258.15 K下五元体系Li+，Na+，Mg2+//SO42-，Cl--H2O相平衡研究

doi:10.19964/j.issn.1006-4990.2022-0273

Abstract

Abstract:

Most lithium salt lakes in China are located in areas with drought,little rain,cold and long winters,such as Qinghai Tibet and Xinjiang.To guide the process of lithium extraction at low temperature,enrich the target ions by using cold energy in winter and clarify the salt precipitation law of lithium-containing salt lake at low temperature,the phase equilibrium of the interactive quinary system of Li⁺,Na⁺,Mg²⁺//SO₄^2-,Cl^--H₂O under saturated NaCl·2H₂O at 258.15 K was investigated by isothermal dissolution method and the phase diagram was constructed.There were four invariant points,six two-salt crystallization fields（NaCl·2H₂O+Na₂SO₄·10H₂O,NaCl·2H₂O+MgCl₂·8H₂O,NaCl·2H₂O+MgSO₄·7H₂O,NaCl·2H₂O+Li₂SO₄·H₂O,NaCl·2H₂O+LiCl·2H₂O, NaCl·2H₂O+LiCl·MgCl₂·7H₂O）and nine univariate solubility curves in the phase diagram.LiCl·MgCl₂·7H₂O was the only double salt in the phase diagram,and its crystallization field was the smallest.The crystallization field of Na₂SO₄·10H₂O was the largest in the phase diagram.Compared with the stable phase diagram of the quinary system at 273.15 K,the sulfate type double salt was disappeared,the double salt crystallization zone was reduced to 1,and the invariant point was reduced to 4,and the correlation system was simplified.Cooling the brine of Seniehu lake to 258.15 K could effectively separate sulfate and achieve the purpose of enriching lithium.

Key words: salt lake, lithium, low temperature, quinary system, phase equilibrium

CLC Number:

TQ131.1

YAN Fangning,GUO Jinchun,HUANG Xueli,ZHOU Tingting,WANG Xueying,LUO Qinglong,ZOU Xuejing. Study on phase equilibrium of quinary system of Li⁺，Na⁺，Mg²⁺//SO₄^2-，Cl^--H₂O at 258.15 K[J]. Inorganic Chemicals Industry, 2023, 55(2): 61-66.

Figures/Tables 8

Table 1

Solubilities of Li+，Na+，Mg2+//SO42-，Cl--H2O system saturated with NaCl·2H2O at 258.15 K"

编号	w（液相组成）/%					相图指数/%				平衡固相组成
编号	Li⁺	Mg²⁺	Cl^-	SO₄^2-	Na⁺	2Li⁺	SO₄^2-	2Na⁺	H₂O	平衡固相组成
1，C₃^[12]	0.000	4.450	15.45	2.521	2.808	0.00	12.54	29.17	2 101	Hy+S₁₀+Eps
2	0.443	4.284	16.79	1.391	1.982	14.33	6.506	19.36	1 873	Hy+S₁₀+Eps
3	0.863	4.280	18.30	2.181	1.960	23.82	8.699	16.33	1 541	Hy+S₁₀+Eps
4，A₁	1.244	2.656	16.50	3.531	3.245	38.03	15.60	29.94	1 715	Hy+S₁₀+Eps+Ls
5	1.788	3.005	18.74	2.484	1.731	46.29	9.292	13.53	1 441	Hy+S₁₀+Ls
6	2.058	2.582	18.79	2.117	1.499	53.62	7.968	11.79	1 464	Hy+S₁₀+Ls
7	2.167	2.399	19.01	2.086	1.613	56.46	7.854	12.69	1 460	Hy+S₁₀+Ls
8	2.389	2.307	20.37	2.048	1.914	59.69	7.395	14.43	1 366	Hy+S₁₀+Ls
9	2.842	1.641	21.31	0.652	1.614	73.37	2.431	12.58	1 431	Hy+S₁₀+Ls
10	3.063	1.183	20.68	0.652	1.332	79.93	2.440	10.50	1 470	Hy+S₁₀+Ls
11	3.090	1.070	21.34	0.670	1.070	81.36	2.549	15.08	1 459	Hy+S₁₀+Ls
12	2.961	0.811	19.89	0.653	1.865	84.15	2.681	16.00	1 616	Hy+S₁₀+Ls
13，C₁	3.052	0.000	17.59	2.336	2.416	90.04	9.956	21.52	1 696	Hy+S₁₀+Ls
14，C₄^[12]	0.000	7.944	23.12	0.477	0.192	0.00	1.497	1.261	1 275	Hy+Eps+M₈
15	0.407	8.011	25.07	0.589	0.034	8.034	1.681	0.203	1 002	Hy+Eps+M₈
16	0.797	7.760	26.51	0.522	0.119	15.03	1.421	0.680	934.0	Hy+Eps+M₈
17	0.960	7.498	26.27	1.114	0.203	17.77	2.979	1.133	912.0	Hy+Eps+M₈
18	1.205	7.038	26.51	1.219	0.470	22.31	3.262	2.638	906.9	Hy+Eps+M₈
19	1.256	6.314	25.11	0.604	0.471	25.38	1.764	2.873	1 031	Hy+Eps+M₈
20	1.380	6.505	26.70	0.743	0.794	26.53	2.064	4.606	946.1	Hy+Eps+M₈
21，A₂	1.482	6.439	27.00	0.389	0.606	28.41	1.079	3.505	946.8	Hy+Eps+M₈+Ls
22	2.360	5.200	27.90	0.280	0.573	43.95	0.753	3.218	913.8	Hy+M₈+Ls
23	3.150	4.314	29.19	0.063	0.365	56.02	0.162	1.957	862.1	Hy+M₈+Ls
24	3.360	3.960	29.43	0.038	0.482	59.71	0.097	2.586	858.9	Hy+M₈+Ls
25	3.420	3.900	29.70	0.028	0.567	60.52	0.073	3.030	850.5	Hy+M₈+Ls
26	3.907	3.198	30.37	0.025	0.714	68.10	0.063	3.760	829.8	Hy+M₈+Ls
27	3.964	3.213	30.55	0.020	0.611	68.32	0.049	3.180	818.5	Hy+M₈+Ls
28	4.680	2.508	31.66	0.028	0.300	76.52	0.065	1.480	766.3	Hy+M₈+Ls
29，A₃	4.790	2.425	32.36	0.026	0.547	77.53	0.060	2.674	746.4	Hy+M₈+Ls+Lic
30，A₄	4.985	2.452	32.62	0.027	0.017	78.02	0.061	0.078	722.3	Hy+Ls+Lic+Lc
31	5.000	2.188	32.30	0.025	0.255	79.96	0.057	1.233	742.1	Hy+Ls+Lc
32	5.201	1.080	32.56	0.013	1.850	89.37	0.032	9.599	785.1	Hy+Ls+Lc
33	5.352	0.518	32.11	0.012	2.120	94.74	0.030	11.33	816.7	Hy+Ls+Lc
34，C₂	6.343	0.000	32.42	0.086	0.054	99.81	0.194	0.258	740.6	Hy+Ls+Lc

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Fig.4

Table 3

Fig.5

References 15

1	杨卉芃，柳林，丁国峰.全球锂矿资源现状及发展趋势[J].矿产保护与利用，2019，39（5）：26-40.
	YANG Huipeng， LIU Lin， DING Guofeng.Present situation and development trend of lithium resources in the world[J].Conservation and Utilization of Mineral Resources，2019，39（5）：26-40.
2	THOMPSON C A.Mineral commodity summaries 2021[R].Virginia：United States Geological Survey，2021.
3	崔瑞芝，李武，董亚萍，等.298 K四元体系LiCl-MgCl₂-CaCl₂-H₂O相平衡实验及溶解度计算[J].化工学报，2018，69（10）：4148-4155.
	CUI Ruizhi， LI Wu， DONG Yaping，et al.Measurements and calculations of solid-liquid equilibria in quaternary system LiCl-MgCl₂-CaCl₂-H₂O at 298 K[J].CIESC Journal，2018，69（10）：4148-4155.
4	CUI Ruizhi， ZHANG Yongming， DONG Yaping，et al.Solid-Liquid equilibria of two quaternary systems LiBr-NaBr-Li₂SO₄-Na₂SO₄-H₂O and LiBr-KBr-Li₂SO₄-K₂SO₄-H₂O at 298.15 K[J].The Journal of Chemical Thermodynamics，2022，165.Doi：10.1016/j.jct.2021.106665 . doi: 10.1016/j.jct.2021.106665
5	ZHUGE Fuyu， YU Xuefeng， ZENG Ying，et al.Phase equilibria for the reciprocal aqueous quaternary system Li⁺，Rb⁺//Cl^-，borate-H₂O at 323.2 K[J].Journal of Solution Chemistry，2020，49（11）：1349-1359.
6	YUAN Fei， JIANG Jie， WANG Shiqiang，et al.Phase equilibria and thermodynamic model of the quinary system（Li⁺，Na⁺，Mg²⁺//Cl^-，SO₄ ^2--H₂O） at 273.15 K and 0.1 MPa[J].Journal of Molecular Liquids，2021，337.Doi：10.1016/j.molliq.2021.116334 . doi: 10.1016/j.molliq.2021.116334
7	ZENG Ying， LIN Xiaofeng， YU Xudong.Study on the solubility of the aqueous quaternary system Li₂SO₄+Na₂SO₄+K₂SO₄+H₂O at 273.15 K[J].Journal of Chemical & Engineering Data，2012，57（12）：3672-3676.
8	QI Xiaoyun， HE Chunxia， SANG Shihua，et al.Solid-liquid equilibria in the quaternary system LiBr-NaBr-KBr-H₂O and its two ternary subsystems at 288.15 K[J].Asia-Pacific Journal of Chemical Engineering，2021，16（2）.Doi：10.1002/apj.2595 . doi: 10.1002/apj.2595
9	王雪莹，黄雪莉，黄河，等.-15 ℃下Na⁺，K⁺，Mg²⁺//Cl^-，NO₃ ^-，SO₄ ^2--H₂O体系相平衡研究[J].化工学报，2020，71（11）：5059-5066.
	WANG Xueying， HUANG Xueli， HUANG He，et al.Study on phase equilibrium of system Na⁺，K⁺，Mg²⁺//Cl^-，NO₃ ^-，SO₄ ^2--H₂O at -15 ℃[J].CIESC Journal，2020，71（11）：5059-5066.
10	朱巧丽，黄雪莉.-15 ℃下Na⁺，K⁺，Mg²⁺//Cl^-，SO₄ ^2--H₂O体系相平衡[J].化工学报，2015，66（4）：1252-1257.
	ZHU Qiaoli， HUANG Xueli.Liquid-solid phase equilibrium of Na⁺，K⁺，Mg²⁺// Cl^-，SO₄ ^2--H₂O system at -15 ℃[J].CIESC Journal，2015，66（4）：1252-1257.
11	牛自得，程芳琴.水盐体系相图及其应用[M].天津：天津大学出版社，2002：172.
12	中科院青海盐湖所.卤水和盐的分析方法[M].北京：科学与技术出版社，1984：61-295.
13	任效京，黄雪莉.273.15 K下四元体系Li⁺，Mg²⁺//Cl^-，SO₄ ^2--H₂O相平衡研究[J].无机盐工业，2016，48（7）：13-15，28.
	REN Xiaojing， HUANG Xueli.Phase equilibria in the quatemary system of Li⁺，Mg²⁺//Cl^-，SO₄ ^2--H₂O at 273.15 K[J].Inorganic Chemicals Industry，2016，48（7）：13-15，28.
14	廖玲，黄雪莉，宋欢.258.15 K下五元体系Na⁺，K⁺//Cl^-，NO₃ ^-，SO₄ ^2--H₂O相平衡研究[J].高校化学工程学报，2016，30（1）：7-12.
	LIAO Ling， HUANG Xueli， SONG Huan.Phase equilibria of quinary system Na⁺，K⁺//Cl^-，NO₃ ^-，SO₄ ^2--H₂O at 258.15 K[J].Journal of Chemical Engineering of Chinese Universities，2016，30（1）：7-12.
15	郑绵平，刘喜方.青藏高原盐湖水化学及其矿物组合特征[J].地质学报，2010，84（11）：1585-1600.
	ZHENG Mianping， LIU Xifang.Hydrochemistry and minerals assemblages of salt lakes in the Qinghai-Tibet plateau，China[J].Acta Geologica Sinica，2010，84（11）：1585-1600.

温度/K	w（Li⁺）	w（Na⁺）	w（SO₄^2-）	w（Cl^-）	w（Mg²⁺）	w（K⁺）
278.15	0.019 5	9.096	2.370	16.06	1.203	0.710
273.15	0.019 2	8.904	1.841	16.02	1.196	0.697
268.15	0.020 8	8.822	1.276	16.42	1.232	0.805
263.15	0.021 7	8.271	0.813	16.13	1.302	0.786
258.15	0.021 9	7.862	0.505	16.08	1.330	0.759

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Study on phase equilibrium of quinary system of Li⁺，Na⁺，Mg²⁺//SO₄^2-，Cl^--H₂O at 258.15 K

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Study on phase equilibrium of quinary system of Li+，Na+，Mg2+//SO42-，Cl--H2O at 258.15 K