Authors Accepted Manuscript

Unravelling flux behavior of superhydrophilic loose

nanofiltration membranes during textile wastewater
treatment
Jiuyang Lin, Chuyang Y. Tang, Wenyuan Ye, ShiPeng Sun, Shadi H. Hamdan, Alexander Volodin,
Chris Van Haesendonck, Arcadio Sotto, Patricia
Luis, Bart Van der Bruggen

PII:
DOI:
Reference:

www.elsevier.com/locate/memsci

S0376-7388(15)30046-6
http://dx.doi.org/10.1016/j.memsci.2015.07.018
MEMSCI13837

To appear in: Journal of Membrane Science

Received date: 9 June 2015
Revised date: 9 July 2015
Accepted date: 10 July 2015
Cite this article as: Jiuyang Lin, Chuyang Y. Tang, Wenyuan Ye, Shi-Peng Sun,
Shadi H. Hamdan, Alexander Volodin, Chris Van Haesendonck, Arcadio Sotto,
Patricia Luis and Bart Van der Bruggen, Unravelling flux behavior of
superhydrophilic loose nanofiltration membranes during textile wastewater
t r e a t m e n t , Journal
of
Membrane
Science,
http://dx.doi.org/10.1016/j.memsci.2015.07.018
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Unravelling

flux

behavior

of

superhydrophilic

loose

nanofiltration membranes during textile wastewater treatment

Jiuyang Lina, Chuyang Y. Tangb, Wenyuan Yea*, Shi-Peng Sunc, Shadi H. Hamdana,
Alexander Volodind, Chris Van Haesendonckd, Arcadio Sottoe, Patricia Luisf, Bart
Van der Bruggena*
* Corresponding author: ye0508@gmail.com (W. Ye); bart.vanderbruggen@cit.kuleuven.be (B. Van
der Bruggen)
a

Department of Chemical Engineering, KU Leuven, Willem de Croylaan 46, B-3001

Heverlee, Belgium
b

Department of Civil Engineering, The University of Hong Kong, Pokfulam

HW619B, Hong Kong

c

National Engineering Research Center for Special Separation Membrane, College of

Chemical Engineering, Nanjing Tech University, 210009 Nanjing, China

d

Laboratory of Solid-State Physics and Magnetism, Department of Physics and

Astronomy, K.U. Leuven, Celestijnenlaan 200D, B-3001 Leuven, Belgium

e

Department of Chemical and Environmental Technology, Rey Juan Carlos

University, 28933 Mstoles, Madrid, Spain

f

Materials & Process Engineering (iMMC-IMAP), Universit catholique de Louvain,

Place Sainte Barbe 2, 1348 Louvain-la-Neuve, Belgium

Abstract: Loose nanofiltration (NF) membranes can be used to treat textile

wastewater effectively, providing an attracted avenue for resource recovery (i.e., dye
purification and salt reuse) at the premise of the integration of high dye retention and
salt permeation. However, the issue of membrane fouling has to be adequately
addressed in view of its practical application. In this study, superhydrophilic loose NF
membranes (Sepro NF 6 and NF 2A, Ultura) were applied for textile wastewater
treatment. Synthetic solutions containing dyes and NaCl were used as the feed stream
of a NF unit. It was found that two factors, namely cake-enhanced concentration
polarization and the formation of a dye cake layer, dramatically deteriorated the flux
of NF membranes with a synergic effect. In viewpoint of realistic application,
diafiltration of a binary dye/salt mixture indicates that cake-enhanced concentration
polarization plays a dominant role for the low membrane flux. As the diafiltration
continued, cake-enhanced concentration polarization was alleviated with a decreasing
concentration of salt in the feed. At the subsequent post-concentration procedure, the
formation of a dye cake layer slightly compromised the membrane flux, but the
negative impact of cake-enhanced concentration polarization was negligible due to the
small quantity of salt remained in the feed.

Keywords: Superhydrophilic loose NF membranes; Flux decline; Dye/salt binary

mixture; Cake-enhanced concentration polarization; Fouling and cleaning

Graphical abstract:

1. Introduction
Sustainable wastewater treatment calls for a new paradigm shift to emphasize on
resource recovery from wastewater in addition to contaminants removal [1, 2]. The
development of advanced technology and practices potentially enables cost-effective
resource recovery, including water, nutrients, bioplastics and energy from the
industrial wastewater [1]. For example, in textile wastewater, a high amount of
organic matters (i.e., dyestuffs) can be applied for energy production or recovered for
further dyeing [3-6]. Furthermore, a high salinity (~6.0% NaCl or ~5.6% Na2SO4) in
the textile wastewater endows its potential reuse as a draw solution for forward
osmosis/pressure retard osmosis or an agent for base/acid generation by bipolar
membrane electrodialysis, expediting the close of water and material loop [7, 8].
However, direct treatment and reuse of textile wastewater can cause the severe fouling
of forward osmosis membrane or ion exchange membrane due to dye adsorption, thus
requiring the effective fractionation of dye and salt in textile wastewater [9, 10].
Nanofiltration (NF)

membranes, with a molecular weight cutoff (MWCO) of

3

200-1000 Da and pore size of ~0.5 to 2.0 nm, exhibit one of the most competitive
separation and purification processes in textile wastewater treatment [11]. The unique
separation mechanism of NF membranes, which involves size exclusion and
electrostatic repulsion, allows for its wide applications in textile wastewater treatment,
endowing high selectivity of dye molecules as well as partial permeation for inorganic
salt solutes [7].
The performance of NF membranes can be severely limited by membrane fouling and
concentration polarization [12-18]. Generally, in textile wastewater treatment,
membrane fouling caused by cake layer formation and pore blocking plays a
dominant role for the permeation flux decline [19-21]. To optimize the operational
conditions of NF membranes for dye/salt separation, Koyuncu et al. intensively
investigated the operation factors involving membrane flux decline in textile
wastewater, indicating that the increasing cross-flow velocity can be a pronounced
factor to improve the membrane flux by alleviating the membrane fouling and
concentration polarization [22]. Furthermore, the adsorption and accumulation of dyes
in the membrane pore structure, mainly resulting from hydrophobic interaction or
electrostatic attraction, gives rise to the high risk of irreversible fouling, which in turn
induces a dramatic flux decline [23]. Inevitably, this requires an increase in frequency
of chemical cleaning, which may shorten the membrane lifespan. Apart from dye
adsorption and accumulation, Van der Bruggen et al. demonstrated that the high
salinity in the textile wastewater has a negative impact on the membrane flux, related
to the high osmotic pressure caused by high salt rejection of commercially available
4

dense NF membranes [8]. Thus, advanced NF membranes with an enhanced

hydrophilicity and high salt transmission (i.e., low salt rejection) are required in the
treatment of textile wastewater for flux enhancement.
The employment of loose NF membrane can be established as an effective strategy
for the fractionation of dye/salt mixture [24-28]. Loose NF membranes with relatively
low salt rejection are preferred to reduce the trans-membrane osmotic pressure
difference and thus the overall energy consumption. Lin et al. applied loose negative
Sepro NF membrane with a MWCO of ~850 Da for the fractionation of direct dye/salt
binary mixture, which allows for ~98% of NaCl pass through the membrane, with
complete retention of direct dye [7]. However, the negative charge of membrane
surface still prevents the free permeation of divalent salts in the textile wastewater,
such as Na2SO4, due to the strong electrostatic repulsion. A loose NF membrane with
positive charge which was fabricated by Yu et al. through incorporating poly (ionic
liquid) brushes modified silica spheres, promotes the free passage of both Na2SO4 and
NaCl [29]. Expectedly, through the process intensification with electrodialysis or
bipolar membrane electrodialysis, a sustainable water recovery and salt reuse can be
achieved from textile wastewater [30]. In order to further explore realistic applications
of these loose NF membranes for the dye and salt fractionation, their flux behavior as
well as the mechanisms for membrane flux decline should be investigated.
Specifically, the use of superhydrophilic loose NF membranes was proposed to avoid
membrane fouling; nevertheless, fouling remains an unknown factor, which needs
confirmation and comparison.
5

In this work, the flux of the superhydrophilic loose NF membranes (Sepro NF 6 and
NF 2A, Ultura) in a single-component (i.e., NaCl or dyes) solution was studied at
variable pressures and concentrations. Furthermore, the flux decline of these NF
membranes was systematically investigated for simulated textile wastewater (i.e.,
dye/salt mixture). In addition, interactions between salt, dyes and the membrane
surface were related to flux decline by characterizing the membrane surface after
fouling. The combination of diafiltration and post-concentration for textile wastewater
was performed to understand the membrane flux behavior in the overall treatment
process, in view of assessing an industrial application.

2. Materials and methods

2.1 Chemicals and NF membranes
Direct dyes, i.e., direct red 80 (Pure, Sigma-Aldrich, Belgium), direct red 23 (Dye
content: >30%, Sigma-Aldrich, Belgium), and Congo red (Pure, Avocado Research
Chemicals Ltd., Belgium), were used at different concentrations, i.e., 50, 200, 500,
1000, and 2000 ppm. The molecular structure of the direct dyes is shown in Fig. 1.
NaCl with analytical grade was supplied by Sigma-Aldrich (Belgium). All the
chemicals were used as received. Ultrapure water (18.2 Mcm) was used throughout
all the experiments.

Fig. 1 Molecular structure of the dyes used in the experiments

Two thin film composite NF membranes with different salt rejections were kindly
supplied by Ultura (USA). The properties of the tested NF membranes are shown in
Table 1.

Table 1 Properties of NF membranes used in this study [31]

Membrane

Sepro NF 2A

Sepro NF 6

Composition of top layer

Semi-aromatic
polyamide

Semi-aromatic
polyamide

Contact angle ()

21.7 1.4

14.3 0.9

Permeability (Lm2h1bar1) at
25 C

10.1

16.7

Molecular weight cutoff (Da)

529

847

Salt rejection (NaCl, %)

21.2

7.3

pH for isoelectric point

3.78

5.06

Process pH limitation

3.0-10.0

3.0-10.0

2.2 Permeation experiments

2.2.1 Steady-state nanofiltration in cross-flow mode
The filtration properties of Sepro NF membranes were evaluated through a lab-scale
cross-flow permeation setup described elsewhere [7]. Before the membrane filtration,
membrane samples with a surface area of 2.29 10-3 m2 were pre-compacted at 10
bar for 2 hours in all the experiments to achieve a stable flux.
Firstly, the NF process was performed by a feed of single-component solution (i.e.,
NaCl or dye) to evaluate the effect of solute concentration and operation pressure on
the membrane flux. The salt concentration was set up to 40 gL-1; the dye
concentration was 0.05, 0.2, 0.5, 1.0 and 2.0 gL-1 (pH~7.6). Then the flux of NF
membranes at 6 bar in dye/NaCl binary solutions with different salt concentrations
(i.e., 5, 10, 20, 30, and 40 gL-1) was further investigated to reveal the effect of salt
addition.

2.2.2 Antifouling test

After the filtration of dye solutions, the fouled NF membranes were cleaned by pure
water or HCl solution (pH~3.0) in the cross-flow setup until the dye was totally
removed from the membranes. The pure water flux of cleaned NF membranes was
8

measured at 6 bar; the pure water flux was recorded to determinate the flux recovery
ratio ():

J w,c
J w,0

100

(1)
where Jw,0 is the pure water flux of original NF membranes, and Jw,c is the pure water
flux of NF membranes after cleanning.

2.2.3 Diafiltration and post-concentration

In order to simulate the application of loose NF membranes in industry, diafiltration
of dye/salt mixture and its post-concentration was performed. In diafiltration, a 350
mL direct red 80/NaCl mixed solution (1.0 gL-1 dye and 20.0 gL-1 NaCl) was
applied as the feed solution. Pure water was continuously added to the feed solution to
keep the feed at a constant volume. The NF permeate was sampled in a fixed time
interval for flux measurement. A total of 1400 mL pure water was added for
diafiltration.
Subsequent post-concentration of dye solution, following diafiltration, was carried out.
625 mL diluted direct red 80 solution (originated from solution after diafiltration with
proper dilution) with a small amount of salt (0.5 gL-1 dye and 0.3 gL-1 NaCl) was
employed as feed solution for continuous concentration with a factor of 4.0. All the
experiments were conducted at 6 bar and 25 1 C.

2.2.4 Membrane flux calculation

NF membranes are subject to fouling and concentration polarization. Taking these
phenomena into consideration, the permeate flux (Jw) can be described by a
resistance-in-series model, given in Equation 2 [32]:

(2)
where P denotes the transmembrane pressure, represents the osmotic pressure
difference between bulk and permeate solution, is the solvent viscosity, Rm is the
intrinsic membrane resistance, Rf is related to the hydraulic resistance caused by
fouling, such as cake layer formation and pore blocking, and Rcp is the resistance
originating from the concentration polarization of salts.
For a multi-component solution, the osmotic pressure difference () is calculated by
superimposing the contribution from each individual component [33]:

(3)
For the dilute solution, the osmotic pressure can be estimated by the Vant Hoff
equation:
(4)
where Ci is the molarity of solute, Rg is the universal gas constant, and T is the
thermodynamic (absolute) temperature.
In Equation 2, the intrisnic membrane resistance (Rm) was calculated from the flux of
pure water, the value of Rf was estimated from independent filtration tests using
individual dye solution, and the resistance caused by the concentration polarization of
10

NaCl (Rcp) was determined by the independent filtration of pure NaCl solutions.

2.3 Characterization of fouled membranes

In order to investigate the alteration of surface chemical functionality of the fouled
membranes, Fourier transform infrared spectroscopy (FTIR) measurements were
performed through an ATR-FTIR spectrometer (Bruker, Germany), which is equipped
with a platinum diamond for single reflection. The FTIR spectra of the dried
membrane samples were taken over the range of 400-4000 cm-1 at a resolution of
1.43 cm-1.
Scanning electron microscopy (SEM) measurements were conducted to visualize the
surface morphology of fouled membranes before and after cleaning. The SEM images
of the membrane samples were taken at a voltage of 10 kV with a Philips Scanning
Electron Microscope XL30 FEG. Prior to the measurements, the membrane samples
were dried in a vacuum chamber, and then sputtered by gold nanoparticles.
Atomic force microscopy (AFM) measurements of the dried membrane samples were
carried out using an Agilent 5500 AFM with scan areas of 11 m2 at ambient
condition. AFM images were obtained in tapping mode using NCSTR probes from
NanoAndMore GmbH.

3. Results and discussion

3.1 Membrane filtration of single salt solutions
Loose NF membranes have potential for fractionation of dye/salt mixtures with a high
11

salt permeation [7, 27, 34]. However, a further investigation of the flux behavior is
essential because of the complexity of the dye/salt system, with enhanced interaction
among salt, dye, and membrane surface. As a reference, the flux behavior was studied
in single-component solutions. Fig. 2 shows the flux of Sepro NF membranes in the
NaCl solutions at variable salt concentrations and operation pressures.
(A) 200

(B) 200
Mea.:
Cal.:

180

2 g/L
2 g/L

5 g/L
5 g/L

10 g/L
10 g/L

20 g/L
20 g/L

40 g/L
40 g/L

Pure water

160

140

140

Mea.:
Cal.:

2 g/L
2 g/L

5 g/L
5 g/L

10 g/L
10 g/L

20 g/L
20 g/L

40 g/L
40 g/L

Pure water

Flux, Lm h

-1

160
-1

120

-2

-2

Flux, Lm h

180

100
80

120
100
80

60

60

40

40

20

20

0
0

Operation pressure, bar

10

Operation pressure, bar

10

Fig. 2 Flux of Sepro NF membranes in NaCl solution filtration. (A): Sepro NF 6; (B):
Sepro NF 2A (Dot: experimental data; Solid line: theoretical flux calculated without
taking concentration polarization into account)

As illustrated in Fig. 2 and Supplementary Fig. S1, the flux of Sepro NF membranes
in the NaCl solutions was positively related with the operation pressures. However,
the flux of NF membranes decreased with the salt concentration at any fixed pressure.
For instance, at 10 bar, the flux of Sepro NF 6 and NF 2A dropped by 22.8% and 53.3%
in the whole range of salt concentration, respectively. This is due to the following
factors:
(1) Firstly, the viscosity of salt solution. As shown in Supplementary Fig. S2, the
12

viscosity of NaCl solutions follows the Jone-Dole equation, and increases with
the salt concentration [35]. Indeed, the solution viscosity increased by 6.38%
when NaCl concentration increased from 0 to 40 gL-1, which will negatively
impact on membrane permeate flux.
(2) Secondly, concentration polarization. In Fig. 2, theoretical flux values have
been calculated taking into consideration of the change in solution viscosity as
well as osmotic pressure difference across the membrane (see Supplementary
Fig. S3). However, the calculation did not take account of concentration
polarization effect. The difference between the theoretical and experimental
results thus revealed the role of concentration polarization. Generally, the
concentration polarization resistance can be negligible at low salt
concentrations. As shown in Fig. 3, Sepro NF 6 had an obvious effect of
concentration polarization at salt concentrations ranging from 20 to 40 gL-1,
whereas Sepro NF 2A experienced a larger impact of concentration
polarization in NaCl solutions from 5 to 40 gL-1. Furthermore, the additional
hydraulic resistance caused by concentration polarization was significantly
greater for Sepro NF 2A. The greater concentration polarization effect for
Sepro NF 2A can be explained by its relatively higher salt rejection compared
to that of Sepro NF 6 (Table 1). Once again, this reveals the advantage of
highly salt-permeable membranes. The low rejection nature of such
membranes allows solutes to easily pass through them, which reduces the
osmotic pressure difference across the membrane and the concentration
13

polarization of salts.
Rm=2.3908E13 m

-1

4 bar
6 bar
8 bar
10 bar

0.3

(B)

Rm=4.1762E13 m

-1

2.5

13

13

CP resistance, Rcp (X10

0.4

0.2

0.1

3.0

-1

CP resistance, Rcp (X10 m )

(A)

-1

m )

0.5

Low conceontration polarization

0.0

2.0

4 bar
6 bar
8 bar
10 bar

1.5
1.0
0.5

Low conceontration polarization

0.0

0.1

0.1

10

10

Concentration of NaCl (g/L)

Concentration of NaCl (g/L)

Fig. 3 Concentration polarization resistance (Rcp) of loose NF membranes in different

NaCl solutions. (A): Sepro NF 6; (B): Sepro NF 2A

3.2 Membrane filtration in pure dye solutions

Fig. 4 shows the flux of Sepro NF membranes in the dye solutions as a function of
dye concentration and pressure. As shown in Fig. 4, the flux of loose NF membranes
in dye solutions was substantially lower than the pure water flux, particularly at high
pressure. This can be attributed to membrane fouling. More severe membrane fouling
tends to occur at higher dye concentrations. Compared to Sepro NF 2A, Sepro NF 6
had greater flux drop which can be attributed to its higher pure water permeability
[36].

14

0.05 g/L
1.0 g/L

(B)

0.2 g/L
2.0 g/L

-2

100
80
60
40
20

Congo red

80
60
40
20

Direct red 23

140
0

-1

120

-2

100

Flux, Lm h

-2 -1

0.2 g/L
2.0 g/L

60
40
20

Congo red

-1
-2

100

Flux, Lm h

Flux, Lm h

-2 -1

120

Flux, Lm h

0.05 g/L
1.0 g/L

0
80

140
0

80
60
40
20
0

Water
0.5 g/L

80

-1

Water
0.5 g/L

120

Flux, Lm h

Flux, Lm h

-2 -1

(A) 140

Direct red 80
0

60
40
20

Direct red 23

0
80
60
40
20

Direct red 80
0

Applied pressure, bar

Applied pressure, bar

Fig. 4 Membrane flux of pure dye solutions for NF membrane at viable operation
pressures and dye concentrations. (A): Sepro NF 6; (B): Sepro NF 2A
The permeability of Sepro NF membranes in the dye solutions showed no obvious
decline at a low pressure (linear relationship between the flux and pressure). However,
as the operation pressure increased, the membrane flux deviated from the linear
relationship, possibly due to the severe compaction of the dye cake layer which
increased the fouling resistance (Rf). In some severe fouling cases (2 gL-1 direct red
23 for both NF membranes), increasing pressure above the threshold value did not
result in enhanced permeability. In the current study, the threshold pressure of Sepro
NF membranes in dye filtration lied at 6 bar. Similar type of limiting flux behavior
has been previously reported for surfactants [37] and macromolecules [38]. Indeed, a
limiting flux value of ~ 40 Lm-2h-1 was observed for both Sepro NF 6 and NF 2A at
6 bar. This type of membrane independence suggests that the threshold flux value was
likely governed by foulant-foulant interaction instead of foulant-membrane interaction
15

[38].
In order to obtain an explanation for the mechanisms of membrane fouling, the
fouling resistance of Sepro NF membranes for these three dyes was calculated, as
shown in Fig. 5. In general, Sepro NF 2A appeared to have a stronger antifouling
property than Sepro NF 6, as indicated by its relatively lower hydraulic resistance
caused by membrane fouling (Rf). At low dye concentrations, Rf for Sepro NF 2A was
relatively small compared to its intrinsic membrane resistance. In contrast, Sepro NF
6 had higher values of Rf despite of its more hydrophilic membrane surface (Table 1).
A plausible explanation may be its relatively large pore size allows dye molecules to
block its membrane pores more easily, leading to greater permeability drop. The
presence of larger nodules on the surface of Sepro NF 6 can also possibly facilitate
the deposit of dye molecules on the valley regions, resulting in a higher hydraulic
resistance of Sepro NF 6 [31]. Furthermore, Sepro NF 6 is less negatively charged
compared to Sepro NF 2A, which may allow the negatively charged dye molecules
(due to their -SO3- groups) to approach Sepro NF 6 more easily. At very high dye
concentrations (e.g., 2.0 gL-1 Congo red or direct red 23), similar Rf values were
observed. In the latter case, fouling was more likely dominated by cake layer
formation (e.g., see SEM images of Sepro NF membranes fouled by 2000 ppm direct
red 23 solution in Fig. 6), where foulant-foulant interaction prevails over
foulant-membrane interaction [39]. Specifically, Sepro NF 2A had a higher calculated
hydraulic resistance in the direct red 23 solution, compared to Sepro NF 6. This is
mainly due to the complexity of the direct red 23 solution (~70% impurity, including
16

5.8% Cl-, 12.6% SO42-, 5.2% HCO3- and other intermediate during dye synthesis),
diminishing the flux of Sepro NF 2A through a higher salt retention.
0.05 g/L
0.2 g/L
0.5 g/L
1.0 g/L
2.0 g/L

(A) 1.4
1.2

1.0

0.8

0.8

0.6

0.6

0.4

0.4

Direct red 23

0.0
5

-1

Rm=2.444E13 m

-1

13

0.2

Congo red

Rf, 10 m

Rf, 10 m

-1

0.0
5

3
2
1

Congo red

Rm=4.0078E13 m

-1

Direct red 23

3
2
1

0.9
0

0.9
0

0.6

0.6

0.3

0.05 g/L
0.2 g/L
0.5 g/L
1.0 g/L
2.0 g/L

1.2

1.0

0.2

13

(B) 1.4

Direct red 80

0.3

Direct red 80

0.0

0.0
2

Applied pressure, bar

Applied pressure, bar

Fig. 5 Hydraulic resistance of Sepro NF membranes caused by fouling (Rf) in

different dye solutions. (A): Sepro NF 6; (B): Sepro NF 2A

Fig. 6 SEM images of Sepro NF membranes fouled by 2000 ppm direct red 23. (A):
Sepro NF 6; (B): Sepro NF 2A
In order to clarify the mechanism of the flux decline for Sepro NF membranes in dye
solutions, digital pictures of NF membranes cleaned by rinsing with water and the
17

FTIR measurements are shown in Figs. 7 and 8, respectively. As shown in Fig. 7, the
fouled Sepro NF 6 was less effectively cleaned after water rinsing, with a small
amount of dye deposited on the membrane, indicating that the reversible membrane
fouling may control the flux behavior. By contrast, the surface of Sepro NF 2A
appeared to be better cleaned, once again confirming its better antifouling ability.
Furthermore, the FTIR spectra in Fig. 8 indicate no obvious alteration in the observed
functional groups, from which it can be concluded the dyes had no chemical reaction
with the surface of Sepro NF membranes. This is in direct contrast to some earlier
studies claiming that chemical interactions (e.g., covalent bonds) between dye and the
surface of polyamide membrane occurs [40].

Fouled by direct red 23

Fouled by direct red 23

Fig. 7 Digital pictures of fouled NF membranes after water rinsing. (A): Sepro NF 6;
(B): Sepro NF 2A
Fouled by direct red 23
Fouled by direct red 80
Fouled by congo red
Original

Absorpiton
1800

Fouled by direct red 23

Fouled by direct red 80
Fouled by congo red
Original

(B)

Absorpiton

(A)

1600

1400

1200

Wavenumber (cm-1)

1000

800

1800

1600

1400

1200

1000

800

Wavenumber (cm-1)

Fig. 8 FTIR spectra for fouled NF membranes. (A): Sepro NF 6; (B): Sepro NF 2A
18

3.3 Membrane filtration in dye/salt binary mixtures

Real textile waste streams have a higher complexity than the single-component
solutions described above. Hence, it is crucial to investigate the membrane flux in
these waste streams. Fig. 9 shows the flux of Sepro NF membranes in dye/salt binary
mixtures.
110

(A)

Direct red 80 (mea.)

Congo red (mea.)
Direct red 23(mea.)
Direct red 80(cal.)
Congo red(cal.)
Direct red 23 (cal.)

100
80

Direct red 80 (mea.)

Congo red (mea.)
Direct red 23 (mea.)
Direct red 80 (cal.)
Congo red (cal.)
Direct red 23 (cal.)

40

-2

70

(B)

50

Flux, Lm h

-2

Flux, Lm h

-1

90

60

-1

120

60
50
40

30
20

30
20

10

10
0

0
0

10

20

30

Concentration of NaCl, gL

40

-1

10

20

30

Concentration of NaCl, gL

-1

40

Fig. 9 Flux of Sepro NF membranes in the dye/salt binary mixtures at 6 bar. (A):
Sepro NF 6; (B): Sepro NF 2A
As shown in Fig. 9, the flux of membrane in the dye/salt mixture decreases with the
salt concentration. This is due to the increase in osmotic pressure difference between
the feed and permeate side of NF membrane (see Supplementary Fig. S4), lowering
the driving force. This is consistent with previous studies [7, 8, 22, 41].
It is worth noting that in the filtration of direct red 23 or Congo red/NaCl mixture,
Sepro NF membranes had an extremely low flux (< 5.0 Lm-2h-1) at high salt
concentrations. As shown in Supplementary Fig. S4, the osmotic pressure difference
levels off at higher salt concentrations, indicating that the driving force almost keeps
constant. However, the measured membrane flux in dye/NaCl solutions with different
salt concentrations is much lower than the calculated theoretical flux. This implies
19

that Sepro NF membranes may have different fouling mechanisms in dye/salt binary
mixture, which are responsible for the greatly enhanced flux decline compared to the
theoretical predictions. One plausible mechanism is 'cake-enhanced concentration
polarization', originally proposed by Hoek and Elimelech [42]. The formation of an
unstirred cake layer of foulant may promote concentration polarization in the porous
cake layer and lead to an increase of the osmotic pressure difference and a significant
flux decline [42-47]. Furthermore, the increased salt concentration (thus higher ionic
strength) weakens the electrostatic repulsive force between foulant-foulant and
foulant-membrane [12]. As shown in Fig. 10, precipitation of dye occurs with the
increasing salt concentration, since the presence of background electrolytes can
effectively shield the electrostatic double layer interaction [12] as well as increase the
hydrophobicity of dyes [48]. This implies a reduced stability of dye molecules which
promotes more severe membrane fouling.

Fig. 10 Digital pictures for the dye/NaCl mixtures with different salt concentrations.
(A): direct red 80; (B): Congo red; (C): direct red 23

3.4 Membrane fouling and cleaning

In the dye/salt mixtures, loose NF membranes are subjected to a severe fouling,
hindering the application of loose NF membranes by a drastic hindrance of the flux.
20

Therefore, effective membrane cleaning strategies are required for industrial

applications [49]. Fig. 11 shows flux recovery after cleaning the fouled membranes by
water and acid flushing.
110

Flux recovery (%)

105

After water flushing (Sepro NF6)

After water flushing (Sepro NF2A)
After HCl cleaning (Sepro NF6)
After HCl cleaning (Sepro NF2A)

100
95
90
85
80
Direct red 80

Direct red 23

Congo red

Dye

Fig. 11 Flux recovery of fouled NF membranes after water rinsing or HCl cleaning
As shown in Fig. 11, Sepro NF membranes have a high flux recovery (>95.6%) after
rinsing with pure water. This is due to their superhydrophilicity which reduces the
affinity of dye molecules on the membrane surface as well as no chemical interactions
between dye molecules and membrane surface [31]. Compared to Sepro NF 2A,
Sepro NF 6 had a lower flux recovery ratio, even though it had a more hydrophilic
surface. This is ascribed to the fact that a trace amount of dye foulant deposited on the
surface of Sepro NF 6, which can be confirmed by SEM images in Fig. 12. After
rinsing with water, Sepro NF 2A exhibits a smooth surface with a ~99% flux recovery.
AFM measurement also shows that the membrane surface can be cleaned with water,
indicating the physical cleaning can be an acceptable approach for flux recovery of
Sepro NF membranes, especially for Sepro NF 2A.

21

(A1)

(B1)

Dye foulant

Impurities

(A2)

(B2)

(A3)

(B3)

Fig. 12 SEM and 3D AFM images of cleaned NF membrane surfaces by water rinsing.
(A): Sepro NF 6; (B): Sepro NF 2A

Additionally, cleaning membranes with HCl gave rise to a nearly complete recovery
(>99.4%) of the water flux for both Sepro NF membranes. Fig. 13 shows that both
Sepro NF membranes had a clean surface, only with a small amount of crystalline
impurity deposited on the membrane surface. Therefore, Sepro NF membranes had an
22

excellent resistance to fouling. HCl cleaning offered a more effective route for the
complete flux recovery of Sepro NF membranes, compared to rinsing with water.

(A1)

(B1)
Impurities

(A2)

(B2)

(A3)

(B3)

Fig. 13 SEM and 3D AFM images of cleaned NF membrane surface by HCl cleaning.
(A): Sepro NF 6; (B): Sepro NF 2A

3.5 Membrane flux in diafiltration and psot-concentration process

23

Fig. 14 shows the flux of Sepro NF membranes for direct red 80/NaCl binary mixture
in diafiltration and post-concentration.
Mea. (Diafiltration)
Mea. (Concentration)

Flux, Lm-2h-1

100

3 times
1 time 2 times

90

(B) 100

Cal. (Diafiltration)
Cal. (Concentration)

Cake
layer

CECP

70
1 time 2 times

60

Postconcentration

Diafiltration

3 times

4 times

40
Postconcentration

Diafiltration

20

50

Cake
layer

50 CECP

30

60

Cal. (Diafiltration)
Cal. (Concentration)

80

4 times

80
70

Mea. (Diafiltration)
Mea. (Concentration)

90

Flux, Lm-2h-1

(A) 110

10
0

100

200

300

400

500

600

200

400

600

800

1000

Operation time, min

Operation time, min

Fig. 14 Flux of Sepro NF membranes in diafiltration and post-concentration. (A):

Sepro NF 6; (B): Sepro NF 2A (CECP:

cake-enhanced concentration polarization;

Mea.: measured; Cal.: calculated)

Fig. 14 indicates that the flux of both Sepro NF membranes had a similar tendency. In
the initial stage of diafiltration, the large gap between the measured and calculated
flux of Sepro NF membranes resulted from the cake-enhanced concentration
polarization. As the diafiltration proceeded, the decrease of salt content mitigated the
cake-enhanced concentration polarization phenomenon, enhancing the driving force
for water transfer through the NF membranes. Furthermore, the reduction of the salt
concentration also alleviated the formation of a cake layer, since the salt effect on the
dye aggregation was limited, as demonstrated in Fig. 10. As the concentration of salt
in the feed was reduced to a fixed small content, the cake-enhanced concentration
polarization phenomenon can be ignored. Fig. 15 schematically shows the evolution
24

of cake-enhanced concentration polarization and cake layer formation in diafiltration

to demonstrate the flux enhancement. During the diafiltration of the direct red
80/NaCl mixture, the flux of Sepro NF 6 and NF 2A membrane increased from 59.6
to 86.3 Lm-2h-1 and from 34.3 to 53.9 Lm-2h-1, respectively.

Fig. 15 Schematic diagram for the evolution of cake-enhanced concentration

polarization phenomenon and cake layer formation in diafiltration

Following the diafiltration, the post-concentration procedure was performed. The flux
of Sepro NF 6 and NF 2A in this stage slightly decreased from 86.6 to 81.9 Lm-2h-1
and from 56.2 to 52.4 Lm-2h-1, after a concentration factor of 4.0, respectively. Due
to the high salt permeation of Sepro NF membranes, the concentration of NaCl in the
feed had a slight increase (see Supplementary Fig. S5), and no obvious adverse effect
on promoting cake-enhanced concentration polarization occurred. Therefore, as
schematically demonstrated in Fig. 16, the mild difference between the calculated and
measured flux of Sepro NF membranes was due to the evolution of dye cake layer in
post-concentration with different concentration factors.

25

Fig. 16 Schematic diagram for the evolution of cake layer formation in

post-concentration with different concentration factors

4. Conclusions
In this study, two superhydrophilic loose NF membranes (Sepro NF 6 and NF 2A
membrane, Ultura) were applied for dye/NaCl fractionation with a full investigation
on flux behavior. It was demonstrated that in the treatment of textile wastewater with
a high salinity, the loose NF membranes can generally suffer the concentration
polarization and the formation of dye cake layer. Particularly, the pore blocking and
dye deposition can be partially involved in the flux decline of loose NF membranes
with a lager pore size and nodules. The enhancing hydrophilicity of surface for Sepro
NF membranes can reduce the physical or chemical adsorption of dye. Furthermore,
in the highly loaded textile wastewater, a specific fouling mechanism, denoted as
cake-enhanced concentration polarization, can significantly deteriorate the
membrane flux through increasing osmotic pressure as well as exacerbating the
formation of dye cake layer.
Application of diafiltration for a dye/salt binary mixture indicates that cake-enhanced
concentration polarization played a dominant role for the low flux at the initial step.
26

As the diafiltration proceeds, cake-enhanced concentration polarization was alleviated,

enhancing the membrane flux. During the subsequent post-concentration, the
evolution of dye cake layer slightly compromised the flux of superhydrophilic loose
NF membranes, ignoring the negative impact of cake-enhanced concentration
polarization. Therefore, the investigation of flux behavior for Sepro NF membranes in
textile wastewater gives the convincing evidence that loose NF membranes can be an
attracted option for textile wastewater treatment, apart from the term of high dye
rejection. However, new strategies should be developed in future to mitigate the
cake-enhanced concentration polarization for flux enhancement.

Acknowledgments
J. Lin and W. Ye would like to acknowledge the support provided by China
Scholarship Council of the Ministry of Education, China. Michle Vanroelen from
CIT, KU Leuven, is acknowledged for performing Ion Chromatography
measurements. Ultura (USA) is greatly thanked for supplying the NF membrane
samples.

References
[1] J.S. Guest, S.J. Skerlos, J.L. Barnard, M.B. Beck, G.T. Daigger, H. Hilger, S.J.
Jackson, K. Karvazy, L. Kelly, L. Macpherson, A new planning and design paradigm
to achieve sustainable resource recovery from wastewater 1, Environ. Sci. Technol.,
43 (2009) 6126-6130.
27

[2] P.L. McCarty, J. Bae, J. Kim, Domestic wastewater treatment as a net energy
producercan this be achieved?, Environ. Sci. Technol., 45 (2011) 7100-7106.
[3] E. Fernando, T. Keshavarz, G. Kyazze, Simultaneous co-metabolic decolourisation
of azo dye mixtures and bio-electricity generation under thermophillic (50 C) and
saline conditions by an adapted anaerobic mixed culture in microbial fuel cells,
Bioresour. Technol., 127 (2013) 1-8.
[4] S. Kalathil, J. Lee, M.H. Cho, Efficient decolorization of real dye wastewater and
bioelectricity generation using a novel single chamber biocathode-microbial fuel cell,
Bioresour. Technol., 119 (2012) 22-27.
[5] S. Burkinshaw, C. Graham, Recycling of exhausted reactive dyebaths, Dyes
Pigments, 28 (1995) 193-206.
[6] Y. Yang, L. Xu, Reusing hydrolyzed reactive dyebath for nylon and wool dyeing,
Am. Dyestuff Rep., 85 (1996) 27-34.
[7] J. Lin, W. Ye, H. Zeng, H. Yang, J. Shen, S. Darvishmanesh, P. Luis, A. Sotto, B.
Van der Bruggen, Fractionation of direct dyes and salts in aqueous solution using
loose nanofiltration membranes, J. Membr. Sci., 477 (2015) 183-193.
[8] B. Van der Bruggen, B. Daems, D. Wilms, C. Vandecasteele, Mechanisms of
retention and flux decline for the nanofiltration of dye baths from the textile industry,
Sep. Purif. Technol., 22 (2001) 519-528.
[9] R. Valladares Linares, Z. Li, V. Yangali-Quintanilla, Q. Li, G. Amy, Cleaning
protocol for a FO membrane fouled in wastewater reuse, Desalin. Water Treat., 51
(2013) 4821-4824.
28

[10] A. Tiraferri, Y. Kang, E.P. Giannelis, M. Elimelech, Superhydrophilic thin-film

composite forward osmosis membranes for organic fouling control: fouling behavior
and antifouling mechanisms, Environ. Sci. Technol., 46 (2012) 11135-11144.
[11] S.P. Sun, T.A. Hatton, S.Y. Chan, T.-S. Chung, Novel thin-film composite
nanofiltration hollow fiber membranes with double repulsion for effective removal of
emerging organic matters from water, J. Membr. Sci., 401 (2012) 152-162.
[12] C.Y. Tang, T. Chong, A.G. Fane, Colloidal interactions and fouling of NF and RO
membranes: a review, Adv. Colloid Interface Sci., 164 (2011) 126-143.
[13] W. Zhang, J. Luo, L. Ding, M.Y. Jaffrin, A review on flux decline control
strategies in pressure-driven membrane processes, Ind. Eng. Chem. Res., 54 (2015)
2843-2861.
[14] J. Luo, Y. Wan, Effects of pH and salt on nanofiltrationa critical review, J.
Membr. Sci., 438 (2013) 18-28.
[15] A.S. Al-Amoudi, Factors affecting natural organic matter (NOM) and scaling
fouling in NF membranes: a review, Desalination, 259 (2010) 1-10.
[16] W. Guo, H.-H. Ngo, J. Li, A mini-review on membrane fouling, Bioresour.
Technol., 122 (2012) 27-34.
[17] A. Zahrim, C. Tizaoui, N. Hilal, Coagulation with polymers for nanofiltration
pre-treatment of highly concentrated dyes: a review, Desalination, 266 (2011) 1-16.
[18] A. Mohammad, Y. Teow, W. Ang, Y. Chung, D. Oatley-Radcliffe, N. Hilal,
Nanofiltration

membranes

review:

Recent

Desalination, 356 (2015) 226-254.

29

advances

and

future

prospects,

[19] T. Chidambaram, Y. Oren, M. Noel, Fouling of nanofiltration membranes by dyes

during brine recovery from textile dye bath wastewater, Chem. Eng. J., 262 (2015)
156-168.
[20] Y.K. Ong, F.Y. Li, S.-P. Sun, B.-W. Zhao, C.-Z. Liang, T.-S. Chung,
Nanofiltration hollow fiber membranes for textile wastewater treatment: Lab-scale
and pilot-scale studies, Chem. Eng. Sci., 114 (2014) 51-57.
[21] Y. Zheng, S. Yu, S. Shuai, Q. Zhou, Q. Cheng, M. Liu, C. Gao, Color removal
and COD reduction of biologically treated textile effluent through submerged
filtration using hollow fiber nanofiltration membrane, Desalination, 314 (2013) 89-95.
[22] I. Koyuncu, D. Topacik, M.R. Wiesner, Factors influencing flux decline during
nanofiltration of solutions containing dyes and salts, Water Res., 38 (2004) 432-440.
[23] I. Koyuncu, D. Topacik, Effects of operating conditions on the salt rejection of
nanofiltration membranes in reactive dye/salt mixtures, Sep. Purif. Technol., 33 (2003)
283-294.
[24] L. Xing, N. Guo, Y. Zhang, H. Zhang, J. Liu, A negatively charged loose
nanofiltration membrane by blending with poly (sodium 4-styrene sulfonate) grafted
SiO2 via SI-ATRP for dye purification, Sep. Purif. Technol., 146 (2015) 50-59.
[25] J. Zhu, Y. Zhang, M. Tian, J. Liu, Fabrication of a mixed matrix membrane with
in situ synthesized quaternized polyethylenimine nanoparticles for dye purification
and reuse, ACS Sustainable Chem. Eng., 3 (2015) 690-701.
[26] L. Yu, Y. Zhang, H. Zhang, J. Liu, Development of a molecular separation
membrane for efficient separation of low-molecular-weight organics and salts,
30

Desalination, 359 (2015) 176-185.

[27] J. Zhu, M. Tian, Y. Zhang, H. Zhang, J. Liu, Fabrication of a novel loose
nanofiltration membrane by facile blending with ChitosanMontmorillonite
nanosheets for dyes purification, Chem. Eng. J., 265 (2015) 184-193.
[28] J. Zhu, N. Guo, Y. Zhang, L. Yu, J. Liu, Preparation and characterization of
negatively charged PES nanofiltration membrane by blending with halloysite
nanotubes grafted with poly (sodium 4-styrenesulfonate) via surface-initiated ATRP, J.
Membr. Sci., 465 (2014) 91-99.
[29] L. Yu, Y. Zhang, Y. Wang, H. Zhang, J. Liu, High flux, positively charged loose
nanofiltration membrane by blending with poly (ionic liquid) brushes grafted silica
spheres, J. Hazard. Mater., 287 (2015) 373-383.
[30] J. Lin, W. Ye, J. Huang, R.B. Castillo, M.-C. Baltaru, B. Greydanus, S. Balta, J.
Shen, M. Vlad, A. Sotto, P. Luis, B. Van der Bruggen, Toward resource recovery from
textile wastewater: dye extraction, water and base/acid regeneration using a hybrid
NF-BMED process, Submitted for publication.
[31] J. Lin, C.Y. Tang, C. Huang, Y. Tang, W. Ye, J. Li, J. Shen, R. Van der Broeck, J.
Van Impe, A. Volodin, C. Van Haesendonck, A. Sotto, P. Luis, B. Van der Bruggen, A
comprehensive physico-chemical characterization of superhydrophilic nanofiltration
membranes, Submitted for publication.
[32] J. Luo, L. Ding, Y. Wan, M.Y. Jaffrin, Threshold flux for shear-enhanced
nanofiltration: experimental observation in dairy wastewater treatment, J. Membr. Sci.,
409 (2012) 276-284.
31

[33] K. Pastagia, S. Chakraborty, S. DasGupta, J. Basu, S. De, Prediction of permeate

flux and concentration of two-component dye mixture in batch nanofiltration, J.
Membr. Sci., 218 (2003) 195-210.
[34] F. Liu, B.-r. Ma, D. Zhou, L.-J. Zhu, Y.-Y. Fu, L.-x. Xue, Positively charged loose
nanofiltration membrane grafted by diallyl dimethyl ammonium chloride (DADMAC)
via UV for salt and dye removal, React. Funct. Polym., 86 (2015) 191-198.
[35] H.-L. Zhang, S.-J. Han, Viscosity and density of water+ sodium chloride+
potassium chloride solutions at 298.15 K, J. Chem. Eng. Data, 41 (1996) 516-520.
[36] C.Y. Tang, Y.-N. Kwon, J.O. Leckie, Fouling of reverse osmosis and
nanofiltration membranes by humic acideffects of solution composition and
hydrodynamic conditions, J. Membr. Sci., 290 (2007) 86-94.
[37] C.Y. Tang, Q.S. Fu, A. Robertson, C.S. Criddle, J.O. Leckie, Use of reverse
osmosis membranes to remove perfluorooctane sulfonate (PFOS) from semiconductor
wastewater, Environ. Sci. Technol., 40 (2006) 7343-7349.
[38] C.Y. Tang, J.O. Leckie, Membrane independent limiting flux for RO and NF
membranes fouled by humic acid, Environ. Sci. Technol., 41 (2007) 4767-4773.
[39] C.Y. Tang, Y.-N. Kwon, J.O. Leckie, Probing the nano-and micro-scales of
reverse osmosis membranesa comprehensive characterization of physiochemical
properties of uncoated and coated membranes by XPS, TEM, ATR-FTIR, and
streaming potential measurements, J. Membr. Sci., 287 (2007) 146-156.
[40] A. Akbari, J. Remigy, P. Aptel, Treatment of textile dye effluent using a
polyamide-based nanofiltration membrane, Chem. Eng. Process., 41 (2002) 601-609.
32

[41] R. Jiraratananon, A. Sungpet, P. Luangsowan, Performance evaluation of

nanofiltration membranes for treatment of effluents containing reactive dye and salt,
Desalination, 130 (2000) 177-183.
[42] E.M. Hoek, M. Elimelech, Cake-enhanced concentration polarization: a new
fouling mechanism for salt-rejecting membranes, Environ. Sci. Technol., 37 (2003)
5581-5588.
[43] T. Mahlangu, E. Hoek, B. Mamba, A. Verliefde, Influence of organic, colloidal
and combined fouling on NF rejection of NaCl and carbamazepine: Role of
solute-foulant-membrane interactions and cake-enhanced concentration polarisation, J.
Membr. Sci., 471 (2014) 35-46.
[44] G. Fimbres Weihs, D. Wiley, CFD analysis of tracer response technique under
cake-enhanced osmotic pressure, J. Membr. Sci., 449 (2014) 38-49.
[45] T. Chong, F. Wong, A. Fane, Implications of critical flux and cake enhanced
osmotic pressure (CEOP) on colloidal fouling in reverse osmosis: experimental
observations, J. Membr. Sci., 314 (2008) 101-111.
[46] D. Vogel, A. Simon, A.A. Alturki, B. Bilitewski, W.E. Price, L.D. Nghiem,
Effects of fouling and scaling on the retention of trace organic contaminants by a
nanofiltration membrane: the role of cake-enhanced concentration polarisation, Sep.
Purif. Technol., 73 (2010) 256-263.
[47] H.Y. Ng, M. Elimelech, Influence of colloidal fouling on rejection of trace
organic contaminants by reverse osmosis, J. Membr. Sci., 244 (2004) 215-226.
[48] K. Yeung, S. Shang, The influence of metal ions on the aggregation and
33

hydrophobicity of dyes in solutions, Color. Technol., 115 (1999) 228-232.

[49] Z. Wang, J. Ma, C.Y. Tang, K. Kimura, Q. Wang, X. Han, Membrane cleaning in
membrane bioreactors: a review, J. Membr. Sci., 468 (2014) 276-307.

Highlights
- A loose nanofiltration (NF) membrane was employed for dye/salt separation
- CECP mechanism substantially deteriorated the flux of loose NF membrane in
dye/salt mixture
- The loose NF membrane had an excellent antifouling against dye due to its
superhydrophilicity
- Water rinsing can be an effective method to recover the flux of loose NF membrane

34