Li+，K+，Ca2+//Cl--H2O四元体系298.2 K固液相平衡研究

doi:10.19964/j.issn.1006-4990.2024-0304

Abstract

Abstract:

Deep brine in Sichuan basin is abundant in lithium and potassium resources，which has significant development potential，however，the interactions among the coexisting ions are complex.To obtain the crystallization law of each salt in the coexistence chloride system of lithium，potassium，and calcium，the solid-liquid phase equilibria of Li⁺，K⁺，Ca²⁺//Cl^--H₂O quaternary system at 298.2 K was investigated by using isothermal dissolution method.The solubilities and densities of the solution were determined，meanwhile the solid phase of the quaternary invariant point was identified by X-ray diffraction.The phase diagram was constructed by using the measured data.The results showed that the system was a complex quaternary system with the double salt LiCl·CaCl₂·5H₂O formed，and the crystalline form of calcium chloride was influenced by the coexisting lithium chloride，with both CaCl₂·6H₂O and CaCl₂·4H₂O forms present simultaneously.The corresponding solid-liquid phase diagram consisted of 3 quaternary invariant points（points E₁ and E₂ were incommensurate type，E₃ belonged to commensurate type），7 univariate curves and 5 crystallization regions，the area of crystallization regions was decreased in the order of KCl，LiCl·H₂O，CaCl₂·4H₂O，LiCl·CaCl₂·5H₂O，CaCl₂·6H₂O.

Key words: phase equilibria, phase diagram, solubility, deep brine, double salt

CLC Number:

TQ131.1

YU Xudong, LI Jing, REN Siying, LUO Jun, ZENG Ying. Study on solid-liquid phase equilibrium of Li⁺，K⁺，Ca²⁺//Cl^--H₂O quaternary system at 298.2 K[J]. Inorganic Chemicals Industry, 2025, 57(3): 30-35.

Figures/Tables 9

Fig.1

Table 1

Solid-liquid phase equilibria data of Li+，K+，Ca2+//Cl--H2O quaternary system at 298.2 K a"

编号	密度/ （g·cm^-3）	液相组成					耶涅克指数				平衡固相
		液相组成					J（LiCl）+J（KCl）+J（CaCl₂）=100
		w（LiCl）× 10²	w（KCl） × 10²	w（CaCl₂）× 10²	w（H₂O）× 10²		J（LiCl）	J（KCl）	J（CaCl₂）	J（H₂O）
a	—	0.00	26.40	0.00	73.60	0.00		100.00	0.00	278.79	KCl^［15］
b	—	45.86	0.00	0.00	54.14	100.00		0.00	0.00	118.05	LiCl·H₂O^［23］
c	—	0.00	0.00	44.83	55.17	0.00		0.00	100.00	123.06	CaCl₂·6H₂O^［15］
1，A	1.466 4	0.00	3.06	44.68	52.26	0.00		6.41	93.59	109.47	KCl +CaCl₂·6H₂O^［15］
2	1.436 2	1.64	3.03	42.28	53.05	3.49		6.45	90.06	112.99	KCl +CaCl₂·6H₂O
3	1.435 0	2.95	2.98	41.35	52.72	6.24		6.30	87.46	111.51	KCl +CaCl₂·6H₂O
4	1.441 9	4.13	2.98	41.02	51.87	8.58		6.19	85.23	107.77	KCl +CaCl₂·6H₂O
5，E₁	1.450 0	5.64	2.93	39.69	51.74	11.69		6.07	82.24	107.21	KCl+CaCl₂·6H₂O+CaCl₂·4H₂O
6	1.435 0	6.10	2.84	39.54	51.52	12.58		5.86	81.56	106.27	KCl+CaCl₂·4H₂O
7	1.431 2	7.18	2.78	38.67	51.37	14.76		5.72	79.52	105.63	KCl+CaCl₂·4H₂O
8	1.425 3	9.80	2.84	36.34	51.02	20.01		5.80	74.19	104.16	KCl+CaCl₂·4H₂O
9	1.423 1	11.88	2.51	35.25	50.36	23.93		5.06	71.01	101.45	KCl+CaCl₂·4H₂O
10	1.436 0	12.89	2.57	33.78	50.76	26.18		5.22	68.60	103.09	KCl+CaCl₂·4H₂O
11，E₂	1.469 6	20.66	2.40	33.53	43.41	36.51		4.24	59.25	76.71	KCl+LCC+CaCl₂·4H₂O
12	1.469 1	22.88	2.18	31.44	43.50	40.50		3.86	55.64	76.99	KCl+LCC^b
13	1.468 6	24.08	1.98	30.61	43.33	42.49		3.49	54.02	76.46	KCl+LCC
14	1.456 1	26.16	2.13	28.79	42.92	45.83		3.73	50.44	75.19	KCl+LCC
15	1.449 1	26.92	2.13	27.91	43.04	47.26		3.74	49.00	75.56	KCl+LCC
16	1.440 1	28.56	2.20	25.92	43.32	50.39		3.88	45.73	76.43	KCl+LCC
17	1.435 5	29.77	2.33	24.05	43.85	53.02		4.15	42.83	78.09	KCl+LCC
18，E₃	1.426 0	31.93	2.51	21.52	44.04	57.05		4.49	38.46	78.70	KCl+LCC+LiCl·H₂O
19	1.305 9	43.47	3.51	1.36	51.66	89.93		7.26	2.81	106.87	KCl+LiCl·H₂O
20	1.319 1	42.23	3.50	3.62	50.65	85.57		7.09	7.34	102.63	KCl+LiCl·H₂O
21	1.323 2	42.20	3.49	4.75	49.56	83.66		6.92	9.42	98.26	KCl+LiCl·H₂O
22	1.338 0	41.11	3.43	5.96	49.50	81.41		6.79	11.80	98.02	KCl+LiCl·H₂O
23	1.342 1	40.93	3.42	6.85	48.80	79.94		6.68	13.38	95.31	KCl+LiCl·H₂O
24	1.305 9	43.47	3.51	1.36	51.66	89.93		7.26	2.81	106.87	KCl+LiCl·H₂O
25	1.351 3	39.86	3.41	8.04	48.69	77.68		6.65	15.67	94.89	KCl+LiCl·H₂O
26	1.356 1	39.42	3.35	8.98	48.25	76.17		6.47	17.36	93.24	KCl+LiCl·H₂O
27	1.363 0	37.73	3.30	11.14	47.83	72.32		6.33	21.35	91.68	KCl+LiCl·H₂O
28	1.373 3	36.66	3.21	13.48	46.65	68.71		6.02	25.27	87.44	KCl+LiCl·H₂O
29	1.388 5	34.93	3.20	14.64	47.23	66.19		6.06	27.75	89.50	KCl+LiCl·H₂O
30	1.407 8	33.70	3.09	16.50	46.71	63.24		5.80	30.96	87.65	KCl+LiCl·H₂O
31	1.409 3	33.27	3.00	18.88	44.85	60.33		5.44	34.23	81.32	KCl+LiCl·H₂O
32，F	1.273 4	44.39	3.52	0.00	52.09	92.65		7.35	0.00	108.72	KCl+LiCl·H₂O^［7］
33，B	1.439 3	6.46	0.00	41.68	51.86	13.42		0.00	86.58	107.73	CaCl₂·6H₂O+CaCl₂·4H₂O^［23］
34	1.435 4	5.78	0.57	40.83	52.82	12.25		1.21	86.54	111.95	CaCl₂·6H₂O+CaCl₂·4H₂O
35	1.449 8	5.64	1.42	40.22	52.72	11.93		3.00	85.07	111.51	CaCl₂·6H₂O+CaCl₂·4H₂O
36，C	1.404 3	19.09	0.00	32.63	48.28	36.91		0.00	63.09	93.35	CaCl₂·4H₂O+LCC^［23］
37	1.440 8	18.94	1.23	31.11	48.72	36.93		2.40	60.67	95.01	CaCl₂·4H₂O+LCC
38	1.456 2	18.46	0.67	31.28	49.59	36.62		1.33	62.05	98.37	CaCl₂·4H₂O+LCC
39	1.459 5	18.34	2.50	33.33	45.83	33.86		4.62	61.52	84.60	CaCl₂·4H₂O+LCC
40，D	1.373 5	31.59	0.00	20.64	47.77	60.48		0.00	39.52	91.46	LiCl·H₂O+LCC^［23］
41	1.395 5	30.25	0.57	21.15	48.03	58.20		1.10	40.70	92.42	LiCl·H₂O+LCC
42	1.410 5	31.77	1.23	21.75	45.25	58.02		2.25	39.73	82.65	LiCl·H₂O+LCC

Table 1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

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Study on solid-liquid phase equilibrium of Li⁺，K⁺，Ca²⁺//Cl^--H₂O quaternary system at 298.2 K

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Study on solid-liquid phase equilibrium of Li+，K+，Ca2+//Cl--H2O quaternary system at 298.2 K