Separation and Purification Technology 207 (2018) 1–11

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Separation and Purification Technology

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

Effect of coexisting ions on recovering lithium from high Mg2+/Li+ ratio T

brines by selective-electrodialysis
⁎
Peng-Yuan Jia,b,c, Zhi-Yong Jia,b,c, , Qing-Bai Chena,b,c, Jie Liua,c, Ying-Ying Zhaoa,c,
⁎
Shi-Zhao Wanga,c, Fei Lia,c, Jun-Sheng Yuana,b,c,
a
Engineering Research Center of Seawater Utilization of Ministry of Education, School of Chemical Engineering and Technology, Hebei University of Technology, 300130
Tianjin, China
b
National-Local Joint Engineering Laboratory of Chemical Energy Saving Process Integration and Resource Utilization, School of Chemical Engineering and Technology,
Hebei University of Technology, Tianjin 300130, China
c
Hebei Collaborative Innovation Center of Modern Marine Chemical Technology, 300130 Tianjin, China

A R T I C LE I N FO A B S T R A C T

Keywords: Selective-electrodialysis (S-ED) is a booming technology for recovering lithium from salt lake brine and (con-
Selective-electrodialysis (S-ED) centrated) seawater, especially from high Mg2+/Li+ ratio brines. The coexisting ions in the solutions containing
Recovering lithium lithium can make some impact on the ion fractionation of lithium and magnesium in high Mg2+/Li+ brines. The
High Mg2+/Li+ ratio effect of the concentration of coexisting cations (Na+, K+) and anions (SO42−, HCO3−) on the separation
Ion-fractionation
coefficient of magnesium and lithium (FMg-Li), recovery ratio of Li+ (RLi), current efficiency (η) and specific
Coexisting ion
energy consumption (ESEC) was evaluated. The results show that an applied voltage of 6 V is more preferable for
lithium ions recovery from high Mg2+/Li+ brines by S-ED. The separation of Mg2+/Li+ tends to unsatisfactory
with increasing cation concentration (Na+, K+), and FMg-Li drops from 8.73 to 1.83 with the increase of Na+/Li+
from 1 to 5 and from 8.33 to 2.13 with the rise of K+/Li+ from 1 to 5. The strength of influence on the separation
of Mg2+/Li+ is K+ > Na+, correlating with the order of their hydrated ion radiuses. However, FMg-Li rises from
7.99 to 14.66 with the increase of SO42−, reversing with the influence of cations concentration. As for HCO3−,
the variation tendency of FMg-Li is opposite to RLi, probably ascribing to the appearance of MgHCO3+. These
observations showed that S-ED has a wide adaptability for the ion fractionation of magnesium and lithium from
brines.

1. Introduction
Lithium and its compounds, as important materials, have excellent
physical and chemical performance, which makes their application
more and more widespread [1,2] in metallurgy, glass, medicine and
energy field [3]. In particular, the demand for lithium used in lithium
ion batteries is huge. Worldwide lithium production increased by an
estimated 13% to 43,000 tons in 2017 in response to increasing lithium
demand for battery applications [4], which can increase to 66% of the
global lithium production by 2025 [5]. Thereby the demand for lithium
and its compounds has been accelerated in recent years.
The majority of world lithium production is derived from minerals,
like three spodumene operations in Australia, and salt lake brines such
as two brine operations each in Argentina and Chile [4]. Extracting
lithium from lithium ores is not only costly but also polluted seriously.
What’s more, after exploiting about a hundred years, lithium ores have
been on the verge of dried up. In recent years, lithium recovery from
salt lake brine is an important means for bridging the gap between the
supply and demand of lithium material, because about 70–80 wt% of
the total lithium resources (about 2.69 × 1010 kg) exists in brines [5,6].
In recent years, most countries in the world turned the direction of li-
thium extraction into the salt lake brine. Additionally, about 2.5 × 1014
kg lithium is reserved in the seawater, which is about ten thousand time
than that on land. Nevertheless, both salt lake brine and seawater are
mixed systems which usually contain various coexisting ions like Na+,
K+, Ca2+, Mg2+, and so on. As we all know, Li+ (radius ≈ 0.076 nm)
has similar ionic property to Mg2+ (radius ≈ 0.072 nm) since their
ionic size is nearly identical [7], making it difficult to separate Li+ and
Mg2+. Besides, the methods for extracting lithium from salt lake brine
are various on account of different ion content in diverse salt lakes. For
example, precipitation has been developed to separate and recover li-
thium from salt lake, in which a certain amount of precipitant needs to
be added to remove the coexisting calcium and magnesium, so that its
economic efficiency is relatively poor for lithium recovery from brine

⁎
Corresponding authors at: Box 307, Hebei University of Technology, No. 8, Guangrong Road, Tianjin, China.
E-mail addresses: jizhiyong@hebut.edu.cn (Z.-Y. Ji), jsyuan@hebut.edu.cn (J.-S. Yuan).

https://doi.org/10.1016/j.seppur.2018.06.012
Received 22 April 2018; Received in revised form 3 June 2018; Accepted 4 June 2018
Available online 05 June 2018
1383-5866/ © 2018 Elsevier B.V. All rights reserved.
P.-Y. Ji et al.
cathode
Membranes
Stack
Concentrate
Solution
Tank
Fig. 1. Process flow diagram of batch S-ED process.
with high Mg2+/Li+ ratio [8,9]. Somrani et al. [10] reported that in the
process of nanofiltration, the magnesium was partially entrapped and
the separation was not exhaustive. At present, other technologies such
as solvent extraction [11,12], ion exchange and adsorption [13–15]
have been developed to extract lithium from brine, and the key of these
methods is to find the right extractant and adsorbent. Considering the
strong electrolyte of aqueous lithium salt solution and the advantages
such as simple operation, environment-friendship, and energy saving of
electrodialysis (ED) process [16], it should be economic and feasible for
selective-electrodialysis (S-ED, a kind of ED) technology to condense
lithium from brine and even (concentrated) seawater [17].
As a new-type electro-membrane process, selective-electrodialysis
(S-ED) uses monovalent selective ion-exchange membrane as separation
medium [18–23]. In S-ED process, monovalent cations in desalting
compartment pass though the selective cation exchange membrane and
arrive in concentrating compartment, while a mass of multivalent ca-
tions such as Mg2+ and Ca2+ are intercepted in desalting compartment,
thus achieving the purpose of separating Mg2+/Li+ and concentrating
lithium. Dall and Boateng [24] concentrated lithium from the high
Mg2+/Li+ brines with the Mg2+/Li+ = 60. First, the Mg2+ in brine
was precipitated with CaCO3, which reduced the ratio of Mg2+/Li+ to
5, and then the recovery ratio of Li+ was up to 78.9% after multistage
electrodialysis. Furthermore, Nie et al. [25] used electrodialysis (ED) to
2
Separation and Purification Technology 207 (2018) 1–11
anode
Electrolyte Desalt
Solution Solution
Tank Tank
treat a bittern with a high Mg2+/Li+ ratio and the Li+ recovery ratio
could be over 90%. Previously, we have explored some factors like the
voltage, liner velocity of desalting and concentrating cell, pH and
Mg2+/Li+ ratio in the separation process of lithium and magnesium in
binary cations solution system. Under the optimized experiment con-
ditions, lithium resource could be recovered from brine with the high
Mg2+/Li+ of 60, and the Mg2+/Li+ ratio could reduce to 7 [26],
classified as low Mg2+/Li+ ratio category [27]. Simultaneously, we
found that the effect of coexisting ions on lithium extraction, especially
for the ions whose concentration is far above that of Li+, cannot be
ignored. In salt lake brine the concentration of coexisting monovalent
cation like Na+ or K+ is much higher than that of Li+, and divalent
anion SO42− has the highest concentration in the divalent anion. Nie
et al. proposed that free ion proportions of both lithium and magnesium
varied as sulfate was added [28]. These previous studies directly focus
on the extraction of lithium from liquid lithium resources mainly with
binary cation system: some influences of parameters on the lithium
migration, lithium recovery ratio, and specific energy consumption.
There is little concern of the migratory differences between lithium and
magnesium, which are the key difficulty for lithium extraction from
high Mg2+/Li+ ratio brine, and the synchronous effects of other co-
existing ions on Li+ and Mg2+. Additionally, HCO3− is a nonnegligible
chemical component in some salt lake brine. Sometimes the
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

concentration of HCO3− is more than that of CO32− [27,29], so the Table 1

influence of HCO3− should not always be ignored for the recovery of The composition in initial desalting compartment.
lithium. However, there is little study on the effects of HCO3− on the Ratio of Coexisting ions Mn ± System of brines Mn ± /Li+
Mg2+/Li+ separation. Mg2+/Li+
To sum up, the coexisting ions like Na+, K+, SO42− and HCO3−
20 Na+ Li+, Mg2+, Na+// 1, 5, 10, 15, 20
should have some direct effect on the migrations of Li+ and Mg2+, and
Cl−—H2O
then affect the separation of Mg2+/Li+ in the brine. In this study, some K+ Li+, Mg2+, K+// 1, 5, 10, 15, 20
investigation was carried out, facing lithium recovery from different Cl−—H2O
ternary cation systems (Li+, Mg2+, M+//Cl−—H2O, M+: Na+, K+) SO42− Li+, Mg2+//Cl−, 0, 0.06, 0.12,
and binary anion systems (Li+, Mg2+//Cl−, SO42−—H2O; Li+, Mg2+, SO42−—H2O 0.18, 0.24, 0.30
HCO3− Li+, Mg2+, Na+//Cl−, 0, 0.001, 0.002,
Na+//Cl−, HCO3−—H2O). And the separation coefficient of magne-
HCO3−—H2O 0.004
sium and lithium, recovery ratio of Li+, current efficiency and specific
energy consumption were used as evaluation index. The results will
hopefully provide some theoretical basis and data support for further (CMg2 +/CLi+)t
application of S-ED technology to produce lithium salt from salt lake FMg − Li =
(CMg2 +/CLi+)0 (1)
brine.
where CMg2 + and CLi+ are the concentrations of magnesium (g/L) and
lithium (g/L) respectively; 0 and t represent the initial and time t in S-
2. Methods and materials
ED process.
Recovery ratio (RLi) is the ratio of percentage for migration of li-
2.1. Experimental apparatus and procedure
thium ions into a concentration compartment at some point to the in-
itial lithium ions in the desalting compartment. RLi was calculated as
Electrodialysis apparatus mainly consists of membrane stack, desalt
Eq. (2).
solution tank, concentrate solution tank, electrolyte solution tank, tube
pump and direct-current (DC) power, as shown in Fig. 1. The core Vct (Cct −Cc0)
RLi (%) = × 100%
component of S-ED is membrane stack, which contains 10 pairs of Vd0Cd0 (2)
monovalent selective ion-exchange membranes with an effective sur-
where Cd0 and Vd0 are the initial concentration (g/L) of lithium ion and
face area of 0.01407 m2 in this study as before in reference [26]. The
solution volume (L) in desalting compartment respectively; both Cc0
desalt solution tank and concentrate solution tank were filled with 2.5 L
and Cct are the concentrations (g/L) at time of 0 min and t min in
artificial brine of chloride type [26,30] with the Mg2+/Li+ molar ratio
concentrating compartment; Vct corresponds to the solution volume (L)
1:20, and 1.5 L certain concentration (0.5 mol/L) NaCl solution re-
at time t in concentrating compartment.
spectively. Meanwhile, the electrolyte solution tank was filled with 2.5
Current efficiency (η) is defined as the ratio of the electric charge
L 5% Na2SO4 solution, cathode compartment shared the same electro-
contributed to the transport of the Li+ to the supplied electric charge
lyte solution tank with anode compartment. In experiment, artificial
totally. It was calculated as Eq. (3).
brine, NaCl solution and Na2SO4 solution were independently conveyed
by three pumps, and measured by rotor flowmeters. The surface flow (nt - n 0)zF
η (%) = × 100%
velocity of the electrolyte compartment, the desalting compartment and N∫0tI (t)dt (3)
the concentrating compartment were 3.8 cm/s, 5.7 cm/s and 5.7 cm/s
+
respectively. After the treatment with the membrane stack, three shares where nt is the number of moles of Li at time t in concentrating
of solution reentered the storage tanks respectively. compartment; n 0 is the initial moles of Li+ in concentrating compart-
ment; z is the valence of Li+ (+1); F is Faraday constant (96485 C/
mol); N is the number of membrane pair in S-ED stack; I and t are
2.2. Experimental design current and operating time.
Specific energy consumption (ESEC) is defined as the consumption of
The experiments were carried out at room temperature. Firstly, the electrical energy when recover 1 mol Li+. It is a significant parameter
influence of applied voltage (3–8 V) on the separation of Mg2+ and Li+ for financial interest and was calculated as Eq. (4):
from the system of Li+, Mg2+, Na+//Cl−—H2O was investigated to t
select the optimum voltage. Then, the effect of concentration variation U ∫0 I(t)dt
ESEC (kWh/mol Li) =
of different monovalent cations (expressed by molar ratio M+/Li+) and nR (4)
concentration variation of SO42− and HCO3− on the separation of
where U is applied voltage; nR is the molar number of lithium ions
Mg2+ and Li+ were studied. According to the average concentration of
increased in concentrating compartment.
lithium ions in brines, the concentration of lithium ion in salt system
was determined at 0.05 mol/L and the molar ratio of Mg2+/Li+ = 20.
In the salt lake brines of China, the HCO3−/Cl− molar ratio is always 3. Results and discussion
between 0 and 0.002. A set of experiments with higher concentration of
HCO3− were carried out in order to make the effect more obvious. 3.1. Voltage optimization
According to concentration of ions in some salt lake brine [27,29,31],
the variation of coexisting ions in initial desalting compartment was The voltage drop is one of most significantly parameter affecting the
shown in Table 1. performance of ED process. Occasionally, the voltage drop across one
cell pair (V/cp) of ED stack is in the range of 0.5–2 V/cp [32]. In order
to explore the influence of coexisting ions on the ion fractionation of
2.3. Data calculations lithium and magnesium and ensure the current density below the lim-
iting current density, different applied voltages in the range of 3–8 V
Separation coefficient of magnesium and lithium (FMg-Li) was de- considering the pairs of ion exchange membranes in the S-ED apparatus
fined as the concentration ratio of Mg2+/Li+ at a given moment to the were selected to investigate.
initial time of Mg2+/Li+ in desalting compartment. FMg-Li was calcu- The curves of the separation coefficient of magnesium and lithium
lated as following Eq. (1). (FMg-Li) at different voltages (3–8 V) are shown in Fig. 2(a). It can be

3
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
9 80
3V
8 70 5V
3V 6V
7 60
5V 7V
6 6V 8V
7V 50
5 8V
FMg-Li

40

RLi(%)
4
30
3
20
2

1 10

0 0
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 13 0
Time (min) Time (min)
(c) (d)
11 0.40
3V
3V 0.35 5V
10 5V 6V
6V 7V
0.30
7V 8V
Current efficiency(%)

ESEC (kWh/mol Li)

9
8V
0.25
8
0.20

7
0.15

6 0.10

5 0.05
10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130

Time (min) Time (min)

Fig. 2. Effect of applied voltage on the separation of Mg2+/Li+. (a) separation coefficient of magnesium and lithium; (b) recovery ratio of Li+; (c) current efficiency;
(d) specific energy consumption.

observed that the FMg-Li value and the applied voltage have positive
correlation. After 120 min, while the FMg-Li at 3 V is only 1.22, it has
higher value (5.23, 6.38 and 7.84, respectively) at 6 V, 7 V and 8 V. It is
indicated that the higher the voltage, the greater the driving force of
lithium ion migration, but the leakage rate of magnesium ion is not
obvious. So a higher applied voltage is beneficial to the ion fractiona-
tion of magnesium and lithium. The recovery ratio of Li+ (RLi) at dif-
ferent voltages (3–8 V) as a function of time is shown in Fig. 2(b). As
shown, RLi increases with the applied voltage going up. RLi reaches to a
plateau (70.91%) at 8 V after 120 min operating time, whereas this
value droppes to 21.91% for the experiment operated at 3 V. Under the
condition of 6 V and 7 V, RLi has reached to 67.65% and 71.89% re-
spectively which belong to higher value. From the FMg-Li and RLi, the
appropriate voltage range is 6–8 V. To select the optimal applied vol-
tage, the current efficiency should be considered.
The variation of current efficiency (η) with time at different voltages
is shown in Fig. 2(c). It indicates that the η decreases with operation
time, and the descending rate increases with the voltage rising ap-
proximately. This should mainly because that the electro-driving force
of transferring each ion at a lower voltage (such as 3 V) is also at an
inferior level. So, the amount of lithium ions migration per unit time is
limited extremely when the operating voltage is too weak. Further, the
current efficiency of migrating lithium ions at lower voltages is smaller.
As the voltage rises, the driving force of ions migration becomes
greater; however, being short of monovalent ion content under batch
operation conditions, the current efficiency decreases fastest at the
voltage of 8 V. When the voltage is 3 V and 5 V, the current efficiency is
lower, while it is higher at 7 V and 8 V. However, the values of η de-
crease rapidly when the voltages are 7 V and 8 V and stay in an unstable
state, which may be a disadvantage of S-ED process to some extent.
When the voltage is 6 V, the current efficiency is higher than that of 3 V
and 5 V, and more stable than that of 7 V and 8 V. Fig. 2(d) shows the
variation of specific energy consumption (ESEC) at different voltages.
With the applied voltage up, the ESEC increases from 0.11 kWh/mol Li
to 0.33 kWh/mol Li. This suggests more energy will be used to transfer
the coexisting ions at high voltage [32]. The ESEC curves under 3–6 V
keep nearly flat with each value, while the ESEC curves under 7 V and
8 V have an upward trend and the values of ESEC can rise to 0.27 kWh/
mol Li and 0.33 kWh/mol Li at 120 min, respectively. When the voltage
is 6 V, the curve is relatively smooth and moderate. Considering both
separation effect and economic aspect, 6 V should be considered to be
an appropriate applied voltage.
3.2. Effect of coexisting cations (Na+, K+) on the separation of Mg2+/Li+
The concentrations of sodium- and potassium ions in salt lake brine
are higher than that of lithium ions extremely, which will inevitably
lead to a competitive migration with lithium ion and inhibit the leakage
of magnesium in S-ED process. Thus, it is necessary to investigate the
influence of coexisting K+ and Na+ on the ion fractionation of mag-
nesium and lithium. In this part section, two artificial brines with
specific ternary chloride type systems (Li+, Mg2+, M+//Cl−—H2O,

4
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
10 80

9 +
Na /Li = 1
+
70
+ +
8 + + Na /Li = 5
Na /Li =1 + +
+ + 60 Na /Li = 10
7 Na /Li =5 + +
+ + Na /Li = 15
Na /Li =10 50 + +
6 + + Na /Li = 20
Na /Li =15
FMg-Li

RLi(%)
+ +
5 Na /Li =20 40

4 30
3
20
2
10
1

0 0
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130

Time (min) Time (min)

(c) (d)
20 1.0

18 0.9
+ + + + + +
Na /Li = 1 Na /Li = 5 Na /Li = 10 +
Na /Li = 1
+ + +
Na /Li = 5
+ +
Na /Li = 10
16 + + + + 0.8
Na /Li = 15 Na /Li = 20 + +
Na /Li = 15
+ +
Na /Li = 20
Current efficiency(%)

14 0.7
ESEC(kWh/mol Li)

12 0.6

10 0.5

8 0.4

6 0.3

4 0.2

2 0.1

0 0.0
10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min) Time (min)

Fig. 3. Effect of Na+ on the separation of Mg2+/Li+. (a) separation coefficient of magnesium and lithium; (b) recovery ratio of Li+; (c) current efficiency; (d) specific
energy consumption.

M+: Na+, K+) were used to explore the effect of concentration varia-
tion (Expressed in molar ratio M+/Li+) on the separation of magne-
sium and lithium.
3.2.1. Effect of coexisting Na+
Fig. 3(a) shows the separation coefficient of magnesium and lithium
(FMg-Li) under different molar ratios of Na+/Li+. It can be seen that the
FMg-Li value is greater than 1 at various Na+/Li+. Then the ion frac-
tionation of magnesium and lithium can be achieved. Moreover, all the
curves of FMg-Li show an upward trend with the decreasing of Na+/Li+
and the FMg-Li reaches to 8.7 at Na+/Li+ = 1 after 120 min. The in-
crease of Na+ concentration is adverse to the separation of Mg2+/Li+.
Because the increasing of sodium ion concentration is not a stronger
inhibition for magnesium ion migration; but it has a very strong impact
on lithium ion migration. Additionally, the FMg-Li increases with time,
especially under the condition of lower sodium ion concentration. This
mainly attributes to the divalent magnesium ions are retained by the
monovalent selectivity ion-exchange membranes, and lithium ions can
permeate the membranes easily in S-ED. When the sodium concentra-
tion is low, it is apparent that the competition transfer between sodium
ion and lithium ion is weak, and the migration of lithium ion is faster.
To sum up, the smaller the Na+/Li+ molar ratio, the better the se-
paration effect of magnesium and lithium. Fig. 3(b) is the variation of
recovery ratio of Li+ with time in different Na+/Li+ molar ratio. It can
be observed that the RLi curves gradually grow with time. Furthermore,
with the adding of Na+ in feed solution, the RLi value is dropped
clearly, and this value decreases from 71.24% to 39.72% after 120 min.
It also can be seen that the curves of RLi (at Na+/Li+ > 15) become
slower gradually after 80 min. This phenomenon can be explained that
the migration rate of lithium ion is faster under lower Na+/Li+ ratio
and there are not enough lithium ions to sustain lithium migration
process in batch operation mode.
As shown in Fig. 3(c) and (d), the curvilinear trend of current effi-
ciency is opposite to that of the specific energy consumption. With the
adding of Na+, the current efficiency curves of Li+ show a downward
trend. It could be attributed to sodium ion, which has a smaller hy-
drated ion radius than lithium ion, preferentially passes through the
membrane to carry part of the current. So, the ratio of the electric
charge contributed to the transport of the Li+ decreased at higher Na+/
Li+ condition. Moreover, the curve is decrease at the condition of Na+/
Li+ = 1, which may be due to the low ionic strength of Na+, the mi-
gration rate of Li+ is faster. As time goes on, the removable lithium ion
in feed solution is reduced, resulting in a significant decline in current
efficiency. Fig. 3(d) exhibits the specific energy consumption (ESEC)
tends to be stable with the operation time in the range of Na+/Li+ from
1 to 20. With the increasing of Na+/Li+, the ESEC shows an upward
trend. In the solution system selected in this experiment, hydrated ion
radius of lithium (0.382 nm) is larger than that of sodium (0.358 nm)
[30], so the migration of sodium exceeds that of lithium. The migration
of Na+ consumed electric energy, causing the increase of ESEC. When
the concentration of Na+ is increased, there are more Na+ competing
with Li+, then the Na+ will preferentially permeates through

5
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
10 80
+ +
9 K /Li =1
70 + +
K /Li =5
8 + + + +
K /Li =1 60 K /Li =10
+ + + +
7 K /Li =5 K /Li =15
+ + + +
K /Li =10 50 K /Li =20
6 + +
K /Li =15
FMg-Li

RLi(%)
+ +
5 K /Li =20 40

4
30
3
20
2
10
1

0 0
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min) Time (min)
(c) (d)
20 1.0
+ +
K /Li =1 +
K /Li =1
+ + +
K /Li =5
+ +
K /Li =10
18 + + 0.9
K /Li =5 + +
K /Li =15
+ +
K /Li =20
+ +
16 K /Li =10 0.8
+ +
K /Li =15
14 0.7
Current effciency (%)

+ +
K /Li =20
ESEC(kWh/mol Li)

12 0.6

10 0.5

8 0.4

6 0.3

4 0.2

2 0.1

0 0.0
10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min) Time (min)

Fig. 4. Effect of K+ on the separation of Mg2+/Li+. (a) separation coefficient of magnesium and lithium; (b) recovery ratio of Li+; (c) current efficiency; (d) specific
energy consumption.

membrane. Thereby, the consumption of electrical energy will increase.
3.2.2. Effect of coexisting K+
The effects of coexisting K+ on the separation of magnesium and
lithium are shown in Fig. 4, which is similar to the effect of Na+. This
can be explained that the hydrated ion radius of K+ (0.331 nm) is more
close to Na+ (0.358 nm) [30]. It can be observed from Fig. 4(a) that
FMg-Li > 1 and the FMg-Li value decreased gradually with the increasing
of K+/Li+ molar ratio, indicating that the higher concentration of K+ is
also negative to the separation of Mg2+/Li+.
Fig. 4(b) shows that the variation of recovery ratio of Li+ with time
in different K+/Li+. With the increasing of K+ concentration, RLi de-
creases from 69.07% to 46.09% (corresponding to K+/Li+ 1–20).
Moreover, RLi increases rapidly in the first 80 min and reaches to a
plateau after 120 min operating time when K+/Li+ = 1. It mainly as-
cribes lower concentration of K+ has less competition for Li+, and li-
thium ions migrate faster in the initial phase. Then the concentration of
Li+ in the desalting compartment decreases with time while the con-
centration of Li+ in the concentrating compartment increases. So it is
possible that the amount of transferable lithium reduces in the desalting
compartment and concentration diffusion enhances with the increase of
the Li+ concentration in the concentrating compartment, and then the
growth trend of the RLi slows down.
As shown in Fig. 4(c), the current efficiency reached nearly each
constant when K+/Li+ ≥ 5, but there is a downward trend in the
current efficiency at the condition of K+/Li+ = 1. The differences
between them mainly result from that fewer ions can be used to migrate
at lower concentration of monovalent cations (K+/Li+ = 1) in S-ED
process. This means that too little transferable potassium ion makes the
competition between K+ and Li+ weaken, and the content of trans-
ferable lithium decreases more quickly as the experiment continues,
which further leads to the decreasing trend of current efficiency curve
with time. Fig. 4(d) shows the variation of specific energy consumption
(ESEC) with time at different K+/Li+. The values of ESEC are relatively
stable with time going on. At the condition of K+/Li+ = 1, the
minimum ESEC was 0.117 kWh/mol Li at 120 min. With K+/Li+ in-
creasing from 1 to 20 in this paper, there are different degrees of rise in
ESEC and its maximum value is 0.83 at the condition of K+/Li+ = 20.
3.2.3. Contrastive analysis of Na+ and K+ effects
Fig. 5(a) and (b) show the comparison of effects of Na+ and K+ on
the variation of FMg-Li and RLi with M+/Li+ ratio increase in brines.
When the coexisting sodium ions are added in the solution, FMg-Li is
higher than adding the same molar ratio of potassium ions. It is ap-
parent that the effect of K+ on FMg-Li is more notable than that of Na+.
At the same ratio of M+/Li+, K+ has greater impact on FMg-Li than Na+,
indicating the competition between K+ and Li+ is stronger. Moreover,
whether the increase of K+ concentration or that of Na+, it is dis-
advantage to Mg2+/Li+ separation.
From the current efficiency as shown in Fig. 5(c), when the

6
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
1.50
24
1.45
+
Na 21 Na
+

1.40 K
+
+
K
1.35 18

1.30

RLi(%)
FMg-Li

15
1.25

1.20 12

1.15
9
1.10
6
1.05
-2 0 2 4 6 8 10 12 14 16 18 20 22 -2 0 2 4 6 8 10 12 14 16 18 20 22
+ + + +
M /Li M /Li
(c) (d)
0.9
18
+ 0.8
16 Na
+ +
K Na
0.7
14 +
K
Current effciency (%)

12 0.6
Esec (kWh/mol)

10 0.5

8 0.4

6 0.3

4 0.2

2 0.1

0 0.0
-2 0 2 4 6 8 10 12 14 16 18 20 22
-2 0 2 4 6 8 10 12 14 16 18 20 22
+ + + +
M /Li M /Li
Fig. 5. Comparison of effects of Na+ and K+ on the separation of Mg2+/Li+. (a) separation coefficient of magnesium; (b) lithium and recovery ratio of Li+; (c)
current efficiency; (d) specific energy consumption.

coexisting sodium ions are added in the solution, the η value is also
higher than that of adding the same molar ratio of coexisting potassium
ions. It also can be seen that the influence of K+ on lithium migration is
greater than that of Na+ at the same M+/Li+. In addition, current ef-
ficiency changes in two-stage with the variation of M+/Li+. When the
ratio of M+/Li+ is less than 10, the competitive effect of sodium ions on
lithium- and magnesium ions is strengthened with the increase of M+/
Li+, and then the value of η decreases rapidly. But when the M+/Li+ is
more than 10, there are enough sodium ions in the solution, so the
migration of sodium ions dominates, and the lithium ions migration
changes a little. Thus, the downward trend of the curves of η is slowing
down. Fig. 5(d) indicates that with the increase of M+/Li+, ESEC of Li+
with the effect of K+ increases faster comparing with the effect of Na+.
It implies that K+ is more likely to migrate through the membrane than
Na+, and then the effect of K+ on Li+ migration is more obvious than
that of Na+.
It is obvious from Fig. 5 that the influence order at the same M+/
Li+ of monovalent coexisting cations on the separation of magnesium
and lithium is K+ > Na+. This is mainly because that the hydrated ion
radius of K+ is smaller than that of Na+, so the migration rate of K+
across monovalent selective cation exchange membrane is easier. In
general, K+ has a greater influence on the transmembrane migration of
Li+ than Na+. The factors of ionic radius, hydrated ionic radius and
Gibbs free energy of various major cations contained in natural brine
were list in our previous study [30]. The influence order of coexisting
cations is reverse to the order of its hydrated ion radius (K+ < Na+),
indicating that the influence order of coexisting ions on the migration of
Li+ is mainly determined by their hydrated ionic radii. In summary, the
higher the concentration of monovalent cations (K+, Na+), the stronger
migration competition toward lithium ions and even more passive to
the separation of Li+ and Mg2+.
3.3. Effect of coexisting anions on separation of Mg2+/Li+
Above, the influence of monovalent cations in salt lake brine on the
separation of magnesium and lithium has been discussed. As we all
know, the composition of salt lake brine is complex, and various anions
(chloride, sulfate, borate and carbonate ions) generally exist. So it is
also meaningful investigating the influence of anions on the ion frac-
tionation of lithium and magnesium.
3.3.1. Effect of coexisting SO42−
The separation of SO42− and Cl−, NO3−, etc. by selective-electro-
dialysis have also been studied [33–35]. All their studies have con-
cluded that ED is an effective technique for the removal of sulfate ions
from some kind of pending solution. In this study, the effects of coex-
isting SO42− on the ion fractionation of lithium and magnesium are
shown in Fig. 6. With the concentration of SO42− increase, FMg-Li, RLi
and η all increase but ESEC decreases, indicating that the higher the
concentration of SO42−, the better the separation effect of Mg2+ and

7
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
20 80

18
2- - 70
SO4 /CI = 0
16 2- -
SO4 /CI = 0.06
14 2- -
60
SO4 /CI = 0.12
2- -
12 SO4 /CI = 0.18 2- -
50 SO4 /CI =0
2- -

RLi(%)
FMg-Li

10 SO4 /CI = 0.24 2- -

2- -
SO4 /CI = 0.06
SO4 /CI = 0.30 40 2- -
8 SO4 /CI =0.12
2- -
6 30 SO4 /CI =0.18
2- -
4 SO4 /CI =0.24
2- -
20 SO4 /CI =0.30
2

0 10
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130

Time (min) Time (min)

(c) (d)
30 0.20
2- - 2- -
28 SO4 /CI = 0 SO4 /CI = 0
0.18 2- -
2- -
SO4 /CI = 0.06 SO4 /CI = 0.06
26
2- - 2- -
SO4 /CI = 0.12 0.16 SO4 /CI = 0.12
24
Current efficiency(%)

2- - 2- -
SO4 /CI = 0.18 SO4 /CI = 0.18
ESEC(kWh/mol Li)

22 0.14 2- -
2- -
SO4 /CI = 0.24 SO4 /CI = 0.24
2- - 2- -
20 SO4 /CI = 0.30 0.12 SO4 /CI = 0.30
18
0.10
16
0.08
14

12 0.06

10 0.04
10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min) Time (min)
Fig. 6. Effect of SO42− on the separation of Mg2+/Li+. (a) separation coefficient of magnesium and lithium; (b) recovery ratio of Li+; (c) current efficiency; (d)
specific energy consumption.

Li+. This is contrary to the observations in previous literatures [36,37],
where it proposed that the transfer of monovalent cations is limited by
the presence of divalent anions to maintain the electroneutrality of the
solution. This discrepancy can be explained by the characteristics of
feed solutions as follows.
The salinity of the feed solution in this study is extremely high
compared with the feed solution in previous literatures [36,37] and the
concentration of magnesium is also much higher than that of lithium.
Under the driving of external electric field, there is a tendency that
SO42− migrates to the anode, and both Mg2+ and Li+ migrate toward
the cathode. Because of the selectivity of monovalent ion exchange
membrane, sulfate ions and magnesium ions are mostly trapped in
desalination compartment. According to Debye-Hückel theory [38–40],
sulfate migrating toward the anode has electrostatic attraction to cation
migrating toward the cathode. The greater the number of charges, the
larger the Coulomb force between ions. So the attraction between Mg2+
and SO42− is greater. As shown in Fig. 7(a), when no sulfate ions exist
in the solution, most of magnesium ions will gather in the adjacent area
of anion exchange membrane facing the desalting compartment. When
sulfate ions are added in feed solution (Fig. 7(b)), there is a certain
decrease of magnesium ions which tend to the adjacent area of anion
exchange membrane, due to the attraction effect of sulfate ions. That is
to say, the addition of SO42− can weaken the competitive migration
between magnesium- and lithium ions; on the other hand, the re-
sistance of lithium ion penetrating membrane can also be reduced due
to weak electric layer of magnesium ions. This slight gravitational
difference makes it easier for Li+ to move toward the cathode. As
shown in Fig. 8, with the increase of sulfate content, the difference of
final concentrations of magnesium ion in desalting- and concentrating
compartments also illustrates aforesaid explanation. It can also be seen
that the effect enhances with the increase of the SO42− concentration.
As shown in Fig. 6(a), when the ratio of SO42−/Cl− ramps up from 0
to 0.3, the FMg-Li increases from 7.99 to 14.66 after 120 min. With the
addition of sulfate, the magnesium ions near the diffusion boundary
layer on the cation exchange membrane reduce and then cause Li+
more likely to migrate. Thus the migration quantity of magnesium ions
become smaller, meanwhile, the migration of Li+ becomes faster at the
same condition. In Fig. 6(b), the value of RLi is the highest when the
ratio of SO42−/Cl− is 0.3, and the lowest at SO42−/Cl− = 0. Since
Mg2+ is not 100% retained by monovalent cation exchange membrane,
there are some competitive migrations of magnesium- and lithium ions.
With the concentration of SO42− increase, the SO42− can attract more
magnesium ions migrating toward cathode, and then both the leakage
ratio of magnesium ions and the migration resistance of lithium ions
reduce in a certain degree. As a result, the competitive migration be-
tween magnesium- and lithium ions will be weakened. Li+ will be
migrated faster with the addition of SO42−, which is more beneficial to
the separation of Mg2+ and Li+ and the purification of lithium ions.
In Fig. 6(c), the values of η increase with the molar ratio of SO42−/
−
Cl going up. The migrate rate of Li+ increases due to the resistance of

8
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

A C A A C A
+ +
2+ Li Li
- Mg
Cl + +
Li - Li Mg
2+
Cl
+ +
Li + Li
Li
+ 2+ +
+ Li Mg Li
+
Li
Li
+ +
Li Li
_
2-
SO4

_
-
- Cl - -

+
Cl

+
Cl Li
+ Cl +
+ 2+ Li
Li Mg +
+
Li Mg
2+
SO
SO44
2-
2-

Li +
+ +
Li Li Li Mg
2+

+ 2+ 2+ +
Li - Mg Mg + Li Mg
2+
2+ +
Cl Li -
Mg Li
Cl
- 2+ 2-
Cl Mg - SO
SO44
2-

Cl +
Li

Concentrating compartment Desalting compartment Concentrating compartment Desalting compartment

a b
Fig. 7. Comparison of magnesium ions migration in solution by adding sulfate ions.

2.50 0.5 values of pH from 6 to 9. The existing form of bicarbonate is MgHCO3+,

Molar number of Mg in concentrating tank

Molar number of Mg in desalting tank

which is more difficult electro-migrated by electric potential due to its

2.25
0.4
large steric hindrance. The increase of the HCO3− concentration can
result in the pH increase in desalting compartment as shown in Fig. 10,
2.00 so more MgHCO3+ can exist in desalting compartments and then the
0.3 concentration of free Mg2+ decreases in desalting compartment.
2+

1.75 Moreover, the ratio of Mg2+ and Li+ with a certain initial value de-
2+

creases as the experiment going on, and then the value of FMg-Li de-
0.2
1.50
creases. Therefore, it is to be sure that the presence of HCO3− positively
influence the separation of Mg2+ and Li+, although the FMg-Li decreases
0.1 with the increase of the HCO3− concentration, ascribing to magnesium
1.25
intercepted in the desalting compartment in the form of free Mg2+ and
MgHCO3+. In addition, because of the large steric hindrance of
1.00 0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 MgHCO3+, it is more difficult to permeate the cation exchange mem-
2- -
brane than the Mg2+, and the migration amount of lithium ions in-
The molar ratio of SO 4 /Cl creases relatively. As a result shown in Fig. 9(b), the value of RLi en-
hances slightly with the increase of HCO3−/Cl−.
Fig. 8. The final molar number of Mg2+ in desalting- and concentrating tank.
With the increasing of the HCO3−/Cl−, the η rises and the ESEC
declines, which can be seen in Fig. 9(c) and (d). These show that the
the migration of Li+ declining, resulting from the decreasing con- higher the concentration of HCO3−, the better the separation of Mg2+
centration of the magnesium ions in the adjacent area of membranes and Li+ from an economic point of view. As a consequence, the pre-
with the addition of sulfate. It is apparent in Fig. 6(d) that the ESEC sence of HCO3− positively affected Mg2+/Li+ separation with the in-
decreases with the SO42−/Cl− ratio rise. Both the variations of η and crease of the HCO3− concentration. However, a detailed analysis for the
ESEC with the increase of SO42− suggest that adding sulfate into brine is extent of the MgHCO3+ or the MgHCO3+ transport requires further
beneficial to the ion fractionation of magnesium and lithium. investigation with additional experiments carried out in the next work.

3.3.2. Effect of coexisting HCO3− 4. Conclusions

HCO3− is also an important ion component of salt lake brine,
especially in China and its content is even more than that of CO32− An S-ED process was used to investigate the effect of coexisting ions
[27,29]. But there are no studies on the effect of HCO3− in the view of (including Na+, K+, SO42− and HCO3−) on the ion fractionation of
lithium extraction by S-ED technology. In this section, monovalent lithium and magnesium in Mg2+/Li+ ratio brines. Through in-
anion HCO3− was investigated on the influence of Mg2+/Li+ separa- vestigating the influence of applied voltage on the separation of Mg2+
tion. and Li+ in the ternary cation systems of Li+ (Li+, Mg2+, Na+//
The curves of FMg-Li and RLi in different HCO3−/Cl− ratios ranging Cl−—H2O), 6 V was considered as the optimum one with overall con-
from 0 to 0.004 are shown in Fig. 9(a) and (b). The value of FMg-Li sideration. With investigating the effect of different cations concentra-
decreases with the increasing of HCO3−/Cl−, but the RLi increases tion (expressed by molar ratio M+/Li+, M+: Na+ and K+) on the se-
slightly. This is an abnormal phenomenon, which should attribute to paration of Mg2+ and Li+, it is obvious that the higher the
the bicarbonate ionization and its hydrolysis in aqueous solution as concentration of coexisting monovalent cations, the stronger the com-
following: petitive migration of coexisting cations relative to Li+, then leading to
more negative effect on the ion fractionation of magnesium and li-
HCO3− ⇌ H+ + CO32− (5) thium. The influence intension of coexisting cations at the same M+/
Li+ on the Mg2+/Li+ separation is in the following order K+ > Na+,
HCO3− + H2O ⇌ OH −
+ H2CO3 (6)
which is reversed to their hydrated ion radius. However, with the
And the hydrolysis of HCO3−
is greater than its ionization, so the pH of concentration of SO42− increase, all FMg-Li, RLi and η are increased and
the solution increase in diluting compartment with the adding of ESEC is decreased. It indicates that the higher the concentration of
HCO3−. Stefansson et al. [41,42] presented that Mg2+ and HCO3− SO42−, the better the separation effect of Mg2+/Li+. That is to say,
could exist in the form of MgHCO3+ (Mg2+ + HCO3− ⇌ MgHCO3+) at sulfate ions could be benefit for lithium ions transfer. Furthermore, the

9
P.-Y. Ji et al. Separation and Purification Technology 207 (2018) 1–11

(a) (b)
5.0 70

4.5 - - - -
HCO 3 /Cl =0 HCO3 /Cl =0
- -
60 - -
4.0 HCO 3 /Cl =0.001 HCO3 /Cl =0.001
- - - -
3.5 HCO 3 /Cl =0.002 HCO3 /Cl =0.002
50
- - - -
3.0 HCO 3 /Cl =0.004 HCO3 /Cl =0.004
FMg-Li

RLi(%)
2.5 40

2.0
30
1.5

1.0
20
0.5

0.0 10
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130

Time(min) Time(min)
(c) (d)
9
- -
- - 0.40 HCO 3 /CI =0
HCO 3 /Cl =0 - -
8 - - HCO 3 /CI =0.001
HCO 3 /Cl =0.001 - -
- - 0.36 HCO 3 /CI =0.002
Current efficiency(%)

HCO 3 /Cl =0.002 - -

7 - -
Esec(kWh/mol Li) HCO 3 /CI =0.004
HCO 3 /Cl =0.004
0.32
6

0.28
5

4 0.24

3 0.20
10 20 30 40 50 60 70 80 90 100 110 120 130 10 20 30 40 50 60 70 80 90 100 110 120 130
Time(min) Time (min)

Fig. 9. Effect of HCO3− on the separation of Mg2+/Li+. (a) separation coefficient of magnesium; (b) lithium and recovery ratio of Li+; (c) current efficiency; (d)
specific energy consumption.

7.0 migration of Mg2+, next Li+.

Acknowledgment
The pH in diluting compartment

6.8

The research was supported by Program for the Top Young

Innovative Talents of Hebei Province, Tianjin Research Program of
6.6 Application Foundation and Advanced Technology (12JCQNJC03300),
Program for Changjiang Scholars and Innovative Research Team in
University (PCSIRT, IRT14R14). And the work is also supported by
6.4
- -
National Natural Science Foundation of China (20806019), Natural
HCO3 /CI =0
Science Foundation of Hebei Province (B2009000024 and
- -
HCO3 /CI =0.001 B2017202246), Education Department of Hebei Province (2008112),
6.2 -
HCO3 /CI =0.002
-
the Key Technologies R&D Program of Hebei Province of China (No.
-
HCO3 /CI =0.004
- 12276713D), and Applied Basic Research Project of Hebei Province
(13963103D).
6.0
-10 0 10 20 30 40 50 60 70 80 90 100 110 120 130
Time (min) References

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