pubs.acs.

org/IECR Article

Treatment of Brackish Water RO Brine via Bipolar Membrane

Electrodialysis
Chunliang Du, Jennifer Runhong Du,* Xiangshan Zhao, Fang Cheng, Mohamed E. A. Ali,
and Xianshe Feng
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ABSTRACT: Due to the demand for acid and base in brackish water reverse
osmosis (RO) desalination plants located in remote areas and the difficulty of
transporting acid and base, bipolar membrane electrodialysis (BMED) was
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employed to convert brackish water RO brine into acid and base on site. The
effects of operating parameters (i.e., initial salt content, current density, content of
electrode solution, and initial HCl and NaOH contents) on the BMED
performance for batch processing of brackish water RO brine were investigated
with NaCl solutions. The operating conditions were optimized via the response
surface methodology. Using the actual RO concentrate from a brackish water
desalination plant as the feed solution for BMED after softening pretreatment, an
acid of 0.7 mol/L and a base of 0.6 mol/L were produced in three BMED cycles,
and the salt content in the feed compartment decreased from 19.8 to 4.1 g/L in
each cycle. While the acid and base produced on site can be used for membrane
cleaning and pH adjustment of the RO influent water, the residual salt solution from the BMED can be pumped to the RO system to
maximize utilization of the water resources. The purities of the acid and base produced were 91.1 and 97.2%, respectively, and the
total process cost was estimated at $1.69/kg NaOH.

1. INTRODUCTION desert areas).8 Unfortunately, the acids and bases needed to run
With the rapid growth of population and economic develop- the RO are not readily accessible, and it would be of great
ment, the global shortage of freshwater is becoming increasingly significance to produce the acids and bases on site for proper
serious.1 For inland areas, such as Northwestern China, Saudi operation of RO desalination in remote areas.
Bipolar membrane electrodialysis (BMED) is a process that
Arabia, Egypt, and Turkey,2 desalination of brackish water has
combines bipolar membranes with conventional electrodial-
been pivotal in solving the freshwater shortage problem.3,4
ysis.9 Water molecules in the bipolar membrane (BM) are
Currently, the main desalination technologies include reverse
dissociated into H+ and OH− under a direct current (DC)
osmosis (RO), nanofiltration (NF), electrodialysis (ED),
electric field. Subsequently, the H+ ions combine with the anions
multistage flash distillation, and multiple-effect distillation.
migrated from the feed salt solution through an anion-exchange
Among them, RO accounts for about 65% of the total installed
membrane (AEM) to form an acid solution in the acid
desalination capacity globally.5
compartment, while the OH− ions combine with the cations
However, a major issue in the application of RO desalination
migrated from the feed salt solution through a cation-exchange
is the treatment of the concentrated brine byproduct. Industrial
membrane (CEM) to form a base solution in the base
RO desalination systems typically run at a recovery of about
compartment.10 Since the BMED technology has the advantages
50%. That is, about half of the feed water is discharged as brine
of environmental friendliness and low energy consumption, it
into the sea or nearby areas, which has significant environmental
has attracted significant attention.11−14 BMED has been
impacts.6 Effective treatment of the RO brine is needed to make
successfully used in biochemical and food processing to generate
good use of water resources, thereby minimizing liquid
or purify organic acids/bases or control the solution pH during
discharge.
Another problem with RO desalination is membrane fouling.
Strong acids (e.g., HCl or H2SO4) and bases (e.g., NaOH) are Received: January 25, 2021
commonly used in RO systems to adjust the pH value during Revised: February 2, 2021
operation or as cleaning reagents in cleaning cycles.7 A number Accepted: February 4, 2021
of medium-/small-scale brackish water RO desalination plants Published: February 12, 2021
are built to produce freshwater for drinking or irrigation in some
remote areas rich in brackish water (mainly mountains and

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.iecr.1c00370

3115 Ind. Eng. Chem. Res. 2021, 60, 3115−3129
Industrial & Engineering Chemistry Research
fermentation or chemical synthesis.15−17 It has also been studied
recently for environmental applications to remove harmful
heavy metals and exhaust gases.18−20 There are some reports on
using BMED to produce acid and base from NaCl-rich
brine.1,9,21−24 For example, Reig et al.25 reported the use of
ED-purified and concentrated SWRO brine as the feed solution
of BMED to produce HCl and NaOH of 2 mol/L. BMED has
some advantages compared with other base-producing
techniques, such as traditional chloride-alkali industry and
direct electrodialysis. BMED makes it possible to produce base
from RO brine, unlike the chloride-alkali industry, which
requires pure NaCl solutions.26 Direct electrodialysis, which
requires a special electrode material, is currently at the proof-of-
concept stage and has not been tested with real RO brine.27
Therefore, BMED has the potential to be a scalable solution for
acid and base production using RO brine.28 However, almost all
of the studies focused on synthetic solutions or seawater RO
brine, and no systematic studies exist on the use of brackish
water RO brine to produce acid and base by the BMED process.
Brackish water usually refers to surface water or groundwater
with a salt content of 1−25 g/L.29 Globally, more than 85% of
brackish water on the earth has a salt content of less than 10 g/
L.2 If the feed salt content of an RO desalination plant is 10 g/L
and the recovery rate is 50%, brine with a salt content of 20 g/L
will be produced. Therefore, the main purpose of this work was
to desalinate brackish water RO brine, especially brine with a salt
content of 20 g/L, and to generate acid and base using the
BMED process. On the one hand, the products acid and base can
be supplied to the desalination unit to meet the operation and/
or cleaning needs of the RO system. On the other hand, the
desalinated brine from the BMED process can be recycled to the
RO system for further desalination to increase the overall
recovery of water resources and to reduce wastewater discharge.
The brackish water RO brine treatment with BMED was carried
out in a batch process. The specific experimental steps are as
follows: (1) the effects of operating parameters (i.e., initial salt
content, current density, initial HCl and NaOH contents, and
the content of the electrode solution) on BMED performance
were investigated with synthetic NaCl solutions; (2) optimiza-
tion of the major BMED operating conditions based on the
response surface methodology (RSM) was performed with
synthetic NaCl solutions; and (3) a case study of BMED for
treatment of an actual brackish water RO brine at optimal
operating conditions was conducted, and the process economics
was evaluated. This work provides a systematic study on the
effects of operating conditions on BMED performance at the
termination of a batch treatment. It is also expected to offer an
insight into the sustainable and environment-friendly approach
for brackish water desalination plants that do not have access to
acid/base and to provide reference data to the literature about
the treatment of brackish water RO brine.
2. EXPERIMENTAL SECTION
2.1. Materials. The cation-exchange membrane (membrane
type: CMB), anion-exchange membrane (membrane type:
ACM), and bipolar membrane (membrane type: BP-1E) were
all purchased from Astom (Japan). Table 1 lists the major
characteristics of the membranes utilized. All of the reagents
used in this study (including HCl, NaCl, Na2CO3, NaOH, and
Na2SO4) were of analytical grades. The RO brine was collected
from a surface brackish water desalination plant at Jinhai Lake
(Tianjin, China). The total dissolved solid (TDS) of the RO
brine was 20.7 g/L.
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Table 1. Major Characteristics of Membranes Utilized in This
Worka
area exchange voltage
thickness resistanceb capacity drop efficiency
membrane (mm) (Ω m2) (meq/g) (V) (%)
CMB 0.18−0.25 2.5−6.0 1.8−2.2
ACM 0.10−0.13 2.0−4.5 1.8−2.0
BP-1E 0.2−0.35 1.2− >98
2.2
a
Data were obtained from the manufacturer’s product manual. bThe
area resistance of the ion-exchange membrane was measured with a
0.5 N NaCl solution, at 25 °C. Membranes were separated by
Plexiglas spacers with a thickness of 1 mm.
2.2. Experimental Section. A BMED stack with the BM-
AEM-CEM-BM configuration was employed in this work (see
Figure 1). The membrane stack had two electrode compart-
ments and 10 repeating units, and each repeating unit contains
three compartments for the acid solution, salt solution, and base
solution. The effective area of each membrane was 510 cm2. The
solution volume in a respective compartment was 4 L. The
compartments were connected to their respective external
solution tanks (see Figure 2), and the solution was recirculated
into the membrane stack using pumps (MP-70RZ, Xinxishan,
China). The flow rate of each loop was set to 130 L/h and
monitored with four rotameters (0−400 L/h). The electrodes
located at the two ends of the membrane stack were connected
to a direct current (DC) power supply (ZJ-2100-70, Zhengjie,
China). Small amounts of HCl and NaOH were added to the
acid and base solution compartments in advance, respectively, to
avoid membrane damage from excessively high voltages in the
initial stage of experiments.21,30 The concentrations of HCl and
NaOH were kept the same. Na2SO4 was used as the electrode
solution. All of the four solutions were circulated for 0.5 h to
remove gas bubbles in this system. The operating temperature
was maintained at 30 °C, and each batch process was terminated
at a fixed voltage drop (25 V). The BMED process was operated
at a constant current mode.
2.3. Experimental Design for RSM. Based on a central
composite design (CCD), the RSM was used to find out the
optimum operating conditions with maximum current effi-
ciency, minimum residual salt content, and minimum energy
consumption. The following operating parameters were
considered: initial NaCl content (X1), current density (X2),
and initial HCl and NaOH contents (X3). Each operating
parameter had five levels, and they are listed in Table 2. The
statistical analysis of experimental data was obtained using
Design-Expert software (version 8.0.6) based on the following
second-order polynomial equation
3 3 3
R = a0 + ∑ aiXi+ ∑ aiiXi2+ ∑ aijXiXj
i=1 i=1 i<j (1)
where R is the value of predicted response, Xi and Xj are the
coded values of the independent factors, and a0, ai, aii, and aij are
the intercept term and the linear, quadratic, and interaction
constant coefficients, respectively.
2.4. Evaluation of BMED Performance. Energy con-
sumption (E) and average current efficiency (η) are two
important parameters characterizing the performance of the
BMED process,31 which were calculated on the basis of the
NaOH content since HCl is cheaper than NaOH,21 E (kWh/kg
NaOH) was obtained from32
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Figure 1. Schematic diagram of BMED for preparation of HCl and NaOH from an aqueous salt solution. (a) Na+ in the salt compartment penetrates
the CEM and combines with OH− dissociated in BM to form NaOH in the base compartment; (b) Cl− in the salt compartment penetrates the AEM
and combines with H+ dissociated in BM to form HCl in the acid compartment.

Figure 2. Schematic diagram of the treatment of brackish water RO brine using the BMED process. (1) BMED membrane stack; (2) salt tank; (3) base
tank; (4) electrode solution tank; (5) acid tank; (6) pump; (7) pretreatment. EC, electrical conductivity meter; pH, pH meter; BC, base concentration
meter; T, thermometer.

Table 2. Codes and Levels of Factors in the CCD η (%) from time 0 to t was calculated by
code level VF(Ct − C0)
factor code −1.682 −1 0 +1 +1.682
η= × 100
NIt (3)
initial NaCl content X1 16.59 20 25 30 33.41
(g/L) where C0 is the initial NaOH content (mol/L), F is the Faraday
current density X2 7.9 12 18 24 28.1 constant (F = 96 485 C/mol), and N is the number of repeating
(mA/cm2)
units of the membrane stack (N = 10). In this work, all
initial HCl and NaOH X3 0.13 0.2 0.3 0.4 0.47
contents (mol/L) experiments were repeated at least three times, and the data
reported represent the average of all measurements or
t UI experiments.
t dt
E= ∫0 CtVM (2)
2.5. Pretreatment of the Brackish Water RO Brine.
Scaling will occur on the BMED membrane surface if water
hardness and the pH is not properly controlled. Pretreatment of
where Ut (V) is the potential at time t (h), Ct (mol/L) is the the RO brine is needed to reduce the divalent cation content
content of NaOH at time t, I (A) is the operating current, V (L) prior to the BMED process. OH− and CO32− can be used to
is the volume of the solution in the base tank (4 L), and M is the precipitate Mg2+ and Ca2+, respectively, due to the low
molar mass of NaOH (40 g/mol). Since the transmission of ions solubilities of the resulting precipitating compounds formed34
occurs in the form of hydrated ions,33 there will be a change in
the solution volume during the operation. In this work, the Ca 2 + + CO32 − → CaCO3 (s) (4)
volume change of the base solution was no more than 2%.
Therefore, to simplify the calculation, the volume change was
ignored. Mg 2 + + 2OH− → Mg(OH)2 (s) (5)

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Figure 3. Influence of initial NaCl content on (a) voltage drop across the stack, (b) products’ base and acid contents, (c) energy consumption and
current efficiency, and (d) residual NaCl content of the salt compartment. Current density: 18 mA/cm2; Na2SO4 content: 0.5 mol/L; initial HCl and
NaOH contents: 0.2 mol/L.
Therefore, NaOH and Na2CO3 were used to lower the hardness
of the RO brine. Specifically, 244 mg/L Na2CO3 and 726 mg/L
NaOH were added to the RO brine, and the precipitates were
removed by a microfiltration membrane (pore size 0.45 μm,
Kewei, China). To keep the pH of the softened brine consistent
with that of the NaCl model solution (pH = 6.7), the pH of the
softened brine was adjusted from 10.9 to 6.7 by adding an
aqueous solution of HCl with a pH of 1.
2.6. Analytical Methods. The contents of salt, acid, and
base were measured online by an electrical conductivity meter
(EC-410, Suntex, China), a pH meter (PC-110, Suntex, China),
and a base concentration meter (DCG-760A, Yidian, China),
respectively. The contents of the main cations were determined
with cation chromatography (ICS-1500, Dionex), and the
contents of SO42−, Cl−, and Br− were determined using anion
chromatography (ICS-2000, Dionex). The content of HCO3−
was obtained by titration (ASTM 15451-2006). The TDS was
measured by the weighing method (ASTM 5750.4-2006). The
total organic carbon concentration (TOC) was measured by a
TOC analyzer (QBD1200, Hach).
3. RESULTS AND DISCUSSION
3.1. Effects of Operating Parameters on BMED
Performance. 3.1.1. Initial NaCl Content. If brackish water
with a salt content of 10 g/L is desalinated by RO and the
recovery rate of the RO system is 50−75%, the salt content of
the RO brine will be 20−40 g/L. Therefore, the investigation
range of the initial salt content of the BMED process was
selected to be 15−45 g/L in this work. The effects of initial NaCl
content on voltage drop are shown in Figure 3a. The voltage
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drop decreased with an increase in the initial NaCl content at a
certain time. This is easy to understand because the electrical
resistance of the membrane stack decreases with a rise in the
NaCl content. Additionally, a higher initial NaCl content
resulted in requiring a longer batch processing time since more
Na+ and Cl− needed to be transferred. At a given initial NaCl
content, the voltage drop experienced a slow increase as BMED
proceeded over time before a drastic growth in the voltage drop
was observed eventually. At the early stage, the decrease in the
salt content as a result of BMED was not drastic enough to cause
a notable increase in the electrical resistance because of the high
conductivity of the salt solution, which resulted in only a
marginal increase in the voltage drop of the membrane stack.
However, when the NaCl in the feed solution was significantly
depleted, further processing with BMED led to a more
significant increase in the voltage drop due to an elevated
electrical resistance of the stack.
The influences of the initial NaCl content on the yields of
products’ acid and base are shown in Figure 3b. As expected,
more acids and bases were produced with a rise in the initial
NaCl content because more ions were transferred when the
initial NaCl content increases.35 When the initial NaCl content
was 45 g/L, the final content of NaOH and HCl in the
corresponding base and acid compartments was about 0.5 mol/
L.
As presented in Figure 3c, the current efficiency slightly
lowered with a rise in the initial NaCl content. Increasing the
initial NaCl content increases the contents of the resulting HCl
and NaOH, and consequently the concentration gradients of H+
and OH− across their respective ion-exchange membranes
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Figure 4. Influence of current density on (a) voltage drop across the stack, (b) products’ base and acid contents, (c) energy consumption and current
efficiency, and (d) residual NaCl content of the salt compartment. Initial NaCl content: 25 g/L; Na2SO4 content: 0.5 mol/L; initial HCl and NaOH
contents: 0.2 mol/L.
increase. As a result, the leakage of H+ and OH− from the acid
and base compartments to the salt compartment is intensified.
On the other hand, the increased concentrations of HCl and
NaOH also mean an augmented osmotic pressure, which slows
down the supply of water molecules to the bipolar membrane
and thus impacts the dissociation of water molecules.36 The
energy consumption gradually increased at higher initial NaCl
contents. This is obvious because the higher NaCl content needs
a longer BMED processing time under the same operating
conditions (see Figure 3a), which in turn consumes more
electrical energy to split water molecules in the bipolar
membrane and to induce transfer of sodium ions and chloride
ions across the corresponding CEM and AEM. This result is
consistent with the report by Reig et al.25
The residual NaCl content in the feed solution is shown in
Figure 3d. When the initial NaCl content was increased from 15
to 35 g/L, the residual NaCl content gradually reduced. As
mentioned before, more acids and bases were produced at a
higher initial NaCl content and thus the electrical resistance was
lowered. This in turn helps in the transport of chloride ions and
sodium ions from the salt solution to the acid and base
compartments, respectively, to form HCl and NaOH. However,
the reduction in the residual NaCl content in the salt
compartment was less significant with a further increase in the
initial NaCl content from 35 to 45 g/L. Overall, an increase in
the initial salt content resulted in an increased product yield,
running time as well as energy consumption, with lowered
current efficiency and residual NaCl content.
3.1.2. Current Density. Figure 4a shows the variation of
voltage drop with time under different current densities. Since
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an increase in current density increases the driving force for ion
migration across the membranes, the transmembrane ion
movement across the membranes and water dissociation in
the bipolar membranes are facilitated. The fast transmembrane
ion transfer leads to a more severe concentration polarization on
the membrane surface,37 resulting in a rise in the electrical
resistance of the stack. Running BMED at a higher current
density accelerates ion transfer across the membrane and leads
to a shorter batch processing time.
Figure 4b exhibits the impacts of the current density on the
contents of the products’ HCl and NaOH. The contents of HCl
and NaOH produced by one batch of BMED were reduced
gradually as the current density increased. An increase in current
density will accelerate the migration rate of ions, thereby
increasing the yield of acid and base produced at the same
operating time (as shown in Figure S1 in the Supporting
Information). In this work, the voltage drop increased sharply
after it reached 25 V. Therefore, a voltage drop of 25 V was used
as the terminal time of a BMED processing batch. An increase in
current density shortened the processing time of a batch of
BMED (see Figure S1 in the Supporting Information). As a
result, the NaCl in the salt compartment solution was not
thoroughly converted into the corresponding acid and base at a
higher current density (Figure 4d). Therefore, the yields of acid
and base produced by a batch process of BMED were reduced
with an increase in the current density. Similar results were also
observed by Shen et al.38
As shown in Figure 4c, the current efficiency increased with an
increase in the current density. This is understandable
considering the fact that the migration rates of Na+ and Cl−
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Figure 5. Influence of the initial HCl and NaOH contents on (a) voltage drop across the stack, (b) products’ base and acid contents, (c) energy
consumption and current efficiency, and (d) residual NaCl content of the salt compartment. Current density: 18 mA/cm2; initial NaCl content: 25 g/
L; Na2SO4 content: 0.5 mol/L.
across the membranes and the dissociation rate of water
molecules are accelerated at a higher current density, while the
transport of their counterions is suppressed,37,39 and thus the
electric energy is used more effectively. The energy consumption
increased slightly with the current density, demonstrating that
the energy consumption required to conquer the higher
electrical resistance due to the usage of a higher current density
is not much different from that required to operate at a lower
current density but for a longer period of processing time.39 In
summary, as the current density increased, although the
operating time of the BMED process was significantly reduced,
the energy consumption increased and the production yield
decreased.
3.1.3. Initial HCl and NaOH Contents. Figure 5a shows the
voltage drop over time at various initial HCl and NaOH
contents; the content of HCl was the same as the NaOH
content. When their initial content was 0.1 mol/L, the voltage
drop slowly decreased first due to the dissociation of water
molecules into H+ and OH− in the bipolar membranes, which
decreases the electrical resistance of the stack. Then, the voltage
drop increased gradually until a sharp increase near the end of
the process because of the consumption of NaCl in the feed
solutions. On the other hand, increasing the initial HCl and
NaOH contents leads to a rise in the osmotic pressure of the
solutions in the acid and base compartments, which reduces the
supply of water to the bipolar membrane and then limits the
dissociation of water molecules, resulting in an increase in the
processing time for a given batch volume. At a given time,
increasing the initial HCl and NaOH concentrations caused a
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decrease in the voltage drop due to a lowered electrical
resistance of the stack.21,32
Figure 5b shows that the contents of HCl and NaOH
increased slightly with an increase in the initial HCl and NaOH
contents because more Na+ and Cl− in the salt compartment can
be transferred to the corresponding base and acid compartments
when the electrical resistance of the solution decreases. A similar
trend has also been reported by Reig et al.21 Figure 5d shows that
increasing the initial HCl and NaOH contents tends to reduce
the residual salt content. However, when the initial HCl and
NaOH contents were high enough (e.g., 0.3 mol/L), there was
little change in the residual salt content.
As displayed in Figure 5c, the current efficiency decreased as
the initial HCl and NaOH contents increased. This is not
surprising in view of the increased osmotic pressures at higher
HCl and NaOH contents, which limit water supply to the
bipolar membrane for dissociation into H+ and OH−.36 In
addition, the increased HCl and NaOH contents will increase
the concentration gradients of H+ and OH− to pass the CEM
and AEM, respectively, and enter the salt compartment. There
was a gradual decline in energy consumption with an increase in
the initial HCl and NaOH contents because of the reduced
electrical resistance of the stack.32
3.1.4. Content of Electrode Solution. An increase in the
Na2SO4 content from 0.1 to 0.5 mol/L resulted in a reduction in
the voltage drop (see Figure 6a). This is due to the fact that the
electrical resistance reduced at higher Na2SO4 contents because
of the increased conductivity of the electrode compartment.
However, when the Na2SO4 content was high enough (e.g., 0.7−
0.9 mol/L), a further increase in the Na2SO4 content had little
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Figure 6. Influence of Na2SO4 content on (a) voltage drop across the stack, (b) products’ base and acid contents, (c) energy consumption and current
efficiency, and (d) residual NaCl content of the salt compartment. Current density: 18 mA/cm2; initial NaCl content: 25 g/L; initial HCl and NaOH
contents: 0.2 mol/L.

Table 3. Observed Response Values from the CCD

code level
runs X1 X2 X3 energy consumption (kWh/kg NaOH) current efficiency (%) residual NaCl content (g/L)
1 0 0 0 0.99 ± 0.058 65.1 ± 1.39 4.21 ± 0.21
2 −1 +1 +1 0.66 ± 0.033 66.1 ± 1.77 6.92 ± 0.14
3 +1 +1 −1 1.41± 0.08 67.8 ± 1.90 6.13 ± 0.29
4 0 +1.682 0 0.87 ± 0.038 67.1 ± 0.56 7.91 ± 0.57
5 0 0 +1.682 0.80 ± 0.032 53.1 ± 0.64 4.09 ± 0.26
6 0 0 0 0.91 ± 0.058 63.6 ± 1.39 3.98 ± 0.21
7 −1.682 0 0 0.68 ± 0.037 71.4 ± 1.08 4.87 ± 0.29
8 0 0 0 0.95 ± 0.058 62.8 ± 1.39 4.36 ± 0.21
9 −1 −1 −1 1.03 ± 0.041 65.6 ± 0.89 3.00 ± 0.17
10 −1 −1 +1 0.75 ± 0.035 54.4 ± 1.50 2.84 ± 0.11
11 0 0 0 0.88 ± 0.058 62.2 ± 1.39 4.11 ± 0.21
12 0 0 0 1.06 ± 0.058 64.4 ± 1.39 4.58 ± 0.21
13 0 0 −1.682 1.66 ± 0.076 69.0 ± 0.94 5.54 ± 0.32
14 0 −1.682 0 0.94 ± 0.032 50.3 ± 0.78 2.00 ± 0.08
15 +1 −1 −1 1.59 ± 0.075 61.3 ± 1.12 2.51 ± 0.10
16 −1 +1 −1 0.91 ± 0.065 69.8 ± 1.44 7.39 ± 0.42
17 0 0 0 0.94 ± 0.058 61.4 ± 1.39 4.20 ± 0.21
18 +1 +1 +1 1.11 ± 0.063 57.7 ± 1.03 5.95 ± 0.36
19 +1.682 0 0 1.26 ± 0.064 64.1 ± 0.73 4.20 ± 0.13
20 +1 −1 1 1.09 ± 0.042 50.3 ± 1.04 2.71 ± 0.11

impact on the voltage drop because the electrical conductivity of
each compartment solution was large enough to be not affected
by a small change in the Na2SO4 concentration. In addition, the
batch processing time needed to complete the BMED process
3121
was moderately affected by the Na2SO4 content over the
experimental range studied.
Figure 6b shows that the content of Na2SO4 solution had no
effects on the yields of products’ base and acid. Similar results
have also been reported elsewhere.30 The current efficiency
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(Figure 6c) and the residual NaCl content of the salt

<0.0001

<0.0001
0.0038

0.0167
0.0760
0.4429
0.4162
0.3551
0.0151
0.0461

0.1167
P value
compartment (Figure 6d) were not affected by the Na2SO4
content either. However, the energy consumption gradually
reduced with an increase in the Na2SO4 content and eventually
leveled off when the Na2SO4 content was high enough. This is

67.2632
13.9950

8.2244
3.9158
0.6383
0.7192
0.9403
8.5813
5.1809

3.1511
F value

565.059
because as the content of the Na2SO4 increased, the ratio of the

residual NaCl content (g/L)

electrical resistance of the electrode solution compartment to
the electrical resistance of the stack decreased, i.e., the

R2 = 0.9837, R2adj = 0.9691, CV% = 6.28

contribution of the electrode solution compartment to the

5.5657
1.1580
46.7562
0.6805
0.3240
0.0528
0.0595
0.0778
0.7101
0.4287
0.0827
0.1256
0.0399
total electrical resistance was reduced. However, there was only a

MS
slight decrease in energy consumption when increasing the
Na2SO4 content above 0.7 mol/L. From the energy and material
consumption standpoints, a Na2SO4 content of 0.7 mol/L was

DF
9
1
1
1
1
1
1
1
1
1
10
5
5
19
chosen in subsequent experiments.
3.2. Optimization of the BMED Process by RSM.
3.2.1. Model Fitting. Based on the experimental results of the

50.0915
1.1580
46.7562
0.6805
0.3240
0.0528
0.0595
0.0778
0.7101
0.4287
0.8275
0.6281
0.1993
50.9190
above one-variable-at-a-time experiments, three operating

SS
parameters that influence the BMED performance (i.e., initial
salt content, initial HCl and NaOH contents, and current
density) may be optimized based on CCD. The CCD matrix and

0.6243
0.1358
0.0518
0.0021
0.0005
0.0237

0.1260
<0.0001
<0.0001
<0.0001
<0.0001
P value
output values are listed in Table 3. The regression equations
obtained by the analysis of variance (ANOVA) for different
responses are

139.1933
163.6549
44.8785
39.7677

0.2254
2.6325
4.8738
16.8200
25.3699
7.0968

3.0079
Energy consumption:

F value
R1 = 1.30 + 0.0498X1 − 0.00664X 2 − 6.97X3 current efficiency (%)

R2 = 0.9758, R2adj = 0.9541, CV% = 2.20

+ 0.000227X1X 2 − 0.0675X1X3 + 0.0491X 2X3

245.9336
289.1536
79.2935
70.2636

0.4513
4.6513
8.6113
29.7185
44.8250
12.5391
1.7668
2.6520
0.8817
+ 0.000238X12 − 0.000609X 2 2 + 9.59X32
MS

Current efficiency:

SS, sum of squares; DF, degree of freedom; MS, mean square. Significant (P < 0.05); highly significant (P < 0.01)
DF
9
1
1
1
1
1
1
1
1
1

5
5
10

19
R 2 = 79.4 − 2.72X1 + 2.22X 2 + 16.8X3 − 0.00817X1X 2
− 1.53X1X3 + 1.77X 2X3 + 0.0574X12 − 0.0515X 2 2
70.2636

13.2602
0.4513
4.6513
8.6113
29.7185
44.8250
12.5391
17.6685

4.4083
713.6415

245.9336
289.1536

731.3100
− 93.3X32
SS

Residual NaCl concentration:

<0.0001
<0.0001

<0.0001
0.0909

0.8072
0.2058
0.2759
0.8332
0.3316
0.0004
P value

0.005
R3 = 3.62 − 0.133X1 + 0.304X 2 − 14.0X3 − 0.00697X1X 2
+ 0.163X1X3 − 0.147X 2X3 + 17.2X32 + 0.00295X12
+ 0.00653X 2 2
117.4504

113.4040
29.6254

3.4997

0.0628
1.8309
1.3286
0.0468
1.0412
26.6536

14.8840
energy consumption (kWh/kg NaOH)
F value

As shown in Table 4, the regression models possessed high F-

values and very low P-values (<0.0001), indicating that the three
models were highly significant. The fitness values of the model
R2 = 0.9639, R2adj = 0.9313, CV% = 6.84
0.1474
0.5845
0.0174
0.5644
0.0003

0.0066
0.0002
0.0052
0.1327
0.0050
0.0093
0.0006

equations as measured by the determination coefficient (R2), the

Table 4. Statistical Significance of the RSM

MS

adjusted determination coefficient (Radj2), and the coefficient of

00091

variation (CV%) are also presented in Table 4. The R2 values for

all three models were higher than 0.96, indicating the adequacy
of the three models to describe the experimental data
DF

10
9
1
1
1
1
1
1
1
1
1

5
5
19

satisfactorily.40 Statistically, the high Radj2 value also confirms

the significant correlation between experimental and predicted
values,41 and the low value of CV% means that the results of the
1.3270
0.5845
0.0174
0.5644
0.0003

0.0066
0.0002
0.0052
0.1327
0.0498
0.0466
0.0031
1.3768

fitted models had good precision and reliability.42

SS

00091

3.2.2. Influences of Variables and Optimization. As shown

in Table 4, the variables that have a significant impact were X1,
X3, and X32 for energy consumption; X1, X2, X3, X12, X22, and X32
for current efficiency; and X1, X2, X3, X22, and X32 for residual
pure error
lack of fit

Cor total
source

residual

NaCl content. All of the interactions between different variables

model

X1X2
X1X3
X2X3

appeared to be insignificant. To determine the optimal levels of

X1
X2
X3

X21
X22
X23

the variables, three-dimensional (3D) response surface plots

3122 https://dx.doi.org/10.1021/acs.iecr.1c00370
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 7. Three-dimensional response surface plots for energy consumption as a function of (a) initial NaCl content and current density, (b) initial
NaCl content and initial HCl and NaOH contents, and (c) current density and initial HCl and NaOH contents.

Figure 8. Three-dimensional response surface plots for current efficiency as a function of (a) initial NaCl content and current density, (b) initial NaCl
content and initial HCl and NaOH contents, and (c) current density and initial HCl and NaOH contents.

3123 https://dx.doi.org/10.1021/acs.iecr.1c00370
Ind. Eng. Chem. Res. 2021, 60, 3115−3129
Industrial & Engineering Chemistry Research
Figure 9. Three-dimensional response surface plots for residual NaCl concentration as a function of (a) initial NaCl content and current density, (b)
initial NaCl content and initial HCl and NaOH contents, and (c) current density and initial HCl and NaOH contents.
were constructed between two operating parameters, while
another operating parameter remained at the zero code level.40
As shown in Figure 7a, at the zero level of initial HCl and
NaOH contents, the energy consumption of the BMED
gradually increased with current density at different initial
NaCl contents, and it also increased with the initial NaCl
content at different current densities. A lower initial NaCl
content or lower current density leads to a decline in the energy
consumption. Figure 7b shows that at the zero level of current
density, the energy consumption declines with an increase in the
initial HCl and NaOH contents regardless of the initial NaCl
content. Moreover, the energy consumption increases with the
initial NaCl content irrespective of the initial HCl and NaOH
contents used. The dependence of energy consumption on the
initial HCl and NaOH contents can also be clearly seen from
Figure 7c. At the zero level of the initial NaCl content, the energy
consumption declined with an increase in initial HCl and NaOH
contents at various current densities, and the impact of current
density on energy consumption was insignificant. Overall, the
effects of the initial HCl and NaOH contents on energy
consumption are more pronounced than the initial salt content
and current density. This is because within the parameter range
selected in this work, the variation of the concentration of acid
and base solutions had a relatively greater impact on the
electrical resistance of the membrane stack than the variation of
current density and initial salt content.
Similarly, Figure 8a,b shows that the current efficiency
decreases with an increase in the initial NaCl content. Regardless
of the initial NaCl content investigated, the current efficiency
increased significantly with an increase in current density
3124
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(Figure 8a) and a decrease in initial HCl and NaOH contents
(Figure 8b). For a low initial NaCl content, the current
efficiency was higher at a higher current density and lower initial
HCl and NaOH contents. Figure 8c shows that at a given NaCl
content, the current efficiency increased to a constant value with
an increase in current density at different initial HCl and NaOH
contents. Clearly, lower initial HCl and NaOH contents and
higher current densities favor the current efficiency of the
BMED for batch treatment of salt solutions.
Figure 9a shows that the content of residual NaCl in the salt
compartment gradually increased with current density. More-
over, it decreased slightly as the initial NaCl concentration
increased at given current densities. Figure 9b shows that the
residual NaCl content reduced with an increase in the initial
NaCl content at different initial HCl and NaOH contents. At an
initial NaCl content of 33.4 g/L, a relatively low residual NaCl
content can be reached when an initial HCl and NaOH content
of 0.3 mol/L was used. The dependence of residual NaCl
content on current density can be seen in Figure 9c. At different
initial HCl and NaOH contents, increasing the current density
resulted in a higher residual NaCl content, whereas the initial
HCl and NaOH contents had little impact on the residual NaCl
content in the salt compartment solution.
To minimize energy consumption and residual NaCl content
while maximizing the current efficiency in practical applications,
the optimal operating conditions for the BMED process were
optimized by ridge analysis and canonical analysis.40 For an
initial NaCl content of 15 g/L, the following performance specs
were obtained: minimum energy consumption of 0.66 kWh/kg
NaOH, minimum residual NaCl content of 3.41 g/L, and
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maximum current efficiency of 70.9% when the BMED was As shown in Figure 10a, the yield of the base and acid
conducted at a current density of 12.4 mA/cm2 and an initial increased linearly with time. The conductivity of the salt
HCl and NaOH content of 0.27 mol/L. However, considering
that the TDS of the actual RO brine to be treated was about 20
g/L, the initial NaCl content was set to a fixed value (20 g/L) to
reoptimize the operating conditions. This yielded a minimum
energy consumption of 0.80 kWh/kg NaOH, minimum residual
salt content of 3.82 g/L, and maximum current efficiency of
66.8% at a current density of 15 mA/cm2 and an initial HCl and
NaOH content of 0.25 mol/L. To verify the model predictions,
three additional independent experiments were run under the
optimized results. The average performance values are as
follows: minimum energy consumption of 0.85 ± 0.05 kWh/kg
NaOH, minimum residual NaCl content of 3.87 ± 0.21 g/L, and
maximum current efficiency of 67.1 ± 1.02%. These results
confirm that the optimization of the operating conditions was
appropriate.
3.3. Case Study for Desalination of RO Brine by BMED.
The Ca2+ and Mg2+ ions in the RO brine can migrate from the
salt compartment to the base compartment and cause the scaling
of Mg(OH)2, Ca(OH)2, and CaCO3 to form on the surface of
the cation-exchange membrane and the bipolar membrane in
the base compartment.43−45 In this work, the contents of Ca2+
and Mg2+ in the RO brine were 203 and 605 mg/L, respectively
(Table 5), and the total hardness was 2987 mg/L (calculated as

Table 5. Main Compositions in the RO Brine with and

without the Pretreatment
main ions concentrate pretreated concentrate
Figure 10. (a) Variation of the base content, acid content, and
Na+ (mg/L) 6798 ± 124.60 6914 ±106.73
conductivity of the salt solution with operation time. (b) Variation of
K+ (mg/L) 142 ± 4.99 138 ± 4.86
energy consumption and the average current efficiency with the number
Ca2+ (mg/L) 203 ± 8.89 2 ± 0.41 of cycles.
Mg2+ (mg/L) 605 ± 11.08 1 ± 0.67
Cl− (mg/L) 10 789 ± 108.97 10 674 ± 162.54
compartment solution decreased almost linearly in the BMED
HCO−3 (mg/L) 61 ± 1.31 43 ± 2.31
cycle, which was reasonable due to the constant rate of ion
Br− (mg/L) 38 ± 1.50 36 ± 2.05
migration under a constant current density. After three BMED
SO2−
4 (mg/L) 1085 ± 15.4 1041 ± 29.98
cycles, the base content and acid content were shown to be 0.6
TDS (g/L) 20.7 ± 1.02 19.8 ± 0.85
and 0.7 mol/L, respectively. On the one hand, the actual RO
TOC (mg C/L) 2.1 ± 0.11 1.9± 0.08
brine also contains other cations and anions in addition to Na+
conductivity (mS/cm) 30.8 ± 0.66 29.4 ± 1.78
and Cl−. On the other hand, the ion migration rate is related to
its hydro-radius or weight in an electric field. Ions with a lower
weight or a smaller hydro-radius would migrate faster than
CaCO3). According to the requirements of the membrane heavier and larger ions.33,46 H+ ions have a higher mobility than
provider, the total hardness of the solution in the salt OH− ions, and therefore, the amount of acid produced was
compartment should not exceed 10 mg/L (calculated as slightly higher than the amount of base.25 According to the
CaCO3). Therefore, the RO brine was chemically softened by technical information supplied by membrane manufacturers,
adding NaOH and Na2CO3. After the chemical pretreatment, HCl solution with a pH of 2 (0.01 mol/L) and NaOH solution
the contents of Ca2+ and Mg2+ were reduced to 2 and 1 mg/L, with a pH of 12 (0.01 mol/L) can be used to clean the fouled RO
respectively. The total hardness of the softened RO brine was 9 desalination membranes and ultrafiltration membranes, which
mg/L, which was low enough to meet the operating require- are usually used for the pretreatment of RO systems. The
ments of BMED. contents of the acid and base generated in the BMED process are
To further investigate the feasibility of using BMED to recover thus sufficient for cleaning of contaminated membranes or
water and produce HCl and NaOH from RO brine, a cyclic adjustment of the RO influent pH. It may be mentioned that the
“continuous” experiment was performed with an actual brine contents of acid and base produced in the batch BMED process
solution. The BMED process was operated under optimized can be controlled by the number of operating cycles, making the
conditions, i.e., current density of 15 mA/cm2, initial HCl and process particularly suitable for uses in remote areas where on-
NaOH content of 0.25 mol/L, and content of electrode solution site manufacturing of the acid and base is desired. It is worth
of 0.7 mol/L. The conductivity of the softened RO brine was mentioning that because of the various ions present in the actual
found to be 29.4 mS/cm. When the conductivity of the feed RO brine, the produced acid and base are a mixture of acids (i.e.,
solution was reduced to about 6 mS/cm, it was replaced with HCl, HBr, H2SO4) or bases (i.e., NaOH, KOH). However, in
another 4 L RO brine to carry out the next cycle of the BMED view of the slower transport rate of divalent ions through an ion-
process. exchange membrane than monovalent ions22 and the low
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

content of other ions (e.g., K+, Br−, and HCO3−), HCl and
NaOH were the main products. The compositions of the acid
and base produced were measured by ion chromatography (see
Table 6). The purities of the acid and base produced were 91.1
Table 6. Composition of the Produced Acid and Base (mg/L)
ion acid
Na+ 117
K+ 4.8
Ca2+ 0 0.2
Mg2+ 0 0
Cl− 24 550
HCO−3 98.9
Br− 82
SO2−
4 2091
and 97.2%, respectively, which were not lower than those
reported by other BMED processes.1,35,46 In addition, the acid
and base produced did not contain impurities harmful to the
membranes. The quality of the acid and base produced via
BMED will not affect their use in applications that do not require
high-quality chemicals such as membrane cleaning and adjust-
ment of influent water pH.1,23,35 If there is a higher quality
requirement, the acid and base produced can be further
upgraded by a purification process (e.g., ion-exchange method)
to remove trace impurities such as sulfate, calcium, and
magnesium.9 In each BMED cycle, the salt concentration in
the salt compartment changed from 19.8 to 4.1 g/L, and the
residual salt solution in the salt compartment can be pumped to
the RO system for further desalination treatment,9 thereby
increasing utilization of water resources to ultimately achieve a
minimized discharge of RO wastewater.
Figure 10b shows that the energy consumption increased and
the current efficiency decreased as the number of BMED
operating cycles increased. At the end of cycle 3, the energy
consumption and current efficiency were 1.81 kWh/kg NaOH
and 66%, respectively. This means that the performance of the
BMED process gradually declines with the generation of acid
and base, presumably due to the non-negligible passages of H+
and OH− across the ACM and CMB when the acid and base
concentrations became remarkably high.42
Table 7 summarizes the reported results for treating various
types of brine by the BMED process using different membrane
base materials. Most of the reports focused on the treatment of
15 902
seawater RO concentrate or high-salinity wastewater. To meet
345
the influent quality requirements of the BMED process,
pretreatments were used to eliminate the effects of adverse
factors (such as hardness and suspended solids). This table
101 shows that a reasonable energy consumption and current
1.5 efficiency were achieved in this work.
2.3 3.4. Estimates of Process Costs. Table 8 shows the total
15 process cost of this study, which was the sum of the capital costs,
chemical cost (including Na2SO4 and Na2CO3), and energy
costs. The capital costs include the costs of membrane stacks and
peripheral equipment. The cost estimates were based on the
following: (1) the cost of the membrane stack was 1.5 times the
membrane cost, and (2) the peripheral equipment cost
(including pumps, monitoring, control panels) was calculated
based on the purchase price in China.
Table 8 demonstrates that the total process cost was $1.69/kg
NaOH. This process cost refers to the cost of simultaneously
producing 1 kg of base and 1.07 kg of acid. The key factor in the
BMED process cost was the cost of membranes, especially the
bipolar membrane. A similar result was also found by Shen et
al.48 Therefore, although this cost was higher than the Chinese
market price of the same amount of commercial acid and base
($0.53 including $0.37 for 1 kg of NaOH and $0.16 for 1.07 kg
of HCl35), if the cost of the membranes can be reduced or if the
processing scale can be enlarged, the total process cost can be
significantly reduced.48 Additionally, for RO desalination plants
in remote areas where transportation and storage of the acid and
base are practical issues, the BMED process is one of the most
promising candidates.

Table 7. Comparison of the Published Data on Brine Treatment by BMED

product yield
membrane (mol/L)
salt
content area I E
influent (g/L)a AEM CEM BP (cm2) HCl NaOH (mA/cm2) η (%) (kWh/kg) refs
industrial saline water after 70 PCA acid PCA SK PCA PBM/ 64 PBM: PBM: PBM: 57.2 PBM: 47
PP filtration 60 Fuma-Tech 1.6 1.7 65
FBM FBM: FBM: FBM: 52.3 FBM:
1.8 2.0 81
synthetic SWD-RO brine 61.2 RALEX RALEX NEOSEPTA 200 0.78 0.82 100 55 23
AMH CMH BP-1
SWD-RO brine after 52.9 PCA acid PCA SK PCA PBM 64 0.66 0.61 44 70 2.6c 21
softening pretreatment 60
SWD-RO brine after ED 52.8 PCA acid PCA SK PCA PBM 64 0.63 0.62 47 67 2.89c 25
concentration 60
c
SWD-RO brine after SED 52 AMX CMX NEOSEPTA 189 0.65 0.6 10 68 1.87 35
concentration BP-1
SWD-RO brine after 42.5 Qianqiu Qianqiu Fuma-Tech 88 0.7 57 60 9.0b 1
softening pretreatment AEM CEM FBM
surface water after ED 26.2 TWEDAI TWEDCI TWBPI 200 0.7 52 5.8b 42
concentration
brackish water RO brine 19.8 ACM CMB NEOSEPTA 510 0.7 0.6 15 66 1.81c this
after softening BP-1E work
pretreatment

a
Main ions: Na+ and Cl−. bkWh/kg (HCl). ckWh/kg (NaOH).

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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table 8. Estimation of the Process Cost Concentration of the produced acid/base vs time curve at
operating conditions different current densities and the calculation of NaOH
annual production capacity (PDF)
flow rate (L/h) 130

■
current density (mA/cm2) 15
initial salt concentration (g/L) 19.8 AUTHOR INFORMATION
initial concentration of HCl and NaOH (mol/L) 0.25
Na2SO4 concentration (mol/L) 0.7 Corresponding Author
working time (h/year) 6000 Jennifer Runhong Du − State Key Laboratory of Separation
effective membrane area (m2) 0.51 Membranes and Membrane Processes, School of Material
energy consumption (kWh/kg NaOH) 1.81 Science and Engineering, Tiangong University, Tianjin
base production capacity (kg NaOH/year)a 384 300387, China; orcid.org/0000-0002-2195-5215;
RO brine process capacity (m3/year) 48 Email: durunhong@tiangong.edu.cn
energy cost
Authors
electricity charge in China ($/kWh) 0.1
Chunliang Du − State Key Laboratory of Separation
energy cost for the membrane stack ($/year) 69.5
Membranes and Membrane Processes, School of Material
energy cost for pumps ($/year) 108
Science and Engineering, Tiangong University, Tianjin
total energy cost ($/kg NaOH) 0.46
300387, China
capital cost
Xiangshan Zhao − State Key Laboratory of Separation
ion-exchange membrane ($/m2) 165 Membranes and Membrane Processes, School of Material
bipolar membrane ($/m2) 945 Science and Engineering, Tiangong University, Tianjin
membrane cost ($) 819 300387, China
stack cost (including membrane cost) ($) 1228.5
Fang Cheng − School of Environmental and Municipal
equipment cost ($) 573
Engineering, Tianjin Chengjian University, Tianjin 300384,
initial capital cost ($) 1801
China
capital cost ($/kg NaOH)b 1.21
Mohamed E. A. Ali − Egyptian Desalination Research Center of
chemical cost ($/kg NaOH) 0.027
Excellence & Hydrogeochemistry Department, Desert Research
total process cost ($/kg NaOH) 1.69
a
Center, Cairo 11753, Egypt
Please see the Supporting Information for the calculation of base Xianshe Feng − Department of Chemical Engineering,
production capacity. bThe life of membrane and membrane stack was University of Waterloo, Ontario N2L 3G1, Canada
calculated as 3 years; the service life of equipment was calculated as 10
years. Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.1c00370
4. CONCLUSIONS Notes
This work investigated the influences of operating parameters The authors declare no competing financial interest.

■
involved in BMED performance and the feasibility of using
BMED to valorize brackish water RO brine for acid and base ACKNOWLEDGMENTS
productions. Specifically, from the work, the following
conclusions can be drawn. This work was supported by the National Key Research and
Development Program of China (Grant no. 2017YFE0114200).
(1) The current density, initial NaCl content, and initial HCl
Research support from the Science and Technology Develop-
and NaOH contents have significant effects on BMED
ment Fund (STDF) of Egypt (Grant no. 30379) is also gratefully
performance, while the content of the electrode solution
acknowledged.

had little impact.
(2) To desalinate a brackish water RO brine at 20 g/L of
NaCl, the optimal operating conditions of the BMED
process were found to be as follows: current density of 15
mA/cm2, initial HCl and NaOH contents of 0.25 mol/L,
and Na2SO4 content of 0.7 mol/L.
(3) To lower the salinity of a brackish water RO brine from
19.8 to 4.1 g/L in each cycle, a base concentration of 0.6
mol/L and an acid concentration of 0.7 mol/L were
obtained in three BMED operating cycles. The energy
consumption and current efficiency were 1.81 kWh/kg
NaOH and 66%, respectively.
(4) The purities of the acid and base produced were 91.1 and
97.2%, respectively. The total process cost was estimated
at $1.69/kg NaOH.
■
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Ind. Eng. Chem. Res. 2021, 60, 3115−3129