Studies on three-dimensional phase diagram of the quinary system NaBr-KBr-MgBr2-CaBr2-H2O at 298.15 K

doi:10.11949/0438-1157.20220811

Abstract

Abstract:

In order to rationally develop the bromine-rich underground brine resources in the Sichuan Basin, the complete phase equilibria and phase diagram of the quinary system NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298.15 K were studied. According to the solubility data measured in the experiment, a complete three-dimensional phase diagram, as well as the dry basis projected phase diagrams of the saturation surface with NaBr·2H₂O, MgBr₂·6H₂O and CaBr₂·6H₂O were plotted respectively, and the corresponding water content diagrams were drawn respectively. The results show that the phase diagram of the quinary system at 298.15 K contains ten univariate curves, three invariant points and six crystallization regions (KBr crystallization region, NaBr crystallization region, NaBr·2H₂O crystallization region, MgBr₂·6H₂O crystallization region, CaBr₂·6H₂O crystallization region, KBr·MgBr₂·6H₂O crystallization region). The KBr crystallization region is the largest and the CaBr₂·6H₂O crystallization region is the smallest, which indicates that the solubility of CaBr₂·6H₂O is the largest and the KBr solubility is the smallest in this system.

Key words: phase diagram, bromide, underground brine resources, phase equilibria

摘要：

为合理开发四川盆地富溴地下卤水资源，对五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O进行了298.15 K条件下完整的相平衡与相图的研究。根据实验测定的溶解度数据，绘制出了完整的空间立体相图，NaBr·2H₂O、MgBr₂·6H₂O和CaBr₂·6H₂O三种盐饱和面的干基投影相图，以及相应的含水量图。研究结果表明该五元体系在298.15 K下的空间立体相图中包含有十条单变量曲线、三个共饱点和六个结晶区（KBr结晶区、NaBr结晶区、NaBr·2H₂O结晶区、MgBr₂·6H₂O结晶区、CaBr₂·6H₂O结晶区、KBr·MgBr₂·6H₂O结晶区）。其中KBr结晶区最大，CaBr₂·6H₂O结晶区最小，表明在该体系中CaBr₂·6H₂O的溶解度最大，KBr溶解度最小。

关键词: 相图, 溴化物, 地下卤水, 相平衡

CLC Number:

TQ 028.8

Changwei PENG, Shihua SANG, Ruizhi CUI, Hongbao REN. Studies on three-dimensional phase diagram of the quinary system NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298.15 K[J]. CIESC Journal, 2022, 73(11): 4850-4858.

彭昌炜, 桑世华, 崔瑞芝, 任红保. 五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O在298.15 K下的空间立体相图研究[J]. 化工学报, 2022, 73(11): 4850-4858.

Figures/Tables 8

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No.	Systems	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)			Equilibria solids	Ref.
No.	Systems	NaBr	KBr	MgBr₂	CaBr₂	CaBr₂	MgBr₂	KBr	Equilibria solids	Ref.
1	MCB	0.00	0.00	4.96	55.71	91.82	8.18	0.00	MB6 + CB6	[30]
2	MCB	0.00	0.00	5.92	54.37	—	—	—	MB6 + CB6	[32]
3	KCB	0.00	1.33	0.00	58.24	97.77	0.00	2.23	KB + CB6	[33]
4	KCB	0.00	0.81	0.00	59.14	—	—	—	KB + CB6	[30]
5	KMB	0.00	0.25	50.18	0.00	0.00	99.50	0.50	MB6 + KMB6	[31]
6	KMB	0.00	3.30	42.85	0.00	0.00	92.85	7.15	KMB6 + KB	[31]
7	NKB	43.94	7.42	0.00	0.00	0.00	0.00	14.45	KB+ NB2	[31]
8	NKB	43.06	7.23	0.00	0.00	—	—	—	KB+ NB2	[33]
9	NCB	0.84	0.00	0.00	58.97	98.60	0.00	0.00	CB6+ NB	[33]
10		10.32	0.00	0.00	42.28	80.38	0.00	0.00	NB + NB2	[33]
11		0.76	0.00	0.00	59.34	—	—	—	CB6+ NB	[32]
12		8.61	0.00	0.00	44.6	—	—	—	NB + NB2	[32]
13	NMB	3.50	0.00	47.96	0.00	0.00	96.81	0.00	MB6 + NB	[31]
14		7.20	0.00	42.74	0.00	0.00	93.44	0.00	NB + NB2	[31]
15		3.52	0.00	47.95	0.00	—	—	—	MB6 + NB	[32]
16		7.16	0.00	42.76	0.00	—	—	—	NB + NB2	[32]
F1	KMCB	0.00	0.14	4.73	55.21	91.89	7.87	0.23	MB6 + KMB6 + CB6	[30]
F2	KMCB	0.00	0.61	4.66	56.05	91.41	7.60	0.99	KB + KMB6 + CB6	[30]
F3	NKCB	0.74	1.50	0.00	57.76	96.27	0.00	2.50	CB6 + NB + KB	[33]
F4	NKCB	10.45	3.05	0.00	40.61	75.05	0.00	5.64	NB + NB2 + KB	[33]
F5	NKMB	3.42	0.22	47.21	0.00	0.00	92.84	0.43	MB6 + NB+ KMB6	[31]
F6		7.06	0.43	42.36	0.00	0.00	84.97	0.86	NB + KMB6 + NB2
F7		8.06	3.81	36.13	0.00	0.00	75.27	7.94	KMB6 + KB + NB2
F8	NMCB	0.59	0.00	5.89	54.16	89.31	9.71	0.00	MB6 + CB6 + NB	[32]
E1	NKMCB	0.73	1.48	4.62	55.21	88.99	7.45	2.39	NB + CB6 + KMB6 + KB	this work
E2		6.66	3.31	28.10	6.97	15.48	62.39	7.35	NB2 + NB + KMB6 + KB
E3		0.54	0.21	4.84	55.15	90.80	7.96	0.35	MB6 + KMB6 + NB + CB6

No.	Systems	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)			Equilibria solids	Ref.
No.	Systems	NaBr	KBr	MgBr₂	CaBr₂	CaBr₂	MgBr₂	KBr	Equilibria solids	Ref.
1	MCB	0.00	0.00	4.96	55.71	91.82	8.18	0.00	MB6 + CB6	[30]
2	MCB	0.00	0.00	5.92	54.37	—	—	—	MB6 + CB6	[32]
3	KCB	0.00	1.33	0.00	58.24	97.77	0.00	2.23	KB + CB6	[33]
4	KCB	0.00	0.81	0.00	59.14	—	—	—	KB + CB6	[30]
5	KMB	0.00	0.25	50.18	0.00	0.00	99.50	0.50	MB6 + KMB6	[31]
6	KMB	0.00	3.30	42.85	0.00	0.00	92.85	7.15	KMB6 + KB	[31]
7	NKB	43.94	7.42	0.00	0.00	0.00	0.00	14.45	KB+ NB2	[31]
8	NKB	43.06	7.23	0.00	0.00	—	—	—	KB+ NB2	[33]
9	NCB	0.84	0.00	0.00	58.97	98.60	0.00	0.00	CB6+ NB	[33]
10		10.32	0.00	0.00	42.28	80.38	0.00	0.00	NB + NB2	[33]
11		0.76	0.00	0.00	59.34	—	—	—	CB6+ NB	[32]
12		8.61	0.00	0.00	44.6	—	—	—	NB + NB2	[32]
13	NMB	3.50	0.00	47.96	0.00	0.00	96.81	0.00	MB6 + NB	[31]
14		7.20	0.00	42.74	0.00	0.00	93.44	0.00	NB + NB2	[31]
15		3.52	0.00	47.95	0.00	—	—	—	MB6 + NB	[32]
16		7.16	0.00	42.76	0.00	—	—	—	NB + NB2	[32]
F1	KMCB	0.00	0.14	4.73	55.21	91.89	7.87	0.23	MB6 + KMB6 + CB6	[30]
F2	KMCB	0.00	0.61	4.66	56.05	91.41	7.60	0.99	KB + KMB6 + CB6	[30]
F3	NKCB	0.74	1.50	0.00	57.76	96.27	0.00	2.50	CB6 + NB + KB	[33]
F4	NKCB	10.45	3.05	0.00	40.61	75.05	0.00	5.64	NB + NB2 + KB	[33]
F5	NKMB	3.42	0.22	47.21	0.00	0.00	92.84	0.43	MB6 + NB+ KMB6	[31]
F6		7.06	0.43	42.36	0.00	0.00	84.97	0.86	NB + KMB6 + NB2
F7		8.06	3.81	36.13	0.00	0.00	75.27	7.94	KMB6 + KB + NB2
F8	NMCB	0.59	0.00	5.89	54.16	89.31	9.71	0.00	MB6 + CB6 + NB	[32]
E1	NKMCB	0.73	1.48	4.62	55.21	88.99	7.45	2.39	NB + CB6 + KMB6 + KB	this work
E2		6.66	3.31	28.10	6.97	15.48	62.39	7.35	NB2 + NB + KMB6 + KB
E3		0.54	0.21	4.84	55.15	90.80	7.96	0.35	MB6 + KMB6 + NB + CB6

No.	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)				Equilibrium solids
No.	NaBr	KBr	MgBr₂	CaBr₂	NaBr	KBr	H₂O	MgBr₂	Equilibrium solids
1, F1	0.00	0.14	4.73	55.21	0.00	0.25	72.12	8.55	MB6 + KMB6 + CB6
2, E3	0.54	0.21	4.84	55.15	0.96	0.38	70.22	8.65	MB6 + KMB6 + NB + CB6
3, F8	0.59	0.00	5.89	54.16	1.08	0.00	71.89	10.76	CB6 + NB + MB6
4	0.54	0.12	5.27	54.20	0.99	0.22	72.65	9.61	CB6 + NB + MB6
5, F5	3.42	0.22	47.21	0.00	93.96	6.04	1350.27	1296.98	NB + KMB6 + MB6
6	1.84	0.23	47.02	2.04	44.79	5.53	1192.56	1147.34	NB + KMB6 + MB6
7	1.91	0.24	45.01	5.88	23.82	3.02	584.66	560.37	NB + KMB6 + MB6
8	1.54	0.23	41.54	9.26	13.93	2.06	430.28	376.83	NB + KMB6 + MB6
9	1.46	0.23	38.24	15.83	8.32	1.33	252.45	218.26	NB + KMB6 + MB6
10	1.14	0.22	30.78	24.02	4.48	0.88	172.70	121.27	NB + KMB6 + MB6
11	1.16	0.21	26.24	28.73	3.84	0.70	145.06	87.20	NB + KMB6 + MB6
12	0.76	0.21	18.28	38.96	1.91	0.52	104.64	45.78	NB + KMB6 + MB6
13	0.69	0.21	10.63	50.21	1.34	0.41	74.90	20.80	NB + KMB6 + MB6
14	0.63	0.22	6.56	53.59	1.16	0.40	71.65	12.05	NB + KMB6 + MB6

No.	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)				Equilibrium solids
No.	NaBr	KBr	MgBr₂	CaBr₂	NaBr	KBr	H₂O	MgBr₂	Equilibrium solids
1, F1	0.00	0.14	4.73	55.21	0.00	0.25	72.12	8.55	MB6 + KMB6 + CB6
2, E3	0.54	0.21	4.84	55.15	0.96	0.38	70.22	8.65	MB6 + KMB6 + NB + CB6
3, F8	0.59	0.00	5.89	54.16	1.08	0.00	71.89	10.76	CB6 + NB + MB6
4	0.54	0.12	5.27	54.20	0.99	0.22	72.65	9.61	CB6 + NB + MB6
5, F5	3.42	0.22	47.21	0.00	93.96	6.04	1350.27	1296.98	NB + KMB6 + MB6
6	1.84	0.23	47.02	2.04	44.79	5.53	1192.56	1147.34	NB + KMB6 + MB6
7	1.91	0.24	45.01	5.88	23.82	3.02	584.66	560.37	NB + KMB6 + MB6
8	1.54	0.23	41.54	9.26	13.93	2.06	430.28	376.83	NB + KMB6 + MB6
9	1.46	0.23	38.24	15.83	8.32	1.33	252.45	218.26	NB + KMB6 + MB6
10	1.14	0.22	30.78	24.02	4.48	0.88	172.70	121.27	NB + KMB6 + MB6
11	1.16	0.21	26.24	28.73	3.84	0.70	145.06	87.20	NB + KMB6 + MB6
12	0.76	0.21	18.28	38.96	1.91	0.52	104.64	45.78	NB + KMB6 + MB6
13	0.69	0.21	10.63	50.21	1.34	0.41	74.90	20.80	NB + KMB6 + MB6
14	0.63	0.22	6.56	53.59	1.16	0.40	71.65	12.05	NB + KMB6 + MB6

No.	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)				Equilibrium solids
No.	NaBr	KBr	MgBr₂	CaBr₂	NaBr	KBr	H₂O	CaBr₂	Equilibrium solids
1, F1	0.00	0.14	4.73	55.21	0.00	2.87	819.71	1133.68	MB6 + KMB6 + CB6
2, E3	0.54	0.21	4.84	55.15	9.62	3.81	702.58	986.59	MB6 + KMB6 + NB + CB6
3, F8	0.59	0.00	5.89	54.16	9.10	0.00	607.41	835.81	MB6 + NB + CB6
4	0.54	0.12	5.27	54.20	9.16	2.00	671.35	914.00	MB6 + NB + CB6
5, F2	0.00	0.61	4.66	56.05	0.00	11.57	733.97	1063.57	KMB6 + KB + CB6
6	0.43	1.04	4.64	55.69	7.04	17.02	625.20	911.46	KMB6 + KB + CB6
7, E1	0.73	1.48	4.62	55.21	10.69	21.67	555.78	808.35	KMB6 + KB + NB + CB6
8, F3	0.74	1.50	0.00	57.76	33.04	66.96	1785.71	2578.57	NB + KB + CB6
9	0.74	1.50	1.21	56.98	21.45	43.48	1146.96	1651.59	NB + KB + CB6
10	0.74	1.50	2.56	56.01	15.42	31.25	816.46	1166.88	NB + KB + CB6
11	0.74	1.49	3.66	55.89	12.56	25.30	648.90	648.90	NB + KB + CB6

Studies on three-dimensional phase diagram of the quinary system NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298.15 K

五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O在298.15 K下的空间立体相图研究

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No.	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)				Equilibrium solids
No.	NaBr	KBr	MgBr₂	CaBr₂	MgBr₂	CaBr₂	H₂O	NaBr	Equilibrium solids
1, F4	10.45	3.05	0.00	40.61	0.00	93.01	105.11	23.93	KB + NB + NB2
2	10.02	3.07	1.99	37.31	4.70	88.06	112.37	23.65	KB + NB + NB2
3	9.86	3.10	4.02	34.20	9.73	82.77	118.15	23.86	KB + NB + NB2
4	9.30	3.13	6.72	29.90	16.91	75.22	128.18	23.40	KB + NB + NB2
5	8.85	3.16	8.87	26.32	23.13	68.63	137.68	23.08	KB + NB + NB2
6	8.46	3.18	12.7	21.79	33.71	57.84	143.01	22.46	KB + NB + NB2
7	7.99	3.21	15.77	18.97	41.55	49.99	142.45	21.05	KB + NB + NB2
8	7.47	3.25	19.76	14.86	52.18	39.24	144.34	19.73	KB + NB + NB2
9	7.01	3.29	24.33	10.60	63.66	27.73	143.30	18.34	KB + NB + NB2
10, E2	6.66	3.31	28.10	6.97	73.22	18.16	143.20	17.35	KB + NB + KMB6 + NB2
11, F7	8.06	3.81	36.13	0.00	90.46	0.00	130.20	20.18	KB + KMB6 + NB2
12	7.40	3.64	32.35	2.90	83.18	7.46	138.11	19.03	KB + KMB6 + NB2
13	6.98	3.50	30.30	4.83	78.44	12.50	140.80	18.07	KB + KMB6 + NB2
14, F6	7.06	0.43	42.36	0.00	99.00	0.00	117.20	16.50	NB + KMB6 + NB2

No.	Composition of liquid phase w(B)/%				Jänecke index of dry slat J/(g/100 g)				Equilibrium solids
No.	NaBr	KBr	MgBr₂	CaBr₂	MgBr₂	CaBr₂	H₂O	NaBr	Equilibrium solids
1, F4	10.45	3.05	0.00	40.61	0.00	93.01	105.11	23.93	KB + NB + NB2
2	10.02	3.07	1.99	37.31	4.70	88.06	112.37	23.65	KB + NB + NB2
3	9.86	3.10	4.02	34.20	9.73	82.77	118.15	23.86	KB + NB + NB2
4	9.30	3.13	6.72	29.90	16.91	75.22	128.18	23.40	KB + NB + NB2
5	8.85	3.16	8.87	26.32	23.13	68.63	137.68	23.08	KB + NB + NB2
6	8.46	3.18	12.7	21.79	33.71	57.84	143.01	22.46	KB + NB + NB2
7	7.99	3.21	15.77	18.97	41.55	49.99	142.45	21.05	KB + NB + NB2
8	7.47	3.25	19.76	14.86	52.18	39.24	144.34	19.73	KB + NB + NB2
9	7.01	3.29	24.33	10.60	63.66	27.73	143.30	18.34	KB + NB + NB2
10, E2	6.66	3.31	28.10	6.97	73.22	18.16	143.20	17.35	KB + NB + KMB6 + NB2
11, F7	8.06	3.81	36.13	0.00	90.46	0.00	130.20	20.18	KB + KMB6 + NB2
12	7.40	3.64	32.35	2.90	83.18	7.46	138.11	19.03	KB + KMB6 + NB2
13	6.98	3.50	30.30	4.83	78.44	12.50	140.80	18.07	KB + KMB6 + NB2
14, F6	7.06	0.43	42.36	0.00	99.00	0.00	117.20	16.50	NB + KMB6 + NB2