Chemical Engineering and Processing 43 (2004) 1561–1567

Removal of methyl orange dye and Na2 SO4 salt from

synthetic waste water using reverse osmosis
Nader Al-Bastaki∗
Department of Chemical Engineering, College of Engineering, University of Bahrain, PO Box 32038, Bahrain, Bahrain

Received 12 January 2004; received in revised form 5 March 2004; accepted 5 March 2004
Available online 18 May 2004

Abstract

The efficiency of reverse osmosis (RO) membranes used for treatment of colored water effluents can be affected by the presence of both salt
and dyes. Concentration polarization of each of the dye and the salt and the possibility of a dynamic membrane formed by the concentrated
dye can affect the performance of the RO membrane. The objective of the current work was to study the effect of varying the Na2 SO4 salt and
methyl orange (MO) dye concentrations on the performance of a spiral wound polyamide membrane. The work also involved the development
of a theoretical model based on the solution diffusion (SD) mass transport theory that takes into consideration a pressure dependent dynamic
membrane resistance as well as both salt and dye concentration polarizations. Control tests were performed using distilled water, dye/water
and salt/water feeds to determine the parameters for the model. The experimental results showed that increasing the dye concentration from
500 to 1000 ppm resulted in a decrease in the salt rejection at all of the operating pressures and for both feed salt concentrations of 5000 and
10,000 ppm. Increasing the salt concentration from 5000 to 10,000 ppm resulted in a slight decrease in the percent dye removal. The model’s
results agreed well with these general trends.
© 2004 Elsevier B.V. All rights reserved.

Keywords: RO; Methyl orange; N2 SO4 ; Color; Dye; Solution diffusion; Model

1. Introduction by the dye and included the effects of salt concentration

Colored wastewater is a significant source of pollution
from a number of industries, particularly the effluents re-
leased from textile dyeing processes. The wastewater from
dyeing units in a textile plant are often rich in color, contains
residuals of dyes and chemicals, and needs proper treatment
before releasing into the environment [1]. Pressure driven
membrane processes have been among the effective meth-
ods used to treat colored wastewater. Reverse osmosis (RO)
and more recently nanofiltration (NF) membranes have been
used in several studies to treat colored wastewater [2–8].
The co-existence of salt and dye in the wastewater, which
is typical in a dye-house effluent, can affect the performance
of the membrane. Koyuncu and Topacik [9] studied the effect
of dye concentrations on the salt rejection in a cross-flow
nanofiltration membrane. They developed a model for a NF
membrane which assumed the presence of a gel layer formed
polarization. The presence of a dynamic membrane (DM)
formed by the concentrated dye at the membrane has been
suggested in a number of works [9–11].
The objective of the current work was to investigate the
efficiency of a spiral wound RO process in removing color
and salt from a synthetic colored waste water using methyl
orange (MO) as a model color at different salt and dye
concentrations and different pressures. A theoretical model
was developed to predict the performance of the process
for mixed salt and dye solutions. The method followed was
generally similar to those used by Koyuncu and Topacik [9]
and Xu et al. [10]. The model was based on the solution dif-
fusion (SD) mass transport theory, where both salt and dye
concentration polarization effects were included as well as
a pressure dependent dynamic membrane resistance.
2. Experimental setup and procedures

∗ Tel.: +973-782-122; fax: +973-684-444. Fig. 1 shows a schematic diagram of the RO process
E-mail address: naderbsk@eng.uob.bh (N. Al-Bastaki). used in this work. The membrane was a FilmTec SW30

0255-2701/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.001
1562 N. Al-Bastaki / Chemical Engineering and Processing 43 (2004) 1561–1567
Fig. 1. Schematic diagram of the RO process.
spiral-wound seawater polyamide membrane with a surface
area of 2.1 m2 . The feed was prepared and mixed in a 300 l
feed tank. After passing through a cartridge filter, it is pres-
surized by the high pressure pump and delivered to the mem-
brane. The pressure is set manually by adjusting the valve
V1 at the exit of the concentrate stream. The flow rates
were measured with the installed rotameters and manually
by measuring the volume change with time. The membrane
was washed with tap water for a period of 60 min after each
experiment.
Methyl orange (C14 H14 N3 NaO3 S), which is an azo dye,
was supplied by Aldrich. The molecular weight of methyl
orange is 327.34 and the chemical structure is
(CH3)2N N N SO3Na
The dye concentration was measured using a Schimadzu
UV-Vis Spectrophotometer (UV-1601PC) at a wavelength
of 465 nm. Anhyrous sodium sulfate salt was supplied by
Fluka.
The samples were prepared using distilled water to pro-
duce solutions containing dye concentrations of 0, 500, and
1000 ppm and for each dye concentration, experiments were
repeated at sodium sulfate salt concentrations of 0, 5000,
and 10,000 ppm. The experiments were conducted at pres-
sures of 10, 20, 30, and 40 bar.
3. Theory
A theoretical model was developed to predict the perfor-
mance of the membrane based on a modification of the so-
lution diffusion mass transport theory. According to the SD
theory the water, salt, and dye fluxes, Jw , Js , and Jd , respec-
tively, are linearly proportional to the pressure and concen-
tration driving forces as follows:
Jw = Kw (P − π) (1)
Js = Ks (Cms − Cps ) (2)
Jd = Kd (Cmd − Cpd ) (3)
where Kw , Ks , and Kd are the water, salt, and dye permeabil-
ities, respectively, P is the pressure difference between the
feed and permeate sides of the membrane. π is the osmotic
pressure difference across the membrane (πm − πp ). Cms
and Cmd are the salt and dye concentrations, respectively,
at the membrane wall on the feed side of the membrane.
Cps and Cpd are the permeate salt and dye concentrations,
respectively.
As mentioned above, it has been postulated in other works
that dynamic membranes are formed by the concentrated dye
at the membrane wall [9–11]. If a dynamic membrane forms
then it is expected that the water permeability is reduced.
Thus, to account for the dynamic membrane, in the model
used in the current work, the water permeability, Kw , was
expressed in terms of the combined resistances of the two
membranes as follows:
1
Kw = M (4)
R + RDM
where RM and RDM are the resistances of the RO mem-
brane and dynamic membrane, respectively. When no dye is
present, then no RDM is present, and hence, the water perme-
ability is mainly controlled by the RM . The permeability in
this case will be referred to as Kw
M . Thus, K M is defined as
w
1
Kw
M
= (5)
RM
The relationship between the osmotic pressure and con-
centration was approximated as
π = φ1 αs Cm + φ2 αd Cd (6)
where the subscripts s and d refer to the salt and dye, re-
spectively, C is the concentration and subscript m refers to
the membrane wall. The Van’t Hoff coefficient, α, for each
of the dye and the salt was obtained as follows:
RT
α= (7)
M
where R, T, and M are the ideal gas constant, the temper-
ature, and the molecular weight of the solute, respectively.
The coefficients φ1 and φ2 are the Debye-Hückel osmotic
coefficients for the salt and dye, respectively [12]. The equa-
tions used to determine these coefficients are presented in
Appendix A. The value of the salt coefficient, φ1 , was about
0.989 while the dye’s coefficient, φ2 , was 0.999 which is
very close to unity. The program allowed for the variation in
these coefficients as the solute concentrations varied. It was
shown by Van Gauwbergen et al. [12] that the Debye-Hückel
method gave an improved osmotic pressure calculation com-
pared to the Van’t Hoff’s method which is applicable to di-
lute solutions only. They also showed that the more recent
method of Pitzer resulted in an even better prediction of the
osmotic pressure for higher concentration solutions [12].
 N. Al-Bastaki / Chemical Engineering and Processing 43 (2004) 1561–1567 1563

The salt concentration at the membrane wall, Cms , was and concentrate flow rates and concentrations. Among the
related to the bulk salt concentration, Cbs , by taking into adjusted variables were the mass transfer coefficient, the
account the concentration polarization according to the fol- Debye-Hückel coefficient and the pressure drop in the feed
lowing formula [13] channel.

 The basic membrane properties were determined first
Cms − Cps Jw
= exp (8) from control tests which were performed at pressures from
Cbs − Cps k
10 to 40 bars. The water permeability, Kw M , was obtained

The concentration polarization of the dye was calculated directly from the slope of the experimental flux versus pres-
using a similar equation: sure curve using distilled water. The remaining parameters,

 namely, the salt and dye permeabilities, Ks and Kd and the
Cmd − Cpd Jw
= exp (9) dynamic membrane resistance, RDM , were obtained from
Cbd − Cpd k control tests on salt solutions and dye solutions carried out
where Cps and Cpd are permeate salt and dye concentrations, at pressures from 10 to 40 bars. Although the method used
respectively. The mass transfer coefficient, k, was estimated in deriving these latter parameters in essence involves indi-
using an empirical mass transfer expression for a spacer rect curve fitting, it may be called back calculation of the
filled channel using the method developed by Da Costa et al. parameters. The procedure involves assuming a value of
[14]. Details of the method used for calculating k and the the required parameter, running the model and generating
dimensions of the spacer are given in [15]. the relevant curve such as salt rejection versus pressure and
The bulk salt and dye concentrations Cbs and Cbd , respec- comparing the computed curve with the experimental one
tively, were calculated by taking the respective averages of obtained from the control test. In this manner it is ensured
the feed and concentrate concentrations, assuming perfectly that all the related hydrodynamic issues such as concen-
mixed solutions tration polarization and spacer effects (incorporated in the
mass transfer coefficient and pressure drop calculations)
Cbs = 21 (Cfs + Ccs ) (10) are included. If the two curves disagree then the process is
repeated using a new set of parameters.
Cbd = 21 (Cfd + Ccd ) (11)
where the subscripts f, c, s, and d refer to the feed, concen-
trate, salt, and dye, respectively. The total and solute mate- 4. Results and discussion
rial balances were written as follows
Table 1 shows the results of the model’s membrane pa-
Qf = Qp + Qc (12) rameters, namely, Kw M , K , and K , which were determined
s d
Qf Cfs = Qp Cps + Qc Ccs (13) from experiments on distilled water, solutions of salt in wa-
ter and solutions of dye in water, respectively. The water
Qf Cfd = Qp Cpd + Qc Ccd (14) permeability coefficient, Kw M , was obtained directly from the

slope of water flux versus pressure from distilled water ex-

The performance was expressed in terms of the percent periments (using Eq. (1) with π taken to be zero). To cal-
dye removal, Rd , the percent salt removal, Rs , and the per- culate each of the salt and dye permeability coefficients, Ks
meate recovery, Rec, defined as follows: and Kd , the model had to be employed together with the ex-
Cfd − Cpd perimental results, to back-calculate each property in an it-
Rd = 100 × (15)
Cfd erative method. Fig. 2 shows the experimental recovery and
salt rejection versus pressure curves which were used to de-
Cfs − Cps rive Ks . The procedure used was to iterate on the value for
Rs = 100 × (16)
Cfs Ks until the theoretical and experimental salt rejection and
Qp recovery versus pressure curves showed a good agreement,
Rec = 100 × (17)
Qf
Eqs. (1)–(14) were solved simultaneously (together with Table 1
Eq. (A1) in Appendix A and the equations for the mass Membrane parameters derived from experiments using the model
transfer coefficient and spacer channel, both of which are Parameter Value
given in [15]) using Mathcad’s solver block. Reasonable
estimates of the initial values for all the adjusted variables Kw
M (m2 s/kg) (from distilled 6.593 × 10−12
water experiments)
are necessary to arrive at converged iterations. The fixed Ks (m/s) 4.2 × 10−8
variables were the feed flow rate, feed salt concentration, Kd (m/s) 3.2 × 10−9
feed dye concentration, feed temperature, and feed pressure. RM (kg/(m2 s)) (membrane resistance) 1.517 × 1011
The main adjusted variables obtained by iteration using the RDM (kg/(m2 s)) (dynamic membrane 4.11 × 1010 e1.25E−7P
model included the bulk concentrations and the permeate resistance, P in Pa)
1564 N. Al-Bastaki / Chemical Engineering and Processing 43 (2004) 1561–1567

60 40
104 Experimental Salt Rejection Expriment, 1000 ppm dye
Model, salt rejection Model, 1000 ppm dye
102 Experimental Recovery Model, 1000 ppm dye, no DM
Salt Rejection, %

Model, recovery 30
Recovery, %

100 40
Recovery, %

98
20
96
20
94
10
92

90 0
0 10 20 30 40 50 0
0 10 20 30 40 50
P, atm
P, Pa
Fig. 2. Calculation of Ks : comparison of experimental and model results
of salt rejection and recovery for a feed concentration of 10,000 ppm Fig. 4. Comparison of experimental recovery for 1000 ppm dye concentra-
Na2 SO4 , with no dye added. tion, with the model with no dynamic membrane, and dynamic membrane
of varying resistance.

as seen in Fig. 2. The value of Ks obtained by this procedure

is given in Table 1. the theoretical water recovery is reduced. Thus, the values
In a similar method, the Kd value shown in Table 1 was of RDM were calculated by iteration from the experimental
determined from experiments on 1000 ppm concentration results for feed solutions containing 1000 ppm of dye. The
dye–water solutions (with no salt added). By iteration, the difference between the theoretical and experimental water
value of Kd was arrived at by comparing the theoretical dye recoveries was used as a measure to check for the conver-
removals calculated using the model at various pressures gence of the calculation, as shown in Fig. 4. The RDM val-
with the experimental values until a good agreement was ob- ues extracted by this procedure exhibited an increasing trend
tained between the two dye removal versus pressure curves, with pressure. The dependence on pressure was expressed
as shown in Fig. 3. The model results shown in Fig. 3 in- as an exponential function, as given in Table 1.
cludes two different cases, namely, the case when no dy- The results of tests on solutions containing mixtures of
namic membrane resistance is assumed and the case with a both salt and dye are given in Figs. 5–10. Figs. 5 and 6
dynamic membrane of a varying resistance is assumed. The show the experimental and theoretical permeate flux versus
difference between the two cases appears to be small. pressure curves obtained from experiments on mixtures con-
Fig. 4 shows the permeate recovery results using the Kd taining 1000 and 500 ppm dye concentrations, respectively.
value measured by the above procedure when zero dynamic Each graph shows results for mixtures with salt concentra-
membrane, RDM , in Eq. (4) is assumed. In other words, Kw tions of 5000 and 10,000 ppm. As expected, in both graphs
is assumed to be the same as Kw M . It is obvious that the model a slight decrease in the flux can be noticed as the salt con-
over-estimates the recovery when no dynamic membrane re- centration is increased. Similarly, the theoretical flux values
sistance is assumed. When RDM is included in Eq. (4) then exhibit lower values as the salt concentrations are increased.

20x10-6
100.5 Experiment, 5000ppm salt
Model, 5000ppm salt
Experiment, 10000ppm salt
Permeate Flux, m/s

15x10-6 Model, 10000ppm salt

Color Removal, %

100.0
10x10-6

99.5 5x10-6
Experiment, 1000 ppm dye
Model, 1000 ppm dye
Model, 1000 ppm dye, no DM
0
99.0 0 10 20 30 40 50
0 10 20 30 40 50
P, atm
P, atm
Fig. 5. Comparison of the experimental and theoretical permeate flux
Fig. 3. Comparison of experimental dye removal for a feed with 1000 ppm values for feed solutions containing 1000 ppm dye and Na2 SO4 salt
dye and no salt (used for the calculation of Kd ). concentrations of 5000 and 10,000 ppm.
 N. Al-Bastaki / Chemical Engineering and Processing 43 (2004) 1561–1567 1565

2.5e-5 100.0
Experiment, 5000ppm salt
Model, 5000ppm salt
2.0e-5 Experiment, 10000ppm salt
Permeate Flux, m/s

Model, 10000ppm salt

Dye Removal, %

1.5e-5 99.8

1.0e-5 Experiment, 10000 ppm salt

Model, 10000 ppm salt
Experiment, 5000 ppm salt
5.0e-6 99.6 Model, 5000 ppm salt

0.0
0 10 20 30 40 50 0 10 20 30 40 50
P, atm P, bar
Fig. 6. Comparison of the experimental and theoretical permeate flux Fig. 9. Dye removal for solutions containing 1000 ppm dye and different
values forfeed solutions containing 500 ppm dye and NaSO4 salt concen- salt concentrations.
trations of 5000 and 10,000 ppm.

Figs. 7 and 8 show salt rejections for solutions with salt

concentrations of 5000 and 10,000 ppm, respectively. It can
100 be seen that increasing the dye concentration from 500 to
1000 ppm resulted in a slight decrease in the salt rejection
for solutions of both salt concentrations. This effect was
99
Salt Rejection, %

more pronounced for the higher salt concentration solutions.

The theoretical results generally show a good agreement
with the experimental results, particularly with respect to
98
the dependence of salt rejection on pressure.
500 ppm dye, experiment Figs. 9 and 10 show the effect of salt concentration on the
1000 ppm dye, experiment
97 Model, 500 ppm dye
percent dye removal for feed solutions containing 1000 and
Model,1000 ppm dye 500 ppm dye, respectively. It can be seen that in both cases
the experimental percent dye removal for the 5000 ppm salt
96 solutions are slightly higher than the 10,000 ppm salt solu-
0 10 20 30 40 50 tions. This difference is more pronounced for the 500 ppm
P, bar dye concentration solutions. The theoretical predictions
show a trend which agrees with the experimental obser-
Fig. 7. Effect of dye concentration on salt rejection for solutions of salt
concentration of 5000 ppm. vations, i.e. higher dye removals for the 5000 ppm salt
concentration solutions and lower dye removals at lower
pressures.

100
100.0

99
Salt Rejection, %

Dye Removal, %

99.8
98

500 ppm dye, experiment

1000 ppm dye, experiment
97 Model, 500 ppm dye Experiment, 10000 ppm salt
Model, 1000 ppm dye 99.6 Model, 10000 ppm salt
Experiment, 5000 ppm salt
Model, 5000 ppm salt
96
0 10 20 30 40 50 0 10 20 30 40 50
P, bar P, bar
Fig. 8. Effect of dye concentration on the salt rejection for 10,000 ppm Fig. 10. Dye removal for solutions containing 500 ppm dye and different
concentration solutions. salt concentrations.
1566 N. Al-Bastaki / Chemical Engineering and Processing 43 (2004) 1561–1567

5. Conclusions Nomenclature
C salt concentration (kg/m3 )
The experimental results showed that increasing the dye J flux (m3 water/(m2 s) or kg salt/(m2 s))
concentration from 500 to 1000 ppm resulted in a decrease Kw water permeability of combined RO/dynamic
in the salt rejection for all of the operating pressures and membrane (m/(s Pa) or m2 s/kg)
for both feed salt concentrations of 5000 and 10,000 ppm. Kw M water permeability of the RO membrane
The percent dye removal for the 50,000 ppm salt solutions (m/(s Pa) or m2 s/kg)
were slightly higher than those obtained with the 10,000 ppm Ks solute (salt) permeability (m/(s Pa) or m2 s/kg)
salt solutions. The model’s results agreed with these general Kd dye permeability (m/(s Pa) or m2 s/kg)
trends. The use of the model in collaboration with experi- k mass transfer coefficient (m/s)
mental results on distilled water, salt–water and dye–water m molality (moltes solutes/kg solution)
solutions made it possible to determine the permeability co- P pressure difference between the feed and
efficients for water, Na2 SO4 salt, and methyl orange dye as permeate sides of the membrane (Pa)
well as the pressure dependent dynamic membrane resis- Q volumetric flow rate (m3 /s)
tance. R salt rejection
RDM resistance of dynamic membrane (kg/m2 s)
Rec recovery
Acknowledgements R M resistance of RO membrane (kg/(m2 s))
zi ionic charge
The author would like to express his gratitude to the Re-
search Deanship, University of Bahrain for the financial sup- Greek letters
port for this work. Thanks are also due to Mrs. Eman Mansur, α Van’t Hoff’s coefficient for calculating the
technician in the chemical engineering department, for her osmotic pressure
assistance in conducting the experiments. ε dielectric constant of the solvent (water) (F/m)
φ Debye-Hückel’s osmotic coefficient
π osmotic pressure difference across the membrane
Appendix A (Pa)
νi number of moles of ion derived from 1 mol
The osmotic coefficient, φ, according to the Debye-Hückel of solute
theory [12] was calculated as follows:
 Subscripts
1 ln(10)Aγ |z1 z2 | K1/2 m3/2 σ[Ba(Km)1/2 ]
φ−1 = − b bulk
m 3 c concentrate

bK d dye
+ m2 (A1) f feed
2
m membrane wall
where zi are ionic charges, m is the molality, ε is the dielectric p permeate
constant of water (78.5 F/m) and the coefficients are defined s salt
as follows:
1.8246 × 106
Aγ = (A2)
(εT)3/2 References
1
K= νi z2i (A3) [1] S. Chakraborty, M.K. Purkait, S. DasGupta, S. De, J.K. Basu,
2
i Sep. Purif. Technol. 31 (2003) 141.
[2] N. Al-Bastaki, F. Banat, Resour., Conservation Recycl., 41 (2004)
where νi is the number of moles derived from 1 mol of solute. 103.
  [3] K. Treffry-Goatley, C. Buckley, G. Groves, Desalination 47 (1983)
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(εT)3/2 609.
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in Eq. (A1) was taken to be 1 [12]. [10] X. Xu, J.L. Gaddis, H.G. Spencer, Desalination 129 (2000) 237–245.
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