Chemical Engineering Journal 285 (2016) 304318

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Chemical Engineering Journal

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

Treatment of textile plant effluent by hollow fiber nanofiltration

membrane and multi-component steady state modeling
Mrinmoy Mondal, Sirshendu De
Department of Chemical Engineering, Indian Institute of Technology, Kharagpur, Kharagpur 721302, India

h i g h l i g h t s

Hollow fiber nanofiltration membranes were prepared upto cut off 360 Da.

At pH 10, zeta potential of optimum membrane was 10 mV.

4 reactive dyes were removed more than 98% from a textile plant effluent.

42% salt recovery was attained.

A predictive multi-component steady state model was developed.

a r t i c l e i n f o a b s t r a c t

Article history: Polysulfone based nanofiltration (NF) hollow fibers upto 360 Da cut off were prepared by interfacial poly-
Received 5 August 2015 merization of meta-phenylenediamine and trimesoyl chloride. Hollow fibers were characterized in terms
Received in revised form 29 September of scanning electron and atomic force microscopy, permeability, molecular weight cut off (MWCO), pore
2015
size distribution and surface zeta potential. Increase in TMC concentration reduced the MWCO and aver-
Accepted 2 October 2015
Available online 8 October 2015
age pore size of the membrane. MWCO was decreased from 780 to 360 Da and average pore radius was
reduced from 7.3 to 5 as TMC concentration increased from 0.1 to 1 wt%. A textile effluent containing
four reactive dyes and salt was successfully treated by this hollow fiber. A completely predictive steady
Keywords:
Hollow fibers
state multicomponent model was developed to quantify the system performance.
Nanofiltration 2015 Elsevier B.V. All rights reserved.
Surface modification
Textile effluent

1. Introduction enhancing dye fixation [3]. In addition to salts, caustic solution of

Textile industries generate huge quantity of wastewater from
dyeing and finishing processes containing 50200 mg/L unfixed
dyes [1,2]. Certain classes of dyes like reactive dyes are generally
found at relatively high concentration due to their lower ability
of fixation to fibers like cotton and viscose. These wastewater
streams are often found to be biorecalcitrant due to presence of
various additional chemicals like fixation, bleaching agents and
surfactants. Large amount of salts are added to the dye baths for
Abbreviations: AFM, atomic force microscopy; COD, chemical oxygen demand;
CFR, cross flow rate; DMF, dimethylformamide; FRR, flux recovery ratio; FDR, flux
decline ratio; MPD, m-phenylenediammine; MWCO, molecular weight cut-off;
NaCl, sodium chloride; PEG, polyethylene glycol; PSF, polysulfone; SEM, scanning
electron microscope; TDS, total dissolved solid; TMC, trimesoylchloride; TMP,
transmembrane pressure drop; TS, total solid.
Corresponding author. Tel.: +91 03222 283926; fax: +91 0322 255303.
E-mail address: sde@che.iitkgp.ernet.in (S. De).
about 23% NaOH is also added to improve properties like fiber
strength, shrinkage resistance, luster, and dye affinity. Therefore,
dye house effluent has high chemical oxygen demand (COD) and
it is a major contributor to pollution in aquatic environment, lead-
ing to stricter environmental regulations [4]. Due to high cost of
treatment, small scale industries discharge the effluent directly
to the surface water.
Hyper-saline effluents are often found to be resistant to biolog-
ical treatment. Biological treatment systems sometimes become
poisoned due to the chemicals present in these effluents. Thus,
they are not efficient for dye removal [5]. Solar evaporation is
one of the low-cost techniques that reduces the volume of the
effluent and concentrates the salts and organic content of saline
effluent [6]. Coagulationflocculation is also used as a pretreat-
ment of hyper saline effluent to remove COD [6,7]. However, coagu
lationflocculation is not efficient for salt removal. The conven-
tional processes used to remove dyes from wastewater include

http://dx.doi.org/10.1016/j.cej.2015.10.005
1385-8947/ 2015 Elsevier B.V. All rights reserved.
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318 305

Nomenclature

ai osmotic coefficient of ith component, Pa m3/kg Ri radius of ith component, m

A0 membrane surface area, m2 rs solute radius, m
Ci,m concentration of ith component on membrane surface, rp effective pore radius of the membrane, m
kg/m3 Re Reynolds number (qu0d/l)
CP concentration of permeate, kg/m3 Sc Schmidt number (l/qD)
CF concentration of feed, kg/m3 Sh Sherwood number (Kd/D), Eq. (9)
d diameter of the hollow fiber, m T temperature, K
Di diffusion coefficient of ith component, m2/s u0 average velocity, m/s
Jss steady state permeate flux, L/m2 h
Jw pure water flux, L/m2 h Greek symbols
Jw1 water flux of the membrane before experiment, L/m2 h a a/DP, Eq. (6)
Jw2 water flux of the membrane after experiment, L/m2 h d film thickness, m
J1 initial flux of the membrane with dye solution, L/m2 h DP transmembrane pressure drop, Pa
Ki mass transfer coefficient of ith component, m/s Dt sampling time, s
kb Boltzmann constant, 1.3805  1023 J/mol K e molar extinction coefficient
L length of the hollow fiber, m g viscosity of solution, Pa s
Lp membrane permeability, m/Pa s k wavelength, nm
Mi molecular weight of ith component, g/mol lp mean effective pore radius, m
MW molecular weight, g/mol ls geometric mean radius of solute, m
Q volumetric flow rate, m3/s pm osmotic pressure at the membrane surface, Pa
Rg ideal gas constant, J/mol K pp osmotic pressure at the permeate, Pa
R rejection, % rg geometric standard deviation of solute radius, m
Ri,r real retention of ith component rp geometric standard deviation of solute radius, m

flotation [8], sedimentation [9], physical and chemical adsorption
[10], advanced oxidation processes like ozonation, photocatalytic
oxidation [11,12], Fentons process, photo-Fenton oxidation
[13,14], ultraviolet irradiation and electrochemical oxidation
[15,16]. The limitations associated with all these conventional pro-
cesses are also significant. For example, ozonation and advanced
oxidation processes are expensive [17,18]. Electro-coagulation is
another recently developed method for removal of dyes [19,20].
But, this process is also expensive and time-consuming. Ozkan-
Yucel and Gokcay reported anaerobic oxidation for treatment of
azo dye [21]. Adsorption is one of the popular methods to treat
dye containing wastewater. Activated carbon, clay minerals, zeo-
lites, metal oxides, agricultural wastes, biomass and polymeric
materials are used as adsorbents by several researchers [2231].
Low cost adsorbents, like, raw and modified rectorite [32], perlite
[33], rice husk [34], marine algae [35], etc., are also used. However,
adsorption is a slow and equilibrium governed process. Moreover,
the powdery form of adsorbents makes their removal difficult from
filtrate [36]. High operating and disposal cost are other
disadvantages.
Membrane based separation processes offer an attractive
alternative in this regard due to various advantages, including (i)
physical separation; (ii) no additives; (iii) low energy intensive;
(iv) high scalability [37]. Nanofiltration (NF) is in between reverse
osmosis and ultrafiltration and is a suitable process for textile
effluent treatment [38]. The operating pressure requirement for
NF membranes is much less (1020 atm) compared to reverse
osmosis. Numerous reports are available in literature on the appli-
cation of NF for treatment of textile effluent [3946]. Most of the
modules are in plate and frame, spiral wound or tubular configura-
tions. On the other hand, in hollow fiber configuration, one can
pack a large number of hollow fibers in a bigger tube so that a large
surface area is obtained in a smaller volume, thereby, providing a
higher throughput of the process. Very few reports are available
in NF grade hollow fibers [4754]. Treatment of textile effluent
using NF hollow fiber is scant in literature [55,56].
Thin film composite hollow fiber NF membrane was devel-
oped by in-situ interfacial polymerization of polysulfone based
ultrafiltration grade fibers using in m-phenylenediamine (MPD)
and trimesoyl chloride (TMC) [50]. In that study, concentration
of MPD was in the range of 0.52 wt% and that of TMC was from
0.01 to 0.1 wt%. With combination of 2 wt% MPD and 0.1 wt%
TMC, a membrane of molecular weight cut off (MWCO) 490 Da
was obtained and synthetic dyes with molecular weight 480
990 Da were successfully removed. A typical dye-house effluent
contains a mixture of dyes with lower range of molecular weight
as low as 400 Da. However, Maurya et al. [50] reported extre-
mely low flux (0.010.035 L/m2 h) with synthetic dye solution.
Therefore, the present work has been undertaken to attain NF
grade hollow fiber with low MWCO (<400 Da) by varying con-
centration of TMC to higher range (0.11 wt%) at a fixed MPD
concentration (2 wt%) for interfacial polymerization of polysul-
fone and to achieve higher permeate flux. The developed hollow
fibers are characterized in terms of surface morphology by scan-
ning electron microscope (SEM), permeability, MWCO, pore size
distribution, atomic force microscopy (AFM) and surface zeta
potential. Efficiency of membranes is evaluated by treating a real
life textile effluent containing four reactive dyes. Performance of
filtration is analyzed in terms of physico-chemicals parameters,
like, chemical oxygen demand (COD), total dissolved solids
(TDS), total solids (TS), conductivity, rejection of dye and salts.
A completely predictive multi component model for steady state
is formulated based on film theory and osmotic pressure model.
Adequacy of the model is quantified by comparing the permeate
flux, permeate concentration of salt and dye with experimental
data. Such simple model can be of great help to design engineers
for scaling up.
2. Theory
In case of an actual textile plant effluent, a steady state model is
proposed to calculate the permeate flux and permeate concentra-
tion. The solvent flow through the porous membrane can be
quantified as [57],
J ss Lp DP  Dp 1
306 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318

where Lp is the membrane permeability. The osmotic pressure dif-

Known parameters:
ference across the membrane is given as, Operating condition: P, Ci,0, u0
Dp p m  p p 2 Fiber dimension: d, L
Membrane property: Lp, Ri,r
where pm and pp are the osmotic pressure at the membrane surface Fluid properties: osmotic coefficient (ai)
and the permeate stream, respectively. Using Vant Hoff relation- Salt and Dye property: Di
Unknown parameters: C1,m, C2,m, C3,m,
ship, osmotic pressure is related to the solute concentration.
C4,m , C5,m and Jss
pi ai C i 3

where a is effective the osmotic coefficient. ai = (RgT)/Mi for dyes

and ai = (2RgT)/M for salt (NaCl). Using Eqs. (1)(3), the permeate Guess the value of membrane surface concentration
flux is described for N-component system, of first component C1,m
" #
X
N
 
J ss Lp DP  ai C i;m  C i;p 4
i1
Calculate the corresponding flux (Jss) value in Eq. (8)
The membranesolute interaction of ith component is charac-
terized by parameter real retention, Ri,r and it is constant for a par-
ticular membranesolute system [58]. Real retention is defined as,
 Using the above flux value calculate the C2,m, C3,m, C4,m,
Ri;r 1  C i;p C i;m 5 and C5,m in Eq.(8)
Substituting the value of Ci,p in Eq. (4), the following equation
for steady state flux is obtained.
" #
X
N Cal
Calculate the permeate flux ( J ss ) using C1,m, C2,m, C3,m,
J ss J 0w 1 ai Ri;r C i;m 6
i1
C4,m, and C5,m value in Eq. (6)

where J 0w Lp DP and ai ai =DP. As discussed in subsequent exper-

imental section there are four reactive dyes and salt (equivalent
sodium chloride), total 5 components are present in the textile
effluent. According to stagnant film theory, the permeate flux is No
expressed in terms of mass transfer coefficient (Ki = Di/d) and solute J ssCal J ssExp <
concentration in feed, membrane surface and permeate stream.
   
C 1;m  C 1;p C 2;m  C 2;p
J ss K 1 ln K 2 ln
C 1;0  C 1;p C 2;0  C 2;p
   
C 3;m  C 3;p C 4;m  C 4;p Yes
K 3 ln K 4 ln
C 3;0  C 3;p C 4;0  C 4;p
  Print the value C1,m, C2,m, C3,m, C4,m, C5,m and Jss
C 5;m  C 5;p
K 5 ln 7
C 5;0  C 5;p
Fig. 1. Algorithm to estimate the Ci,m and Jss value.
Substituting the value of Cp from Eqs. (5) into (7), the following
equations are resulted.
2.1. Solution scheme
   
C 1;m R1;r C 2;m R2;r
J ss K 1 ln K 2 ln Eqs. (1)(10) represents a set of algebraic equations and are
C 1;0  1  R1;r C 1;m C 2;0  1  R2;r C 2;m
    solved numerically according to the algorithm presented in Fig. 1.
C 3;m R3;r C 4;m R4;r
K 3 ln K 4 ln
C 3;0  1  R3;r C 3;m C 4;0  1  R4;r C 4;m
  3. Experimental
C 5;m R5;r
K 5 ln 8
C 5;0  1  R5;r C 5;m 3.1. Materials

Leveques equation is used to calculate the mass transfer coeffi- Polysulfone (PSF, average molecular weight 22,400 Da) was
cient under laminar flow conditions [57] obtained from Solvay chemicals, India. N,N-dimethylformamide
 1=3 (DMF) and sodium chloride (NaCl) were supplied by Merck (India)
Kd d
Sh 1:86 ReSc 9 Ltd., Mumbai. Various molecular weight of polyethylene glycol
D L
(PEG) fractions, e.g., 200, 400, 600, 4000, 20,000 and 35,000 Da
The expression of mass transfer coefficient corresponding to ith were obtained from SRL, India. m-phenylenediammine (MPD),
component is presented as, trimesoylchloride (TMC) and polyvinylpyrrolidone (PVP) were
!1=3 procured from Sigma Aldrich, USA.
u0 D2i
K i 1:86 10
dL 3.2. Spinning of hollow fibers

where d is diameter and L is the length of the hollow fiber mem- Dry wet method was used to spin PSF based hollow fibers. The
brane. Real retention and diffusivity of ith component are estimated complete setup for spinning is presented in Fig. 2(a). Two coaxial
separately as elaborated in subsequent experimental section. needle assembly was used to extrude the polymer solution as
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318
Fig. 2. (a) The schematic of the hollow fiber spinning unit; (b) the schematic of the needle assembly.
Table 1
Conditions for spinning hollow fiber.
Inner diameter of smaller needle, m
Outer diameter of smaller needle, m
Air gap between extrusion point and gelation bath, m
Casting temperature, K
Pressure in polymer-melt tank, kPa
Water flow rate, m3/s
Flow rate of polymer solution, kg/s
Inner diameter of hollow fiber, m
Outer diameter of hollow fiber, m
Inner diameter of cartridge, m
Length of cartridge, m
Number of hollow fibers
Total membrane area, m2
shown in Fig. 2(b) [59]. Operating parameters and other specifica-
tions of spinning of hollow fibers are presented in Table 1. PSF was
heated to 70 C for 2 h to evaporate the moisture completely in an
air circulated oven. Fixed amount (3 wt%) of PVP (55 kDa) was
added to a 17 wt% PSF and the mixture was dissolved in DMF at
60 C. The polymer solution was left for 12 h at room temperature
(30 C) under mild stirring (150 rpm) to remove air bubbles. The
polymer solution was then fed into the polymer tank of spinning
assembly and was extruded under nitrogen pressure at 69 kPa.
The water was used as non-solvent through the inner needle to
create the hollow core of the fiber. The fibers were then allowed
to fall in gelation bath (tap water) and wound in a spool. The spool
was kept in water 24 h. The other detailed spinning specifications
are available in Table 1.
3.3. Surface modification of hollow fibers to get nanofiltration (NF)
membrane
Surface modification of the hollow fiber was carried out by the
following protocol. In the first step, the hollow fibers were put in
an oven at 70 C for 15 min. Then, they were immersed in 2%
MPD solution for 15 min, followed by air exposure for 15 min. After
that, the fibers were kept in TMC (0.11 wt% in hexane) solution for
15 min and again exposed to air for 15 min. The fibers were than
cured at 70 C for 10 min and finally, they were immersed in
307
distilled water and left overnight. Poly-m-phenylene-trimesamide
layer was formed on the porous polysulfone substrate membrane
0.0005 by the reaction of water-soluble MPD (2 wt%) and hexane soluble
0.012 TMC solution (0.11 wt%). Three NF membranes were prepared
0.25 by surface modification at fixed MPD concentration 2 wt% and
300
three TMC concentrations 0.1, 0.5 and 1.0 wt%.
35
3.3  107 After the modification, a bundle of 80 such fibers was packed in
5  105 a 12.5 cm inner diameter PVC pipe of length 20 cm making the car-
0.0006 tridge. Two ends of the cartridge were potted using epoxy resin
0.0009 (brand name: araldite). The cartridge was than fitted in a cross flow
0.0118
0.18
filtration set up. Details of the experimental set up are available
80 [59].
0.027
3.4. Characterization of membranes
3.4.1. Membrane morphology
The morphology of outer surface and the cross section of the
hollow fiber were studied by scanning electron micrograph
(model: ESM-5800, JEOL, Japan). In case of, cross sectional images,
membranes were dipped in liquid nitrogen for 1 min and then
fractured.
3.4.2. Permeability, molecular weight cut off (MWCO) and pore size
distribution
Distilled water was used at 138 kPa for 2 h to compact the
membrane and the permeate flux was measured at four transmem-
brane pressure drop. Following expression was used to calculate
the permeate flux.
J w Q =A0 Dt 11
where Jw is pure water flux; Q is the permeate volume in time Dt; A0
is effective surface area of the membrane. The permeate flux was
plotted against the transmembrane pressure drop and the slope of
the straight line through origin indicated membrane permeability.
Neutral solutes of different molecular weights (glucose 180 Da,
PEG 200 Da, 400 Da, 600 Da, 1.5 kDa and 4 kDa) were used to
estimate MWCO of the membranes using a solution with concen-
tration 10 g/L at 69 kPa transmembrane pressure drop (TMP) and
10 L/h cross flow rate. Solute rejection was expressed as:
R 1  C P =C F  100% 12
308 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318

where R is solute rejection; CP and CF are solute concentration
in permeate and feed, respectively. MWCO of the membrane
corresponds to molecular weight at 90% solute rejection.
Rejection values were used to estimate the pore size distribu-
tion of the membrane by using a log-normal probability function,
as follows [48].
Z First, the hollow fibers were compacted at a pressure of 138 kPa
1 y
2 =2 ln r s  ln ls
R erf y p eu du where; y
2p 1 ln rg
where rs the solute radius, ls the geometric mean radius of solute at
R = 50% and rg is the geometric standard deviation about ls. ls is
defined as the ratio of rs at R = 84.13% and 50%. Rejection as a func-
tion of solute radius in a semi-log scale was a straight line defined
as,
FR A Bln r s
The mean effective pore radius (lp) and the geometric standard
deviation (rp) can be assumed to be equivalent to ls and rg by
neglecting steric and hydrodynamic interaction between solute
and pores. Thus, the pore size distribution of membrane can be
expressed based on lp and rp by following density function [60]:
" 2
# lowed by washing with distilled water for half an hour by recycling
dRr p 1 ln r p  ln lp
p exp  2
dr p r p ln rp 2p 2ln rp
where rp is the effective pore radius of the membrane. lp and rp
indicate the average radius and width of the distribution curve.
The average pore radius estimated from MWCO curve at 90% reten-
tion was related to molecular weight of solutes by the following
equation [61],
log r s 1:5575 0:4911 log MW
where MW is g/mol and rs is nm.
3.4.3. Atomic force microscopy (AFM)
Membrane surface roughness was measured using atomic force
microscope (model: 5500 AFM, Agilent Technologies, USA) with a
scan size of 2 lm  2 lm by tapping mode. The hollow fibers were
sliced by scalpel and flattened before measurement.
3.4.4. Zeta potential measurement with electrolyte solution
Membrane surface zeta potential was measured using surface
charge analyzer by streaming potential method (model:
ZETACAD-DC, supplied by M/s, Cad Instruments, France).
3.5. Characterization of textile effluent
The textile effluent used in this study was collected from a
textile industry, Kothari Processors Pvt. Ltd., located near Kolkata,
India. The effluent contained four reactive dyes: cibacron yellow
(CIB Y), cibacron red (CIB R), cibacron black (CIB B) and basic blue
(BB 3).
pH, conductivity, total dissolved solids (TDS), total solid (TS),
salinity and COD of the effluent are measured. The complete char-
acterization of the effluent is presented in Table 2.
3.6. Experimental procedure
13 for 2.0 h using distilled water. After compaction the membrane
permeability was estimated as described in Section 3.4.2. The tex-
tile effluent was pumped into the cartridge from a 2 L capacity tank
and the cross flow rate (CFR) and TMP across cartridge were inde-
pendently set by controlling the needle valves in bypass and the
retentate lines. Four different TMPs, i.e., 69, 104, 121 and 138 kPa
and three CFR, i.e., 10, 20 and 30 L/h were used to perform the
experiments in total recycle mode for 1 h. The corresponding
14
cross-flow velocities were 0.19, 0.23 and 0.35 m/s, respectively.
The permeate flux was determined from the slope of cumulative
volume versus time plot with a measurement error 3%. Permeate
samples were analyzed after steady state was reached.
The modules was washed by tap water without recycling the
retentate and permeate for 1 h after the experimental run, fol-
the retentate to the feed tank. This washing cycle was repeated
15
twice. Before conducting the next experiment, the membrane per-
meability was checked again.
3.7. Analysis
A digital refractometer (supplied by M/s, Cole-Parmer, Kolkata,
India) was used to measure the concentration of neutral solutes for
16 MWCO analysis. A multimeter (model: PCSTestr 35, Eutech Instru-
ments, Germany) was utilized to measure conductivity, pH, salinity
and total dissolved solids (TDS) of feed and all permeate samples at
room temperature. Total solids (expressed in g/L) of feed and per-
meate were measured gravimetrically in a hot air oven at
104 2 C [62]. A COD testing kit (supplied by M/s, Merck, Darm-
stadt, Germany) was used to measure COD of feed and permeate
samples. Dye concentration in feed and permeate samples were
analyzed by a UVVisible Spectrophotometer (M/s, Perkin Elmer,
Connecticut, USA). The wavelength (k) at maximum absorption
were 402, 535, 599 and 657 nm for CIB yellow, CIB R, CIB B and
BB 3 dyes, respectively. Simultaneous spectrophotometric method
was used to measure the concentration of each dye in the effluent
[63] under the assumptions of (i) additivity of absorbances in
absence of reaction; (ii) insignificant overlap between the absorp-
tion spectra of the dyes. If k1, k2, k3, k4 are wavelengths for
maximum absorption of the pure dyes in the solution, in case of
the mixture, the absorbance values at these four wavelengths are
measured and following 4 equations can be written,
Ak1 Ak11 Ak21 Ak31 Ak41 17

Table 2 Ak2 Ak12 Ak22 Ak32 Ak42 18

Effluent characteristics after collection from textile plant.

Effluent characteristics Quantity Ak3 Ak13 Ak23 Ak33 Ak43 19

pH 11.2 0.3
Conductivity, mS/cm 14 1.2 Ak4 Ak14 Ak24 Ak34 Ak44 20
Total dissolved solids (TDS), g/L 10 0.2
Total solid (TS), g/L 13.4 0.3 A ecl. If l = 1 cm, the above four equations can be simplified,
Salinity, g/L 8.1 0.2
COD, mg/L 1400 120 Ak1 ek11 c1 ek21 c2 ek31 c3 ek41 c4 21
CIB yellow (CIB Y), concentration, mg/L 67.0 2
Cibacron red (CIB R), concentration, mg/L 240.0 5
Cibacron black (CIB B), concentration, mg/L 204.0 4 Ak2 ek12 c1 ek22 c2 ek32 c3 ek42 c4 22
Basic blue (BB3), concentration, mg/L 93.0 2
Salt content (equivalent NaCl), mg/L 9096 20 Ak3 ek13 c1 ek23 c2 ek33 c3 ek43 c4 23
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318 309

Ak4 ek14 c1 ek24 c2 ek34 c3 ek44 c4 24 4. Results and discussions

Molar extinction (absorption) coefficients e1 ; e2 ; e3 ; e4 are

obtained from absorbance of pure component solutions at wave-
lengths, k1, k2, k3, k4. Thus, eight cross molar extinction coefficients
were determined (ek11 ; ek22 , etc.). Eqs. (21)(24) were then solved
simultaneously to get concentration of four dyes from the absor-
bance values at four wavelengths. This method is highly accurate,
as the interaction effects of the species are included [63] and it was
used by Chakraborty et al. [64], in a two dye system in an actual
textile effluent.
3.8. Estimation of parameters
3.8.1. Real retention of ith component (Ri,r)
Real retention value of each component was estimated
experimentally. For each component, separate experiment was
conducted at low polarization conditions, i.e., high CFR (40 L/h),
low TMP (14 kPa) and low feed concentration (10 mg/L). The
observed retention under these conditions was equal to real reten-
tion assuming complete mixing [65]. Values of real retention for
various solutes are presented in Table 3.
3.8.2. Diffusivity of ith component (Di)
5 mg/L dye solution was sonicated in a glass beaker by a sonica-
tor (Optic Invymen System, supplied by ASE Instruments Agency
Pvt. Ltd., model CY-500) for 15 h and diffusivity of dye was evalu-
ated using StokesEinstein equation. The StokesEinstein equation
is expressed as
kb T
Di
6pgRi
where D is diffusivity of dye, kb is the Boltzmann constant, T is the
room temperature, g is the viscosity of water, Ri is the radius of ith
dye. Equivalent radius of dye particles was estimated from particle
size distribution using Zetasizer (model: Zetasizer nano ZS 90) sup-
plied by M/s, Malvern instruments, Worcestershire, U.K. Diffusivity
of NaCl was obtained from literature [66]. Molecular weight, radius
and diffusivity of dyes are presented in Table 3.
3.9. Flux recovery ratio (FRR) and flux decline ratio (FDR) of membrane
Flux decline ratio (FDR) and flux recovery ratio (FRR) are two
parameters quantifying the antifouling characteristics of the mem-
brane. Irreversible fouling is related to FRR, presented by pure
water flux of the membrane before and after the dye experiment.
 
J w2
FRR%  100
J w1
where Jw2 is water flux of the membrane after experiment; Jw1 is
water flux of the membrane before experiment.
Flux decline during an experiment is quantified by FDR.
 
J 1  J ss
FDR%  100
J1
where J1 and Jss are initial and flux at steady state with dye solution.
4.1. SEM
The cross section and top view of SEM images of unmodified
and modified polysulfone (PSF) membranes are shown in Figs. 3
(a) and (b), respectively. Fig. 3a(i) shows that in case of unmodified
PSF, there exists finger like pores extending throughout the cross
section of the fiber. Fig. 3a(i)(iv) shows the composite membranes
are prepared by a coating of thin polyamide layer on the outer sur-
face of the polysulfone hollow fibers by interfacial polymerization
between m-phenylene diamine (MPD) in water and trimesoyl
chloride (TMC) in hexane. The SEM pictures clearly show two dis-
tinctive layers with a dense layer coated on top of the porous layer.
At 0.1 wt% TMC concentration, a very thin dense layer is found on
top of the porous structure whereas at higher TMC concentration
(1.0 wt%), this dense layer becomes thicker with the thickness
around 70 lm. The rate of polymerization is higher with TMC
concentration resulting in thicker outer skin of the hollow fiber
membrane [67].
Top view of various membranes is presented in Fig. 3(b). Fig. 3b
(i) shows the existence of pores of unmodified PSF hollow
fiber. The effect of concentration of TMC is demonstrated in
Fig. 3b(ii)(iv). The number of pores decreases with TMC concen-
tration. It is observed that increase in concentration of TMC makes
the membranes denser.
4.2. Permeability, molecular weight cut off (MWCO) and pore size
distribution
25
Table 4 presents the permeability and molecular weight cut off
(MWCO) of the modified and unmodified membrane. The perme-
ability values of the modified membranes are decreased from
21  1011 to 2.94  1011 m/Pa s (with 0.1 wt% TMC). It is found
that as the concentration of TMC is increased, the permeability is
reduced. Permeability decreases from 2.94  1011 to
11
1.14  10 m/Pa s as the concentration of TMC increases from
0.1 to 1.0 wt%.
Molecular weight cut off (MWCO) of various membranes is
shown in Fig. 4. It is observed from this figure that MWCO of mem-
brane decreases from 44,000 to 780 Da as PSF hollow fiber mem-
brane is modified by 2 wt% MPD and 0.1 wt% TMC. MWCO of the
membrane decreases from 780 Da to 360 Da as TMC concentration
increases from 0.1 to 1.0 wt%.
Pore size distributions of different membranes are shown in
Fig. 5. It is observed from Fig. 5, that the pore size distribution
26 curves shifts towards left with surface modification of PSF mem-
brane indicating reduction of pore radius. The maxima of pore size
distribution curves are 4.4, 0.42, 0.31, and 0.26 nm for pure PSF
membrane and surface modified membranes by TMC concentra-
tion 0.1, 0.5 and 1 wt%, respectively. The average pore radius of
these membranes is estimated using Eq. (16) as described in
27 Section 3.4.2 and presented in Table 4.
4.3. Atomic force microscopy (AFM)

Table 3 Three-dimensional AFM images of different membranes are

Property of dyes and equivalent salt contained in effluent.
presented in Fig. 6. It is observed from this figure (Fig. 6a and b)
Property CIB Y (1) CIB R (2) CIB B (3) BB3 (4) NaCl (5) that as PSF membrane is modified, the average surface roughness
MW* (Da) 551 854 923 360 58.5 of the membrane decreases from 11.4 nm to 5.1 nm. The pore size
Radius (nm) 1.05 1.5 1.84 0.84 of the modified membrane decreases and surface becomes
D (m2/s)  1010 2.09 1.47 1.19 2.62 15.2 smoother indicating denser membrane [68,69]. Average roughness
Rr 0.99 1.0 1.0 0.99 0.65
of the NF membranes ranges from 5.1 to 4.3 nm as the concentra-
*
MW: molecular weight. tion of TMC increases from 0.1 to 1 wt%.
310 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318
(i)
(iii)
Fig. 3a. Cross-sectional SEM images of (i) PSF, (ii) TMC 0.1%, (iii) TMC 0.5%, (iv) TMC 1.0%.
4.4. Zeta potential
Zeta potential of NF membranes is presented in Fig. 7. It is
observed from the figure that at normal pH (6.55) all the mem-
branes show negative zeta potential value. The zeta potential
decreases with concentration of TMC. For example, at pH 6.55 zeta
potential of TMC 0.1 wt% membrane is 1.25 mV and that for TMC
1 wt% membrane is 5 mV. At pH 10, zeta potential of the mem-
brane with 0.5 wt% TMC decreases further to 10 mV.
4.5. Membrane selection for textile effluent treatment
Three NF hollow fibers (as discussed in Section 3.3) are used for
textile effluent treatment. Experiments are conducted using trans-
membrane pressure drop of 104 kPa and cross flow rate 20 L/h. The
permeate flux profiles are shown in Fig. 8. It is observed that in all
cases steady state is reached within 20 min. The steady state per-
meate flux are about 4.7, 3.4 and 2.5 L/m2 h for TMC-0.1, TMC-
0.5 and TMC-1 wt% membrane, respectively. These are in direct
consequence of the pore size of the membrane. Average pore size
of these three membranes also decreases in that order. Various
physico-chemical properties of the permeate (textile effluent) are
also shown in Table 5 for these membranes.
It is observed from this table that COD values of the filtrate are
within permissible limit (250 mg/L) for TMC-0.5 wt% and TMC-
1 wt% membrane. Permeate concentration of different dyes are less
(ii)
(iv)
than 1 mg/L for TMC-0.5 wt% and TMC-1 wt% membrane. In case of
TMC-0.1 wt% membrane the permeate concentration of dyes are
above 3 mg/L. The zeta potential of the TMC-0.1 wt% membrane
is less negative than TMC-0.5 wt% and TMC-1 wt% membrane.
Hence, chargecharge repulsion is less (between negatively
charged membrane surface and dyes) in TMC-0.1 wt% membrane
than other two NF membranes.
In case of TDS and TS, the trend is clear with the MWCO of the
membrane. As the pore size of the membrane increases, more
solids are permeated. Permeate conductivity and salinity depends
upon the surface charge of the membrane. More negative mem-
brane surface shows better percentage of rejection of salinity and
conductivity. For example, TMC-1 wt% membrane shows 68% and
54% rejection of conductivity and salinity whereas TMC-0.1 wt%
membrane shows 45% and 36% rejection of conductivity and
salinity.
Antifouling capacities of different NF membranes are quantified
in terms of FRR and FDR values. A good antifouling membrane
shows high FRR and low FDR. From Fig. 9, it is observed that,
TMC-0.5 wt% and TMC-1 wt% membrane have almost same FRR
value around 88%. These two membranes show higher FRR value
than TMC-0.1 wt% membrane. It is also found that TMC-0.5 wt%
and TMC-1 wt% membrane show lesser FDR (around 20%) value
than TMC-0.1 wt% membrane. Thus, considering the characteriza-
tion of permeate quality and antifouling characterization,
TMC-0.5 wt% and TMC-1 wt% membranes exhibit comparable
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318 311

(i) (ii)

(iii) (iv)

Fig. 3b. Top surface SEM images of (i) PSF, (ii) TMC 0.1%, (iii) TMC 0.5%, (iv) TMC 1.0%.

Table 4
Permeability, molecular weight cut off (MWCO) and average pore radius of the membrane.

PSF TMC-0.1 wt% TMC-0.5 wt% TMC-1.0 wt%

Lp (m/Pa s)  1011 21 1.1 2.94 0.3 1.45 0.5 1.14 0.4
MWCO (Da) 44,000 1500 780 40 440 30 360 20
Average pore radius () 64.1 1.6 7.3 0.18 5.5 0.17 5 0.15

performance. Considering throughput of the process, TMC-0.5 wt% At a fixed CFR, the permeate flux increases with TMP. This is due
membrane performs better and results 40% more steady state per- to increased driving force. At 30 L/h CFR, the permeate flux
meate flux compared to TMC-1 wt% membrane. Thus, TMC-0.5 wt% increases from 2.2 to 5.9 L/m2 h, when the TMP increases from
membrane is selected for studying the effects of operating 69 to 138 kPa.
conditions.
110
4.6. Effects of TMP and CFR on permeate flux 100
90
Rejection (%)

The profiles of permeate flux for various operating conditions

80
are presented in Fig. 10. Effects of both transmembrane pressure TMC-0.1 wt%
drop (TMP) and cross flow rate (CFR) are evident from these fig- 70 TMC-0.5 wt%
ures. It is observed from Fig. 10 that steady state is reached within TMC-1.0 wt%
60
20 min during filtration. Two trends are observed from this figure. PSF
For a fixed TMP, the permeate flux increases with the cross flow 50
rate. With increase in cross flow rate, the concentration of solute 40
deposited on the membrane surface decreases due to forced con-
Error bar: 5%
30
vection, leading to lowering in concentration polarization and
increase in permeate flux. For example, at 104 kPa pressure drop, 20
100 1000 10000 100000
the permeate flux increases from 3.8 to 4.4 L/m2 h. When cross Molecular Weight (Da)
flow rate increases from 10 to 30 L/h, at 138 kPa, the corresponding
increase in permeate flux is from 5.4 to 5.9 L/m2 h. Fig. 4. MWCO of the various membranes.
312 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318

Probability density function (nm-1) 0.5 TMC (wt%)

(a) PSF 0
0.1 0.5 1.0
0.4

Zeta Portential (mV)

0.3 -4

0.2 -8

0.1 pH-6.55
-12 pH-10
Error bar: 5%
0.0
-16
0 2 4 6 8 10 12
Fig. 7. Zeta potential of the different NF membranes.
Pore radius, r (nm)
4
Probability density function (nm-1)

(b) 10
TMC-0.1% TMP: 104 kPa
3 TMC-0.5% Cross Flow Rate: 20 l/h

Permeate Flux (l/m 2.h)

TMC-1.0% 8 Error bar: 5% TMC-0.1 wt%
TMC-0.5 wt%
TMC-1.0 wt%
2 6

4
1
2

0 0
0.0 0.5 1.0 1.5 2.0 0 10 20 30 40 50 60
Pore radius, r (nm) Time (min)
Fig. 5. Pore size distribution of (a) PSF, (b) TMC 0.1%, TMC 0.5% and TMC 1.0%. Fig. 8. Permeate flux profile for different NF membranes.

Ra= 11.4 nm Ra= 5.13 nm

(a) (b)
Ra= 4.35 nm Ra= 4.31 nm

(c) (d)
Fig. 6. AFM images of (a) PSF, (b) TMC 0.1%, (c) TMC 0.5%, (d) TMC 1.0%.
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318 313

Table 5
Permeate characteristic of different NF membrane.

104 kPa, pH Equivalent Nacl TDS TS Salinity COD Dye rejection (%)
20 L/h (g/L) (g/L) (g/L) (g/L) (mg/L)
Blue Black Red Yellow
TMC-0.1 10.6 0.4 4.95 0.05 6.39 0.06 7.12 0.07 5.17 0.04 280 10 94.62 0.08 97.10 0.1 98.42 0.08 92.24 0.1
TMC-0.5 10.6 0.5 3.56 0.04 5.32 0.04 6.25 0.05 4.37 0.06 240 6 99.7 0.06 99.95 0.02 99.91 0.03 99.9 0.02
TMC-1.0 10.6 0.3 2.90 0.06 5.09 0.03 5.85 0.06 3.71 0.05 235 5 99.78 0.04 99.95 0.02 99.91 0.02 99.9 0.02

4.6.1. Effect of TMP and CFR on permeate quality Table that the rejection of dyes is almost 99% in all the cases due
Quality of permeate after NF at different operating conditions is to size exclusion (MWCO of the membrane 440 Da) and charge
presented in Table 6. Dye rejection (%), conductivity, TDS, TS and charge repulsion. In the textile effluent out of four dyes, three dyes,
COD are presented in this Table. It is observed from this namely, CIB Y, CIB R, CIB B are acidic and BB3 is basic dye. Due to
presence of negativity charged sulfonic groups and lower pKa val-
ues, acidic dyes remain in anionic state. The membrane at pH  10,
has negative zeta potential (11 mV, refer Fig. 7). Thus, there is
100 strong electrostatic repulsion of negatively charged sulfonic end
Error bar: 5% FRR
FDR groups of acidic dyes and the membrane surface. Also, average
80 diameter of three acidic dyes is much larger (2.1, 3 and 3.7 nm
FRR & FDR (%)

for CIB Y, CIB R and CIB B, refer Table 3). Therefore, both charge-
60 charge repulsion and size exclusion act in tandem, resulting in
extremely high rejection of CIB Y, CIB R and CIB B by the mem-
40 brane. In case of basic cationic dye (BB3), there is strong attractive
electrostatic interaction between this dye and the membrane sur-
20 face and dye gets adsorbed on the surface [70]. On the other hand,
data in Tables 3 and 4 reveals that average diameter of dye BB3
0 (1.6 nm) is more than the average pore diameter of the membrane
0.1 0.5 1.0
TMC (%) (1.1 nm). Therefore, size exclusion of BB3 results its rejection but
electrostatic interaction facilitates its permeation through the
Fig. 9. FRR and FDR of textile effluent for different NF membranes. membrane. However, size exclusion become dominant but due to
attractive forces more dye molecules permeate making its rejec-
tion lower than other three acidic dyes (refer Table 6). COD of per-
meate increases with TMP, due to enhanced forced convection. For
8 example, at fixed CFR (30 L/h) the COD value increases from 165 to
Error bar: 5%
7 69 kPa,10 l/h 348 mg/L, when TMP increases from 69 kPa to 138 kPa. At same
69 kPa,20 l/h
TMP, CFR has marginal effect on COD in permeate. Thus, with a
Permeate Flux (l/m2.h)

6 69 kPa,30 l/h
104 kPa,10 l/h feed containing COD of 1400 mg/L, 7690% COD reduction is
5 104 kPa,20 l/h
104 kPa,30 l/h obtained for different TMP and CFR in TMC-0.5 wt% membrane.
4 121 kPa,10 l/h
TS and TDS of permeate increases with TMP due to same reason
121 kPa,20 l/h
3 121 kPa,30 l/h and permeation of solids through the membrane pores is
138 kPa,10 l/h
2 138 kPa,20 l/h increased. At same TMP, CFR has insignificant effect on TS and
138 kPa,30 l/h
TDS in permeate. With a feed TS of 13.4 g/L, 5158% TS reduction
1
is achieved with permeate concentration in the range
0 5.656.64 g/L, for various operating conditions.
0 10 20 30 40 50 60
Time (min) Conductivity and salinity of permeate increases with TMP, as
expected at constant CFR. At higher TMP, convective flux through
Fig. 10. Flux decline during textile effluent treatment for TMC 0.5 wt% membrane. the NF membrane dominates resulting to reduction in rejection

Table 6
Property parameters of permeate at different operating condition for TMC 0.5 wt% NF membrane.

Pressure Flow rate pH Equivalent TDS Salinity TS (g/L) COD Dye rejection (%)
drop (kPa) (L/h) Nacl (g/L) (g/L) (g/L) (mg/L)
Blue Black Red Yellow
69 10 10.6 0.3 3.46 0.02 5.27 0.03 3.95 0.04 5.65 0.04 147 5 98.93 0.03 99.9 0.01 99.88 0.01 99.85 0.04
20 10.6 0.4 3.48 0.03 5.34 0.04 3.92 0.06 5.71 0.02 153 4 98.93 0.02 99.9 0.02 99.88 0.03 99.85 0.03
30 10.6 0.5 3.50 0.02 5.45 0.02 4.12 0.03 5.64 0.05 165 6 98.93 0.04 99.9 0.01 99.88 0.02 99.85 0.04
104 10 10.6 0.4 3.56 0.03 5.48 0.02 4.17 0.04 5.81 0.03 220 5 98.93 0.02 99.9 0.03 99.88 0.04 99.84 0.05
20 10.6 0.5 3.58 0.02 5.51 0.03 4.22 0.03 5.94 0.02 238 4 98.82 0.04 99.87 0.04 99.83 0.05 99.84 0.04
30 10.6 0.6 3.63 0.04 5.53 0.04 4.19 0.04 5.92 0.04 241 6 98.80 0.05 99.85 0.05 99.79 0.05 99.84 0.03
121 10 10.6 0.3 3.72 0.03 5.71 0.02 4.24 0.05 6.34 0.06 265 5 98.70 0.06 99.85 0.06 99.75 0.06 99.84 0.06
20 10.6 0.5 3.65 0.04 5.64 0.05 4.31 0.03 6.31 0.07 272 4 98.70 0.07 99.85 0.05 99.7 0.08 99.82 0.04
30 10.6 0.4 3.71 0.02 5.73 0.04 4.29 0.03 6.37 0.04 281 5 98.66 0.04 99.8 0.06 99.67 0.08 99.82 0.05
138 10 10.6 0.5 3.75 0.03 5.86 0.03 4.35 0.04 6.60 0.05 327 6 98.6 0.04 99.78 0.07 99.65 0.06 99.82 0.03
20 10.6 0.6 3.73 0.05 5.91 0.01 4.27 0.06 6.57 0.06 332 7 98.55 0.04 99.75 0.08 99.65 0.05 99.8 0.08
30 10.6 0.5 3.77 0.03 5.87 0.04 4.46 0.02 6.64 0.05 348 4 98.5 0.08 99.7 0.04 99.67 0.04 99.79 0.07
314 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318
and increase in salt permeation. At higher TMP, highest salt recov-
ery is obtained. It is observed that 4855% salt recovery is attained
under the range of operating TMP and CFR studied herein.
The osmotic coefficient for solutes (ai), CIB yellow, CIB red, CIB
black, basic blue and NaCl are estimated from Eq. (3). The bulk dif-
fusivities of CIB yellow, CIB red, CIB black, basic blue, are reported
in Table 3. The real retention (Rr) value of all dyes and NaCl are esti-
mated experimentally as presented in Section 3.8.1. These values
are reported in Table 3. Permeate flux and permeate concentration
of the species are calculated using the algorithm presented in
Fig. 1.
The comparison between experimental and calculated perme-
ate flux is presented in Fig. 11. It is observed from Fig. 11 that
the calculated permeate flux values are within 15% of the exper-
imental data. The concentration of salt (as equivalent NaCl) in the
permeate and its comparison with that of experimental values is
given in Fig. 12(a). The calculated permeate concentrations are
within 7% of the experimental data.
Similarly, Fig. 12(b) shows the concentration of blue dye in the
permeate and its comparison with that of experimental values.
Here calculated permeate concentrations are within 15% of the
experimental data. Rest of the dyes are rejected almost 100%.
Variations of polarization modulus with TMP and CFR are
shown in Fig. 13. Polarization modulus increases with TMP and
decreases with CFR. With increase in TMP, more solutes are con-
vected towards the membrane surface increasing the membrane
surface concentration and hence the polarization modulus. For
example, in case of yellow dye at 10 L/h CFR, polarization modulus
increases from 1.1 to 1.3 as TMP increase from 68 to 140 kPa.
Increase in CFR causes enhanced shearing action on the concentra-
tion polarization layer, restricting its growth, thereby, reducing
polarization modulus. For example, in case of yellow dye at 140
TMP, polarization modulus decreases from 1.3 to 1.17 as CFR
increase from 10 to 30 L/h.
5. Comparison of the surface modified PSF hollow fibers and
this performance with other NF membranes
A comparison of surface modified PSF hollow fiber membrane
developed in this work with other NF grade hollow fiber mem-
branes is presented in Table 7. It is observed from this table that
most of NF membranes were prepared by surface modification of
ultrafiltration membrane and two case of direct phase inversion
[48,53]. These hollow fibers were applied in removal of chromate,
salts, dyes, etc. In Table 7, MWCO of membranes of three refer-
ences are beyond 1000 Da but they have been used for removal
7
6
Flux experiment (l/m2.h)
+10%
5
4 -10%
3
2
1 0.5
1 2 3 4 5 6
Flux Calculated (l/m2.h)
Fig. 11. Comparison of calculated and experimental volumetric flux in osmotic
pressure model.
of lower sized solutes like, salt, dye, etc., by exploiting charge-
charge interaction [47,49,52]. Rest of the hollow fibers in Table 7
have MWCO in normal range of NF, i.e., 330870 Da. NF mem-
branes developed in present work have a wide range of MWCO
from 360 to 780 Da. The specific permeate flux attained by hollow
fibers developed in this work is in the range of 0.040.11 L/m2
h kPa for various operating conditions and it can be compared very
well with the throughput values of other NF membranes.
A comparison of performance of the present NF hollow fibers
with other NF membranes for treatment of textile effluent is pre-
sented in Table 8. It is observed from this table that most of the
works reported are hybrid filtration system including more than
one step with NF as the final one. These are adsorptionNF [40],
microfiltrationNF [41], ultrafiltrationNF [71], coagulationNF
[72] and catalysis, coagulationNF [73]. The process performance
is presented in last four columns of this table. The specific perme-
ate flux which is the throughput of such hybrid systems is gener-
ally higher due to the reduced load of dye and other solids in NF
step and it is in the range of 0.00030.06 L/m2 h kPa. For other
cases, where direct NF is used [4244,46,55,56,74,75], this value
is in the range of 0.020.078 L/m2 h kPa. The range of specific flux
in the present work is in the range of 0.020.05 L/m2 h kPa, which
is quite high among the hollow fiber modules as well as hybrid sys-
tems. Dye removal was very high 9899.8% compared to that of
even two step processes [40,71]. In the present work, COD removal
attained is as high as 90%, thereby brining its value below permis-
sible level (250 mg/L) in India and is comparable with other refer-
ences. Reasonable salt recovery (42%) is also achieved. Therefore,
the present work provides formulation of a surface modified hol-
low fiber NF membrane capable of treatment of a real life textile
effluent effectively.
4000
Experimental salt concentration (mg/l)
(a)
3750 +7%
3500
-7%
3250
3000
3000 3250 3500 3750 4000
Calculated salt concentration (mg/l)
Experimental concentration of blue dye (mg/l)
2.0
(b) +15%
1.5
-15%
1.0
0.5
1.0 1.5 2.0
7 Calculated concentration of blue dye (mg/l)
Fig. 12. Comparison of calculated (a) NaCl permeate concentration with the
experimental data (b) blue (BB3) dye permeate concentration with the experimen-
tal data.
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318 315

1.35 1.40
10 l/h 10 l/h
1.30 20 l/h 1.35
20 l/h
30 l/h 1.30 30 l/h
1.25

C1,m/C1,0

C2,m/C2,0
1.25
1.20
1.20
1.15
1.15
1.10
1.10
1.05 1.05
60 80 100 120 140 60 80 100 120 140
TMP (kPa) TMP (kPa)

1.45 1.24
10 l/h
1.40 10 l/h 20 l/h
20 l/h 1.20
1.35 30 l/h
30 l/h
1.16
C3,m/C3,0

C4,m/C4,0
1.30
1.25
1.12
1.20
1.15 1.08
1.10
1.04
60 80 100 120 140 60 80 100 120 140
TMP (kPa) TMP (kPa)

1.05
10 l/h
1.04 20 l/h
30 l/h
C5,m/C5,0

1.03

1.02

1.01
60 80 100 120 140
TMP (kPa)

Fig. 13. Variation of polarization modulus at various operating conditions for different solutes.

Table 7
Comparison of PSF NF hollow fibers developed in present study with other NF hollow fibers membrane.

Reference Polymer
Akbari et al. [47] Polysulfone (PSF)
Wang and Chung [48] Polybenzimidazole
(PBI)
Sun et al. [49] Polyamide-imide (PAI),
cellulose acetate (CA)
Maurya et al. [50] PSF
Zheng et al. [51] Polypropylene
Song et al. [52] Polyethersulfone (PES)
Mondal and De [53] PSF, PEG (polyethylene
glycol), ZnCl2
Ingole et al. [54] PES
Present study PSF
Preparation technique of hollow fiber NF Specific water flux MWCO (Da) Application
membrane (L/m2 h kPa)
UV-photografting of sodium p-styrene 0.040.15 20004600 Treatment of synthetic
sulfonate (NaSS) and [2-(acryloyloxy)ethyl] anionic dye solutions
trimethyl ammonium chloride (AO) on the
surface of ultrafiltration
Direct phase inversion 0.18 525 Removal of chromate from
waste water
Dual-layer fabricated by the simultaneous 0.0190.12 11158175 Salt rejection
coextrusion
3
Thin film composite membranes from (0.0580.20)  10 490730 Treatment of synthetic dye
ultrafiltration by using in-situ interfacial solutions
polymerization between m-phenylenediamine
(MPD) and trimesoyl chloride (TMC)
Microfiltration grade polypropylene hollow 0.086 650 Removal of synthetic
fiber was dip coated using polyvinyl alcohol cationic dyes through sub-
and polyquaternium-10. Glutaraldehyde used merged filtration
as cross-linking agent
Coating of sulfonated polyether ether ketone 0.10.13 40006000 Recovery of glyphosate
(SPEEK) onto a PES ultrafiltration (UF) from saline wastewater
membrane
Direct phase inversion 0.0750.123 330870 Treatment of synthetic
reactive dye solutions
Polydopamine (PDA) coating and interfacial 0.010.18 Salt rejection
polymerization of MPD with TMC as well as
piperazine (PIP) with TMC
In-situ interfacial polymerization of PSF based 0.0410.11 360780 Treatment of textile effluent
ultrafiltration fibers using in MPD and TMC
 316
Table 8
Comparison of performance of PSF NF hollow fibers developed in present study with other NF membranes for treatment of textile effluent.

Reference Experimental technique TMP (kPa) Cross flow Dye name Dye concentration Specific permeate Dye COD Salt recovery
velocity (m/s) (mg/L) flux (L/m2 h kPa) removal (%) removal (%)
Gomes et al. [40] Adsorption followed by 1600 0.87 C.I. Acid Orange 7 350 0.00031 95
NF (flat sheet)
Capar et al. [41] Microfiltration followed 590 0.083 0.031 97

M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318

by NF (flat sheet)
Chen et al. [42] Single stage NF (flat sheet) 2001200 0.050.07 95
Koyuncu and Topacik [43] Single stage NF (flat sheet) 2400 0.111.1 Reactive black 5 80 0.025 67% for 20 g/L NaCl
Qin et al. [44] Single stage NF (flat sheet) 1000 4-Amino 2,5 dimethoxy 0.0350.038 99
phenyl, 4-amino phenyl
4-B hydroxyl ethyl
sulfone sulfate ester
Chakraborty et al. [46] Single stage NF (flat sheet) 276550 0.14.28 Cibacron Black B and 2040 0.0520.078 9294 7294
Cibacron Red RB
Zheng et al. [55] Single stage NF (hollow 80 0.064 99.3 Color 91.5
fiber)
Ong et al. [56] Single stage NF (hollow 500 0.25 Reactive yellow 81, 1001000 0.0030.005 98 95 80% for 0.5 g/L NaCl
fiber) Reactive black 5, Reactive
blue 19
Fersi and Dhahbi [71] Ultrafiltration followed by 3001300 0.0060.06 95 Color 20% salt
NF (flat sheet)
Ellouze et al. [72] Coagulation/flocculation 1000 0.028 100 Color 60
followed by NF (flat sheet)
Khouni et al. [73] Enzymatic catalysis, 1000 Blue Bezaktiv 150, Black 40 0.030.04 9999.8 5273 5565% for 4 g/L NaCl
coagulation/flocculation Novacron R
followed by NF (flat sheet)
Bruggen et al. [74] Single stage NF (flat sheet) 1000 Sandolan Jaune, Sandolan 0.0330.05 7485 30% for 7.8 g/L Na2SO4
Rubinol, Bleu Alizarine,
Lanasyn Jaune, Isolan Rot,
Lanasyn Bleu, Lanasyn
Bordeaux, Erionyl Black
Liu et al. [75] Single stage NF (flat sheet) 10001250 0.20.38 0.0320.045 8696
Present study Single stage NF (hollow 69138 0.120.35 CIB Y, CIB R, CIB B, BB3 67240 0.020.05 9899.8 7590 42% for 9 g/L NaCl
fiber)
 M. Mondal, S. De / Chemical Engineering Journal 285 (2016) 304318
6. Conclusions
Polysulfone based hollow fiber nanofiltration membranes were
prepared by interfacial polymerization of MPD and TMC at a higher
concentration range of TMC upto 1.0 wt%. MWCO of 360 Da was
obtained at TMC concentration 1 wt%, with a permeability of
1.14  1011 m/Pa s and the average pore radius of this membrane
was 5 . Zeta potential of the membrane prepared with 0.5 wt%
TMC was found to be negatively charged (10 mV) at pH 10. A real
textile plant effluent plant effluent containing from dyes was salt
was treated by these hollow fibers. Reactive black, red and yellow
dyes were rejected by 99.9% and that of blue dye was 98.8%, at
104 kPa TMP and 30 L/h CFR. COD of the treated stream was also
within permissible limit with salt recovery 42%. A completely pre-
dictive multi-component model was developed using osmotic
pressure and film theory equations to analyze the system perfor-
mance accurately.
Acknowledgments
This work is supported by a grant from the Board of Research in
Nuclear Sciences (BRNS), Department of Atomic Energy, Govern-
ment of India, India under the scheme No. 2012/21/03-BRNS, Dt.
25-07-2012. Any opinions, findings, and conclusions expressed in
this paper are those of the authors and do not necessarily reflect
the views of BRNS.
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