CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 57 (2017) 126–133

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CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Phase diagram of the quaternary system LiCl+MgCl2+KCl+H2O at 323.15 K MARK

a,b c c,⁎ a,⁎ d
Haitang Yang , Tengyu Liang , Dewen Zeng , Jianling Yue , Yong Du
a
Hunan Key Laboratory of Advanced Fibers and Composites, Central South University, 410083 Changsha, PR China
b
School of Metallurgical and Materials Engineering, Hunan University of Technology, 412007 Zhuzhou, PR China
c
College of Chemistry and Chemical Engineering, Central South University, 410083 Changsha, PR China
d
State Key Laboratory of Powder Metallurgy, Central South University, 410083 Changsha, PR China

A R T I C L E I N F O A BS T RAT

Keywords: Solubility isotherms as well as the corresponding solid phases of the quaternary system LiCl+MgCl2+KCl+H2O
LiCl and the eutectic points for the ternary systems LiCl+MgCl2+H2O, LiCl+KCl+H2O and MgCl2+KCl+H2O at
MgCl2 323.15 K have been elaborately determined by an isothermal equilibrium method. Five crystallization fields
KCl including two double salts (LiCl·MgCl2·7H2O(s) and KCl·MgCl2·6H2O(s)), two hydrate salts (MgCl2·6H2O(s)
Phase diagram
and LiCl·H2O(s)) and one single salt (KCl(s)) were detected in the quaternary system. The reliability of the
experimental results were verified both by testing the phase diagram rule and comparing with the literature
data. It was found that all of the results were accordance with the phase diagram rule, and moreover, the
excellent agreement between the experimental data and the literature data was also obtained, which indicate
that the solubility data obtained in this work are reliable. Based on the quaternary phase diagram, the example
was provided for industrial application. The measured phase diagram reported in this work are the essential tool
to guide industrial process of extracting Li from the salt lake brine containing MgCl2 and LiCl using KCl reagent.

1. Introduction
After multi-step evaporation of the Qaidam salt-lake brine (mainly
containing the ions K+, Na+, Li+, Mg2+, Cl−, SO42−, CO32−, B4O72−, and
H2O) by solar ponds technology, the brine can be roughly treated as the
system LiCl + MgCl2 + H2O [1]. For this system, the mass ratio of
Mg:Li is approximately 20–60. Nevertheless, the method for economic-
ally separating the Mg and Li with such a high Mg:Li ratio is a
challenge for all chemical engineers [2]. Among all the separating
methods, Voigt [3] suggested an economical and practical method, by
which the reagent KCl was proposed to add into the salt brine to
crystallize out MgCl2 as double salt MgCl2·KCl·6H2O (s). The obvious
solubility difference between MgCl2·KCl·6H2O(s) and LiCl·H2O(s)
ensures the practicability of this method. Meanwhile, the abundant
KCl(s) product in the process of evaporating the salt lake brine
guarantees the economy of this method. However, to apply this method
to guide the practical production, information on the phase diagram of
the quaternary system LiCl+MgCl2+KCl+H2O and its sub-ternary
systems from 273.15 to 323.15 K are urgent required.
To date, the phase diagrams of the ternary systems MgCl2+LiCl
+H2O [4–6], LiCl+KCl+H2O [7,8] and KCl+MgCl2+H2O [9–13] have
been widely reported from 298.15 to 373.15 K. The stable phase
diagram for the quaternary system at 298.15 K has been reported by
Zhang [14]. Meanwhile, the metastable phase diagram for this qua-
ternary system at 323.15 K has also been determined by Yu [15], but
the crystallization zones are quite different with the results reported by
Zhang [14]. For a solar pond technique in summer, however, the stable
solubility isotherms of this quaternary system at 323.15 K are even
more important but have been unknown so far.
In order to obtain the accurate phase diagram of the quaternary
system LiCl+MgCl2+KCl+H2O at T=323.15 K, we elaborately deter-
mined the stable phase diagram by the isothermal equilibrium method
in this work. To verify the reliability of the experimental data in this
work, we also determined the eutectic points of the ternary systems
MgCl2+LiCl+H2O, LiCl+KCl+H2O and KCl+MgCl2+H2O at 323.15 K
and compared with the literature data.
2. Experimental section
2.1. Materials
LiCl was prepared by neutralizing Li2CO3 with HCl and then
purified by twice crystallization. MgCl2 and KCl were directly recrys-
tallized four times from water. Doubly distilled water (S ≤1.2×10−4 S/
m), silver nitrate (wt% > 0.999), EDTA (wt% > 0.999) and KB(C6H5)4
(wt% > 0.999) were also used in the experiment. The main impurity

⁎
Corresponding authors.
E-mail addresses: dewen_zeng@hotmail.com (D. Zeng), jlyue2010@csu.edu.cn (J. Yue).

http://dx.doi.org/10.1016/j.calphad.2017.04.001
Received 20 December 2016; Received in revised form 31 March 2017; Accepted 3 April 2017
0364-5916/ © 2017 Elsevier Ltd. All rights reserved.
H. Yang et al. CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 57 (2017) 126–133

Table 1
Specifications of chemicals used in this work.

Chemical Name Source Initial Mass Fraction Purification Final Mass Fraction Analysis Method
Purity Method Purity

Potassium chloride (KCl) Sinopharm Chemical > 0.999 recrystallized four times 0.9999 ICP
Reagent Co.

Magnesium chloride hexahydrate Sinopharm Chemical > 0.999 recrystallized four times 0.9999 ICP
(MgCl2·6H2O) Reagent Co.

Lithium chloride synthesized by ourselves recrystallized two times ≥0.9999 ICP

(LiCl·H2O)

Lithium chlorate Shanghai China-Lithium 0.9995 none ICP

(Li2CO3) Industry
Hydrochloric acid (HCl) Sinopharm Chemical Reagent 0.9998 none ICP
Co.

Silver nitrate Sinopharm Chemical 0.9998 none ICP

(AgNO3) Reagent Co.

Hydrogen nitrate Sinopharm Chemical 0.9998 none ICP

(HNO3) Reagent Co.

Zinc oxide Sinopharm Chemical 0.9999 none ICP

(ZnO) Reagent Co.

Disodium EDTA Sinapharm Chemical 0.9998 none ICP

Reagent Co.
Absolute Sinapharm 0.9998 none ICP
ethylalcohol Chemical
(C2H5OH) Reagent Co.
Normal butylalcohol Sinapharm Chemical 0.9998 none ICP
(C4H9OH) Reagent Co.

Sodium tetraphenylboron (NaB(C6H5)4) Sinapharm Chemical 0.9998 none ICP

Reagent Co.

Potassium tetraphenylborate (KB(C6H5)4) Sinapharm Chemical 0.9998 none ICP

Reagent Co.

Acetic acid glacial (C2H5COOH) Sinapharm Chemical 0.9998 none ICP

Reagent Co.
−4
Water (H2O) distilled three times σ≤ 1.1×10 S/m TDS

elements Ca, Mg, Li, Na, K, Fe and Ba in the prepared reagents were
analyzed by Inductively Coupled Plasma (ICP) emission spectrometry
(US Perkin Elmer Corporation, Optima 5300DV), and the content of
each element was determined to be less than 200 ppm. Table 1 gives
the instructions of all the chemical reagents used in this work.
2.2. Experimental apparatus
A vertical section of the isotherm equilibrium apparatus used in this
work is presented in Fig. 1a. The thermostat (Germany, LAUDA E219)
consists of four parts, including a stainless steel tank (A), the digital
heating controller (B), the heating coils (C) and a stirring pump (D),
exhibiting the temperature stability ± 0.01 K. The temperature differ-
ence between the diagonal lying corners of the thermostat is less than
0.008 K. The temperature was determined using a calibrated glass
thermometer with an accuracy of ± 0.005 K. A sealing plate (F) was
used to separate the water vapor from the mixture of the bath (E). The
plastic pads with holes (J) were used to make the temperature of the
samples more uniform. A Sartorius (CPA225D) balance was used for
weighing with an error of ± 0.1 mg.
2.3. Experimental procedures
As reported in the literature [1], solid-liquid equilibrium experi-
ments were carried out in a ground 250 cm3 glass equilibrium flask (G)
which was immersed in the thermostat filled with a glycol-water
mixture (E). The solution and solid in the flask were stirred with a
magnetic stirrer (I) outside the thermostat. Each sample was placed
and stirred in the thermostat for approximately 200 h, and then kept
static for approximately 12 h. The sample of the saturated solution was
then removed using a pipette, with the tip covered in glass cloth as a
filter, and transferred to two weighed 30 cm3 quartz bottles (a, b, c).
The wet solid was transferred using a glass scoop into a 25 cm3 sintered
glass filtering crucible. The solid was analyzed by X-ray diffraction and
the solution was analyzed according to the following procedures:
(1) The concentration of MgCl2 in this system was determined by
titrating the Mg2+ ions in bottle (a) with EDTA, as described in the
literature [16,17].
(2) The concentration of KCl in this system was determined by
precipitating K+ ions in bottle (b) with NaB(C6H5)4, as described
in the literature [16,17] except for some slight differences: (i) the
NaB(C6H5)4 solution was prepared ahead of a night to analyze the
solution; (ii) the mass of KB(C6H5)4 precipitation was controlled
between 0.2 g to 0.3 g; (iii) a drop of saturated HNO3 solution and
2 mL 1% CH3COOH solution were added before NaB(C6H5)4
solution added into the system, which is benefit to get a coarse
grained KB(C6H5)4. Through the above improvements, the analysis
error can be reduced from 0.5% to 0.2%.
(3) The total concentration of MgCl2, LiCl and KCl in the quaternary
system was determined by precipitating Cl− ions in bottle (c) with
AgNO3, as described in the literature [16,17]. The difference

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H. Yang et al. CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 57 (2017) 126–133

Fig. 2. Phase diagram of the ternary system MgCl2+LiCl+H2O at 323.15 K. ■, the

eutectic points of the ternary system; □, the wet-solid composition in the ternary system; □,
the solution-(wet-solid) line of the ternary system; ▬, the isotherm curve of the ternary
system; Bis=MgCl2·6H2O(s); Li-Car=LiCl·MgCl2·7H2O(s).

2.5. Equilibrium time

The equilibrium time of the ternary system were set by determining

Fig. 1. (a) Vertical section of the apparatus for sample equilibrium. A, stainless steel
thermostat; B, digital heating controller; C, heating rings; D, circulation pump (LAUDA
E219, Germany); E, glycol-water bath; F, plastic plate of sealed cover; G, glass
equilibrium flask; H, equilibrium sample; I, multi-magnetic blender; J, plastic pad. (b)
Top view of the apparatus.
between the total amount (3) and the sum of the other two
components (1)+(2) gives the concentration of LiCl.
2.4. Experimental method
The experimental solubility isotherms of the quaternary system
were determined by adding a third salt from the eutectic points of the
ternary systems MgCl2+LiCl+H2O, LiCl+KCl+H2O and KCl
+MgCl2+H2O respectively. The solid phases in equilibrium with the
saturated solution were determined by powder X-ray diffraction and
moreover examined by drawing the stereo phase diagram for this
system.
the eutectic points of each system two times after the system was
balanced x hours and (x+24) hours respectively. Until the deviation
between these two results was less than 0.1%, the equilibrium time was
set to be x hours. The equilibrium time of the quaternary system was
extended 72 h based on the longest equilibrium time of the ternary
system.
2.6. Accuracy analysis
The relative analysis accuracy for the concentrations of Mg2+, K+
and Cl− in the solution were 0.1 wt%, 0.2 wt% and 0.05 wt%, respec-
tively. Considering the errors from other procedures, e.g., the purities
of the chemical substances and equilibrium time, we can reasonably
evaluate that the maximal relative uncertainty of the experimental
solubility results in this work is less than 0.45%.
3. The eutectic points of the ternary system
To obtain the accurate eutectic points of the title sub-ternary
systems, we analyzed the content of the saturate solution and the
corresponding wet-solid after the sample had stirred 120 h and 144 h
respectively. If these two times results of the solution fall within the
error range of 0.1%, we can confirm the average content is the eutectic
composition for the ternary system. Meanwhile, each solution and wet-

Table 2
The experimental eutectic results for the ternary system MgCl2+LiCl+H2O at 323.15 K.

The composition of solution The composition of wet-solid Solid phasea and source

LiCl MgCl2 H2O LiCl MgCl2 H2O

0.1881 0.2273 0.5846 0.1011 0.3392 0.5597 BiSb

A 0.2274 0.2087 0.5639 A′ 0.1526 0.3084 0.5391 BiS+Li-Carb

B 0.2271 0.2085 0.5644 B′ 0.1736 0.2911 0.5353 BiS+Li-Carb
0.2285 0.2060 0.5654 0.1988 0.2711 0.5301 Li-Carb
0.3518 0.1129 0.5354 0.2907 0.1874 0.5218 Li-Carb
0.3937 0.0867 0.5196 0.2806 0.2193 0.5001 Li-Carb

C 0.3950 0.0862 0.5187 C′ 0.3211 0.1934 0.4856 Li-Car+LiCl·H2Ob

D 0.3942 0.0861 0.5197 D′ 0.3922 0.1450 0.4627 Li-Car+LiCl·H2Ob

a
BiS = MgCl2·6H2O, Li-Car = LiCl·MgCl2·7H2O.
b
Determined in this work.

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Table 3
The experimental eutectic results for the ternary system LiCl+KCl+H2O at 323.15 K.

The composition of solution The composition of wet-solid Solid phase and source

LiCl KCl H2O LiCl KCl H2O

E 0.4658 0.0560 0.4782 E′ 0.4007 0.2406 0.3587 LiCl·H2O+KCla

F 0.4650 0.0559 0.4792 F′ 0.3521 0.3033 0.3446 LiCl·H2O+KCla
0.4659 0.0561 0.4780 LiCl·H2O+KClb

a
Determined in this work.
b
literature data [7].

Fig. 3. Phase diagram of the ternary system LiCl+KCl+H2O at 323.15 K. ■, the eutectic
points of the ternary system; □, the wet-solid composition in the ternary system; •,
eutectic point in ternary systems reported in literature [7]; □, the wet-solid line of the
ternary system; ▬, the isotherm curve of the ternary system.
Fig. 4. Phase diagram of the ternary system MgCl2+KCl+H2O at 323.15 K. ■, the
eutectic points of the ternary system; □, the wet-solid the composition in the ternary
system; •, eutectic points in ternary systems reported in literature [13]; □, the wet-solid
line of the ternary system; ▬, the isotherm curve of the ternary system; Bis=MgCl2·
6H2O(s); K-Car=KCl·MgCl2·6H2O(s).

solid contents were plotted in the phase diagram of the ternary system
of system MgCl2+LiCl+H2O at 323.15 K. As presented in Fig. 2, the
and were connected to form a line. If the intersection point of the two
points A and B are almost overlapped in the phase diagram and
solution-(wet-solid) lines in the phase diagram agree with the average
furthermore, the solution-(wet-solid) lines AA’ and BB’ are converged
content, we can further confirm that this content is the eutectic point
at the point A (B). According to the phase diagram rule, point A (B) is
for the ternary system. At the other hand, we compared the experi-
the eutectic point for the two phases MgCl2·6H2O and LiCl·MgCl2·
mental eutectic results with the literature data.
7H2O. At the same time, it can also be verified that point C (D) is the
eutectic point for the two phases LiCl·MgCl2·7H2O and LiCl·H2O in the
3.1. The ternary system MgCl2+LiCl+H2O ternary system MgCl2+LiCl+H2O.

The experimental eutectic points of the ternary systems MgCl2+LiCl

+H2O at T=323.15 K are listed in Table 2 and presented in Fig. 2.
As shown from Table 2, there is no solubility experimental data
reported from literature for the ternary system MgCl2+LiCl+H2O at
323.15 K up until now. In this work, we not only determined the
eutectic points for this system, but also determined some solubility
isotherm data, which is serve to establish the complete phase diagram
3.2. The ternary system LiCl+KCl+H2O
The experimental eutectic point of the ternary systems LiCl+KCl
+H2O at T=323.15 K are listed in Table 3 and presented in Fig. 3.
As shown from Table 3 and Fig. 3, the conclusion can also be
obtained for the ternary systems LiCl+KCl+H2O that the point E (F) is

Table 4
The experimental eutectic results for the ternary system MgCl2+KCl+H2O at 323.15 K.

The composition of solution The composition of wet-solid Solid phasea and source

MgCl2 KCl H2O MgCl2 KCl H2 O

G 0.3724 0.0019 0.6257 G′ 0.3796 0.0772 0.5432 K-Car+BiSb

H 0.3714 0.0019 0.6267 H′ 0.4057 0.0380 0.5563 K-Car+BiSb
0.3715 0.002 0.6265 K-Car+BiSc

I 0.2804 0.0449 0.6746 I′ 0.2988 0.1588 0.5424 K-Car+KClb

J 0.2808 0.0452 0.6740 J′ 0.2038 0.3656 0.4305 K-Car+KClb
0.2790 0.0450 0.6760 K-Car+KClc

a
K-Car=KCl·MgCl2·6H2O, BiS=MgCl2·6H2O.
b
Determined in this work
c
literature data [13].

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Table 5
Experimental isotherm data for the system LiCl+MgCl2+KCl+H2O at 323.15 K.

No. Composition of solutiona Composition of wet−solida Solid Phaseb

LiCl MgCl2 KCl H2O LiCl MgCl2 KCl H2O

1 0.4658 0 0.0560 0.4782 0.4007 0 0.2406 0.3587 LiCl·H2O+KCl

2 0.4650 0 0.0559 0.4792 0.3521 0 0.3033 0.3446 LiCl·H2O+KCl
3 0.4484 0.0193 0.0503 0.4820 0.3365 0.0363 0.2981 0.3292 LiCl·H2O+KCl+K-CarA
4 0.4497 0.0194 0.0504 0.4806 0.3415 0.0507 0.2458 0.3621 LiCl·H2O+KCl+K-Car
5 0.4098 0.0236 0.0443 0.5224 0.2113 0.1254 0.2662 0.3972 KCl+K-Car
6 0.3745 0.0292 0.0425 0.5538 0.1771 0.1189 0.3258 0.3782 KCl+K-Car
7 0.3294 0.0426 0.0375 0.5904 0.1305 0.1977 0.2319 0.4399 KCl+K-Car
8 0.2150 0.1045 0.0381 0.6425 0.0918 0.2320 0.1914 0.4848 KCl+K-Car
9 0.1004 0.1958 0.0426 0.6612 0.0437 0.2660 0.1977 0.4926 KCl+K-Car
10 0 0.2804 0.0449 0.6746 0 0.2988 0.1588 0.5424 KCl+K-Car
11 0 0.2828 0.0442 0.6730 0 0.2038 0.3656 0.4305 KCl+K-Car
12 0 0.3724 0.0019 0.6257 0 0.3796 0.0772 0.5432 K-Car+Bis
13 0 0.3714 0.0019 0.6267 0 0.4057 0.0380 0.5563 K-Car+Bis
14 0.0930 0.2991 0.0021 0.6058 0.0445 0.3743 0.0231 0.5581 K-Car+Bis
15 0.1682 0.2442 0.0023 0.5852 0.0746 0.3342 0.0713 0.5198 K-Car+Bis
16 0.2098 0.2162 0.0026 0.5714 0.0982 0.3250 0.0560 0.5207 K-Car+Bis
17 0.2208 0.2093 0.0027 0.5672 0.1667 0.2767 0.0316 0.5249 K-Car+Bis+ Li-CarB
18 0.2210 0.2093 0.0026 0.5671 0.1572 0.2986 0.0110 0.5331 K-Car+Bis+ Li-Car
19 0.2274 0.2087 0 0.5639 0.1526 0.3084 0 0.5391 Bis+Li-Car
20 0.2269 0.2085 0 0.5646 0.1736 0.2911 0 0.5353 Bis+Li-Car
21 0.2610 0.1764 0.0032 0.5595 0.1835 0.2561 0.0566 0.5039 K-Car+Li-Car
22 0.3999 0.0817 0.0116 0.5068 0.3151 0.1603 0.0662 0.4583 K-Car+Li-Car+ LiCl·H2OC
23 0.3982 0.0814 0.0116 0.5087 0.3225 0.1569 0.0747 0.4459 K-Car+Li-Car+LiCl·H2O
24 0.3950 0.0863 0 0.5186 0.3211 0.1934 0 0.4856 Li-Car+LiCl·H2O
25 0.3942 0.0861 0 0.5197 0.3922 0.1450 0 0.4627 Li-Car+LiCl·H2O
26 0.4372 0.0339 0.0307 0.4981 0.2748 0.1677 0.1291 0.4284 LiCl·H2O+K-Car

A, B, C
The corresponding X-ray diffraction figures for the solid phases are shown in Figs. 7, 8, and 9 respectively.
a
The mass fraction of the salt.
b
Li-Car=LiCl·MgCl2·7H2O, K-Car=KCl·MgCl2·6H2O, Bis=MgCl2·6H2O.

Table 6
Water content as a function of dry−salt on the solubility isothermal curves for the quaternary system LiCl+MgCl2+KCl+H2O at 323.15 K.

No. Composition of solutiona Composition of dry−solid and watera Solid phaseb

LiCl MgCl2 KCl H2O LiCl MgCl2 KCl H2O

1 0.4658 0 0.0560 0.4782 0.8926 0 0.1074 0.9163 LiCl·H2O+KCl

2 0.4650 0 0.0559 0.4792 0.8927 0 0.1073 0.9196 LiCl·H2O+KCl
3 0.4484 0.0193 0.0503 0.4820 0.8658 0.0373 0.0969 0.9308 LiCl·H2O+KCl+K-CarA
4 0.4497 0.0194 0.0504 0.4806 0.8657 0.0373 0.0969 0.9252 LiCl·H2O+KCl+K-Car
5 0.4098 0.0236 0.0443 0.5224 0.8579 0.0494 0.0927 1.0937 KCl+K-Car
6 0.3745 0.0292 0.0425 0.5538 0.8393 0.0655 0.0952 1.2412 KCl+K-Car
7 0.3294 0.0426 0.0375 0.5904 0.7985 0.1037 0.0977 1.4350 KCl+K-Car
8 0.2150 0.1045 0.0381 0.6425 0.6012 0.2923 0.1065 1.7970 KCl+K-Car
9 0.1004 0.1958 0.0426 0.6612 0.2964 0.5778 0.1257 1.9516 KCl+K-Car
10 0 0.2804 0.0449 0.6746 0 0.8619 0.1381 2.0735 KCl+K-Car
11 0 0.2828 0.0442 0.6730 0 0.8648 0.1352 2.0579 KCl+K-Car
12 0 0.3724 0.0019 0.6257 0 0.9949 0.005 1.6716 K-Car+Bis
13 0 0.3714 0.0019 0.6267 0 0.9949 0.0052 1.6790 K-Car+Bis
14 0.0930 0.2991 0.0021 0.6058 0.2359 0.7588 0.0053 1.5369 K-Car+Bis
15 0.1682 0.2442 0.0023 0.5852 0.4056 0.5888 0.0057 1.4108 K-Car+Bis
16 0.2098 0.2162 0.0026 0.5714 0.4895 0.5045 0.0060 1.3330 K-Car+Bis
17 0.2208 0.2093 0.0027 0.5672 0.5102 0.4836 0.0062 1.3104 K-Car+Bis+Li-CarB
18 0.2210 0.2093 0.0026 0.5671 0.5105 0.4834 0.0061 1.3098 K-Car+Bis+ Li-Car
19 0.2274 0.2087 0 0.5639 0.5214 0.4786 0 1.2929 Bis+Li-Car
20 0.2269 0.2085 0 0.5646 0.5212 0.4788 0 1.2967 Bis+Li-Car
21 0.2610 0.1764 0.0032 0.5595 0.5924 0.4003 0.0073 1.2700 K-Car+Li-Car
22 0.3999 0.0817 0.0116 0.5068 0.8107 0.1657 0.0236 1.0275 K-Car+Li-Car+LiCl·H2OC
23 0.3982 0.0814 0.0116 0.5087 0.8107 0.1659 0.0234 1.0370 K-Car+Li-Car+LiCl·H2O
24 0.3950 0.0863 0 0.5186 0.8206 0.1794 0 1.0774 Li-Car+LiCl·H2O
25 0.3942 0.0861 0 0.5197 0.8208 0.1792 0 1.0822 Li-Car+LiCl·H2O
26 0.4372 0.0339 0.0307 0.4981 0.8712 0.0676 0.0612 0.9925 LiCl·H2O+K-Car

A, B, C
The corresponding X-ray diffraction figures for the solid phases are shown in Figs. 7, 8, and 9 respectively.
a
The mass fraction of the salt.
b
Li-Car=LiCl·MgCl2·7H2O, K-Car=KCl·MgCl2·6H2O, Bis=MgCl2·6H2O.

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Fig. 7. The X-ray diffraction results for the solid phase of eutectic point A in the
quaternary system LiCl+MgCl2+KCl+H2O.

Fig. 5. Phase diagram of the quaternary system LiCl+MgCl2+KCl+H2O at 323.15 K (dry-salt

and water content figures). ○, the experimental data determined in this work; •: eutectic
points of A, B, C in the quaternary system; ■: literature data [8,13]; □, experimental
isotherms; Li-Car=LiCl·MgCl2·7H2O, K-Car=KCl·MgCl2·6H2O, Bis=MgCl2·6H2O; →, the
crystallization behavior of a mixed brine solution (LiCl: 0.284 mol kg−1; MgCl2: 5.69 mol kg−1)
while adding KCl.

Fig. 8. The X-ray diffraction results for the solid phase of eutectic point B in the
quaternary system LiCl+MgCl2+KCl+H2O.

Fig. 6. The stereo figure for the quaternary system LiCl+MgCl2+KCl+H2O at 323.15 K.
■: the solution points for the quaternary system; □: the wet-solid points for the
quaternary system; ○: the dry-solid points according to the solution points; the number
Fig. 9. The X-ray diffraction results for the solid phase of eutectic point C in the
in the figure is according to the number in Tables 5, 6; •: the composition points for the
quaternary system LiCl+MgCl2+KCl+H2O.
solid phase in the quaternary system; Li-Car=LiCl·MgCl2·7H2O, K-Car=KCl·MgCl2·
6H2O.
3.3. The ternary system MgCl2+KCl+H2O
the eutectic points for the phases KCl and LiCl·H2O. Meanwhile, the
composition of points E(F) are compared with the literature data. The The experimental eutectic points of the ternary systems KCl
good agreement between them can further verify that point E(F) is the +MgCl2+H2O at T=323.15 K are listed in Table 4 and presented in
eutectic point for the ternary systems LiCl+KCl+H2O at 323.15 K. Fig. 4.

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Fig. 10. Phase diagram comparing between 298.15 and 323.15 K for the quaternary
system LiCl+MgCl2+KCl+H2O (dry-salt figure). •: eutectic points at 323.15 K; □:
literature data [14]; □, experimental isotherm curves at 323.15 K; —: experimental
isotherm curves at 298.15 K.
Fig. 11. The stable and meta-stable phase diagram for the quaternary system LiCl
+MgCl2+KCl+H2O at 323.15 K (dry-salt figure). •: eutectic points at 323.15 K in this work;
□: literature data [15]; □, experimental isotherm curves in this work; —: meta-stable
experimental isotherm curves in the literature [15].
According to the phase diagram rule and the composition compar-
ing, it can also be obtained for the ternary systems MgCl2+KCl+H2O
that points G(H) and I(J) are the eutectic points for the phases (KCl
and KCl·MgCl2·6H2O) and (KCl·MgCl2·6H2O and MgCl2·6H2O) respec-
tively (shown from Table 4 and Fig. 4). At the same time, good
agreement was obtained by comparing the composition of points G(H)
and I(J) with the literature data, which can further verify that the
points G(H) and I(J) are the eutectic points for the ternary systems
MgCl2+KCl+H2O at 323.15 K (shown from Fig. 4).
In conclusion, the eutectic results for the ternary systems
MgCl2+LiCl+H2O, LiCl+KCl+H2O and MgCl2+KCl+H2O at 323.15 K
are considered to be reliable and we can set about to determinate the
phase diagram of the quaternary system MgCl2+LiCl+KCl+H2O at
323.15 K.
4. The phase diagram of the quaternary system LiCl
+MgCl2+KCl+H2O at 323.15 K and comparison with
literature
4.1. Phase diagram results
The results for the quaternary system LiCl+MgCl2+KCl+H2O at
T=323.15 K are presented in Tables 5, 6 and plotted in Figs. 5, 6.
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 57 (2017) 126–133
4.2. Discussion for the phase diagram
As shown from Tables 5, 6, the experimental data are evenly located
on all the isothermal curves of the quaternary system LiCl+MgCl2+KCl
+H2O, which yield a complete and accurate phase diagram of the
quaternary system. Moreover, the most important points (three
eutectic points) in the quaternary system were elaborately determined
by two times and the slightly deviation between the two times results
are all fallen within the range of analysis error.
According to Figs. 5 and 6, the phase diagram of the quaternary
system LiCl+MgCl2+KCl+H2O consists of five crystallization fields
corresponding to two double salts (LiCl·MgCl2·7H2O(s) and KCl·
MgCl2·6H2O(s)), two hydrate salts (MgCl2·6H2O(s) and LiCl·H2O)
and one single salt (KCl). The main crystallization fields are the single
salt of KCl and the double salt KCl·MgCl2·6H2O(s), whereas the fields
of LiCl·MgCl2·7H2O(s) and MgCl2·6H2O(s) are extremely narrow. The
crystallization field of the double salt KCl·MgCl2·6H2O(s) is so large
that it extends to the area where the LiCl contents (in dry-salt figure) is
greater than 0.8. The above results are coincidence with the results at
298.15 K reported by Zhang [14]. As shown from water-content figure
of Fig. 6, the lowest water content point of this system located on A
eutectic point.
To verify the reliability of the experimental solubility data in this
work, we adopted two methods. Firstly, the composition of the solution
and the corresponding wet-solid of each equilibrium sample were
elaborately determined (as shown from Table 5). At the same time, as
shown from Table 6, the composition of the dry-solid and water
content for each solution were also determined. According to the phase
diagram rule, if these three parts of composition can form a straight
line, the determined results can be considered to be reliable. To form a
good visual effect, only partial results in Tables 5, 6 were selected to
draw in Fig. 6. As shown from the stereo figure (Fig. 6) for the
quaternary system LiCl+MgCl2+KCl+H2O, the solution composition
(filled squares), the wet-solid composition (unfilled squares) and the
dry-solid composition for the solution (unfilled circles) can all success-
fully fall in a straight line, which verify the experimental data
determined in this work are reliable. Secondly, the experimental data
in this work were compared with the literature data. As shown from
Fig. 5, the good agreement was also achieved between each other.
The type of the solid phases in this quaternary system were also
examined. As shown from Fig. 6, we can intuitively find out that the
equilibrium solid phases of eutectic points 3(A), 17(B) and 22(C) in the
quaternary system LiCl+MgCl2+KCl+H2O are (LiCl·
H2O(s)+KCl(s)+KCl·MgCl2·6H2O(s)), (KCl·MgCl2·6H2O(s)+ MgCl2·
6H2O(s)+LiCl·MgCl2·7H2O(s)) and (KCl·MgCl2·6H2O(s)+LiCl·MgCl2·
7H2O(s)+ LiCl·H2O(s)) respectively. Moreover, the powder X-ray
diffraction was used to the solid phases of these points and the results
were presented in Figs. 7, 8 and 9. As shown from these figures, the X-
ray results for the solid phases of points A, B, C can get a good
agreement with the standard patterns of (LiCl·H2O(s)+KCl(s)+KCl·
MgCl2·6H2O(s))(KCl·MgCl2·6H2O(s)+MgCl2·6H2O(s)+LiCl·MgCl2·
7H2O(s)) and (KCl·MgCl2·6H2O(s)+LiCl·MgCl2·7H2O(s)+LiCl·H2O(s))
respectively.
Conclusively, it can be stated that the phase diagram results
including the composition and the phase type of the quaternary system
LiCl+MgCl2+KCl+H2O at 323.15 K are all accurate and reliable.
4.3. Comparison with data
The stable phase diagram of the quaternary system LiCl
+MgCl2+KCl+H2O at 323.15 K in this work was compared with the
data at 298.15 K reported by Zhang [14], illustrated in Fig. 10. As the
temperature raising from 298.15 to 323.15 K, the type of the equili-
brium phases and the trend of the crystallization zones are the same,
and only the area of the crystallization fields are different: (1) the
crystallization fields LiCl·H2O (s), KCl·MgCl2·6H2O (s) and LiCl·MgCl2·
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7H2O (s) become larger, while (2) the KCl(s) crystallization field
becomes smaller.
While comparing the stable phase diagram in this work and the
meta-stable results in literature [15] (Fig. 11) at 323.15 K, it can easily
found that the crystallization zones and the crystallization fields area
are quite different between each other, which means the meta-stable
phase diagram is variable and it is only a special equilibrium state for
the quaternary system LiCl+MgCl2+KCl+H2O.
4.4. An industrial application example for the phase diagram of the
title quaternary system
Based on the complete stable phase diagram of the quaternary
system LiCl+MgCl2+KCl+H2O at 323.15 K, profound understanding
can be obtained on the crystallization phenomena in the lithium
extraction process from the brine containing MgCl2 and LiCl using
KCl chemical reagent in summer (around 50 ℃ in the daytime).
For example, a typical brine balanced with the solid phase MgCl2·
6H2O(s) after evaporation in a solar pool contains 5.69 mol kg–1 MgCl2
and 0.284 mol kg–1 LiCl, as shown in point M in Fig. 5. When KCl is
added into the brine, due to the large crystal field for the double salt of
KCl·MgCl2·6H2O (as shown from Fig. 5), MgCl2 will be crystallized out
in the form of KCl·MgCl2·6H2O. Based on the phase diagram of the
quaternary system, the crystallization process and the final composi-
tion of the brine can also be calculated, as the red arrow line shown in
Fig. 5.
5. Summary
The phase diagram of the quaternary system LiCl+MgCl2+KCl+H2O
and the eutectic points of the ternary systems LiCl+MgCl2+H2O, LiCl
+KCl+H2O and MgCl2+KCl+H2O at 323.15 K were elaborately deter-
mined with a relative accuracy of 0.45% by the isothermal equilibrium
method. The results of the solution and wet-solid composition for these
systems are consistent with the phase rule very well and the good
agreement was also reached between the data in this work and in the
literature, which support the reliability of the experimental data in this
work.
In the quaternary system, it reveals that this phase diagram consists
of five crystallization fields: two double salts (LiCl·MgCl2·7H2O(s) and
KCl·MgCl2·6H2O(s)), two hydrate salts (MgCl2·6H2O(s) and LiCl·
H2O(s)) and one single salt (KCl(s)). The largest two crystallization
fields are found to be of the single salt of KCl(s) and the double salt KCl·
MgCl2·6H2O(s), and the narrow fields are LiCl·MgCl2·7H2O(s) and
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 57 (2017) 126–133
MgCl2·6H2O(s). Both of the X-ray measurement technique and the
geometrical principle of the phase diagram verified the type of the
crystallization fields.
Based on the phase diagram of this quaternary system, application
example was also given to understand the crystallization phenomena in
the Li-extraction process from the brine containing LiCl and MgCl2 by
adding KCl reagent.
Acknowledgment
The authors gratefully acknowledge financial support from the
United Chaidamu Saline Chemical Industry Project between National
Nature Science Foundation and China-Qinghai People's Government
(Grand No. U1507110) and Nature Science Foundation of Hunan
Province (2016JJ6035). H. T. Yang also greatly appreciates the
financial support of Science and Technology Plan Project of Hunan
Province (2015RS4003), Hunan Provincial Department of Education
Project (15C0387).
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