mass transfer coefficient values are
presented in Table 2.
The real rejection value (R) was found to vary between 4% from the observed rejection
R0. This confirms that the concentration polarization has little influence on the flux rate under the
present experimental conditions. It appears for relatively low concentration of 2000 mg/L of
NaCl; concentration polarization does not practically influence 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 filtration, the overall flux 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 flux (RF) may be defined as
&

RF = ( & ' )100

(11)

and the total flux decline (FDT) may be obtained from RF using
FDT =100-RF

(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 filtration. The water flux obtained after this washing process (Jf)
may be used to calculate flux (FR) recovery:
&

FR = (& ( ) 100

(13)

and the irreversible flux decline caused by fouling, FDF is given by

FDF = 100-FR

(14)

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

FDCP = FR-RF

(15).

3. Results and discussion

3.1 Comparative behavior of dyes AR 87 (COO-) and DB 53 (SO3-)
Fig. 3a shows the water flux 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 flux decline at pH-3. For pH-7 and pH-10, the flux rates are
significantly higher. The strong sulfonic acid containing DB 53 species exhibits a high flux 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 significant adsorption of the dye and flux 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 flux 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.
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
9

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 (SO3-) differ only slightly (51-57%) 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 significantly 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 (SO3-) 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.
Ar COO- +H+

Ar COOH

(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+)
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 significant flux 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
10

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 (82-91%) 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 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 flux 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
(Fig.5-7). The findings are highlighted in the following paragraphs.
Electrostatic interaction between the membrane and charged molecules is an important
parameter which determines the flux decline. The pH value of the effluents from the dyeing
industry generally lies between 7 and 12. 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 significantly reduce the flux rate (Fig. 5b
and 5c). Positively charged molecules accumulate near the membrane surface (Fig.5b and 5c)
and cause flux decline. The flux decline also increases with increasing pH for these molecules,
since the electrostatic interaction leads to blocking of 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
11

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 flux 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 flux 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 29-45% in acidic pH, 46-58% in neutral pH and 53-74%
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 6c). 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 (SO3- , 869.8 g/mol) and AB 1 (SO3- , 570.5 g/mol) are significantly different though both are
strong acids. Hence, their flux 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 solubility does not appear to be an important factor for
the flux decline. For example, among the negatively charged molecules, AR 87 (COO-) is much
more water soluble than DB 53 (SO3-). However, the weak acid containing molecules show
stronger electrostatic interaction with the membrane, despite its higher solubility. The solubility
12

factor may, however, become more important when much higher concentrations of dye
molecules are involved in the nanofiltration process.
3.4 Contribution of membrane fouling towards flux decline
The experimental flux values discussed so far correspond to the overall flux values
obtained for each dye under three different pH conditions. From the flux values of solution, Jsd,
the total flux decline (FDT) was calculated using Eqs. (13) and (14). As discussed in the
experimental section, the flux recovery was obtained using Eq. (15), after washing with water at
the same pH without dye molecules. The flux 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 flux decline also indicates significant flux 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 flux decline in neutral
medium. The total flux 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 flux 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 flux decline in these cases.
3.5 Characterization of membrane fouling
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 flux decline, the
normalized flux decline defined as J/J0 in each case was plotted against time (Fig. 9). As
expected, the strong acid molecule AB 1 exhibits high steady flux rate and normalized flux for
10 h. The weak carboxylic acid containing AR 87 exhibits much lower flux rate (Fig. 3a), lower
13

normalized flux and fouling (Fig. 9). The alkali region of two positively charged molecules
generally exhibits significant flux decline and fouling. For BB 9, the normalized flux decline
remains steady throughout the experiment. BG 4, which is a complex dye involving oxalate
anions, exhibits significant decline in normalized flux 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 film 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 film formation on the NF 270 membrane which could not be washed away by
water (Fig. 10c to 10f). 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 film (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 magnification (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 cm-1 due to the dye molecule (Fig. 11a and 11b). Pure membrane
however does not exhibit any signal in this region. Many FTIR signals present in the low wave
number region (<1500 cm-1) of the fouled membrane (Fig. 11a) also correspond to the pure NF
270 membrane signals (Fig. 11c). In the wave number range of 1500-2000 cm-1 (Fig. 11a) many
signals of the dye molecule can be identified with the specific functional groups of the dye
molecules. For example, the transmittance of peak at 1725 cm-1 (Fig.11a and 11b) may be
attributed to the -C=O group. The asymmetric stretching of the carboxylic acid (-COO-) group is
identified in the range of 1448 cm-1 to 1466 cm-1 . The absorption noticed at 1590 cm-1 in both
Fig.11a and Fig.11b are due to C-N stretching of the amide group.
14

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 3500-4000 cm-1. This is attributed to the amide (-N+) present in the dye molecules BB 9 and BG 4 (Table 3). For instance, signals at 3910 cm-1, 3755
cm-1 and 3791 cm-1 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 confirm
irreversible molecular adsorption on the fouled membranes, whenever flux decline due to
membrane fouling is prevalent.
4. Conclusion and scope
Some important conclusions drawn from the present work are given below.
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 flux
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
11f). 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 efficient nanofiltration.
Strong sulphonic 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

15

medium would also be a factor in membrane fouling, when dye concentrations are closer to their
solubility limits.
Acknowledgement
The authors would like to thank Karunya University for providing financial 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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16

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17

20. I. Koyuncu , D. Topacik, Effects of operating conditions on the salt rejection of

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18

Table captions
Table 1. Real rejection corrections based on the concentration polarization values
Table 2. Real rejection for the 2000 ppm of NaCl solution
Table 3. Characteristics of the dye molecules used for this study
Table 4: pKa values of the textile dye molecules used for this study

19

Table 1

Samples
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

Jsd (m/s)

Re

Rep

Sc

Sh

Km
(10-5 m/s)

CP

R0

(%)

(%)

0.00002881 725.7586 0.065929 708.75

155.61

9.59

1.00 38.19 38.18

0.00003079 725.7586 0.070468 708.75

160.38

9.89

1.00 44.45 44.44

0.00003122 725.7586 0.071441 708.75

161.40

9.95

1.00 67.41 67.40

0.00001719 725.7586

708.75

127.73

7.88

1.00 47.50 47.49

0.00003278 725.7586 0.075013 708.75

165.14

10.2

1.00 55.86 55.85

0.00003278 725.7586 0.075013 708.75

165.14

10.2

1.00 54.89 54.88

0.00002711 725.7586 0.062051 708.75

151.55

9.34

1.00 30.89 30.89

0.00003133 725.7586 0.071708 708.75

161.68

9.97

1.00 53.40 53.39

0.00002975 725.7586 0.068084 708.75

157.87

9.73

1.00 59.94 59.94

0.00002856 725.7586 0.065351 708.75

155.01

9.56

1.00 35.67 35.66

0.00003172 725.7586 0.072598 708.75

162.61

10.0

1.00 58.10 58.09

0.00003119 725.7586

708.75

161.34

9.95

1.00 66.31 66.30

0.00003014 725.7586 0.068974 708.75

158.81

9.79

1.00 45.30 45.29

0.00002381 725.7586 0.054486 708.75

143.61

8.85

1.00 50.31 50.30

0.00001611 725.7586 0.036871 708.75

125.13

7.71

1.00 68.44 68.44

0.00002539 725.7586 0.058104 708.75

147.40

9.09

1.00 50.73 50.72

0.00001878 725.7586 0.042974 708.75

131.53

8.11

1.00 65.12 65.11

0.00001494 725.7586 0.034201 708.75

122.33

7.54

1.00 76.62 76.62

0.00002539 725.7586 0.058116 708.75

147.42

9.09

1.00 51.26 51.25

0.00002090 725.7586 0.047824 708.75

136.62

8.42

1.00 49.42 49.41

0.00001402 725.7586 0.032084 708.75

120.11

7.41

1.00 76.61 76.60

0.03935

0.07139

20

Table 2
Flow rate
(L/h)
120

Jsd (m/s)

Slope (1/k)

km (10-5m/s)

0.0000298

6083.8

0.1643

21

Intercept
ln (1/R-1)
0.149

CP

R (%)

R0 (%)

1.05

46.29

44.44

Table 3

S.
No

Dyes

Acid red
87 (AR
87)

Molecular
Formula/mo
lecular
weight
(g/mol)
(C20H6Br4Na
+
2O5) .2Na
(645.88)

Solubility (g/L)

Absor
bance
(max)

pH-3

pH-7

pH-10

280

280

280

Molecular structure

515-518

COO Br

Br
-

Br

Br

SO 3H
N

Direct
(C34H24N6O14S4
blue
).4Na+
53(DB 53)
(869.81)

130

165

180

606-611

SO3-

N
O

NH2 O
-

O3S

N
H

NH2

4Na+

SO3-

Acid black
1(AB 1)

(C22H14N6O9S2)
22Na+

+Na -O S
3

9.5

10

15

618-624

SO3- Na+

N
OH

(570.49)

+
Azure A (C14H14N3S) Cl
(AZ A)
(256.3)

15

10

14

625-632

+
Basic blue (C16H18N3S) Cl
9 (BB 9)
(284.3)

46

45

40

668-669

NH2

(C23H25N2)2
2C2HO4.C2H2O4

NO2

N
Cl-

H3C

S+

N
CH3

NH2

N
ClS+

Basic
green 4
(BG 4)

HO

46

50

39

OH

OH

616-620
N+

(329.4)
-

22

OH

N+

Table 4
Dyes

pKa1

pKa2

AR 87

4.3

7.95

DB 53

4.8

8.5

AB 1

4.5

8.3

AZ A

4.5

8.3

BB 9

4.6

8.0

BG 4

4.3

8.0

23

Figure captions
Fig. 1. Schematic diagram of cross flow 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. Flow meter, 10. Chiller, 11. Heat exchanger).
Fig. 2. Mechanism of electrostatic interaction between membrane and dye molecules
Fig. 3. Comparison of nanofiltration performance for dye solution with 2000 ppm of NaCl under
constant operating condition (a) Flux 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.
Fig. 4. Comparison of nanofiltration performance for dye solution with 2000 ppm of NaCl under
constant operating condition (a) Flux 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
Fig. 5. Permeate flux rate for all the dye molecules a) at pH-3 b) at pH-7 c) at pH-10
Fig. 6. Salt rejections for all the dye molecules a) at pH-3 b) at pH-7 c) at pH-10
Fig. 7. Dye rejections for all the dye molecules a) at pH-3 b) at pH-7 c) at pH-10
Fig. 8. Flux decline due to concentration polarization and fouling a) at pH-3 b) at pH-7 c) at pH10
Fig. 9. Normalized flux for long term studies of four dye molecules
Fig. 10. SEM image for nanofiltration membrane after dye waste separation a) Pure in 1500x b)
AB 1 at pH 7 in 1500x c) AR 87 at pH-3 d) BB 9 at pH-10 e) BG 4 at pH-10 in 2000x
magnification f) BG 4 at pH-10 in 200x magnification.
Fig. 11. ATR- FTIR spectra for a) AR 87 dye b) Pristine membrane (NF-270) c) Fouled
membrane by AR 87 dye separation.
Fig. 12. ATR-FTIR spectra of fouled membranes by a)AR 87 b) BB 9 c) BG 4

24

Fig. 1

11
10
1

9
6

8
7

25

Fig. 2.

26

Fig. 3
140
Flux rate (L/h/m2)

120

AR 87

(a)

DB 53

100
80
60
40
20
0
pH-3

AR 87

(b)

pH-10

DB 53

Salt rejection (%)

100
90
80
70
60
50
40
30
20
10
0

pH-7
Solution pH

pH-3

100
90 (c)
80
70
60
50
40
30
20
10
0

pH-7
Solution pH

pH-10

AR 87

Dye rejection (%)

DB 53

pH-3

pH-7
Solution pH

27

pH-10

Fig. 4
140

BB 9

(a)

120

BG 4

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
Solution pH

BB 9

BG 4

Salt rejection (%)

(b)

pH-10

pH-3

BB 9

(c)

pH-10

BG 4

Dye rejection (%)

100
90
80
70
60
50
40
30
20
10
0

pH-7
Solution pH

pH-3

pH-7
Solution pH

28

pH-10

Fig. 5
140

(a) pH-3
120
Flux (L/h/m2)

100
80
60
40
20
0

AR 87

DB 53

AB 1

AZ A
Dyes

BB 9

BG 4

NaCl

DB 53

AB 1

AZ A
Dyes

BB 9

BG 4

NaCl

AZ A
Dyes

BB 9

BG 4

NaCl

140
120

(b) pH-7

Flux (L/h/m2)

100
80
60
40
20
0

AR 87

140

(c) pH-10

Flux (L/h/m2)

120
100
80
60
40
20
0

AR 87

DB 53

AB 1

29

Salt rejection (%)

Fig. 6
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

NaCl

BB 9

BG 4

NaCl

BB 9

BG 4

NaCl

Salt rejection (%)

Dyes

100
90
80
70
60
50
40
30
20
10
0

(b) pH-7

AR 87

DB 53

AB 1

AZ A

Salt rejection (%)

Dyes

100
90
80
70
60
50
40
30
20
10
0

(c) pH-10

AR 87

DB 53

AB 1

AZ A
Dyes

30

Dye rejection (%)

Fig. 7
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

AZ A

BB 9

BG 4

AZ A

BB 9

BG 4

Dye rejection (%)

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

(b) pH-7

Dye rejection (%)

AR 87

100
90
80
70
60
50
40
30
20
10
0

DB 53

AB 1

DB 53

AB 1

Dyes

(c) pH-10

AR 87

31

Dyes

Fig. 8

32

Fig. 9

33

Fig. 10

(a)

(b)

(c)

(d)

(e)

(f)

34

Fig. 11

35

Fig.12

36

GRAPHICALABSTARCT

37

HIGHLIGHTS

Electrostatic interactions between charged dye molecules and NF membrane during

nanofiltration 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.

38