298 K和323 K条件下五元体系NaBr-KBr-MgBr2-CaBr2-H2O相平衡研究

doi:10.11949/0438-1157.20190244

摘要/Abstract

摘要：

针对四川盆地地下卤水富含钾、溴资源的特点，采用等温溶解平衡法研究了五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O在298 K和323 K时的相平衡关系，测定了该五元体系在相应温度条件下平衡溶液的溶解度，根据相平衡实验数据绘制相应的干盐相图(KBr饱和)。研究结果表明：该五元体系在298 K和323 K条件下(KBr饱和)均有复盐生成，其中298 K温度下有复盐KBr·MgBr₂·6H₂O生成，相图中含有两个共饱点，五条单变量曲线和四个结晶区(KBr·MgBr₂·6H₂O、NaBr·2H₂O、NaBr、CaBr₂·6H₂O的结晶区)；323 K温度下有两种复盐KBr·MgBr₂·6H₂O、2MgBr₂·CaBr₂·12H₂O生成，相图中含有三个共饱点，七条单变量曲线和五个结晶区(KBr·MgBr₂·6H₂O、NaBr·2H₂O、NaBr、CaBr₂·4H₂O、2MgBr₂·CaBr₂·12H₂O的结晶区)。同时，对该五元体系在两个不同温度下的相图、KBr图以及水含量图进行了对比分析。

关键词: 相平衡, 四川盆地, 地下卤水, 溶解度, 溴化物

Abstract:

According to the multi-component system Na-K-Ca-Mg-Sr-Li-Cl-B₄O₇-Br-SO₄-I-H₂O of underground brine in Sichuan basin, the phase equilibrium relationships of quinary systems NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298 and 323 K were studied by isothermal solution equilibrium method, the solubilities of the equilibria solution of the quinary system were determined under the corresponding temperatures, and the corresponding phase diagrams were plotted according to the phase equilibrium experiment data (saturated with KBr). The results of research show that the quinary system has complex salt at 298 K and 323 K. There is complex salt KBr·MgBr₂·6H₂O formation at 298 K and the phase diagram contains two co-saturated points, five dissolution isotherms and four solid crystallization regions (corresponding to KBr·MgBr₂·6H₂O, NaBr·2H₂O, NaBr and CaBr₂·6H₂O, respectively). There are two kinds of complex salts KBr·MgBr₂·6H₂O and 2MgBr₂·CaBr₂·12H₂O formation at 323 K and the phase diagram contains three co-saturated points, seven dissolution isotherms and five solid crystallization regions (corresponding to KBr·MgBr₂·6H₂O, NaBr·2H₂O, NaBr, CaBr₂·4H₂O and 2MgBr₂·CaBr₂·12H₂O, respectively).

Key words: phase equilibria, Sichuan basin, underground brine, solubility, bromide

中图分类号:

O 642

聂国亮, 桑世华, 崔瑞芝. 298 K和323 K条件下五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O相平衡研究[J]. 化工学报, 2019, 70(9): 3267-3274.

Guoliang NIE, Shihua SANG, Ruizhi CUI. Phase equilibria in quinary system NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298 K and 323 K[J]. CIESC Journal, 2019, 70(9): 3267-3274.

图/表 8

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No.	Composition of liquid phase w(B)×100				J?necke index of dry salt/(g/(100 g salt))				Equilibrium solids
	Composition of liquid phase w(B)×100				J(NaBr) +J(MgBr₂)+J(CaBr₂) = 100
	w(NaBr)	w(KBr)	w(MgBr₂)	w(CaBr₂)	J(NaBr)	J(MgBr₂)	J(H₂O)	J(KBr)
1, G1	0.00	0.61	4.66	56.05	0.00	7.68	63.71	1.00	CB6 + KMB6 + KB
2	0.43	1.04	4.64	55.69	0.71	7.64	62.87	1.71	CB6 + KMB6 + KB
3, X1	0.73	1.48	4.62	55.21	1.21	7.63	62.68	2.44	CB6+KMB6+NB+KB
4, E1	0.74	1.50	0.00	57.76	1.26	0.00	68.38	2.56	CB6 + NB + KB
5	0.74	1.50	1.21	56.98	1.26	2.05	67.15	2.55	CB6 + NB + KB
6	0.74	1.50	2.56	56.01	1.25	4.32	66.08	2.53	CB6 + NB + KB
7	0.74	1.49	3.66	55.89	1.23	6.07	63.39	2.47	CB6 + NB + KB
8, N1	8.06	3.81	36.13	0.00	18.24	81.76	117.67	8.62	KMB6 + NB2 + KB
9	7.40	3.64	32.35	2.90	17.35	75.85	125.93	8.53	KMB6 + NB2 + KB
10	6.98	3.50	30.30	4.83	16.58	71.95	129.16	8.31	KMB6 + NB2 + KB
11, Y1	6.66	3.31	28.10	6.97	15.96	67.34	131.70	7.93	KMB6+NB2+NB+KB
12	5.92	3.01	25.82	11.24	13.77	60.07	125.66	7.00	KMB + NB + KB
13	5.29	2.74	22.67	17.72	11.58	49.63	112.92	6.00	KMB6 + NB + KB
14	4.61	2.33	19.30	23.47	9.73	40.73	106.14	4.92	KMB6 + NB + KB
15	3.65	2.01	15.27	30.90	7.33	30.65	96.69	4.03	KMB6 + NB + KB
16	1.98	1.79	9.45	41.02	3.78	18.02	87.24	3.41	KMB6 + NB + KB
17	1.33	1.57	6.31	49.32	2.33	11.08	72.81	2.76	KMB6 + NB + KB
18, F1	10.45	3.05	0.00	40.61	20.47	0.00	89.87	5.97	NB + NB2 + KB
19	10.02	3.07	1.99	37.31	20.32	4.03	96.53	6.22	NB + NB2 + KB
20	9.86	3.10	4.02	34.20	20.51	8.36	101.54	6.45	NB + NB2 + KB
21	9.30	3.13	6.72	29.90	20.25	14.63	110.95	6.82	NB + NB2 + KB
22	8.85	3.16	8.87	26.32	20.10	20.14	119.89	7.18	NB + NB2 + KB
23	8.46	3.18	12.70	21.79	19.70	29.57	125.42	7.40	NB + NB2 + KB
24	7.99	3.21	15.77	18.97	18.70	36.91	126.52	7.51	NB + NB2 + KB
25	7.47	3.25	19.76	14.86	17.75	46.95	129.86	7.72	NB + NB2 + KB
26	7.01	3.29	24.33	10.60	16.71	58.01	130.59	7.84	NB + NB2 + KB

No.	Composition of liquid phase w(B)×100				J?necke index of dry salt/(g/(100 g salt))				Equilibrium solids
	Composition of liquid phase w(B)×100				J(NaBr) +J(MgBr₂)+J(CaBr₂) = 100
	w(NaBr)	w(KBr)	w(MgBr₂)	w(CaBr₂)	J(NaBr)	J(MgBr₂)	J(H₂O)	J(KBr)
1, G1	0.00	0.61	4.66	56.05	0.00	7.68	63.71	1.00	CB6 + KMB6 + KB
2	0.43	1.04	4.64	55.69	0.71	7.64	62.87	1.71	CB6 + KMB6 + KB
3, X1	0.73	1.48	4.62	55.21	1.21	7.63	62.68	2.44	CB6+KMB6+NB+KB
4, E1	0.74	1.50	0.00	57.76	1.26	0.00	68.38	2.56	CB6 + NB + KB
5	0.74	1.50	1.21	56.98	1.26	2.05	67.15	2.55	CB6 + NB + KB
6	0.74	1.50	2.56	56.01	1.25	4.32	66.08	2.53	CB6 + NB + KB
7	0.74	1.49	3.66	55.89	1.23	6.07	63.39	2.47	CB6 + NB + KB
8, N1	8.06	3.81	36.13	0.00	18.24	81.76	117.67	8.62	KMB6 + NB2 + KB
9	7.40	3.64	32.35	2.90	17.35	75.85	125.93	8.53	KMB6 + NB2 + KB
10	6.98	3.50	30.30	4.83	16.58	71.95	129.16	8.31	KMB6 + NB2 + KB
11, Y1	6.66	3.31	28.10	6.97	15.96	67.34	131.70	7.93	KMB6+NB2+NB+KB
12	5.92	3.01	25.82	11.24	13.77	60.07	125.66	7.00	KMB + NB + KB
13	5.29	2.74	22.67	17.72	11.58	49.63	112.92	6.00	KMB6 + NB + KB
14	4.61	2.33	19.30	23.47	9.73	40.73	106.14	4.92	KMB6 + NB + KB
15	3.65	2.01	15.27	30.90	7.33	30.65	96.69	4.03	KMB6 + NB + KB
16	1.98	1.79	9.45	41.02	3.78	18.02	87.24	3.41	KMB6 + NB + KB
17	1.33	1.57	6.31	49.32	2.33	11.08	72.81	2.76	KMB6 + NB + KB
18, F1	10.45	3.05	0.00	40.61	20.47	0.00	89.87	5.97	NB + NB2 + KB
19	10.02	3.07	1.99	37.31	20.32	4.03	96.53	6.22	NB + NB2 + KB
20	9.86	3.10	4.02	34.20	20.51	8.36	101.54	6.45	NB + NB2 + KB
21	9.30	3.13	6.72	29.90	20.25	14.63	110.95	6.82	NB + NB2 + KB
22	8.85	3.16	8.87	26.32	20.10	20.14	119.89	7.18	NB + NB2 + KB
23	8.46	3.18	12.70	21.79	19.70	29.57	125.42	7.40	NB + NB2 + KB
24	7.99	3.21	15.77	18.97	18.70	36.91	126.52	7.51	NB + NB2 + KB
25	7.47	3.25	19.76	14.86	17.75	46.95	129.86	7.72	NB + NB2 + KB
26	7.01	3.29	24.33	10.60	16.71	58.01	130.59	7.84	NB + NB2 + KB

No.	Composition of liquid phase w(B)×100				J?necke index of dry salt/(g/(100 g salt))				Equilibrium solids
	Composition of liquid phase w(B)×100				J(NaBr)+J(MgBr₂)+J(CaBr₂) = 100
	w(NaBr)	w(KBr)	w(MgBr₂)	w(CaBr₂)	J(NaBr)	J(MgBr₂)	J(H₂O)	J(KBr)
1, E2	0.00	0.49	7.16	61.85	0.00	10.38	44.20	0.71	MCB12 + KMB6 + KB
2	1.31	0.88	6.84	57.20	2.00	10.47	51.68	1.35	MCB12 + KMB6 + KB
3, Z2	2.18	1.09	6.49	53.32	3.52	10.47	59.56	1.76	MCB13+KMB6+NB+KB
4,G2	0.72	0.67	0.00	70.22	1.01	0.00	40.02	0.94	CB4 + NB + KB
5	0.70	0.61	1.21	66.98	1.02	1.76	44.27	0.89	CB4 + NB + KB
6, X2	0.65	0.54	3.22	63.51	0.96	4.78	47.61	0.80	CB4+NB+MCB12+ KB
7, N2	12.81	4.54	30.15	0.00	29.82	70.18	122.21	10.57	MB6 + NB2 + KB
8	12.11	4.32	28.15	2.90	28.06	65.22	121.69	10.01	MB6 + NB2 + KB
9	10.98	3.98	25.30	6.83	25.47	58.69	122.73	9.23	MB6 + NB2 + KB
10	10.22	3.64	23.10	9.97	23.61	53.36	122.59	8.41	MB6 + NB2 + KB
11, Y2	9.27	3.41	20.57	13.44	21.42	47.53	123.17	7.88	NB+NB2+KMB6+KB
12	7.99	3.21	16.77	18.87	18.31	38.44	121.84	7.36	MB6 + KMB6 + KB
13	6.32	2.78	13.63	24.86	14.10	30.42	116.96	6.20	MB6 + KMB6 + KB
14	5.01	2.11	11.11	31.75	10.47	23.21	104.49	4.41	MB6 + KMB6 + KB
15	3.76	1.58	9.45	41.02	6.93	17.43	81.49	2.91	MB6 + KMB6 + KB
16, D2	45.93	8.15	0.00	2.48	94.88	0.00	89.73	16.84	NB + NB2 +KB
17	42.31	7.73	1.29	3.79	89.28	2.72	94.70	16.31	NB + NB2 +KB
18	39.77	7.21	2.87	4.56	84.26	6.08	96.59	15.28	NB + NB2 +KB
19	36.45	6.89	4.80	5.32	78.26	10.31	99.92	14.79	NB + NB2 +KB
20	32.21	6.41	6.21	6.78	71.26	13.74	107.06	14.18	NB + NB2 +KB
21	26.77	5.91	10.29	7.73	59.77	22.97	110.07	13.19	NB + NB2 +KB
22	23.34	5.04	12.39	8.69	52.54	27.89	113.78	11.35	NB + NB2 +KB
23	17.51	4.38	15.82	10.33	40.11	36.23	119.01	10.03	NB + NB2 +KB
24	14.67	3.97	17.82	11.09	33.66	40.89	120.35	9.11	NB + NB2 +KB
25, F2	0.00	0.52	3.26	63.39	0.00	4.89	49.26	0.78	MCB12 + CB4 + KB
26	0.33	0.52	3.25	63.44	0.49	4.85	48.43	0.78	MCB12 + CB4 + KB

No.	Composition of liquid phase w(B)×100				J?necke index of dry salt/(g/(100 g salt))				Equilibrium solids
	Composition of liquid phase w(B)×100				J(NaBr)+J(MgBr₂)+J(CaBr₂) = 100
	w(NaBr)	w(KBr)	w(MgBr₂)	w(CaBr₂)	J(NaBr)	J(MgBr₂)	J(H₂O)	J(KBr)
1, E2	0.00	0.49	7.16	61.85	0.00	10.38	44.20	0.71	MCB12 + KMB6 + KB
2	1.31	0.88	6.84	57.20	2.00	10.47	51.68	1.35	MCB12 + KMB6 + KB
3, Z2	2.18	1.09	6.49	53.32	3.52	10.47	59.56	1.76	MCB13+KMB6+NB+KB
4,G2	0.72	0.67	0.00	70.22	1.01	0.00	40.02	0.94	CB4 + NB + KB
5	0.70	0.61	1.21	66.98	1.02	1.76	44.27	0.89	CB4 + NB + KB
6, X2	0.65	0.54	3.22	63.51	0.96	4.78	47.61	0.80	CB4+NB+MCB12+ KB
7, N2	12.81	4.54	30.15	0.00	29.82	70.18	122.21	10.57	MB6 + NB2 + KB
8	12.11	4.32	28.15	2.90	28.06	65.22	121.69	10.01	MB6 + NB2 + KB
9	10.98	3.98	25.30	6.83	25.47	58.69	122.73	9.23	MB6 + NB2 + KB
10	10.22	3.64	23.10	9.97	23.61	53.36	122.59	8.41	MB6 + NB2 + KB
11, Y2	9.27	3.41	20.57	13.44	21.42	47.53	123.17	7.88	NB+NB2+KMB6+KB
12	7.99	3.21	16.77	18.87	18.31	38.44	121.84	7.36	MB6 + KMB6 + KB
13	6.32	2.78	13.63	24.86	14.10	30.42	116.96	6.20	MB6 + KMB6 + KB
14	5.01	2.11	11.11	31.75	10.47	23.21	104.49	4.41	MB6 + KMB6 + KB
15	3.76	1.58	9.45	41.02	6.93	17.43	81.49	2.91	MB6 + KMB6 + KB
16, D2	45.93	8.15	0.00	2.48	94.88	0.00	89.73	16.84	NB + NB2 +KB
17	42.31	7.73	1.29	3.79	89.28	2.72	94.70	16.31	NB + NB2 +KB
18	39.77	7.21	2.87	4.56	84.26	6.08	96.59	15.28	NB + NB2 +KB
19	36.45	6.89	4.80	5.32	78.26	10.31	99.92	14.79	NB + NB2 +KB
20	32.21	6.41	6.21	6.78	71.26	13.74	107.06	14.18	NB + NB2 +KB
21	26.77	5.91	10.29	7.73	59.77	22.97	110.07	13.19	NB + NB2 +KB
22	23.34	5.04	12.39	8.69	52.54	27.89	113.78	11.35	NB + NB2 +KB
23	17.51	4.38	15.82	10.33	40.11	36.23	119.01	10.03	NB + NB2 +KB
24	14.67	3.97	17.82	11.09	33.66	40.89	120.35	9.11	NB + NB2 +KB
25, F2	0.00	0.52	3.26	63.39	0.00	4.89	49.26	0.78	MCB12 + CB4 + KB
26	0.33	0.52	3.25	63.44	0.49	4.85	48.43	0.78	MCB12 + CB4 + KB

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298 K和323 K条件下五元体系NaBr-KBr-MgBr₂-CaBr₂-H₂O相平衡研究

Phase equilibria in quinary system NaBr-KBr-MgBr₂-CaBr₂-H₂O at 298 K and 323 K

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