Journal of Membrane Science 469 (2014) 306315

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Journal of Membrane Science

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

Treatment of highly concentrated wastewater containing multiple

synthetic dyes by a combined process of coagulation/occulation
and nanoltration
Can-Zeng Liang, Shi-Peng Sun n, Fu-Yun Li, Yee-Kang Ong, Tai-Shung Chung n
Department of Chemical & Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576, Singapore

art ic l e i nf o

a b s t r a c t

Article history:
Received 11 April 2014
Received in revised form
26 June 2014
Accepted 29 June 2014
Available online 8 July 2014

The treatments of dyes (acid, basic and reactive dyes) wastewater were studied by applying individual
coagulation/occulation (CF) and nanoltration (NF) processes as well as their combination (referred as
CFNF). For the treatment of highly concentrated multiple dyes wastewater (MDW, 1000 ppm),
polyaluminum chloride (PAC) and polydiallyldimethyl ammonium chloride (PDDA) were found to be
the most effective coagulant and occulant, respectively. The CF process can achieve about 90% of dye
removal at the optimal dosage of PAC/PDDA400/200 ppm, and the MDW with pH 4 3 is favorable for
the CF treatment. A positively charged NF hollow ber membrane was fabricated and used for NF
treatment. It is able to remove almost 100% dyes with a permeate ux of about 1.0 L m  2 h  1 under an
operating pressure of 1 bar. The combination of CF and NF can complement each other's strengths and
overcome their individual limitations. The NF treatment can completely remove the strong color left in
CF treated dye solutions, while the efciency of coagulant/occulant is improved by treating NF
concentrated streams and subsequently results in much less sludge. In addition, membrane fouling is
abated and NF permeate ux is increased by applying the CF process as a pretreatment. Thus, the
combination of CFNF improves the overall performance for the dyes wastewater treatment.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Multiple dye wastewater
Coagulation/occulation
Nanoltration
Hollow ber membranes

1. Introduction
A dye molecule consists of two components; namely, the dye
chromophore and the dye auxochrome. When the dye molecule is
exposed to light, the chromophore structure which includes
double bonds (CQC) oscillates to absorb light and generates
visible color [1,2]. By estimation, more than 100,000 synthetic
dyes and over 700,000 t of dyestuff are produced annually [3,4].
The color that appears in industrial wastewater efuents caused
by residual dyes is esthetically undesirable and harmful to the
environments and the ecosystems. Even a very low concentration
of dyes can generate strong color [5]. The dye wastewater is
generated during dye-related activities such as dye production,
textile dyeing, leather tanning and paper production, etc [6].
Particularly in the textile industry, about 1015% dyes are lost in
dyeing processes, and typically 200350 m3 wastewater are generated to produce one ton nished product [7]. It is becoming
more difcult to directly discharge this kind of wastewater

Corresponding authors. Tel.: 65 6516 6645; fax: 65 6779 1936.

E-mail addresses: chesuns@nus.edu.sg (S.-P. Sun),
chencts@nus.edu.sg (T.-S. Chung).
http://dx.doi.org/10.1016/j.memsci.2014.06.057
0376-7388/& 2014 Elsevier B.V. All rights reserved.

because the legislations related to environments are becoming

more stringent in many countries [8].
Generally, there are two decolorization methods [9]; namely,
destruction of dye molecules and separation of dyes from water.
To destruct or transform the dyes, conventional processes are
usually applied, such as chemical oxidation, photo-catalysis and
biodegradation [10]. However, the destruction methods is found to
be inadequate and require extensive energy to break down the dye
molecules, most of which are stable to light, oxidizing agents and
microbiological degradation [1,6,11]. The separation methods
include adsorption, coagulation/occulation (CF) and membrane
separation [9]. Adsorption of dyes on powder activated carbon is
popular and effective. However, the activated carbon is not cheap,
and the adsorption performance is reduced sharply after regeneration or reactivation, which also results in a 1015% loss of the
sorbent [3,7,12]. Coagulation/occulation is widely used for dyes
removal due to its low capital cost and simple operation [1214].
Coagulation of dye solutions is a process of destabilizing the dye
solution systems to form agglomerates or ocs. Flocculation is the
process of destabilizing suspended particle systems and bridging
the aggregated ocs to form larger agglomerates that settle down
under gravity [15,16]. Charge neutralization is regarded as a
prerequisite condition in most of coagulation processes [17].
The CF process generates sludge and but sometimes it is ineffective

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

for some soluble dyes. In fact, it is always challenging in selecting

appropriate coagulant/occulant due to the large number of existing and emerging dyes that have complex structures [7]. Another
important separation method is the pressure-driven membrane
technology including ultraltration (UF), nanoltration (NF) and
reverse osmosis (RO) [1]. Ultraltration has been successfully used
for separating high molecular weight and insoluble dyes from
water. However, UF is not able to remove those water-soluble dyes
with low molecular weights [1,18]. Although efcient dye removal
can be achieved by RO, the high pressure required in the RO process
hinders its wide applications to treat dye wastewater. NF is
positioned in between UF and RO [9], the nominal molecular weight
cutoff (MWCO) of NF membranes is in the range of 100 to 1000 Da
and with the pore size of about 0.52.0 nm [19,20]. NF was
introduced in the early 1980s and has become popular due to its
low operating pressures and relatively low capital and operating
costs [20].
Currently most NF membranes are negatively charged atsheet composite membranes, which may have high fouling tendency because most foulants are positive charged. In recent years,
there is a growing interest to fabricate hydrophilic and positively
charged NF membranes which are less prone to organic fouling
[1930]. Compared to the sophisticated module fabrication process for at-sheet or spiral-wound membranes, it is convenient to
fabricate hollow ber membrane modules, which also provide a
high surface area per unit volume and thus to reduce manufacturing costs [31]. NF hollow ber membranes have attracted much
attention due to its superiorities to the conventional at-sheet NF
membranes. Recently, several efforts have been made on the
development and application of NF hollow ber membranes for
removing dyes from water. For instance, Sun et al. employed both
crosslinking and interfacial polymerization to coat a positively
charged polyethyleneimine (PEI) layer on the outer surface of a
negatively charged polyamideimide (PAI) hollow ber substrate to
produce a double-repulsive NF membrane that can remove 99.8%
of the positively charged Safranin O and 98.8% of the negatively
charged Orange II sodium salt [19,21]. Shao et al. developed a thinlm composite NF hollow ber membrane by interfacial polymerization on the inner surface of polyetherimide (PEI) hollow ber
supports for removal of Safranin O and Aniline blue and achieved
higher than 90% dye rejections [25]. Wei et al. fabricated a NF
hollow ber membrane through interfacial polymerization on a
polysulfone/polyethersulfone supporting membrane for the treatment of reactive brilliant blue X-BR and acid red B dye solutions
and obtained above 99.9% dye rejections [26]. Zheng et al. developed positively charged TFC hollow ber NF membranes via the
dip-coating method on polypropylene hollow ber microltration
membranes. The resultant NF membrane can achieve dye rejections

307

of 99.8%, 99.8% and 99.2% for Brilliant green, Victoria blue B and
Crystal violet, respectively [27].
However, the drawbacks of membrane technologies including
NF are the ux decline caused by membrane fouling and the
generation of concentrated streams [32]. To minimize the ux
reduction, one approach is to implement a right pretreatment
process [33], the other approach is to produce fouling-resistant
membranes [34]. The generation of concentrated streams is an
intrinsic issue for membrane separation processes since membranes only achieve separation rather than destruction or transformation. For the dye-containing wastewater treatment, the
concentrated stream is usually an unwanted by-product. It must
be further treated before discharge [35,36]. To overcome the
aforementioned problems, a combination of various separation
methods is necessary to achieve a high dye removal and high
separation efciency.
To our best knowledge, there is no study on treatment of
synthetic dye wastewater containing multiple dyes of different
classes by a combined process of CF and NF with a positively
charged NF hollow ber membrane. In this work, reactive, acid
and basic dyes were chosen because of their popularity in textile
and dye industries as well as environmental concerns [6,7,12,37].
The representative dye concentrations in dye wastewater streams
are in the range of 0.050.1 g/L [38]. For this study, aqueous dye
solutions with a dye concentration of 1000 ppm (1.0 g/L) were
prepared to simulate the highly concentrated dye house waste
efuent and the concentrated stream after membrane ltration.
In order to maximize the efcacy of the CF process and
minimize the generation of sludge, proper CF formulations were
carefully evaluated, screened and selected. To reduce membrane
fouling, hydrophilic and positively charged NF hollow ber membranes were made in our laboratory for this study. The CF, NF and
the combination of CFNF were studied to remove dye(s) from
synthetic dye wastewaters, which consist of either single dye or
multiple dyes. The objectives of this work are to demonstrate that
both CF and NF techniques can remove dyes from wastewater
effectively and the combination of CFNF is able to improve the
overall performance. This could lead to a new approach for the dye
wastewater treatment by a hybrid system.

2. Experimental
2.1. Chemicals and materials
7 inorganic and 4 organic chemicals, listed in Table 1, were
chosen and used as coagulants and occulants in this study. 5 dyes
(2 acid dyes, 2 reactive dyes and 1 basic dye, purchased from

Table 1
Characteristics of coagulants and occulants used in this work.
Name of coagulant/occulant

Code name

Molecular formula

Molecular weight
(g/mol)

Purity

Polyaluminum chloride
Aluminum sulfate-octadecahydrate
Aluminum potassium sulfate-dodecahydrate
Iron(III) chloride-anhydrous
Iron(III) sulfate-pentahydrate
Calcium oxide
Magnesium chloride-anhydrous
Cationic polyacrylamide
Anionic polyacrylamide
Polydiallyldimethyl ammonium chloride (cationic, dissolved in water)
Cyanoguanidine

PAC
AS
APS
IC
IS
CO
MC
CPAM
APAM
PDDA
CYGU

Aln(OH)mCl(3n  m) (0o mo 3n)

Al2(SO4)3  18H2O
AlK(SO4)2  12H2O
FeCl3
Fe2(SO4)3  5H2O
CaO
MgCl2
a
(CH2CHCONH2)m
a
(CH2CHCONH2)m
(C8H16ClN)n
NH2C(NH)NHCN

Z 115b
666
474
162
490
56
95
8001000 million
8002500 million
200,000350,000
84

Z30% (as Al2O3)

Extra pure
99.5%
98%
97%
Z98 %
pure
Z90%
Z90%
20 wt%
Z99 %

a
b

Obtained from the specication of the products.

Calculated by assuming mn 1 for PAC.

308

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

Aldrich-Sigma (Singapore)) were selected for CF and NF studies. Their

characteristics are compiled in Tables 2 and 3. For simplicity and easy
reading, these coagulants, occulants and dyes will be referred in the
text as their corresponding code names shown in Tables 1 and 2
thereafter unless state otherwise. Deionized water (DI water, Milli-Q
water) was used to prepare the dye wastewater during the experiments. Sodium hydroxide (NaOH, 1.0 M) and hydrochloric acid (HCl,
1.0 M) were applied to adjust the solution pH.
2.2. The preparation of the positively charged NF hollow ber
membrane
The membrane used in this work is a recently developed
positively charged NF hollow ber membrane, which was prepared by cross-linking hyperbranched PEI on the outer surface of a
PAI hollow ber [19]. The PAI hollow ber was dry-jet wet-spun
from a dope formulation of PAI/ethylene glycol (EG)/N-methyl-2pyrrolidinone (NMP) 21.5/13.5/65.0 wt% using a dope ow rate
of 6.0 ml/min, bore uid ow rate of 3.6 ml/min, air gap of 5.0 cm,
and a take up speed of 50 m/min. The resultant PAI hollow ber
was cross-linked by 0.5 wt% PEI (60,000 g/mol, 50 wt% aqueous
solution, Acro, USA) that was dissolved in a 1:1 mixture of
Table 2
Characteristics of dyes tested in this work.
Name of dye

Code
name

Type of
dye

Molecular
formula

Molecular weight
(g/mol)

Indigo carmine
Remazol brilliant
blue R
Brilliant blue R
Reactive black 5

INCA
RBBR

C16H8N2Na2O8S2
C22H16N2Na2O11S3

466
627

BB-R
RB-5

C45H44N3NaO7S2
C26H21N5Na4O19S6

826
992

Alcian blue 8GX

AB-8

Acid dye
Reactive
dye
Acid dye
Reactive
dye
Basic dye

C56H68Cl4CuN16S4

1299

isopropanol (IPA) and water. The cross-linking process was conducted at 70 1C for 60 min. A full description about this NF
membrane can be found elsewhere [19].
2.3. Coagulation/occulation experiments
The 1000 ppm synthetic single dye wastewater (SDW) was
prepared by dissolving one dye of 1000 mg in 1.0 L DI water. SDW
for each of the aforementioned 5 dyes was therefore prepared.
Synthetic multiple dye wastewater (MDW) is a mixture of 5 SDWs
in an equivalent volume ratio. The total dye concentration of MDW
is 1000 ppm and each individual dye concentration is 200 ppm.
The other dye concentrations were diluted from the 1000 ppm
stock dye solutions according to working conditions. The jar-test
technique was adopted to carry out coagulation/occulation
experiments, where an appropriate amount of coagulant and/or
occulant was added to a 100 g dye solution in a 250 ml glass
beaker and stirred at a speed of 200 rpm for 1 min via using an
agitator (Heidolph, RZR 2041) equipped with a plastic stirring
blade. After 1-h settling, the supernatant solution was carefully
poured out and ltered through Whatman #1 (diameter47 mm,
pore size 11 m) and Whatman #42 (diameter 47 mm, pore
size2.5 m) lter papers by using a vacuum ltration apparatus
(Synthware glass ltration apparatus, 47 mm fritted disc, I L ask,
KNF/Germany diaphragm vacuum pump). The ltrates were then
kept for further analyses.
2.4. NF experiments
The NF experiments were performed in a lab-scale NF setup [39].
Each membrane module contains 40 pieces of hollow ber membranes, which have inner and outer diameters of around 280 and
430 mm, respectively. The effective length and membrane area of
each module is about 22 cm and 120 cm2, respectively. The feed
solution was circulated at the shell side of the hollow ber module at

Table 3
Molecular structures of dyes and polydiallyldimethyl ammonium chloride.

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

where Q is the volume (L) of permeate collected during a specic

period of sampling time t (h), A is the effective membrane area
(m2), and P is the transmembrane pressure (bar).
The permeate ux (J, L m  2 h  1) can be determined by the
following equation:
J

Q
At

where Q is the volume (L) of permeate collected during a specic

period of sampling time t (h), and A is the effective membrane
area (m2).
2.5. Physicochemical analyses
Two methods were chosen to determine the dye concentration;
namely, total organic carbon (TOC) method and UVvis integral
method. The implementation of these two methods depends on
specic situations as discussed later.
The TOC method was based on the TOC concentration determined by a TOC analyzer (TOC, ASI 5000A, Shimazu). Appendix
Fig. 1 shows the calibration curves of TOC values as a function of
dye concentration for various dyes. The TOC value has an almost
linear relationship with dye concentration in the range of 0 to
1000 ppm. The dye removal (Rd, %) was calculated by the following
equation:
Rd

C b  C a
 100%
Cb

I b  I a
 100%
Ib

where Ib and Ia are the UVvis integral values of the dye solution
before and after the CF treatment, respectively.
The dye removal (Rd, %) by the NF membrane was calculated by
the following equation:
Rd

I f  I p
 100%
If

where If and Ip are the UVvis integral values of the feed and the
permeate solutions, respectively.
It is worthy to point out that the concentrated dye solutions
had to be diluted to around 100 ppm when the UVvis integral
method was used in order to achieve reasonable accuracy.
The normalized efciency of coagulant/occulant (Ec) is dened
as
Ec

md
mc

where md is the weight of the dye removed by CF, while mc is the

total weight of coagulant/occulant added for the CF treatment.
The particle size of the settlement after CF was analyzed by
using a laser diffraction particle size analyzer (Beckman Coulter
LS230, analysis range: 0.04 mm to 2000 mm). The solution pH was
determined by using a pH meter (pH/ion S220, Mettler Toledo).
The aluminum concentration was measured using Inductively

100

4.0
3.5

90
MDW=1000 ppm

80
70

2.0

Ec

1.5
1.0
0.5

50
0

400

800

1200

1600

100

4.0
3.5

Rd (%)

Dye removala (%)

INCA

RBBR

BB-R

RB-5

AB-8

3.0
MDW=100 ppm

80

Rd
Ec

70

MDW

95.6
64.2
51.1
72.8
27.4
0
29.2

90.0
42.6
42.7
59.2
44.9
0
12.6

85.5
81.0
84.3
84.6
84.1
43.1
24.5

87.6
44.3
25.6
22.3
21.3
0
0

0
0
0
0
0
75.2
0

90.2
75.7
72.1
69.5
65.3
59.9
34.4

a
Dye removal was based on the TOC method. The coagulant dosage was
1000 ppm, the original dye concentration was 1000 ppm.

2.5
2.0
1.5
1.0

60
PAC
AS
APS
IC
IS
CO
MC

0.0
2000

PAC dosage (ppm)

90

Coagulant

2.5

Rd

60

where Cb and Ca are the TOC concentrations of the dye solution

before and after the CF treatment, respectively.
The UVvis integral method was based on the UVvis integral
(integrated range: 350650 nm) obtained through scanning the
sample by a UVvis spectrophotometer (Pharo 300, Merck).
Appendix Fig. 2 shows the calibration curves of UVvis integral
values as a function of dye concentration for various dyes. The UV
vis integral has a linear relationship with dye concentration when
Table 4
Preliminary performance evaluation of coagulants on dye removal.

3.0
Ec

Q
PAt

Rd

Ec

PWP

the dye concentration is below 100 ppm. However, the relationship becomes non-linear when the dye concentration is above
100 ppm. Based on UVvis integral, the dye removal (Rd, %) by CF
was calculated by the following equation:

Rd (%)

a ow rate of 0.15 L/min and a pressure of 1.0 bar. The permeate

solution was collected from the lumen side of the membrane. The
retentate stream was circulated back to the feed solution. Each NF
experiment included 3 steps: (1) the initial pure water permeability
(PWP, L m  2 bar  1 h  1) was measured using DI water at 1 bar; (2) a
1.0 L dye solution was used as the feed solution and circulated at
1 bar. Then permeate samples were taken at each consecutive time
interval of 1 h. Finally, DI water was used to ush the system and the
module thoroughly until the circulating water was clean, then the
nal PWP was measured.
Pure water permeability (PWP, L m  2 bar  1 h  1) was calculated according to the following equation:

309

0.5
50
0

40

80
120
160
PAC dosage (ppm)

0.0
200

Fig. 1. Coagulation performance of PAC for MDW treatment at different dye

concentrations: (a) the dye concentration in MDW was 1000 ppm; (b) the dye
concentration in MDW is 100 ppm. Dye removal is based on the UVvis integral
method.

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

3. Results and discussions

3.1. Coagulation and occulation
Both single dye and multiple dye wastewaters (referred to as
SDW and MDW, respectively, hereafter) were studied in order to
evaluate the effectiveness of coagulants and occulants in removing various types of dyes, and to select the most proper coagulant
and occulant. The following procedures were carried out: rstly
to screen and select a proper coagulant; secondly to optimize the
coagulant dosage; thirdly to identify the suitable occulant (or
coagulant aid); and nally optimize the occulant dosage.

3.1.2. Optimization of the coagulant dosage

The dye removal is also studied by the UVvis integral method
to identify the optimal coagulant dosage because of the following
reasons: (1) the PAC solution induces no visible color change;
(2) the organic occulant may contribute to the TOC value. Fig. 1
shows examples of multiple dyes removal from MDW at different
dye concentrations. For the 1000 ppm MDW treated by PAC, the dye
removal increases sharply with an increase in PAC dosage initially,
but nally approaches a plateau, which indicates that the maximum
dye removal by coagulation is around 97%. Mathematically, the
2.5

90

2.0

80

1.5

70

1.0
Rd

50
0

100

200

300

0.0
400

Dosage of PDDA (ppm)

Fig. 3. Effect of different dosages of PDDA combined with 400 ppm PAC to treat
1000 ppm MDW. Ec refers to the overall normalized efciency of PAC and PDDA.
The dye removal was based on the UVvis integral method.

100

100

80

80

60

60

40

0.5
Ec

20

40
20

0
APAM

PAC

PAC -APAM

100

100

80

80

60

60

Rd (%)

Rd (%)

100

60

Rd (%)

Rd (%)

3.1.1. Selection of the proper coagulant

Table 4 summarizes the dye removal for both SDW and MDW
based on the TOC method. The reasons of choosing the TOC
method are: (1) to exclude the color interference introduced by
ironic ion (Fe3 ); (2) To avoid a large pH change that may change
the intensity of UVvis absorbance caused by the coagulants. This
is particularly true for calcium oxide (CO) because 1000 ppm CO
can dramatically change the pH value of dye solutions; (3) there is
an almost linear relationship between TOC and dye concentration
in the range of 01000 ppm, which makes it simple and reliable
for analyses.
It can be observed from Table 4 that an inorganic coagulant can
be very effective in treating certain dyes, but totally ineffective for
the others. In the case of MDW, every coagulant appears to be
more or less effective, this may suggest that interactions between
dyes take place and subsequently change the MDW's charge
characteristics. As a result, when a coagulant is added into the
dyes solution, charge neutralization initially occurs and promotes
to formation of particles/ocs; then dyes may be also involved in
the process of co-precipitation and sorption onto ocs; nally the

coagulation happens and dyes are removed [7,15,17,40]. The

ability of removing dyes from the MDW sample by the 7 coagulants
is in the order of PAC 4AS 4APS 4IC 4IS 4CO4MC. Therefore,
PAC was identied as the most proper coagulant for further
studies.

Ec

Coupled Plasma-Optical Emission Spectrometry (ICP-OES, iCAP

6000 Series, Thermal Scientic).

Rd (%)

310

40
20

CPAM

PAC

PAC -CPAM

PDDA

PAC

PAC -PDDA

40
20

0
CYGU

PAC

PAC -CYGU

Fig. 2. Performance of PAC and different organic occulants to treat 1000 ppm MDW. The dosage of each PAC, APAM, CPAM, CYGU and PDDA was 400 ppm; For the PACocculant combination, the dosage of each component was 400 ppm. Dye removal was based on the UVvis integral method.

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

6
Volume (%)

4
PDDA=0 ppm
PDDA=100 ppm
2

PDDA=200 ppm
PDDA=300 ppm
PDDA=400 ppm

0
3

9
12
Particle size (m)

15

20

40

60

80

100

Particle size (m)

Fig. 4. Particle size (or diameter) distributions of CF settlements when 1000 ppm
MDW was treated by 400 ppm PAC without and with PDDA.

12

100

10

80
Rd: PAC

Rd: PAC-PDDA

60

Final pH: PAC

6

Final pH: PAC-PDDA

40

Final pH (-)

3.1.4. Optimization of the occulant dosage

The effects of different PDDA dosages on dye removal were
studied by xing the PAC dosage at 400 ppm. Fig. 3 displays that
the dye removal increases with an increase in PDDA dosage. This
might be attributed to: (1) PDDA possesses a high positive charge
density (as shown in Table 3) and water solubility. It can function
as an effective coagulant in the PAC-dye solution system; (2) PDDA
serves as a occulant that enhances the bridging mechanism for
coagulation and improves the aggregating capacity [16], thus
increasing the coagulation ability of PAC. However, the Ec value
(i.e., the efciency per gram of the total coagulants (400 ppm
PAC PDDA)) decreases when the PDDA dosage increases. Therefore, The CF settlement's particle size was investigated to optimize
the PDDA dosage.
Fig. 4 displays the particle size (or diameter) distributions of CF
settlements when 1000 ppm MDW was treated by 400 ppm PAC

Volume (%)

3.1.3. Identication of the suitable occulant

A typical coagulation/occulation process involves two stages of
mixing process; namely, rapid stirring (75700 rpm) for 0.53 min in
order to achieve a good dispersion of the coagulant/occulant, and
slow stirring (30150 rpm) for 530 min in order to propagate the
growth of ocs and minimize the breakdown of formed aggregates
[16,42]. In this work, the experiments associated with both coagulant
and occulant, the rapid and slow stirring processes were combined
into one single stirring scheme; namely, stirring at 200 rpm for
1 min. Adopting the single stirring scheme is due to the following
reasons: (1) to simplify the process; (2) to allow the coagulation and
occulation take place together. Some organic polyelectrolytes, such
as CPAM and PDDA, exhibit the ability of functioning as both
coagulant and occulant, which is demonstrated in Fig. 2 with
following discussions. In terms of dyes removal by coagulation/
occulation, as depicted in Fig. 2(a) and (c), neither APAM nor CYGU
is effective in dye removal. The combination of PAC-APAM does not
make much improvement compared with PAC alone; while the
combination of PAC-CYGU produces antagonistic effect, which
reduces the efcacy of PAC. As shown in Fig. 2(b) and (d), both
CPAM and PDDA alone are effective but with less efciency than PAC.
The combinations of PAC-CPAM and PAC-PDDA generate synergetic
effects, which improve the total dye removal compared to that of PAC
alone. Both CPAM and PDDA are positive charged, but PDDA is
superior to CPAM according to its individual or combined performance. Additionally, the suspension produced by PAC-PDDA was
easier to lter out than that by CPAM-PDDA. This is due to the fact
that CPAM possesses a huge molecular weight (8001000 million)
which is prone to entangling with the lter paper and forming a gellike sticky lm that blocks the lter pores. In summary, PDDA was
identied as the most proper occulant among the 4 examined
occulants.

without and with PDDA. The particle sizes were analyzed after CF
experiments and 1 h settling. As observed at the bottom of Fig. 4,
trace amounts of large-size particles in the range of 50100 mm are
formed with the addition of PDDA. In contrast, there are no
particles with a size larger than 30 mm for the CF settlement
without adding PDDA. This is probably owing to the fact that the
ne precipitates formed by PAC are not able to grow bigger
without the aid of occulant (PDDA). As shown in the enlarged
picture of Fig. 4, the particle size distribution curve shifts toward
the right side when increasing the PDDA dosage. This suggests that
the mean particle size becomes larger with an increase in PDDA
dosage. Without PDDA, a mean particle size of 7.4 mm is produced
by PAC, the mean particle size increases to about 7.8, 9.2, 9.3, or
9.7 mm when adding 100, 200, 300 or 400 ppm PDDA, respectively.
The bigger the particle size, the easier the ltration is. It is found
that the combination of 400 ppm PAC and 200 ppm PDDA produces a settlement with a moderate size of  9.3 mm and an
acceptable dye removal of  90% with a relatively high normalized
efciency (Ec) of 1.5. Therefore, the (400/200 ppm) PAC/PDDA
dosage was chosen to study the effects of pH.

Rd (%)

removal efciency per gram of the coagulant (Ec) declines accordingly. For the 100 ppm MDW treated by PAC, Fig. 1(b) shows that
the dye removal reaches a maximum when about 100150 ppm
PAC is added and then decreases with a further increment in PAC
dosage. The exceeded amount of PAC might lead to the reverse of
surface charge of the coagulated particles/ocs, thus resulting in
particles re-stabilization and lowering the treatment efciency [41].
Before the dye removal reaches the maximum, the Ec value of Fig. 1
(a) is always greater than that of Fig. 1(b), which implies coagulation
taking place more favorably in a high dye concentration than a low
dye concentration. In order to achieve a high dye removal without
much compromising the coagulant efciency, we chose a PAC
dosage of 400 ppm because it can remove about 85% dyes with
an Ec value of about 2.1 for further studies to identify a proper
occulant.

311

4
20

2
0

0
0

10

12

Initial pH (-)
Fig. 5. Effects of the initial pH on the dye removal for 1000 ppm MDW when using
PAC (400 ppm) and PAC-PDDA (400/200 ppm). Dye removal was based on the UVvis
integral method.

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

3.2. Combination of CF and NF treatments

Since the CF treatment is not able to achieve a complete dye
removal and a strong color is still visible, NF was adopted to
further process the wastewater after the CF treatment. 1.5 L of
1000 ppm MDW was rst subjected to the CF treatment using the
optimal CF formulation of (400/200 ppm) PAC/PDDA. After 90.4%
dyes were removed and their settlements were ltered out, the
left-over CF-treated solution was used as the feed solution for
subsequent NF experiments.
3.2.1. Performances of the NF treatment
NF experiments were performed for various dye solutions.
As shown in Table 5, almost 100% dye removal was achieved for
all dye solutions. In order to evaluate membrane fouling, pure
water permeability was measured before and after NF experiments. The membrane modules have initial PWP values of around
3.0 to 3.2 L m  2 h  1 bar  1. The nal PWP values vary from 0.9 to
3.0 L m  2 h  1 bar  1. Except for AB-8, the overall PWP recovery of
all membrane modules is about 30%. The PWP reduction caused by
fouling on such positively charged hollow ber membranes can be
effectively recovered through chemical cleaning, which has been
reported in our recent paper [43] and is out of the scope in this
study. It was observed that the membranes were colored after NF
experiments, this happened because the hollow ber membrane
used in this study was made of polyamideimide (PAI). Polyamide

based bers can be dyed by most acid and reactive dyes through
physiochemical bonding and impregnation of colloidal dye particles into the ber [1]. Interestingly, for the case of AB-8, the
membrane was not colored after NF experiments, and its nal
PWP was nearly equal to its initial PWP. This suggests that the
membrane was not fouled by the AB-8 dye probably due to: (1)
AB-8 has a relative large molecular weight (1299 g/mol) and
therefore it is difcult to enter the pores of membranes; (2) Both
AB-8 and the membrane are positively charged, they would
repulse each other; and (3) A basic dye does not often adhere
onto the polyamide-based ber without properly regulating pH
[1,20]. In summary, the NF process reveals excellent results in
terms of dye removal or rejection regardless of their types and
molecular weights. Except for the case of AB-8, the permeate ux
is around 1.0 L m  2 h  1, which is about one third of the initial
PWP. By comparing the case of 1000 ppm MDW with the one of
100 ppm, the initial dye removal and permeate ux are independent of dye concentration in these wastewater streams.
The charge of acid dyes is negative while that of basic dyes is
positive. As shown in Tables 2 and 5, the dye removals for both acid
dyes (Indigo carmine (INCA), Brilliant Blue R (RB-5)) and basic dye
(Alcian Blue 8GX (AB-8)) are nearly equally high. This might be
ascribed to the double-repulsion effect coupling with the sterichindrance and the solute electro-neutrality effects [21]. In other
words, since the selective layer (PEI) of the membrane is positively
charged while the support (PAI) is negatively charged [19,21], the
NF membrane possesses double-repulsion functions. The positively
charged selective layer repulses positive dyes (basic dyes) while the
negatively charged substrate repulses negative dyes (acid dyes). As

1.5

100.0

1.3
95.0

1.1
90.0

Rd (%)

The effects of the initial pH on dye removal when PAC

(400 ppm) and PAC-PDDA (PAC/PDDA 400/200 ppm) were
applied for the treatment of 1000 ppm MDW are shown in
Fig. 5. Both PAC and PAC-PDDA exhibit a very stable and good
dye removal capacity at the initial pH ranging from 3 to 10. Above
pH 10, dye removal by PAC-PDDA increases with an increase in pH.
On the contrary, dye removal efciency by PAC alone decreases.
This implies that an initial pH value higher than 10 is favorable for
PAC-PDDA but unfavorable for PAC. However, at an initial pH value
lower than 3, both PAC and PAC-PDDA show much lower performance. Moreover, the dye removal efciency of PAC-PDDA is
superior to PAC in the whole pH range. For a given dye solutions,
in the CF process, the nal pH is determined by the initial pH and
the added chemicals (coagulant/occulant). The original pH of
1000 ppm MDW is around 4.6, after CF treatment, the initial alkali
pH ( 47) decreases dramatically and downs to below 5. When PAC
is used with PDDA, the nal pH is slightly higher than that of using
PAC alone, this might suggest that the nal pH is majorly affected
by PAC. Based on the above results and discussions, and by
considering the balance between the factors of dye removal
efciency, normalized coagulant/occulant efciency (Ec), easiness
of ltration and workable pH values, a conclusion is therefore
drawn that PAC/PDDA 400/200 ppm is chosen as the optimal CF
formulation to treat 1000 ppm MDW for the further study in the
following CFNF process.

J (Lm-2h-1)

312

0.9
J:100 ppm
J:1000 ppm
J: After CF
Rd:100 ppm
Rd:1000 ppm
Rd: After CF

0.7

0.5
1

85.0

80.0
4

Running time (hour)

Fig. 6. Performance of the NF process for MDW without and with the CF treatment.
Operating pressure is 1 bar. Dyes removal was based on the UVvis integral
method.

Table 5
Performance of the NF treatment on various dye solutionsa.
Dye concentration:

1000 ppm

Dye solution
2

1

1

Initial PWP (L m h bar )

Permeate ux (L m  2 h  1)
Dye removalb (%)
Final PWP (L m  2 h  1 bar  1)
a
b
c

After CF

100 ppm

INCA

BRBR

RBBR

RB-5

AB-8

MDW

MDW

MDW

3.0
1.0
99.9
0.9

3.0
0.7
99.9
0.9

3.0
0.6
99.9
1.1

3.2
0.9
100.0
1.1

3.1
3.0
100.0
3.0

3.0
1.1
99.9
1.3

3.2
0.9
99.3
1.0

3.2
1.1
99.7
1.2

Operating pressure was 1 bar. The values were the average of two results measured at the rst two hours of each experiment.
Dyes removal was based on the UVvis integral method.
1000 ppm MDW was treated by CF, 90.4% dyes were removed and about 100 ppm dyes were remained.

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

60.0

100.0
90.0

70.0

40.0

60.0
30.0

NF permeate

40.0
CF treated MDW

10.0

CF settlement stream

20.0

50.0

0.0

30.0

Distribution of Al (%)

80.0

Total added Al for CF

Concentration of Al (ppm)

50.0

20.0
10.0
0.0

Total

Solid

Feed

Effluent

Fig. 7. The fate and distribution of aluminum during the CFNF treatment process.

Original
After CF
After CF-NF

50

40
Absorbance

a result, the NF membrane shows excellent rejections for both

positively and negatively charged dye molecules.
Fig. 6 displays the permeate ux and dye removal as a function
of time for MDW. Two MDW concentrations were employed;
namely, 100 and 1000 ppm. The 1000 ppm MDW was treated
with and without the CF treatment. For all cases, the permeate ux
declines initially but becomes stable after 7 h, while the dye
removal remains above 99%. For the 100 ppm and 1000 ppm
MDW, they have almost the same initial permeate ux and decline
in the same speed until the fourth hour. After the fourth hour, the
permeate ux of the 100 ppm sample tends to drop slightly,
whereas that of the 1000 ppm sample drops dramatically. After
7 h, both permeate uxes become stable, and the permeate ux of
the 100 ppm sample is approximately 20% higher than that of the
1000 ppm sample. These phenomena may be explainable as
follows: (1) the dyes adhered to the membrane surface and
partially blocked the surface pores in the beginning; (2) membrane
fouling due to the concentration polarization of the dyes became
serious for the 1000 ppm sample after 4 h. Since the higher the
dye concentration, the heavier the concentration polarization is
[44], the ux decline of the 100 ppm sample is mainly controlled
by membrane fouling, while that of the 1000 ppm sample is
affected by both membrane fouling and concentration polarization
fouling.
Since about 90% dyes were removed after the CF treatment, the
dye concentration in the CF treated sample is around 100 ppm. As
a result, the relationship between permeate ux vs. time of the CF
treated sample is nearly parallel with that of the 100 ppm MDW
sample, but the former has a lower ux (i.e., about 10%) than the
latter. The similar relationship between permeate ux vs. time
indicate that membrane fouling for both cases are similar due to
their similar dye concentrations. The lower ux of the CF treated
sample may arise from the osmotic pressure increase in the CF
treated sample. As shown in Fig. 7, about 24 ppm aluminum ion is
found in the CF treated solution. As a consequence, the effective
driving force across the NF membrane is reduced even though
they have the same transmembrane pressure [45,46]. Since the CF
treated sample has less fouling propensity, it has a higher ux than
that of the 1000 ppm sample after the 7-h test (i.e., about 10%
higher). Clearly, applying the CF process as a pretreatment, not
only can it lower membrane fouling but also sustain the
permeate ux.
In terms of rejections, nearly 100% dyes were removed by the
NF for all the 3 cases over 8-h tests. The fate of added aluminum
was also studied for the CFNF process. As shown in Fig. 7, about
58% of the total added aluminum (i.e., 57 ppm) reacted and

313

30
20

10

b
0
200

c
300

400

500

600

700

800

Wave length (nm)

Fig. 8. The UVvis absorbance spectra of (a) the original MDW (1000 ppm),
(b) solution after the CF treatment and (c) solution after the NFNF treatment.
The UVvis spectrum of the original MDW was obtained via diluting the original
MDW by 20 times, then the diluted sample was measured, the resultant absorbance was multiplied by a factor of 20.

remained in the settlement as the solid stream, while around

41% dissolved and left in the treated solution as the feed stream for
the NF process, and about 0.5% nally went to the permeate ux as
the efuent stream. Ideally, there should be no aluminum in the
NF feed stream after the CF process since the aluminum ion would
lead to an increase in osmotic pressure and ultimately a decrease
in effective driving force across the membrane. Additionally, the
less aluminum in the efuent stream, the better it is since the
efuent would eventually be discharged or reused.
The UVvis was also used to conrm the above conclusion.
Fig. 8 displays the UVvis spectra in a wavelength range between
200 and 800 nm for the original 1000 ppm MDW, the CF treated
MDW, and the NF permeate of the CF treated sample. The
absorbance decreases signicantly after the CF treatment because
of about 90% dyes removal at this stage. The UV absorbance drops
to almost zero after the NF process. This is consistent with the
aforementioned results of almost 100% dye removal. The pictures
at the up right side of Fig. 8 show the color changes during the
processes. The original 1000 ppm MDW is deeply dark blue. After
the CF treatment, it becomes light blue, and then the color
completely disappears after the CF-NF treatment.

4. Conclusions
The treatments of synthetic dye wastewaters were studied by
applying coagulation/occulation (CF), nanoltration (NF) and the
combination of CFNF. It is found that the removal of dye through
CF from single dye wastewater (SDW) depends on both dye and
coagulant. Some coagulants are very effective in treating certain
SDW, but totally ineffective for the others. The efciency of
removing dyes from the highly concentrated multiple dyes wastewater (MDW, 1000 ppm) by the 7 coagulants follows the order of
PAC 4AS 4APS4IC 4 IS4CO4MC. For the treatment of MDW,
polyaluminum chloride (PAC) is the best coagulant and polydiallyldimethyl ammonium chloride (PDDA) is the best occulant.
A dosage of 400/200 ppm PAC/PDDA is the optimal CF formulation,
which is able to remove about 90% of dyes from 1000 ppm MDW.
With the optimal dosage, the CF process is more favorable for dye
solutions with a higher concentration and pH.
The positively charged hollow ber NF membrane shows dye
removal of almost 100% for both anionic and cationic dyes. The NF
performance is also nearly independent of dye concentration with
a permeate ux of about 1.0 L m  2 h  1 under an operating

314

C.-Z. Liang et al. / Journal of Membrane Science 469 (2014) 306315

pressure of 1 bar. Additionally, this NF membrane shows an

excellent rejection of trivalent ions (e.g., Al3 ).
The generation of concentrated stream and membrane fouling
is inevitable in the NF process, while the production of sludge and
the remaining strongly visible color are encountered in the CF
process. The combination of CF and NF can complement each
other's strengths and overcome their individual limitations. The
NF treatment can completely remove the color left in the CF
treated MDW, meanwhile the efciency of coagulant/occulant is
signicantly enhanced by treating the concentrated streams of the
NF process. As a result, much less sludge is generated. In turn, by
applying CF process as a pretreatment method, the membrane
fouling is reduced and the NF permeate ux is increased. Those
benets and strengths lead to better performance for the treatment of synthetic dye wastewater. Future works will aim at
developing a proper CF formulation and a higher ux positively
charged NF membrane for the treatment of real dye wastewater.

Acknowledgments
The authors would like to acknowledge the nancial supports
provided by National Research Foundation (NRF) of Singapore
under its NRF Proof-of-Concept 8th Grant Call (NRF2012NRFPOC001-059) for the project entitled Development of advanced
nanoltration membranes for high removing rate of dyes in textile
wastewater (NUS grant number: R-279-000-389-281) as well as
the Singapore-MITAlliance for Research and Technology (SMART)
Centre under its Innovation Grant (ING12045-ENG) for the project
entitled Development of robust high-performance nanoltration
membranes for textile wastewater treatment (NUS grant number:
R-279-000-377-592). Special thanks are given to Mr. Bai-Wang
Zhao for his supports during the preparation of this work.

Appendix. Supporting information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.memsci.2014.06.057.
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