Desalination 465 (2019) 94–103

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Desalination
journal homepage: www.elsevier.com/locate/desal

Anion exchange membrane organic fouling and mitigation in salt T

valorization process from high salinity textile wastewater by bipolar
membrane electrodialysis
Yifru Waktole Berkessaa,b, Qiaolin Langa,b, Binghua Yana,b, Shaoping Kuanga, Debin Maob,
Li Shuc, Yang Zhanga,b,
⁎

a
College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
b
Waste Valorization and Water Reuse Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Laoshan
District, Qingdao 266101, China
c
School of Engineering, RMIT University, Melbourne, VIC 3000, Australia

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: To achieve a cleaner production, textile wastewater with high organic and salt content can be treated by using
Critical salt concentration Bipolar Membrane Electrodialysis (BMED) to minimize acid and base consumption in a dyeing process. While the
Zeta potential dye molecules may foul the ion exchange membranes and strongly affect the desalination process. This work
Membrane fouling aimed to investigate the performance and fouling mechanisms of BMED during desalination of sodium sulfate
Charged foulants
from Remazol Brilliant Blue R (RBBR). Results showed that maintaining the zeta potential of RBBR above
Bipolar membrane electrodialysis
Textile wastewater
−25 mV may mitigate fouling of AEM during the BMED process. This confirms that, zeta potential of charged
foulants (RBBR) plays a key role in terms of controlling membrane fouling. Accordingly, a new parameter
“critical salt concentration” was introduced to control membrane fouling. Furthermore, energy dispersive X-ray
spectroscopy (EDS), FT-IR and electrochemical analysis confirmed that fouling of anion exchange membrane by
RBBR was due to electrostatic interaction. Finally, it was calculated that 72.02% of sodium and 66.9% of sulfate
in the feed were converted to NaOH and H2SO4, respectively. This study proves that BMED process may be an
alternative way treating textile wastewater with high salinity and the presence of dye molecules.

⁎
Corresponding author at: College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China.
E-mail address: zhangyang@qibebt.ac.cn (Y. Zhang).

https://doi.org/10.1016/j.desal.2019.04.027
Received 13 November 2018; Received in revised form 7 March 2019; Accepted 23 April 2019
Available online 08 May 2019
0011-9164/ © 2019 Published by Elsevier B.V.
Y.W. Berkessa, et al.
1. Introduction
The water consumption of textile industry is estimated to be be-
tween 200 and 500 m3 per ton of dyed textile product [1]. Most im-
portantly, 90% of the water consumption in textile industry goes to
processing, [2] which results in a large volume of wastewater that
mainly consists of waste dye as high as 1.5 g/L [3] and high salinity of
5–6% NaCl and 5% Na2SO4 [1,3]. A group of dyes called anthraquinone
dyes are known to have low fixation rate of ~50%, which leads to high
dye concentration in the effluent from textile industry [4]. The low
fixation rate of anthraquinone dyes in general and Remazol Brilliant
Blue R (RBBR) in particular demands addition of even higher salt
concentration to enhance dye fixation rate, this results in a higher
salinity in the effluent [2]. Direct discharge of effluent from textile
industry is detrimental to the aquatic environment due to its impact on
photosynthetic activity [5], bioaccumulation [6] and adsorption to
microbes resulting in reaction with biologically important molecules
[7]. Thus, the challenge related to effluent from textile industry needs
to be addressed in view of sustainable production of textile without
polluting the environment.
Conventional textile wastewater treatment methods focus on the
removal and decolorization of dye molecules by using biological
treatment, advanced oxidation based processes, adsorption or coagu-
lation [8–12]. Besides the aforementioned conventional treatment
methods, recent works revealed the possibility of valorizing textile
wastewater by standalone as well as integrated methods, e.g. tight ul-
trafiltration [13] and electrodialysis (ED) [14], nanofiltration in-
tegrated with bipolar membrane electrodialysis [1] and reverse os-
mosis-advanced oxidation-bipolar membrane electrodialysis [15]. ED
was reported to be effective in desalinating sodium chloride from dye
wastewater, yet a high energy requirement is needed as a pre-con-
centration method (to 150–200 g/L NaCl) prior to evaporation and
crystallization process to recover or dispose solid salt. In addition, solid
salt disposal is not a preferable way in view of its disposal expenditures
and potential environmental impacts. BMED offers special advantage
over ED since it simultaneously converts salt to acid and base, this
suggesting an economic value of BMED for desalination of high salinity
textile wastewater. Moreover, the converted acid and base may be re-
cycled in the dyeing process and the waste salt disposal can be avoided.
However, ion exchange membrane fouling caused by dye molecules
is still a main obstacle and the properties and functionalities of the
membranes can be shifted due to electrostatic interaction of these
charged dye molecules with membranes [14]. Furthermore, literature
report revealed aromatic compounds may cause severe organic fouling
of ion exchange membranes due to hydrophobic interaction [15–17]. It
is reported that acid blue-19 fouled anion exchange membrane (AEM)
showed selectivity to monovalent ions over divalent ions during desa-
lination of mixture of NaCl, Na2SO4 and acid blue-19 using electro-
dialysis [18]. The selectivity developed due to organic fouling of AEM
dictates the difficulty of desalinating divalent ions from textile waste-
water mainly when the effluent contains mixture of monovalent and
divalent salts. Likewise, Lee et al. [16] reported negatively charged
foulants with high adsorption capacity can significantly affect the
performance of electrodialysis desalination process by forming irre-
versible fouling. Studies on fouling behavior of AEM rely on using
standard foulants such as Bovine Serum Albumin (BSA), humate and
Sodium Dodecyl Benzene Sulfonate (SDBS) [16,19,20], and aromatic or
aliphatic organic foulants with various alkyl chain lengths [21].
By far, fouling mechanism of AEM in view of desalinating high
salinity textile wastewater using bipolar membrane electrodialysis
(BMED) has not been given due attention. In this study, production of
sulfuric acid and sodium hydroxide from direct desalination and con-
version of salt in the saline textile wastewater were performed.
Concomitantly, fouling mechanism of the anion exchange membrane
caused by negatively charged dye molecules (RBBR) was investigated.
Factors that affect the membrane fouling such as feed pH, salt
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Desalination 465 (2019) 94–103
Fig. 1. Molecular structure of RBBR with molecular formula
C22H16N2Na2O11S3 (625.5 Da).
concentration, feed surface velocity and RBBR concentration were as-
sessed. Furthermore, fouling characteristics of RBBR and its interaction
with AEM in terms of zeta potential, electrochemical impedance spec-
troscopy (EIS), membrane resistance, and on line stack voltage mon-
itoring were undertaken to study the fouling mechanisms in detail. As a
result, a concept of “Critical Salt Concentration” was proposed to il-
lustrate the correlation between salt concentration and membrane
fouling tendency caused by charged organic compounds in BMED
process. This concept is expected to provide a guideline to desalinate
water containing charged organic molecules by electromembrane pro-
cesses in various industrial applications.
2. Method and material
2.1. Chemicals and instruments
Remazol Brilliant Blue R (~50% pure) was purchased from
Shanghai Yuanye Bio-Technology Co., Ltd (Fig. 1). The ion exchange
membranes were purchased from Hefei Chemjoy Co., Ltd., China.
Analytical grade anhydrous sodium sulfate (99% pure), NaOH and
H2SO4 were bought from Sinopharm Chemical Reagent Co., Ltd.
2.2. BMED set-up
The electrodialysis stack used in this work was manufactured by
Hefei Chemjoy Co., Ltd., China. Heterogeneous bipolar membrane
(BPM) was manufactured by MEGA A.S., Czech Republic. The BPM had
a thickness of 500 μm. Two triplets of membranes were used during all
experiment runs with three chambers; namely, acid, feed (diluate) and
base chambers as indicated in Fig. 2. Three, two and two pieces of
heterogeneous bipolar membranes (BPM), cation exchange membranes
(CEM) and anion exchange membranes (AEM) were installed in the
stack, respectively. The effective area of each membrane was 94.5cm2.
The ED stack consisted of electrode materials made of titanium coated
with iridium. The thickness of the polypropylene spacer used in the
stack was 0.79 mm. Characteristics of CEMs and AEMs provided by the
manufacturer were presented in the Table 1.
2.3. Evaluation of BMED performance
2.3.1. Desalination rate
The desalination ratio of ions during BMED experiment was calcu-
lated:
Ci Cf
Desalination ratio (%) = × 100
Ci (1)
where Ci and Cf refer to initial and final salt concentration, respectively.
2.3.2. Current efficiency (η)
Current efficiency of the BMED process was calculated according to
the following equation [23].
ZFV C
= × 100
NIt (2)
−1
where η: current efficiency, F: Faraday constant (A-s∙mole ), z: charge
of the ion, V: initial volume (L), ∆C: change in diluate concentration
Y.W. Berkessa, et al. Desalination 465 (2019) 94–103

Fig. 2. Schematic diagram of the BMED stack configuration used in this study.

Table 1 2.6. Zeta potential of RBBR molecules

Properties of the cation exchange and anion exchange membranes.
Parameters CEM AEM
The zeta potential of RBBR molecule was determined using dynamic
light scattering technique by Zetasizer series Nano ZS from Malvern
Thickness (μm) 180–210 140–160 Instruments, UK. The samples were prepared by dissolving 0.25 g/L
Ion exchange capacity (meq/g) 0.8–1.0 0.5–0.6 RBBR and varying concentrations of Na2 SO4 (0%, 0.5%, 1%, 5% and
Water content (%) 40–50 15–20
10%) were dissolved in ultrapure water. The pH of RBBR synthetic
Blasting strength (MPa) > 0.35 > 0.35
Membrane resistance (Ωcm2) 2.5–3.5 3.5–4.5 wastewater samples were adjusted to the required pH by 0.1 M HCl and
Ion transport number > 0.93 > 0.93 0.1 M NaOH. Furthermore, water was used as dispersant during mea-
surement of RBBR zeta potential and the viscosity of RBBR solution was
0.887. The refractive index and dielectric constants of the dispersant
(mol∙L−1), N: number of cell triplets, I: applied current (A) and t: time were 1.33 and 78.5, respectively. Disposable folded capillary cells
(s). (DTS1070) were injected with 1 mL samples and installed on Nano ZS.
The zeta potential measurements were undertaken at room temperature
(25 °C) where triplicate measurements were made and average values
2.4. Nyquist plot of clean and fouled membrane were reported.

The alternating current (AC) impedance measurements were carried
out in a two chamber electrodialytic cell and separated by the measured
membrane with effective area of 7.1 cm2. Flow rate of 60 mL/min was
applied to circulate solutions in the chambers. Two Ag/AgCl planar
electrodes with projected area of 1.0 cm2 were used as reference elec-
trodes, fixed near to IEM surface. Sinusoidal AC were supplied by an
electrochemical workstation (CHI660E, CH Instrument Co., LTD,
Shanghai, China), with amplitude of 10 mV and frequency range of
10−1-105 Hz. 0.5 M NaCl solution was used as electrolyte.
2.5. Ion transport number measurement
The ion transport through ion exchange membranes in this work
was calculated using the following formula [24]:
RT C1
Em = (2t 1) ln
F C2
where, Em = voltage measured across the membrane. R, T and F were
molar gas constant, temperature and Faraday's constant.
Em = E E0
where, E = voltage measured between two concentrations of solution
(0.01 M and 0.05 M Na2SO4) and E0 was the voltage measured in the
same concentration of solution (0.01 M).
2.7. Analytical methods
The conductivity and pH of samples at all stages of the experiment
were measured by conductivity meter (FG3-ELK, Mettler-Toledo
Instruments Co. Ltd., USA) and pH meter (FG2, Mettler-Toledo
Instruments Co. Ltd., USA), respectively. Measurement of direct current
supply was recorded using DC power source (MCH-k305D, Shenzhen,
China). Measurement of voltage difference between electrodes during
resistance measurement was recorded using digital multimeters (model:
UT39A/B/C, UNI-T technology Co., Ltd., Donggua, China). The ion
transport number of AEM samples was measured using electrochemical
work station from CH instruments (CHI660E, Shanghai, China) and ion
exchange membrane (IEM) resistances were measured using Chemjoy
resistance cell (CJ-AMD-01, Chemjoy Polymer Materials Co., Ltd.,
Hefei, China).
The concentrations of sulfuric acid and sodium hydroxide produced
from BMED experiment were determined using titration method. 0.1 M
(3)
NaOH and 0.1 M H2SO4 were used as titrant solutions to determine the
concentrations of sulfuric acid and sodium hydroxide at stoppage time
of BMED experiment, respectively.
Scanning electron microscopy (SEM) technique was used to quali-
(4) tatively characterize foulant layer on fouled AEM samples. Pristine and
fouled membrane samples were prepared before SEM imaging by
coating with a thin layer of gold in order to reduce membrane surface
charge. SEM images of the membrane surface were taken at voltage of
5 kV using the Hitachi S-4800, Japan. Moreover, Energy-dispersive x-

96
Y.W. Berkessa, et al.
Fig. 3. Effect of RBBR concentration on BMED performance.
ray spectroscopy (EDS) was used to quantitatively determine the atom
composition on the pristine and fouled AEM samples at an approximate
penetration depth of 2-5 μm. Furthermore, the expected changes in
functional groups on pristine and fouled AEMs were analyzed using
Fourier transform infrared spectroscopy (FTIR) at a penetration depth
of 0.8 μm (Thermo Scientific™ Nicolet™ iN™10, China).
3. Result and discussion
3.1. Desalination performance of BMED
3.1.1. Effect of RBBR concentration on BMED performance
RBBR concentration was found to adversely affect BMED perfor-
mance, where desalination performance for the same initial Na2SO4
concentration (5%) under 3A applied current decreased from 97.7% to
70% (based on conductivity decrease in feed chamber) with increasing
RBBR concentration from 0 g/L to 1 g/L, as presented in Fig. 3a. This
can be explained by the facts that RBBR molecules are negatively
charged and also the aromatic structure interacts with AEM through
hydrophobic interaction [18]. Apart from the decreasing desalination
performance, with increasing RBBR concentration from 0 to 0.25 g/L
the operation time increased from 3.5 h to 4.0 h as indicted in Fig. 3a.
This is due to the fact that with the increase in dye concentration, a
higher stack resistance was built up (Fig. 3b) due to increasingly
dominant effect of organic fouling. It forced the system shutdown after
3.5 h operation since the voltage reached 30 V. The effect of RBBR
concentration (0 g/L, 0.25 g/L and 1 g/L) on BMED desalination per-
formance revealed that the final diluate conductivity was adversely
affected by the RBBR concentrations. 0.78mS/cm, 3.69mS/cm and
13.02mS/cm of the final diluate were obtained with the above men-
tioned RBBR concentrations in the respective order at stoppage time of
BMED process where the stack voltage reached 30 V (Fig. 3a & b). It was
97
Desalination 465 (2019) 94–103
also found that RBBR did not present in the acid or base streams, this
indicates that RBBR molecules (MW 625.5 Da) could not penetrate
through the anion/cation exchange membranes.
Fig. 3c shows the correlations between the conductivity of the final
diluate and RBBR concentration (5% Na2SO4 in the initial feed). A
linear correlation (R2 = 0.99) between the RBBR concentration and the
corresponding conductivity of the final diluate was found in Fig. 3c.
This could be attributed to increased intensity of forming fouling layer
caused by accumulation of RBBR onto the membrane surface corre-
sponding to increased RBBR in the initial feed. In other words, the final
salt concentration in the diluate that can be achieved by BMED is a
function of the RBBR concentration in the feed. Consequently, a con-
cept of “critical salt concentration” is proposed to correlate the final salt
concentration in BMED and the RBBR concentration in the feed. “Cri-
tical salt concentration” refers to the salt concentration below which
desalination cannot proceed as a result of organic fouling by charged
organic molecules.
3.1.2. Effect of anion species and salt concentration
Low salt concentration (< 0.5 M) was found to increase membrane
stack resistance and in turn cause transport limitation [25]. As seen in
Fig. 4a, the decrease in conductivity of diluate for NaCl and Na2SO4 as a
function of time showed a similar trend and endpoint (~3.5mS∙cm−1)
in view of the diluate conductivity. On the other hand, a similar end-
point (~3.5mS∙cm−1) is also found when different initial salt con-
centration (1% and 5% Na2SO4) was experimented, as seen in Fig. 4c.
This may indicate that AEM fouling by RBBR was mainly influenced by
the diluate conductivity, while the fouling tendency is regardless of
anion spices (chloride or sulfate). The dominant effect of AEM fouling
by RBBR at low salt concentration could be attributed to the decreased
shielding effect of salt on RBBR allowing increased interaction with
AEM.
Y.W. Berkessa, et al.
Fig. 4. Effect of initial salt concentration on BMED performance. a and c, conductivity variation with operation time. b and d, voltage profile with operation time.
The applied current for a and b was 1A, I = 3A for c and d.
This work however contradicts with a previous report where a dif-
ferent fouling tendency was found on AEM fouling by acid blue-9 with
the presence of chloride over sulfate (21 and 36 mmol∙L−1, respec-
tively) [14]. The reason for the difference may attribute to the fact that
the feed conductivity was well below the “critical salt concentration”,
therefore the negatively charged fouling layer formed by blue-9 im-
proved the monovalent anion selectivity.
On the other hand, voltage was recorded to show the evolution of
stack resistance as a function of time during the experiment, as seen in
Fig. 4b. The fact that ion transport was hindered by membrane fouling
can be further confirmed by comparing Fig. 3b (5% Na2SO4 with 0 g/L
RBBR) and Fig. 4b (5% Na2SO4 with 0.25 g/L RBBR) where the stack
voltage was stable until the membrane was fouled by RBBR when the
salt concentration was lowered. This resulted in an insufficient desali-
nation due to the stack voltage increased above 30 V, as seen in Fig. 4
(5% Na2SO4 with 0.25 g/L RBBR).
3.1.3. Effect of surface flow velocity
Concentration polarization in the diluate chamber of BMED is
controlled by diffusion and migration [26]. The development of con-
centration polarization and affinity of RBBR to AEM may have sy-
nergistically acted together to increase resistance to permeation of
sulfate especially at low salt concentration. Hence, feed surface flow
velocity was assessed to investigate its impact on the performance of
BMED. The result reveled that low feed surface flow velocity (4.17 cm/
s) registered the lowest performance compared to the other two higher
surface flow velocities (8.35 cm/s and 12.52 cm/s) as presented in
Fig. 5a. Moreover, the electrochemical stack resistance presented as
voltage profile also proved higher stack voltage at lower feed surface
flow velocities and vice versa (Fig. 5b). In conclusion, a higher flow rate
was found to reduce the stack resistance which may attribute to
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Desalination 465 (2019) 94–103
destabilization of the RBBR fouling layer and the concentration polar-
ization layer at higher flow rates. Hence, 8.35 cm/s was chosen as op-
timal feed surface flow velocity to run all experiments in this work.
3.1.4. Effect of feed pH
The effect of feed pH on BMED performance revealed that relatively
low stack voltage and stable operation were achieved at lower pH
(pH = 3.0) compared to pH 7.0 and 11.0, as shown in Fig. 6. The lower
stack resistance at pH 3.0 may be attributed to protonation of RBBR
molecules depicting less interaction with AEM and hence low fouling
tendency compared to pHs 7.0 and 11.0 (Fig. 6a). Moreover, there was
proton leakage from acid chamber to feed chamber which might have
resulted in opening of ion transport channels blocked by dye molecules
and/or dissolving the RBBR adsorbed on the membrane surface.
On the other hand, the surface charge of RBBR molecules becomes
increasingly negative at pH 7.0 and 11.0 due to less protonation at
higher pH as opposed to pH 3. The increasingly negative surface charge
of RBBR could explain the high stack voltages for pH 7.0 and 11.0
which arise from stronger electrostatic and hydrophobic interactions
between RBBR and AEM compared to similar phenomenon at pH 3 (the
above mentioned results will be further quantitatively analyzed and
explained in Section 3.2). Further, high pH is well known to facilitate
gel formation and/or precipitation which might in this case relate to
suppression of proton effect due to continuous addition of hydroxide
ion to maintain high pH (7.0 and 11.0). In conclusion, better BMED
performance was observed at pH 3 compared to pH 7 and 11 due to less
interaction of RBBR with AEM at pH 3 and hence showed lower fouling
tendency.
Y.W. Berkessa, et al.
Fig. 5. Effect of feed flow rate on performance of BMED during desalination of sodium sulfate from RBBR based synthetic wastewater (Na2SO4 concentration in feed
chamber was 5% and the applied current was 3A).
3.2. Zeta potential of RBBR
Membrane fouling mechanisms in electromembrane processes pre-
dominantly depends on electrostatic interaction between the IEMs and
foulants [30]. Hence, zeta potential measurement of RBBR molecules
was undertaken to understand the fouling phenomena during BMED
process. Fig. 7a and b show the trends of RBBR zeta potential as a
function of salt concentration at constant pH and pH effect on zeta
potential at constant salt concentration, respectively. The zeta potential
of RBBR was found to become increasingly negative (−16.75 mV,
−23.1 mV, −33.7 mV and −58.3 mV) corresponding to decreasing of
Na2SO4 concentration (10%, 5%, 1%and 0%) at 0.25 g∙L−1 RBBR and
constant pH = 3 as indicated in Fig. 7a. The increasingly negative zeta
potential of RBBR with corresponding decrease of Na2SO4 concentra-
tion might be due to the decreased shielding effect of Na2SO4 on RBBR
molecules. Further, the increasingly negative zeta potential of RBBR at
low Na2SO4 concentration may explain the high stack resistance of
desalinating Na2SO4 from RBBR at low salt concentration due to the
dominant effect of AEM fouling by RBBR as indicated in Fig. 7a.
On the other hand, the effect of feed solution pH on zeta potential of
RBBR was presented in Fig. 7b. The result revealed that effect of pH on
zeta potential was minimal at 5% Na2SO4 where zeta potential of RBBR
showed slight change from −15.2 mV to −19.2 mV corresponding to
change in pH from 1 to 11, respectively (Fig. 7b). On the contrary,
significant change in zeta potential of RBBR was observed at 0.5%
Na2SO4 where the zeta potential of RBBR decreased from −18.83 mV
to -42 mV corresponding to pH increase from 1 to 11, respectively
Fig. 6. Effect of feed pH on BMED performance, (a) conductivity profile of feed chamber; (b) stack voltage profile (Na2SO4 concentration in feed chamber was 5%
and concentration of RBBR was 0.25 g/L, I = 3A).
99
Desalination 465 (2019) 94–103
(Fig. 7b). Thus, the effect of pH on zeta potential of RBBR was sig-
nificant when concentration of Na2SO4 decreased from 5% to 0.5% at
similar pH (pH = 3) where the corresponding zeta potential values
were −18.9 and −35 mV, respectively. According to the membrane
fouling results from Section 3.1.2 and Section 3.1.4, membrane fouling
can be mitigated under a higher salt concentration or/and a lower pH.
These findings may be further linked with the above mentioned zeta
potential measurement of RBBR and a “critical zeta potential” (around
-25 mV) can be drawn in Fig. 7 to manipulate membrane fouling from
engineering aspect.
Lee et al. [16] reported the zeta potentials of standard organic
foulants as humate, BSA and SDBS (measured in 10 mM KCl at constant
pH values of 6.5 ± 0.3 and room temperature) were − 8.2 ± 3.1 mV,
−25.3 ± 4.5 mV, and − 26.9 ± 5.3 mV, respectively. Nevertheless,
the zeta potential of RBBR measured in 35 mM Na2SO4 at pH 7 was
−38.75 mV, which was more negative compared to the standard fou-
lants mentioned above. This justifying the possibility of stronger elec-
trostatic interaction between RBBR and AEM. Thus, it can be concluded
that initial salt concentration played a vital role in controlling the
fouling behavior RBBR towards AEM. Furthermore, it can be further
induced that when the zeta potential of RBBR was above the critical
zeta potential (−25 mV), the likelihood of AEM fouling can be miti-
gated. Hence, it is recommended to maintain the zeta potential of RBBR
above −25 mV to control AEM fouling and improve BMED perfor-
mance in industrial application of this work.
Y.W. Berkessa, et al. Desalination 465 (2019) 94–103

-10
(a) (b)
-20
Zeta potential (mV)
-30
pH effect at 5% Na2SO4
Zeta potential of RBBR pH effect at 0.5% Na2SO4
-40

-50

-60

0 20 40 60 80 100 0 2 4 6 8 10 12
-1
Concentration of Na2SO4 (g L ) pH

Fig. 7. Zeta potential of RBBR a, Effect of Na2SO4 concentration on RBBR zeta potential (pH = 3 and RBBR concentration = 0.25 g/L) b, Effect of pH on RBBR zeta
potential at different Na2SO4 concentration. Red dash line: “critical zeta potential”.

3.3. Fouling mechanism and the effect on desalination
According to the above presented results, schematic diagrams of
membrane fouling mechanism are presented in Fig. 8a & b. As illu-
strated in Fig. 8a, permeation of sulfate and retention of RBBR are in-
fluenced by the feed pH under 5% of Na2SO4 and 0.25% of RBBR. The
increase in sulfate rejection (leads to a high stack resistance) from pH 3
to 11 is attributed to the formation of a negatively charged layer as the
increased affinity of AEM to RBBR molecules through electrostatic in-
teractions. This mechanism can be confirmed by Section 3.1.4 and
Fig. 6b, the stack voltage (represents the stack resistance) was sig-
nificantly higher when the feed pH was 11 than that under a lower pH.
On the other hand, the influence of RBBR concentration to the de-
salination of sulfate is schematically presented in Fig. 8b. As reported in
Section 3.1.1, a higher RBBR concentration resulted in a higher sulfate
rejection due to severe fouling of AEM, and this leaded to a higher stack
resistance (Fig. 3b). The increasing fouling tendency as a function of
increasing RBBR concentration brought about increased salt con-
centration in the final diluate. The final salt concentration that varied
with RBBR concentration was named “critical salt concentration”. The
critical salt concentration was found to have a linear (first order) cor-
relation with RBBR concentration (Figs. 3c & 8b). This first order cor-
relation is inferred to be induced by the accumulation of RBBR mole-
cules with a “gel layer” formation on the anion exchange membrane

Fig. 8. Schematics of RBBR fouling mechanism with the presence of sulfate ion as a function of (a) pH of the feed and (b) RBBR concentration in the feed.

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Y.W. Berkessa, et al.
Table 2
Ion transport number of the pristine and fouled membranes.
Membrane type Transport number
Pristine AEM 0.99 ± 0.04
Fouled AEM 0.85 ± 0.04
surface. The gel layer thickness was only dependent on the RBBR
concentration and thus resulted in a proportional relationship with the
sulfate transport and the final salt concentration.
3.4. Ion transport number and electrochemical analysis
Ion transport number was measured on pristine and fouled AEMs to
evaluate fouling severity by RBBR. The result showed that ion transport
number decreased from 0.99 ± 0.04 to 0.85 ± 0.04 after RBBR
fouling (Table 2). Lee et al. [16] reported organic fouling of AEM by
humate, BSA and SDBS resulted in decrease of ion transport number
from 0.96 for pristine membrane to 0.94, 0.93 and 0.92 for fouled
membranes, respectively. The decrease in ion transport number after
the AEM got fouled by RBBR was found to be more significant com-
pared to the literature reports. This may be attributed to strong elec-
trostatic interaction between AEM and RBBR resulting in high mem-
brane resistance and low transport number, owing to a higher negative
zeta potential of RBBR at the operational conditions.
Besides, electrochemical analysis was conducted and Nyquist plots
of the pristine and fouled membrane samples are shown in Fig. 9. Both
the pristine and fouled AEM showed typical Nyquist curves of IEM. The
cross point with real axis in high frequency region stands for the sum of
solution and trans-membrane resistance. On the other hand, the semi-
circle in middle frequency region shows heterogeneous transfer im-
pedance from membrane surface to ion concentration polarization
layer. Further, the slope line in low frequency region corresponds to the
sum of solution and trans-membrane resistance. The later stands for
Warburg impedance as indicated in Fig. 9. Compared to pristine
membrane, the semicircle of fouled AEM was relatively bigger both in
real and imaginary direction, dictating the fouling layer increased the
resistance and capacitive reactance of fouled AEM during hetero-
geneous transfer process of ions.
Furthermore, parameters obtained from fitting Nyquist plots de-
picted the sum of solution (Rs) and trans-membrane resistance (Rt) had
a slight increase for fouled AEM (Table. 3). The small increase in the
sum of solution and trans-membrane resistance might be related to
application of alternating current signal during measurement process of
Nyquist plot instead of direct current as in the case of BMED
Fig. 9. Nyquist plots of clean and fouled IEM.
101
Desalination 465 (2019) 94–103
Table 3
Parameters from Nyquist plot for clean and fouled AEM.
Parameters Pristine AEM Fouled AEM
2
Rs (ohm·cm ) 26.92 27.51
Rt (ohm·cm2) 24.17 29.66
Wo (S·sec5·cm−2) 0.001575 0.001672
experiment. Likewise, the heterogeneous transfer resistance (Rt) ob-
viously increased for fouled AEM. Corresponding to Nyquist plot re-
sults, this suggests that the increase in resistance of fouled AEM was not
only due to trans-membrane resistance but also due to contribution
from heterogeneous transfer of ions. Thus, it can be concluded that the
ions transfer was affected by the fouling layer both from the resistance
introduced by fouling layer and from the effect on AEM surface struc-
ture.
3.5. Membrane surface fouling analysis
SEM, EDS and FTIR spectroscopy were used to characterize AEM
before and after BMED experiment. As shown in Fig. 10b, AEM surface
was covered and exhibited less roughness after the experiment, when it
is compared with Fig. 10a (pristine membrane). EDS analysis of pristine
and fouled AEM showed clear variation of the different elements de-
tected on the membrane surface. In particular, the atom percentage of
nitrogen increased from 15.05% in pristine AEM to 17.97% in fouled
AEM justifying adsorption of RBBR molecules to AEM surface. Fur-
thermore, sulfur which was not detected on EDS analysis of pristine
membrane appeared for the fouled AEM. Accordingly, about 0.27%
(atom percent) sulfur was detected on the fouled membrane indicating
adsorption of RBBR to the AEM.
As seen in Fig. 10e and f, the FTIR spectra of pristine and fouled
AEMs showed broad bands at 3406.36 and 3421.85 which is the
stretching vibration of NeH or OeH, respectively [28,29]. The NeH
stretching vibration represents NeH group joining aromatic structures
in RBBR. Interestingly, unique peaks appeared for fouled AEM at
1570.65 and 1538.18 related to skeletal vibration of aromatic structure
that probably emanate from RBBR [29]. Furthermore, a new peak was
observed at 1388.99 that associated to CH3 symmetrical deformation
mode following fouling of AEM [28]. Apart from the above mentioned
peaks the FTIR spectra of both pristine and fouled AEM samples were
nearly similar. Thus, the appearance of new peaks on FTIR spectra re-
lated to NeH and skeletal vibration of aromatic structure confirms
fouling of AEM by RBBR.
3.6. Current efficiency and acid-base production
Accordingly, BMED desalination performance for the same initial
Na2SO4 concentration (5%) decreased from 98.30% to 74.43% with
increasing RBBR concentration from 0 g/L to 1 g/L, as presented in
Fig. 3c. Likewise, the corresponding current efficiency decreased from
44.16% to 35% when the RBBR concentration was increased from 0 g/L
to 0.25 g/L. However, the current efficiency was 39.01% when the
RBBR concentration was further increased to 1 g/L. The higher current
efficiency at the highest RBBR concentration may be attributed to early
shutdown of BMED after 3.5 h operation due to severe fouling.
The lower current efficiency reported in this work is due to the
following reasons: (i) shunt voltage on the electrodes due to redox re-
duction; (ii) proton and hydroxyl leakage through AEMs and CEMs
thereby increasing energy consumption; (iii) fouling of AEM by RBBR
resulting in increased resistance to transport of sulfate.
On the other hand, the balanced equation representing desalination
of sodium sulfate and acid-base production from RBBR wastewater is
presented below:
Y.W. Berkessa, et al.
Fig. 10. SEM images (a) & (b), EDS (c) & (d), and FTIR (e) & (f) results of pristine and fouled AEM, respectively.
Na2 SO4(aq) + 2H2 O(l)
Electrical energy
2NaOH(aq) + H2 SO4(aq)
Neutralization reaction
Accordingly, theoretical yield of NaOH and H2SO4 from 50 g/L
Na2SO4 (0.352 mol) is expected to be a maximum of 0.704 mol of NaOH
and 0.352 mol of H2SO4. The results obtained from BMED experiment
were 0.507 M NaOH and 0.236 M H2SO4. Therefore, the current effi-
ciencies to produce the base and acid were 72.02% and 66.9%, re-
spectively, with the desalination rate of 74.43%. from 5% Na2SO4
(under 0.25 g/L RBBR and 3A applied current). The unbalanced yield of
H2SO4 compared to NaOH was due to continuous proton leakage from
Desalination 465 (2019) 94–103
the acid chamber to feed chamber through the AEM.
(5)
4. Conclusion
This work presents an investigation on membrane fouling me-
chanisms of a medium size (625.5 Da) negatively charged organic
compound (RBBR) during BMED process. Zeta potential of RBBR under
different pH and salt concentration was correlated with AEM fouling
tendency. Specifically, maintaining the zeta potential of RBBR above
-25 mV may mitigate fouling of AEM during the BMED process. This
proves that, zeta potential of a charged foulant (RBBR) plays a key role
102
Y.W. Berkessa, et al.
in terms of controlling membrane fouling.
Apart from this, a linear relationship between feed RBBR con-
centration and final diluate salt concentration was found. A new
parameter “critical salt concentration” was introduced according to this
correlation. More specifically, the critical salt concentration was found
to be 0.78mS/cm, 3.6mS/cm and 13.02mS/cm at RBBR concentrations
of 0 g/L, 0.25 g/L and 1 g/L, respectively. This new parameter may
provide a guidance for the prediction of desalination rate when medium
size negatively charged foulants present in the feed.
Furthermore, the fouled AEM membranes were characterized by
different methods in comparison with pristine ones. Energy dispersive
x-ray spectroscopy confirmed that the atom percent of nitrogen in-
creased from 6.56% to 17.97% following fouling of AEM by RBBR
suggesting adsorption of RBBR to AEM. Likewise, sulfur was detected
on RBBR fouled AEM which was not detected on the pristine sample.
Moreover, Nyquist plots showed that the ions transfer was affected by
the RBBR fouling layer with respect to the membrane resistance and the
AEM surface structure.
Last but not least, BMED performance showed that a good desali-
nation rate was obtained and membrane fouling was mitigated when
the diluate salt concentration was controlled above the “critical salt
concentration”. In particular, desalination rate of 74.43% was obtained
from 5% Na2SO4 under 0.25 g/L RBBR and 3A applied current.
Meanwhile, 72.02% of sodium and 66.9% of sulfate in the feed were
converted to NaOH and H2SO4, respectively.
This study proves that BMED process may be an alternative way of
treating textile wastewater with high salinity and the presence of dye
molecules. Membrane fouling by medium size charged dye molecules
can be mitigated by carefully choosing operational parameters as pH
and desalination rate.
Acknowledgment
The authors would like to appreciate the financial support of
National Natural Science Foundation of China (21878319, 41673112),
the Shandong Provincial Key Science and Technology Program
(2018CXGC1005, 2017GSF17114), and Belt and Road Initiative Project
of the Chinese Academy of Sciences (211134KYSB20170010) and
MEGA group for the free gift of heterogeneous bipolar membranes.
References
[1] J. Lin, W. Ye, J. Huang, B. Ricard, M.-C. Baltaru, B. Greydanus, S. Balta, J. Shen,
M. Vlad, A. Sotto, Toward resource recovery from textile wastewater: dye extrac-
tion, water and base/acid regeneration using a hybrid NF-BMED process, ACS
Sustain. Chem. Eng. 3 (2015) 1993–2001.
[2] Z. Carmen, S. Daniela, Textile organic dyes–characteristics, polluting effects and
separation/elimination procedures from industrial effluents–a critical overview,
Organic Pollutants Ten Years after the Stockholm Convention-Environmental and
Analytical Update, InTech, 2012.
[3] A. Ammar, I. Dofan, V. Jegatheesan, S. Muthukumaran, L. Shu, Comparison be-
tween nanofiltration and forward osmosis in the treatment of dye solutions, Desalin.
Water Treat. 54 (2015) 853–861.
[4] I. Koyuncu, Reactive dye removal in dye/salt mixtures by nanofiltration membranes
containing vinylsulphone dyes: effects of feed concentration and cross flow velocity,
Desalination 143 (2002) 243–253.
[5] A. Gürses, M. Yalçin, C. Doğar, Electrocoagulation of some reactive dyes: a
103
Desalination 465 (2019) 94–103
statistical investigation of some electrochemical variables, Waste Manag. 22 (2002)
491–499.
[6] G.A. Borges, L.P. Silva, J.A. Penido, L.R. de Lemos, A.B. Mageste, G.D. Rodrigues, A
method for dye extraction using an aqueous two-phase system: effect of co-occur-
rence of contaminants in textile industry wastewater, J. Environ. Manag. 183
(2016) 196–203.
[7] I.M. Banat, P. Nigam, D. Singh, R. Marchant, Microbial decolorization of textile-
dye-containing effluents: a review, Bioresour. Technol. 58 (1996) 217–227.
[8] A. Asghar, A.A.A. Raman, W.M.A.W. Daud, Advanced oxidation processes for in-situ
production of hydrogen peroxide/hydroxyl radical for textile wastewater treatment:
a review, J. Clean. Prod. 87 (2015) 826–838.
[9] E. Bazrafshan, M.R. Alipour, A.H. Mahvi, Textile wastewater treatment by appli-
cation of combined chemical coagulation, electrocoagulation, and adsorption pro-
cesses, Desalin. Water Treat. 57 (2016) 9203–9215.
[10] S. Jorfi, G. Barzegar, M. Ahmadi, R.D.C. Soltani, A. Takdastan, R. Saeedi, M. Abtahi,
Enhanced coagulation-photocatalytic treatment of acid red 73 dye and real textile
wastewater using UVA/synthesized MgO nanoparticles, J. Environ. Manag. 177
(2016) 111–118.
[11] M.C. Tomei, D.M. Angelucci, A.J. Daugulis, Sequential anaerobic-aerobic deco-
lourization of a real textile wastewater in a two-phase partitioning bioreactor, Sci.
Total Environ. 573 (2016) 585–593.
[12] A. Yurtsever, B. Calimlioglu, M. Görür, Ö. Çınar, E. Sahinkaya, Effect of NaCl
concentration on the performance of sequential anaerobic and aerobic membrane
bioreactors treating textile wastewater, Chem. Eng. J. 287 (2016) 456–465.
[13] J. Lin, W. Ye, M.-C. Baltaru, Y.P. Tang, N.J. Bernstein, P. Gao, S. Balta, M. Vlad,
A. Volodin, A. Sotto, Tight ultrafiltration membranes for enhanced separation of
dyes and Na 2 SO 4 during textile wastewater treatment, J. Membr. Sci. 514 (2016)
217–228.
[14] C. Xue, Q. Chen, Y.-Y. Liu, Y.-L. Yang, D. Xu, L. Xue, W.-M. Zhang, Acid blue 9
desalting using electrodialysis, J. Membr. Sci. 493 (2015) 28–36.
[15] J. Yao, D. Wen, J. Shen, J. Wang, Zero discharge process for dyeing wastewater
treatment, J. Water Proc. Eng. 11 (2016) 98–103.
[16] H.-J. Lee, M.-K. Hong, S.-D. Han, S.-H. Cho, S.-H. Moon, Fouling of an anion ex-
change membrane in the electrodialysis desalination process in the presence of
organic foulants, Desalination 238 (2009) 60–69.
[17] H.-J. Lee, S.-H. Moon, Enhancement of electrodialysis performances using pulsing
electric fields during extended period operation, J. Colloid Interface Sci. 287 (2005)
597–603.
[18] S. Mikhaylin, L. Bazinet, Fouling on ion-exchange membranes: classification,
characterization and strategies of prevention and control, Adv. Colloid Interf. Sci.
229 (2016) 34–56.
[19] J.-S. Park, H.-J. Lee, S.-J. Choi, K.E. Geckeler, J. Cho, S.-H. Moon, Fouling mitiga-
tion of anion exchange membrane by zeta potential control, J. Colloid Interface Sci.
259 (2003) 293–300.
[20] J.S. Park, T.C. Chilcott, H.G.L. Coster, S.H. Moon, Characterization of BSA-fouling
of ion-exchange membrane systems using a subtraction technique for lumped data,
J. Membr. Sci. 246 (2005) 137–144.
[21] N. Tanaka, M. Nagase, M. Higa, Organic fouling behavior of commercially available
hydrocarbon-based anion-exchange membranes by various organic-fouling sub-
stances, Desalination 296 (2012) 81–86.
[23] X. Sun, H. Lu, J. Wang, Recovery of citric acid from fermented liquid by bipolar
membrane electrodialysis, J. Clean. Prod. 143 (2017) 250–256.
[24] M. Reboiras, Electrochemical properties of cellulosic ion-exchange membranes II.
Transport numbers of ions and electro-osmotic flow, J. Membr. Sci. 109 (1996)
55–63.
[25] P. Długołęcki, B. Anet, S.J. Metz, K. Nijmeijer, M. Wessling, Transport limitations in
ion exchange membranes at low salt concentrations, J. Membr. Sci. 346 (2010)
163–171.
[26] Y. Tanaka, Concentration polarization in ion-exchange membrane electro-
dialysis—the events arising in a flowing solution in a desalting cell, J. Membr. Sci.
216 (2003) 149–164.
[28] K.S.V. Krishna Rao, B. Vijaya Kumar Naidu, M.C.S. Subha, M. Sairam,
T.M. Aminabhavi, Novel chitosan-based pH-sensitive interpenetrating network
microgels for the controlled release of cefadroxil, Carbohydr. Polym. 66 (2006)
333–344.
[29] J. Fang, P.K. Shen, Quaternized poly(phthalazinon ether sulfone ketone) membrane
for anion exchange membrane fuel cells, J. Membr. Sci. 285 (2006) 317–322.
[30] S. Suwal, A. Doyen, L. Bazinet, Characterization of protein, peptide and amino acid
fouling on ion-exchange and filtration membranes: review of current and recently
developed methods, J. Membr. Sci. 496 (2015) 267–283.