多温下三元体系Li+，Na+∥Cl--H2O固液相平衡研究

doi:10.19964/j.issn.1006-4990.2023-0302

Abstract

Abstract:

The enrichment of LiCl in brine system is high，and high-purity LiCl is widely used in industry.Because of the similar properties of Na⁺ and Li⁺，the removal of NaCl from brine has become the difficulty of producing high-purity LiCl.The solid-liquid equilibrium data of Li⁺，Na⁺∥Cl^--H₂O ternary system is an important basic data for the separation of LiCl and NaCl.The solid-liquid phase equilibrium relationship of ternary system of Li⁺，Na⁺∥Cl^--H₂O at 348.15 K，358.15 K and 363.15 K under atmospheric pressure was investigated by an isothermal dissolution equilibrium method and the equilibrium phase diagram was constructed.The results showed that the phase diagrams at different temperatures were composed of one eutectic invariant point，two single salt crystallization fields（NaCl and LiCl·H₂O） and two univariate solubility curves，and it formed neither double salt nor solid solution.With the increase of the temperature，the crystallization region of NaCl was expanded slightly，while the crystal region of LiCl·H₂O was changed little.LiCl had a strong salting-out effect on NaCl.The modified BET model was used to correlate the phase equilibrium data，and the correlation value was in good agreement with the experimental value，indicating that the model was more suitable for predicting phase equilibrium relation in this water-salt system at high temperature and high concentration.The density of the saturated solution of the system was measured and the apparent molar volume was calculated from the density value.The results showed that the density was decreased at first and then increased with the increase of LiCl composition，and reached the maximum at the co-saturation point.These results supplemented the thermodynamic data of Li⁺，Na⁺∥Cl^--H₂O system at high temperature and played a basic guiding role in the removal of Na⁺ and purification of LiCl.

Key words: lithium chloride, sodium chloride, solid-liquid equilibrium, fixed BET model, apparent molar volume

CLC Number:

O642.42

WANG Yanfei, YANG Chaofan, CAO Di, XU Shijie. Study on solid-liquid phase equilibrium of ternary system of Li⁺， Na⁺∥Cl^--H₂O at different temperatures[J]. Inorganic Chemicals Industry, 2024, 56(1): 33-39.

Figures/Tables 10

Table 1

Experimental and calculated phase equilibrium data of ternary system of Li+，Na+ ∥Cl--H2O at 348.15~363.15 Ka"

液相组分实验值/%±标准不确定度/%			液相组分计算值/%				相对偏差（RD）/%			平衡固相^b
w（LiCl）	w（NaCl）	w（H₂O）	w（LiCl）	w（NaCl）	w（H₂O）		w（LiCl）	w（NaCl）	w（H₂O）	平衡固相^b
T=348.15 K
0.00	26.72±0.12	73.28±0.21	0.00	26.62		73.38	0.00	-0.37	0.14	N
3.56±0.39	24.98±0.75	71.46±0.36	3.56	25.02		71.42	0.00	0.16	-0.06	N
7.00±0.56	18.16±0.29	74.84±0.86	7.00	18.15		74.85	0.00	-0.06	0.01	N
11.37±0.18	15.24±0.22	73.39±0.04	11.37	15.23		73.40	0.00	-0.07	0.01	N
16.85±0.45	12.87±0.21	70.27±0.28	16.85	12.92		70.23	0.00	0.39	-0.06	N
21.04±0.63	8.97±0.20	70.00±0.43	21.04	8.91		70.05	0.00	-0.67	0.07	N
24.44±0.50	5.98±0.86	69.58±0.36	24.44	5.96		69.60	0.00	-0.33	0.03	N
32.72±0.43	3.68±0.41	63.61±0.19	32.72	3.67		63.61	0.00	-0.27	0.00	N
36.97±0.01	1.55±0.39	61.48±0.38	36.97	1.55		61.48	0.00	0.00	0.00	N
46.50±0.10	1.00±0.07	52.50±0.13	46.50	1.00		52.50	0.00	0.00	0.00	N
51.11±0.54	0.57±0.02	48.31±0.56	51.11	0.56		48.33	0.00	-1.75	0.04	N+L
51.41±0.11	0.00	48.59±0.23	51.41	0.00		48.59	0.00	0.00	0.00	L
T=358.15 K
0.00	26.85±0.17	73.15±0.11	0.00	26.83		73.17	0.00	-0.07	0.03	N
3.48±0.01	24.80±0.03	71.72±0.10	3.48	24.82		71.70	0.00	0.08	-0.03	N
7.11±0.02	19.22±0.81	73.67±0.57	7.11	19.22		73.67	0.00	0.00	0.00	N
11.31±0.04	16.38±0.71	72.31±1.13	11.31	16.38		72.31	0.00	0.00	0.00	N
17.21±0.03	12.27±0.36	70.52±0.03	17.21	12.38		70.41	0.00	0.90	-0.16	N
22.95±0.60	8.73±0.14	68.32±1.73	22.95	8.69		68.36	0.00	-0.46	0.06	N
28.09±0.05	6.00±0.17	65.91±0.63	28.09	6.00		65.91	0.00	0.00	0.00	N
34.67±0.78	3.41±0.08	61.92±1.89	34.67	3.37		61.96	0.00	-1.17	0.06	N
40.86±0.04	2.27±0.49	56.87±0.91	40.86	2.18		57.36	0.00	-3.96	0.16	N
46.61±0.07	1.63±0.18	51.76±0.72	46.61	1.68		51.61	0.00	3.07	-0.10	N
52.23±0.40	0.64±0.09	47.13±0.91	52.23	0.61		47.16	0.00	-4.69	0.06	N+L
53.25±0.14	0.00	46.75±0.27	53.25	0.00		46.75	0.00	0.00	0.00	L
T=363.15 K
0.00	27.10±0.27	72.90±0.11	0.00	27.11		72.89	0.00	0.04	-0.01	N
3.66±0.13	25.31±0.58	71.03±0.45	3.66	25.34		71.00	0.00	0.12	-0.04	N
7.05±0.14	19.13±0.95	73.82±0.81	7.05	19.13		73.82	0.00	0.00	0.01	N
12.22±0.67	15.66±0.76	72.13±1.43	12.22	15.68		72.10	0.00	0.13	-0.04	N
23.46±1.12	9.21±0.27	67.33±0.85	23.46	9.22		67.32	0.00	0.11	-0.02	N
26.20±0.76	6.28±0.11	67.52±0.66	26.20	6.29		67.51	0.00	0.16	0.02	N
34.97±0.39	2.39±0.05	62.64±0.34	34.97	2.38		62.65	0.00	-0.42	0.03	N
47.80±0.97	0.98±0.26	51.22±1.23	47.80	0.98		51.22	0.00	0.00	0.00	N
54.35±0.20	0.79±0.01	44.86±0.22	54.35	0.78		44.87	0.00	-1.27	0.02	N+L
54.87±0.10	0.00	45.13±0.61	54.87	0.00		45.13	0.00	0.00	0.00	L

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Solubility constants ln Ks of solid phases and salt-salt interaction parameterΩNaCl-LiCl∙H2O［13］"

温度/K	ln K_NaCl	ln K $L i C l · H 2 O$	Ω $N a C l - L i C l · H 2 O$
348.15	-6.763 13	-5.161 726	1 164.839 5
358.15	-6.629 76	-4.958 668	1 298.139 5
363.15	-6.564 08	-4.861 333	1 364.789 5

Table 2

Table 3

Table 4

Fig.4

Table 5

Table 6

References 21

1	况新亮，刘垂祥，熊朋.锂离子电池产业分析及市场展望［J］.无机盐工业，2022，54（8）：12-19，32.
	KUANG Xinliang， LIU Chuixiang， XIONG Peng.Industry analysis and market prospect of lithium ion battery［J］.Inorganic Chemicals Industry，2022，54（8）：12-19，32.
2	YU Xiaoping， FAN Xuebing， GUO Yafei，et al.Recovery of lithium from underground brine by multistage centrifugal extraction using tri-isobutyl phosphate［J］.Separation and Purification Technology，2019，211：790-798.
3	WANG Shulei， ZHENG Shili， WANG Zheming，et al.Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves［J］.Chemical Engineering Journal，2018，332：160-168.
4	王彦飞，胡佳琪，卫丽莎，等.添加剂对碳酸锂结晶的影响［J］.无机盐工业，2018，50（6）：42-46.
	WANG Yanfei， HU Jiaqi， WEI Lisha，et al.Effect of additives on lithium carbonate crystallization［J］.Inorganic Chemicals Industry，2018，50（6）：42-46.
5	王彦飞，李亚楠，胡佳琪，等.去除氯化锂中氯化钠的研究进展［J］.无机盐工业，2018，50（2）：13-15.
	WANG Yanfei， LI Yanan， HU Jiaqi，et al.Progress in separating sodium chloride from lithium chloride［J］.Inorganic Chemicals Industry，2018，50（2）：13-15.
6	SMITS A， ELGERSMA J， HARDENBERG M M E.A critical mixing point in the solid phase of the system NaCl-LiCl［J］.Recueil des Travaux Chimiques des Pays-Bas，1924，43（9）：671-676.
7	FARELO F， FERNANDES C， AVELINO A.Solubilities for six ternary systems：NaCl+NH₄Cl+H₂O，KCl+NH₄Cl+H₂O，NaCl+LiCl+H₂O，KCl+LiCl+H₂O，NaCl+AlCl₃+H₂O，and KCl+AlCl₃+H₂O at T=（298 to 333） K［J］.ChemInform，2005，36（40）：200540019.
8	WANG Shiqiang， GUO Yafei， LIU Dongfang，et al.Phase equilibria in system LiCl-NaCl-H₂O at 308 and 348 K［J］.Russian Journal of Physical Chemistry A，2016，90（13）：2532-2537.
9	YANG Haitang， ZENG Dewen， CHEN Yifeng，et al.Revisiting the thermodynamic properties of the LiCl-NaCl-KCl-H₂O quaternary and its sub-ternary systems at 298.15 K［J］.Calphad，2015，50：161-169.
10	RATHGEBER C， SCHMIT H， HIEBLER S，et al.Application of the modified BET model to concentrated salt solutions with relatively high water activities：Predicting solubility phase diagrams of NaCl+H₂O，NaCl+LiCl+H₂O，and NaCl+CaCl₂+H₂O［J］.Calp- had，2019，66：101633.
11	LOVERA J， TÍJARO-ROJAS R， MERUANE G，et al.Prediction of solubilities in the system Li⁺+Na⁺+K⁺+Cl^–+H₂O at 25 ℃ and industrial process of refining muriate of potash［J］.Journal of Chemical & Engineering Data，2019，64（5）：2027-2035.
12	CUI Ruizhi.Solubility measurement and prediction of phase equilibria in the quaternary system LiCl+NaCl+KCl+H₂O and ternary subsystem LiCl+NaCl+H₂O at 288.15 K［J］.Chinese Journal of Chemical Engineering，2020，28（8）：2137-2141.
13	LI Cheng， ZHAO Bin， WANG Shuo，et al.Phase diagrams of the quinary system K⁺，NH₄ ⁺，Mg²⁺∥SO₄ ^2-，Cl^--H₂O at 273.15 K and 298.15 K and their application［J］.Fluid Phase Equilibria，2019，499：112238.
14	LI Cheng， WU Jingxue， GUO Hongfei，et al.Phase diagrams of the quaternary system K⁺，NH₄ ⁺∥Cl^-，SO₄ ^2--H₂O at 273.15 K and their application［J］.The Journal of Chemical Thermodynamics，2019，134：136-145.
15	ZHANG Jijun， REN Mengyuan， LI Dongchan，et al.Solid-liquid phase equilibrium in the quaternary system（LiCl+NaCl+KCl+H₂O） at 288.15 K［J］.Russian Journal of Physical Chemistry A，2020，94（8）：1565-1572.
16	VOIGT H， VOIGT W.Solubility isotherm of the system LiNO₃-KNO₃-H₂O at 373 K［J］.Monatshefte Für Chemie-Chemical Monthly，2018，149（2）：283-288.
17	MARCUS Y.BET modeling of solid-liquid phase diagrams of co-mmon ion binary salt hydrate mixtures.I.The BET parameters［J］.Journal of Solution Chemistry，2005，34（3）：297-306.
18	NGUYEN M T H， TICHACEK O， MARTINEZ-SEARA H，et al.Resolving the equal number density puzzle：Molecular picture from simulations of LiCl（aq） and NaCl（aq）［J］.The Journal of Physical Chemistry B，2021，125（12）：3153-3162.
19	HASSEINE A， MENIAI A H， KORICHI M.Salting-out effect of single salts NaCl and KCl on the LLE of the systems（water+toluene+acetone），（water+cyclohexane+2-propanol） and（water+xylene+methanol）［J］.Desalination，2009，242（1/2/3）：264-276.
20	申屠雁明，于养信，李以圭.混合电解质溶液的密度和表观摩尔体积的研究［J］.清华大学学报（自然科学版），1993，33（6）：61-72.
	SHENTU Yanming， YU Yangxin， LI Yigui.Study on densities and apparent molal volumes of mixed electrolyte aqueous solutions［J］.Journal of Tsinghua University（Science and Technology），1993，33（6）：61-72.
21	林联君，房春晖，房艳，等.一个预测溶液密度的新模型［J］.盐湖研究，2006，14（2）：56-61.
	LIN Lianjun， FANG Chunhui， FANG Yan，et al.A new model for predicting density of electrolyte solutions［J］.Journal of Salt Lake Research，2006，14（2）：56-61.

体系	T/K	r	c
NaCl-H₂O^［10］a		2.94	5.00
NaCl-H₂O^［10］a	348.15	3.334 508	12.189 822
LiCl-H₂O^［10］b	358.15	3.277 708	11. 472 191
LiCl-H₂O^［10］b	363.15	3.249 308	11.143 333

编号	饱和溶液密度/（g∙cm^-3）			相对偏差（RD）/%
编号	ρ_e±标准不确定度^a	ρ_c（1）	ρ_c（2）	RD^（1）	RD^（2）
T=348.15 K
1，A₁	1.173 5±0.001 3	1.163 8	1.171 7	-0.83	-0.15
2	1.169 0±0.002 6	1.173 8	1.171 0	0.41	0.17
3	1.155 3±0.001 9	1.144 0	1.155 4	-0.98	0.01
4	1.152 5±0.000 9	1.150 1	1.152 4	-0.21	-0.01
5	1.149 6±0.004 1	1.167 8	1.149 1	1.58	-0.04
6	1.155 2±0.003 2	1.165 2	1.155 2	0.86	0.00
7	1.160 8±0.002 9	1.164 5	1.161 6	0.32	0.07
8	1.192 1±0.003 8	1.201 8	1.193 8	0.82	0.15
9	1.214 2±0.004 3	1.213 8	1.212 3	-0.04	-0.15
10	1.278 0±0.002 7	1.276 3	1.276 1	-0.13	-0.14
11，E₁	1.312 9±0.007 8	1.306 3	1.310 5	-0.51	-0.19
12，B₁	1.309 9±0.001 6	1.303 5	1.313 8	-0.49	0.30
T=358.15 K
1，A₂	1.162 3±0.001 7	1.155 3	1.159 5	-0.60	-0.25
2	1.160 9±0.001 1	1.162 6	1.164 3	0.15	0.29
3	1.154 3±0.001 7	1.144 2	1.154 3	-0.88	0.00
4	1.150 7±0.003 8	1.150 2	1.151 2	-0.05	0.04
5	1.147 8±0.002 8	1.157 7	1.146 4	0.87	-0.12
6	1.153 6±0.001 8	1.168 7	1.153 8	1.31	0.02
7	1.169 6±0.002 2	1.182 0	1.171 6	1.06	0.17
8	1.199 3±0.003 2	1.206 3	1.202 1	0.58	0.24
9	1.242 6±0.003 7	1.240 2	1.237 2	-0.19	-0.44
10	1.273 2±0.012 1	1.276 0	1.275 0	0.22	0.14
11，E₂	1.319 6±0.002 9	1.308 9	1.317 3	-0.82	-0.18
12，B₂	1.318 6±0.005 6	1.311 0	1.322 3	-0.58	0.28
T=363.15 K
1，A₃	1.167 8±0.002 5	1.155 4	1.160 6	-1.07	-0.62
2	1.160 2±0.002 3	1.166 2	1.168 5	0.52	0.72
3	1.150 3±0.001 0	1.141 6	1.148 3	-0.76	-0.18
4	1.146 7±0.000 8	1.149 5	1.146 8	0.25	0.01
5	1.145 3±0.005 4	1.151 6	1.145 9	0.56	0.05
6	1.153 8±0.001 3	1.175 6	1.152 0	1.90	-0.15
7	1.162 6±0.004 2	1.171 5	1.167 9	0.76	0.45
8	1.202 7±0.003 0	1.201 3	1.205 9	-0.12	0.27
9	1.258 4±0.012 9	1.248 5	1.252 5	-0.78	-0.47
10	1.290 6±0.006 6	1.282 0	1.286 4	-0.66	-0.32
11，E₃	1.332 2±0.001 1	1.330 0	1.327 7	-0.17	-0.33
12，B₃	1.323 3±0.005 5	1.327 0	1.332 7	0.28	0.71

T/K	拟合常数						相关系数R²	最大离子强度 I_max/（mol∙kg^-1）
T/K	A	B	C	D	E	F/10^-7	相关系数R²	最大离子强度 I_max/（mol∙kg^-1）
348.15	0.024 37	0.077 14	-0.003 38	-0.002 16	-0.018 25	1.533 09	0.999 09	25.157 7
358.15	0.023 48	0.071 16	-0.002 23	-0.001 99	-0.016 27	2.309 73	0.998 24	26.868 3
363.15	0.027 00	0.055 65	-0.002 14	-0.002 65	-0.009 89	-1.928 68	0.994 41	28.874 8

编号	348.15 K			358.15 K			363.15 K
编号	m₁/ （mol∙kg^-1）	m₂/ （mol∙kg^-1）	V_φ / （cm³∙mol^-1）	m₁/ （mol∙kg^-1）	m₂/ （mol∙kg^-1）	V_φ / （cm³∙mol^-1）	m₁/ （mol∙kg^-1）	m₂/ （mol∙kg^-1）	V_φ / （cm³∙mol^-1）
1	—	6.238 1	21.967 4	—	6.281 2	22.886 8	—	6.360 2	21.802 0
2	1.176 3	5.980 4	23.930 0	1.143 1	5.916 2	23.879 2	1.214 8	6.097 2	24.270 7
3	2.207 0	4.151 7	20.565 4	2.276 6	4.462 8	21.289 9	2.253 6	4.435 3	21.193 4
4	3.653 5	3.553 1	21.710 7	3.690 9	3.874 8	22.387 2	3.995 6	3.714 4	22.458 3
5	5.656 8	3.134 7	24.119 7	5.757 6	2.975 9	23.244 0	5.668 2	2.796 2	22.416 6
6	7.088 8	2.192 0	22.722 4	7.925 3	2.185 5	23.381 9	8.217 3	2.340 7	23.800 6
7	8.286 9	1.471 0	21.767 7	10.055 0	1.557 5	22.808 7	9.152 9	1.591 8	22.145 8
8	12.133 2	0.989 1	22.334 2	13.208 8	0.940 9	22.206 4	13.170 4	0.654 3	21.087 6
9	14.185 7	0.432 0	21.469 6	16.949 4	0.682 9	21.706 5	17.969 4	0.484 7	20.950 5
10	20.893 7	0.325 9	21.900 0	21.245 6	0.538 9	22.271 2	22.014 5	0.327 3	21.346 1
11	24.954 7	0.203 0	21.888 4	26.139 6	0.231 8	21.818 7	28.575 4	0.299 5	22.068 2
12	24.961 2	0.000 0	21.852 2	26.868 3	0.000 0	21.951 7	28.682 6	0.000 0	22.265 6

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Study on solid-liquid phase equilibrium of ternary system of Li⁺， Na⁺∥Cl^--H₂O at different temperatures

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Study on solid-liquid phase equilibrium of ternary system of Li+， Na+∥Cl--H2O at different temperatures