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Abstract
This paper reviews the application of polymeric nanofiltration membranes (NF) in the specific waste stream in
the textile industry, which typically generates large volumes of wastewater containing complex contaminants from
its daily operation. It is necessary that as much of this waste as possible is recycled instead of being disposed of in
landfill sites. Most of the conventional technologies seem unable to provide sufficient treatment for the effluents.
Therefore, it is generally accepted that NF membranes offer solutions for the problem. Of these NF membranes, the
thin-film composite nanofiltration (TFCNF) membrane is the most widely used by researchers in their studies. The
effects of the manufacturing conditions of TFCNF are discussed to provide valuable information for those who are
going to choose NF membranes in textile wastewater treatment. The preliminary performances of commercial NF
membranes have been examined in terms of dye rejection, salt rejection, permeate flux and COD rejection. Some
of the commercial membranes achieved maximum separation of dye and salts while some achieved higher flux. This
is because of the large variability of the parameters of textile wastewater and the NF membranes chosen. Due to the
scarcity of published papers covering the transport model that is specifically suitable for textile coloured wastewater,
a brief review of transport models of NF membranes with the presence of the dyes and salts is given. Membrane
fouling mechanisms and methods to control fouling are also reviewed. Future directions in NF membrane research
are also discussed to further expand research and development related to textile wastewater treatment.
Keywords:
*Corresponding author.
0011-9164/09/$ See front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2007.12.058
322
1. Introduction
Textile industries traditionally use a huge
amount of water, which is normally discharged
after the wastewater treatment system to decrease
the pollution load in order to meet the legislative
requirement for the discharge. With increasing
regulatory pressures and demand for cost reduction of water and chemicals, such treatment
systems have been enhanced to address these
challenges. Textile manufacturers have therefore
converted the traditional money-wasting process of pollution control to a profitable operation
through recycling the waste effluent [1]. This
operation allows for the recovery of the valuable
chemical components and water from a number
of different textile process streams. Due to inefficiency of conventional treatment systems, nanofiltration (NF) frequently becomes the chosen
treatment process.
NF has been recognized having the properties
in between ultrafiltration (UF) and reverse
osmosis (RO) and thus offers significant advantages, e.g. lower osmotic pressure difference,
higher permeate flux, higher retention of multivalent salts and molecular weight compounds
(>300), relatively low investment and low operation and maintenance costs [2]. Many researchers
have evaluated the performance of NF membranes in terms dye retention, salt rejection, permeate flux and COD retention. The effects of
different operating conditions of wastewater and
membrane properties have been systematically
studied. The results have proven that NF membranes are the suitable separation process to be
employed for the treatment of textile wastewater
and generally showed an acceptable rejection [3].
However, to maintain the efficiency of NF membranes at a reasonable operating cost, it is necessary to use a suitable pre-treatment in order to
prevent fouling and severe module damage [4].
In view of integrating the various aspects of
NF membranes for the treatment of textile
wastewater, the aim of this paper is to review and
Value
pH
Temperature, EC
COD, mg/L
BOD, mg/L
TSS, mg/L
Organic nitrogen, mg/L
Total phosphorus, mg/L
Total chromium, mg/L
Color, mg/L
210
3080
505000
200300
50500
1839
0.315
0.20.5
>300
323
324
Table 2
Method of dye application and estimated degree of fixation for different dye fiber combinations [3,9,10]
Class
Characteristics
Substrates
Method of application
Fiber
Degre of fixation
(loss to effluent), %
Acid
Anionic, water
soluble
Nylon, wool,
silk
Basic
Cationic, water
soluble
PAN, modified
nylon, inks,
polyester
Acrylic
Direct
Anionic, water
soluble
Cotton, rayona,
leather, nylon
Disperse
Polyester
Reactive
Anionic, water
soluble
Cotton, wool,
silk, nylon
Sulfur
Colloidal,
insoluble
Cotton, rayona
Vat
Colloidal,
insoluble
Cotton, rayona
95100 (05)
90100 (010)
biological process and a physicochemical process. However, most of these traditional methods
were found inadequate due to the large variability
of composition of textile wastewater.
Table 3 illustrates the efficiencies of various
treatment systems on decolorization and COD
removal which have been employed on textile
reactive dyeing effluent. According to Marmagne
and Coste [15], the coagulation and flocculation
process is not an excellent one for reactive dye
removal. The poor quality of floc resulted in
uneven settlement even after introduction of a
flocculant. This treatment method, however, was
325
Coagulationflocculation
Activated
carbon
Ozonationa
UF
MF
NF
RCOD
RColor
RCOD
RColor
RCOD
RColor
RCOD RColor
28.5
31.0
23.4
60.0
19.0
53.0
88.8
22.6
38.3
35.4
70.6
89.8
69.4
74.6
19.2
69.0
78.5
77.6
57.4
94.6
67.3
45.8
85.2
44.8
85.9
99.7
99.0
99.7
99.5
99.4
2.3
0.9
0.6
0.4
0.5
89.6
94.2
89.1
93.3
93.8
5.2
4.2
6.7
7.4
5.0
80.0
76.5
80.9
76.1
81.3
95.5
94.0
96.2
94.0
92.3
97.9
97.0
98.3
97.2
96.9
Ozone used in the ozonation process: Reactive Blue 204, 83.1 mg/L; Reactive Blue 209, 80.3 mg/L; Reactive Red 184,
82.2 mg/L; Reactive Blue 41, 88.7 mg/L; Reactive Blue 49, 81.4 mg/L.
326
Table 4
Summary of applications of combined treatment systems on textile effluent
Treatment processes
First
stage
Second
stage
Remarks
Physical/membrane
treatment (2007)
Coagulation
UF
Membrane
treatment (2006)
UF
NF
Physical/membrane
treatment (2005)
Coagulation/
flocculation
NF
Chemical/membrane
treatment (2005)
Electrochemical
oxidation
Membr.
Chemical/biological
treatment (2003)
Ozonation
Aerobic
Physical/membrane
treatment
Sand
filtration
and MF
NF
Physical/chemical
treatment (1997)
Coagulation
and electrochemical
oxidation
Ion
exchange
327
Treatment processes
First
stage
Second
stage
Remarks
Physical/chemical/
biological treatment
(1996)
Coagulation
and electrochemical
oxidation
Activated
sludge
Physical/chemical
treatment (1994)
Coagulation
Ozonation
328
processes in Tirupur, India. Babursah and coworkers [27] reported that the cost of recovering
wastewater within the textile industry using a
membrane recovery system was US $0.55/m3
based on the current market conditions in Istanbul, Turkey. Details of economic analysis based
on the membrane technologies can be found
elsewhere [30,31]. With this limited information,
there is a need for comprehensive studies to
assess the economic feasibility of using NF
membrane technology for producing purified
water from wastewater, particularly in the textile
industry.
329
330
Fig. 2. Reaction scheme of trimesoyl chloride with piperazine and 3,5 diaminobenzoic acid [41].
331
332
Table 5
Summary of the applications of commercially available polymeric NF membranes on textile effluent
Membrane
(manufacturer)
Configuration
(polymer material)
MWCO
(Da)
Process conditions
Evaluation
MPS 31
(Weizmann)
Spiral wound
(NA)a
NAa
NF45
Spiral wound
(Dow/Film Tec) (PA)b
200
Same as above.
DK 1073
(Osmonics)
Spiral wound
(PA)b
300
Same as above.
ATF 50
(Adv. Membr.
Tech.)
Spiral wound
(TFCc of PIPd on
PSf e)
340
TFCSR2
(Fluid System)
Flat sheet
(TFCc of PSf e)
200
400
DK 2540
(Osmonics)
Spiral wound
(NA)a
NAa
NTR 7450
(NittoDenko)
Flat sheet
(sPES)f
600800
UTC 20
(Toray Ind.)
Flat sheet
(PA)b
180
P = 64 L/(m2.h)
Rdye = 92.1%
Rsalt = 87.3% at
operating pressure
of 20 bar
333
MWCO
(Da)
Process conditions
NF 70
Flat sheet
(Dow/Film Tec) (PA)b
250
DL 4040F
(Osmonics)
Spiral wound
(NA)a
150300
Desal 5 DK
(Osmonics)
Flat sheet
(TFCcPAb)
150300
a
f
Configuration
(polymer material)
b
Not available.
Polyamide.
Sulfonated polyethersulfone.
d
Thin-film composite.
Piperazineamide.
Pave = average permeability.
R = rejection.
Evaluation
RCOD = >93%
RTSS = >60%
Rconductivity = 40.5%
Polysulfone.
Q s K s ( C ) A /
(1)
334
concentration. Inorganic salt (NaCl) can be ionized completely into Na+ and Cl! in acid, alkali
or pure water. When the salt concentration
increases, so does the concentration of Na+. Based
on the principle of the Donnan equilibrium,
repulsive force from the negatively charged
membrane decreases with increasing electrolyte
concentration. Lower repulsive force means that
more Cl! anions are allowed to pass through the
membrane and thus salt rejection is reduced.
Moreover, higher salt concentration could lead to
a build-up of concentration polarization on the
membrane surface resulting in lower flux and
separation. Other researchers attributed the
decrease in NaCl rejection with increasing NaCl
concentration to the shield effect [60]. The undesirable effect of concentration polarization,
however, can be minimized by maintaining a high
flow rate of the liquid phase along the membrane
surface and by applying turbulence promoters
(spacers) between the membranes [61].
Previous studies demonstrated that adoption of
a NF hollow fiber membrane (HA 3110, Toyobo,
Japan) in a submerged MBR was feasible because
it could provide extra-clean permeate for reuse
[62]. The rejection rates of monovalent and
divalent ion by this NF membrane varying from
40% to 60% and from 70% to 90%, respectively,
during the initial 80 days of filtration process.
The lower rejection rates of monovalent salt compared to divalent salts were also reported previously [51,60]. Choi and co-workers [62] found
that salt rejections tended to decrease gradually
after 80 days, which was probably due to the
increase in pore size and decrease in the surface
charge of membranes, which deteriorated the
membrane properties.
A neutral surface membrane typically shows
a lower salt rejection as compared to a charged
membrane for a given pore size. The mechanism
of salt rejection is primarily based on the steric
effect in neutral surface membrane. The Donnan
exclusion, however, plays an important role in
retaining salt in negatively charged membranes.
Di
kT
n a
4#n#6
(2)
Dbulk, I
(10!9 m2/s)
AW or
MW
rH2O,
nm
NaCl/Na2SO4 salt
mixture:
SO42!
Na+
Cl!
(lowest to
highest)
1.06
1.66
2.03
96.06
22.99
35.45
NA
0.36
0.33
NaCl/CaCl2 salt
mixture:
Ca2+
Cl!
Na+
(highest to
lowest)
0.92
2.03
1.33
40.08
35.45
22.00
0.41
0.33
0.36
335
(3)
336
Re
Dv
(4)
vc j
RT
M
(5)
RTM s
vm
1000vs
(6)
337
1
RCOD
1
RsCOD
BsCOD 1
.
RsCOD J v
(7)
338
due to their unknown structure and the complexity in composition of textile effluent. To date,
there are numerous studies reported in the literature regarding various salt removals using NF.
Generally, two main approaches have been used
to model the transport of inorganic salts through
NF. The first was based on the extended Nernst
Plank model (ENP) [41,77,78] and the second
was based on the Spiegler and Kedem model (SP)
[7981]. Other than these models, the Teorem
MeyerSiever (TMS) and the DonnanSteric
pore model (DSPM) also were used to determine
salt rejection [79,80,8284].
To model dye mixture separation, an
unsteady-state mass transfer model was
developed and successfully tested for prediction
of permeate flux and permeate concentration
polarization of dye components without considering the presence of salt in an unstirred NF
batch [85]. The research was continuously conducted to investigate the effects of different
operating parameters on per-eate flux and permeate concentration of dye in an unstirred batch
and a cross-flow cell [86]. Nevertheless, in the
literature there are no studies covering the
transport model that specifically is versatile for
textile colored wastewater. The mechanism of salt
transport in NF is complicated in the presence of
organic dye and many other components, thus
making the analysis of transport much more
difficult.
Generally, the fouling layer or gel polarization
layer occurs from the absorption of dye onto the
membrane. The situation could be worsened in
the presence of other components, e.g., wax,
fibers, oil, etc. in the textile effluent. Therefore,
the currently available transport models are
insufficient to predict the performance of NF in
textile wastewater. More intensive studies are
therefore desired. However, a brief review of
transport models of NF membranes relevant to
textile dyeing effluent is made below to provide
the basic knowledge for those who are interested
in further improving transport models.
1
kavg
1
1
k s k sd
(8)
339
Kw
RM
1
R DM
(9)
340
341
342
343
StokesEinstein radius, m
Membrane surface area, m2
Concentration of component j,
kg/m3
Salt concentration difference across
the membrane, kg/m3
Diameter of tube, m
Diffusivity, m2/s
Permeate flux, m3/m2.h
Boltzmanns constant
Average mass transport coefficient
of salt
Mass transport coefficient of salt
Mass transport coefficient of salt
inside the gel layer of organic ion
Membrane permeability coefficient
Water permeability of combined dynamic membrane, m2.s/kg
Molecular weight, g/mol
Molecular weight of the solvent,
g/mol
StokesEinstein coefficient
Gas constant, J/mol.K
Resistance of membrane, kg/m2.s
Resistance of dynamic membrane in
the presence of dye, kg/m2.s
Reynolds number
Permeate flow, kg/m2
Salt flow through membranes, kg/m2
Water temperature, EC
Average velocity of liquid, m/s
Number of ions
Number of positive ions
Molar volume of solvent, m3/mol
Greek
344
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