四元体系CaCl2-CaSO4-CaB6O10-H2O 308.15 K相平衡研究

doi:10.11949/0438-1157.20191148

摘要/Abstract

摘要：

采用等温溶解平衡法研究了四元体系CaCl₂-CaSO₄-CaB₆O₁₀-H₂O在308.15 K下的稳定相平衡。测定了该体系的溶解度及平衡溶液的物化性质(包括折射率、密度和pH)。根据实验数据，分别绘制了该四元体系的干基图、水图以及相应的物化性质–组成图。研究结果表明：该体系在308.15 K时有1个共饱点(CaCl₂·4H₂O + CaSO₄·2H₂O + CaB₆O₁₀·5H₂O)，3条单变量溶解度曲线，3个单盐结晶区,分别对应于CaCl₂·4H₂O、硬石膏(CaSO₄·2H₂O)和高硼钙石(CaB₆O₁₀·5H₂O)。其中，硬石膏CaSO₄·2H₂O结晶区最大、高硼钙石CaB₆O₁₀·5H₂O结晶区次之，而CaCl₂·4H₂O结晶区最小，表明硬石膏最易于结晶析出。此外，该四元体系在308.15 K下没有复盐和固溶体生成，属于简单水合物I型。平衡液相的物化性质随着CaCl₂浓度的增大呈规律性变化，并在共饱点处发生转折。其中，折射率和密度的变化规律相近，而pH的变化规律则与之相反。对该四元体系的稳定相平衡进行研究，将为综合开发利用油田卤水中的钙、硼等资源提供理论依据。

关键词: 水盐体系, 相平衡, 等温溶解平衡法, 钙硼酸盐

Abstract:

In this work, an isothermal dissolution method was used to study the phase equilibria for the quaternary system (CaCl₂-CaSO₄-CaB₆O₁₀-H₂O) at 308.15 K. The solubilities, densities, refractive indices and pH were investigated experimentally. According to the experimental data, the phase diagram, water-phase diagram and the diagrams on physicochemical properties including density, refractive index and pH against composition were plotted. The phase diagrams for the quaternary system at 308.15 K include one invariant point, three univariate solubility curves and three crystalline regions corresponding to CaCl₂·4H₂O, gypsum (CaSO₄·2H₂O) and gowerite (CaB₆O₁₀·5H₂O). The crystallizing area of gypsum (CaSO₄·2H₂O) is the largest, the gowerite (CaB₆O₁₀·5H₂O) is the second, and the CaCl₂·4H₂O is the smallest, indicating that the gypsum is most easily crystallized. In addition, the quaternary system was of the hydrate type I, neither double salt nor solid solution were formed. The physicochemical properties change regularly with the increasing of CaCl₂ concentration and appeared a turning point at invariant point. The distributive behaviors of density and refractive index against the concentration of calcium chloride in the equilibrium solution are similar. On the contrary, the change law of pH is opposite. The phase equilibrium study of quaternary system (CaCl₂-CaSO₄-CaB₆O₁₀-H₂O) will provide a theoretical basis for the development and utilization of calcium and boron resources in oilfield brines.

Key words: salt-water system, phase equilibria, the method of isothermal dissolution equilibrium, calcium borate

中图分类号:

O 642.4

袁菲, 宋江涛, 胡佳音, 郭亚飞, 王士强, 邓天龙. 四元体系CaCl₂-CaSO₄-CaB₆O₁₀-H₂O 308.15 K相平衡研究[J]. 化工学报, 2020, 71(1): 209-215.

Fei YUAN, Jiangtao SONG, Jiayin HU, Yafei GUO, Shiqiang WANG, Tianlong DENG. Phase equilibria of quaternary system CaCl₂-CaSO₄-CaB₆O₁₀-H₂O at 308.15 K[J]. CIESC Journal, 2020, 71(1): 209-215.

图/表 8

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No.	Liquid composition, w_B/%				Dry-salt composition, Z_B/[g·(100 g·S)^-1]				Solid phase
No.	CaCl₂	CaSO₄	CaB₆O₁₀	H₂O	CaCl₂	CaSO₄	CaB₆O₁₀	H₂O	Solid phase
1, A	51.98	0.23	0	51.56	99.56	0.44	0	91.51	CaCl₂·4H₂O + Gyps
2	51.65	0.19	0.15	48.01	99.35	0.37	0.29	92.34	CaCl₂·4H₂O + Gyps
3	51.74	0.16	0.45	47.65	98.83	0.31	0.86	91.02	CaCl₂·4H₂O + Gyps
4	51.70	0.15	0.62	47.53	98.53	0.29	1.18	90.59	CaCl₂·4H₂O + Gyps
5, E	49.59	0.14	1.00	49.27	97.75	0.27	1.98	97.12	CaCl₂·4H₂O+Gyps+Gowerite
6, B	50.01	0	0.04	49.95	99.92	0	0.08	99.80	CaCl₂·4H₂O + Gowerite
7, C	0	0.63	1.55	97.82	0	29.04	70.96	4705.16	Gyps + Gowerite
8	0.50	0.85	1.97	96.68	15.08	25.50	59.42	2916.50	Gyps + Gowerite
9	1.40	0.71	1.47	96.42	39.11	19.83	41.06	2693.30	Gyps + Gowerite
10	3.00	0.40	0.79	95.81	71.60	9.55	18.85	2286.63	Gyps + Gowerite
11	7.02	0.11	0.77	92.09	88.86	1.41	9.73	1164.98	Gyps + Gowerite
12	10.82	0.11	0.95	88.12	91.08	0.93	7.99	741.72	Gyps + Gowerite
13	27.19	0.48	0.80	71.53	95.50	1.69	2.81	251.25	Gyps + Gowerite
14	42.41	0.32	1.83	55.44	95.18	0.72	4.10	124.43	Gyps + Gowerite
15	48.28	0.27	1.89	49.55	95.71	0.54	3.75	98.23	Gyps + Gowerite

No.	Liquid composition, w_B/%				Dry-salt composition, Z_B/[g·(100 g·S)^-1]				Solid phase
No.	CaCl₂	CaSO₄	CaB₆O₁₀	H₂O	CaCl₂	CaSO₄	CaB₆O₁₀	H₂O	Solid phase
1, A	51.98	0.23	0	51.56	99.56	0.44	0	91.51	CaCl₂·4H₂O + Gyps
2	51.65	0.19	0.15	48.01	99.35	0.37	0.29	92.34	CaCl₂·4H₂O + Gyps
3	51.74	0.16	0.45	47.65	98.83	0.31	0.86	91.02	CaCl₂·4H₂O + Gyps
4	51.70	0.15	0.62	47.53	98.53	0.29	1.18	90.59	CaCl₂·4H₂O + Gyps
5, E	49.59	0.14	1.00	49.27	97.75	0.27	1.98	97.12	CaCl₂·4H₂O+Gyps+Gowerite
6, B	50.01	0	0.04	49.95	99.92	0	0.08	99.80	CaCl₂·4H₂O + Gowerite
7, C	0	0.63	1.55	97.82	0	29.04	70.96	4705.16	Gyps + Gowerite
8	0.50	0.85	1.97	96.68	15.08	25.50	59.42	2916.50	Gyps + Gowerite
9	1.40	0.71	1.47	96.42	39.11	19.83	41.06	2693.30	Gyps + Gowerite
10	3.00	0.40	0.79	95.81	71.60	9.55	18.85	2286.63	Gyps + Gowerite
11	7.02	0.11	0.77	92.09	88.86	1.41	9.73	1164.98	Gyps + Gowerite
12	10.82	0.11	0.95	88.12	91.08	0.93	7.99	741.72	Gyps + Gowerite
13	27.19	0.48	0.80	71.53	95.50	1.69	2.81	251.25	Gyps + Gowerite
14	42.41	0.32	1.83	55.44	95.18	0.72	4.10	124.43	Gyps + Gowerite
15	48.28	0.27	1.89	49.55	95.71	0.54	3.75	98.23	Gyps + Gowerite

No.	Liquid phase composition CaCl₂, w_b/%	Physicochemical properties
No.	Liquid phase composition CaCl₂, w_b/%	Refractive index, n_D	Density, ρ/(g·cm^-3)	pH
1, A	51.98	1.466014	1.50209	4.87
2	51.65	1.466722	1.51007	4.69
3	51.74	1.467257	1.51089	3.84
4	51.70	1.467872	1.51525	3.34
5, E	49.59	1.470097	1.51522	2.80
6, B	50.01	1.473100	1.52760	2.01
7, C	0	1.334924	1.00666	7.77
8	0.50	1.336978	1.01205	7.70
9	1.40	1.335609	1.00898	7.75
10	3.00	1.337875	1.01887	7.69
11	7.02	1.349667	1.05984	7.25
12	10.82	1.360155	1.09354	6.84
13	27.29	1.401389	1.26400	5.50
14	42.41	1.443401	1.40641	4.24
15	48.28	1.457317	1.48112	3.42

No.	Liquid phase composition CaCl₂, w_b/%	Physicochemical properties
No.	Liquid phase composition CaCl₂, w_b/%	Refractive index, n_D	Density, ρ/(g·cm^-3)	pH
1, A	51.98	1.466014	1.50209	4.87
2	51.65	1.466722	1.51007	4.69
3	51.74	1.467257	1.51089	3.84
4	51.70	1.467872	1.51525	3.34
5, E	49.59	1.470097	1.51522	2.80
6, B	50.01	1.473100	1.52760	2.01
7, C	0	1.334924	1.00666	7.77
8	0.50	1.336978	1.01205	7.70
9	1.40	1.335609	1.00898	7.75
10	3.00	1.337875	1.01887	7.69
11	7.02	1.349667	1.05984	7.25
12	10.82	1.360155	1.09354	6.84
13	27.29	1.401389	1.26400	5.50
14	42.41	1.443401	1.40641	4.24
15	48.28	1.457317	1.48112	3.42

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四元体系CaCl₂-CaSO₄-CaB₆O₁₀-H₂O 308.15 K相平衡研究

Phase equilibria of quaternary system CaCl₂-CaSO₄-CaB₆O₁₀-H₂O at 308.15 K

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