Study on phase equilibrium of system Na+, K+, Mg2+//Cl-, NO3-, SO42--H2O at -15℃

doi:10.11949/0438-1157.20200059

Abstract

Abstract:

Xinjiang brine nitrate mine mainly contains six kinds of ions: Na⁺, K⁺, Mg²⁺, Cl^-, NO₃^-, and SO₄^2-, belonging to a high-element complex system, and its rational utilization and development require phase equilibrium studies at different temperatures as theoretical support. The phase equilibrium of the system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O saturated with NaCl·2H₂O at -15℃ was investigated using the isothermal solution equilibrium method. According to the measured data, the phase diagrams were constructed. Only one double salt KCl·MgCl₂·6H₂O was found in the system. There are six invariant points and eight two-salt crystallization fields corresponding to NaCl·2H₂O+Na₂SO₄·10H₂O, NaCl·2H₂O+NaNO₃, NaCl·2H₂O+KCl, NaCl·2H₂O+KNO₃, NaCl·2H₂O+MgSO₄·7H₂O, NaCl·2H₂O+MgCl₂·8H₂O, NaCl·2H₂O + Mg(NO₃)₂·6H₂O and NaCl·2H₂O+KCl·MgCl₂·6H₂O. The crystallization area of NaCl·2H₂O+Na₂SO₄·10H₂O occupies the largest part because of its low solubility, and they will crystallize out easily from the mixed solution in the cooling process. Compared with the phase diagram of the system at 25℃, there are 5 types of double salts reduced, 19 zero variable points reduced, and the phase relationship is greatly simplified.

Key words: nitrate, low temperature, phase equilibrium, solubility, solution

摘要：

新疆卤水硝酸盐矿主要含有Na⁺、K⁺、Mg²⁺、Cl^-、NO₃^-、SO₄^2-六种离子，属于高元复杂体系，其合理利用和开发需要不同温度下的相平衡研究作为理论支撑。采用等温溶解平衡法，对Na⁺， K⁺， Mg²⁺//Cl^-， NO₃^-， SO₄^2--H₂O体系在-15℃、NaCl·2H₂O饱和条件下的相平衡进行了研究，并构建了相图。相图中有六个零变量点和八个两盐结晶区，只存在一种复盐KCl·MgCl₂·6H₂O。八个两盐结晶区，分别对应于NaCl·2H₂O+Na₂SO₄·10H₂O、NaCl·2H₂O+NaNO₃、NaCl·2H₂O+KCl、NaCl·2H₂O+KNO₃、NaCl·2H₂O+MgSO₄·7H₂O、NaCl·2H₂O+MgCl₂·8H₂O、NaCl·2H₂O+Mg(NO₃)₂·6H₂O和NaCl·2H₂O+KCl·MgCl₂·6H₂O，其中NaCl·2H₂O+Na₂SO₄·10H₂O共晶区最大，在低温时，硫酸钠的溶解度最小，降温过程中较易结晶析出。与该体系在25℃下的相图相比，复盐种类减少5种，零变量点减少19个，相关系得以极大简化。

关键词: 硝酸盐, 低温, 相平衡, 溶解度, 溶液

CLC Number:

O 642

Xueying WANG,Xueli HUANG,He HUANG,Qinglong LUO,Xuejing ZOU. Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃[J]. CIESC Journal, 2020, 71(11): 5059-5066.

王雪莹,黄雪莉,黄河,罗清龙,邹雪净. -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.

Figures/Tables 8

References 32

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No.	Composition of solution, w_B/%						Solid phase
No.	K⁺	Mg²⁺	Cl^-	NO₃^-	SO₄^2-	Na⁺	Solid phase
1,A₁	0.79	6.35	20.24	0.00	0.00	0.65	Hy+Sy+Car
2,A₂	0.04	8.26	24.29	0.00	0.00	0.11	Hy+Car+M₈
3,A₃	0.00	8.08	18.66	9.44	0.00	0.32	Hy+NN+Nit
4,A₄	0.00	8.42	20.01	8.66	0.00	0.26	Hy+M₈+Nit
5,A₅^①	2.06	0.00	9.88	17.41	0.00	11.66	Hy+KN+NN
6,A₆^①	4.21	0.00	14.49	4.91	0.00	8.75	Hy+KN+Sy
7,A₇^①	0.00	0.00	9.75	14.42	0.23	11.78	Hy+NN+S₁₀
8,A₈^①	0.00	4.45	15.45	0.00	2.52	2.81	Hy+Eps+S₁₀
9,A₉^①	0.00	7.94	23.12	0.00	0.48	0.19	Hy+Eps+M₈
10,A₁₀^①	3.30	0.00	15.60	0.00	0.34	8.34	Hy+S₁₀+Sy
11,B₁	0.71	6.63	16.64	9.36	0.00	1.30	Hy+NN+KN+Nit
12,B₂	1.37	5.91	18.78	2.82	0.00	1.24	Hy+KN+Sy+Car
13,B₃	0.42	7.72	18.03	9.67	0.00	0.43	Hy+KN+Car+Nit
14,B₄	0.15	8.36	20.34	8.52	0.00	0.45	Hy+Car+Nit+M₈
15,B₅	0.00	4.79	14.02	8.39	1.15	3.69	Hy+Eps+S₁₀+NN
16,B₆	0.00	8.24	18.76	9.86	0.54	0.50	Hy+Eps+Nit+NN
17,B₇	0.00	8.50	19.97	8.82	0.77	0.51	Hy+Eps+M₈+Nit
18,B₈^①	2.03	0.00	9.81	17.34	0.24	11.71	Hy+NN+S₁₀+KN
19,B₉^①	4.13	0.00	14.34	4.97	0.29	8.86	Hy+S₁₀+Sy+KN
20,B₁₀^①	1.72	4.12	16.07	0.00	2.37	2.76	Hy+Eps+S₁₀+Sy
21,B₁₁^①	0.84	6.45	19.45	0.00	0.93	0.37	Hy+Eps+Car+Sy
22,B₁₂^①	0.04	8.57	24.92	0.00	0.57	0.21	Hy+Eps+Car+M₈
23,C₁	0.37	7.70	17.45	11.04	0.79	1.00	Hy+Eps+Nit+NN+KN
24,C₂	0.29	7.40	19.28	4.99	0.60	0.46	Hy+Eps+Sy+Car+KN
25,C₃	0.09	8.36	19.98	8.78	0.76	0.70	Hy+Eps+Nit+Car+KN
26,C₄	0.09	8.56	19.62	9.00	0.55	0.08	Hy+Eps+M₈+Car+Nit
27,C₅	0.84	5.83	15.14	8.84	0.81	1.97	Hy+Eps+NN+S₁₀+KN
28,C₆	1.28	6.22	18.62	2.81	0.89	1.03	Hy+Eps+Sy+S₁₀+KN
29	0.67	7.14	17.09	9.90	0.61	1.14	Hy+NN+KN+Nit
30	1.07	6.37	18.75	3.27	0.93	1.15	Hy+KN+Sy+Car
31	0.62	6.96	19.59	4.22	0.78	1.12	Hy+KN+Sy+Car
32	0.10	8.48	19.74	9.01	0.58	0.33	Hy+KN+Car+Nit
33	0.10	8.39	19.66	8.68	1.21	0.61	Hy+Car+Nit+M₈
34	0.09	8.35	20.12	8.83	0.69	0.80	Hy+Car+Nit+M₈
35	2.09	1.63	10.38	16.52	0.33	8.71	Hy+NN+S₁₀+KN
36	1.01	4.71	13.87	9.37	1.20	3.54	Hy+NN+S₁₀+KN
37	0.91	5.03	14.07	8.96	1.37	3.06	Hy+NN+Eps+S₁₀
38	0.84	5.65	15.05	8.72	0.83	2.20	Hy+NN+Eps+S₁₀
39	1.52	5.40	17.06	2.92	1.28	1.65	Hy+Eps+S₁₀+Sy
40	0.10	8.35	19.86	8.66	0.62	0.52	Hy+NN+Eps+Nit
41	0.27	7.59	20.61	3.26	0.74	0.41	Hy+Eps+Car+Sy
42	0.10	7.98	21.92	3.75	0.60	0.73	Hy+Eps+Car+Sy
43	0.05	8.38	21.66	4.24	0.60	0.01	Hy+Eps+Car+Sy
44	0.07	8.31	20.46	6.32	0.56	0.13	Hy+Eps+Car+Sy
45	0.05	8.26	21.84	3.29	0.68	0.05	Hy+Eps+Car+M₈
46	0.03	8.71	23.37	3.70	0.71	0.37	Hy+Eps+Car+M₈
47	0.05	8.45	21.03	6.66	0.73	0.44	Hy+Eps+Car+M₈
48	0.09	8.39	19.29	8.62	0.56	0.05	Hy+Eps+Nit+M₈
49	0.09	8.49	19.51	8.60	0.65	0.03	Hy+Eps+Nit+M₈
50	3.61	1.32	15.13	4.15	0.54	7.00	Hy+Sy+KN+S₁₀
51	3.12	2.27	14.84	3.76	0.84	5.29	Hy+Sy+KN+S₁₀

No.	Composition of solution, w_B/%						Solid phase
No.	K⁺	Mg²⁺	Cl^-	NO₃^-	SO₄^2-	Na⁺	Solid phase
1,A₁	0.79	6.35	20.24	0.00	0.00	0.65	Hy+Sy+Car
2,A₂	0.04	8.26	24.29	0.00	0.00	0.11	Hy+Car+M₈
3,A₃	0.00	8.08	18.66	9.44	0.00	0.32	Hy+NN+Nit
4,A₄	0.00	8.42	20.01	8.66	0.00	0.26	Hy+M₈+Nit
5,A₅^①	2.06	0.00	9.88	17.41	0.00	11.66	Hy+KN+NN
6,A₆^①	4.21	0.00	14.49	4.91	0.00	8.75	Hy+KN+Sy
7,A₇^①	0.00	0.00	9.75	14.42	0.23	11.78	Hy+NN+S₁₀
8,A₈^①	0.00	4.45	15.45	0.00	2.52	2.81	Hy+Eps+S₁₀
9,A₉^①	0.00	7.94	23.12	0.00	0.48	0.19	Hy+Eps+M₈
10,A₁₀^①	3.30	0.00	15.60	0.00	0.34	8.34	Hy+S₁₀+Sy
11,B₁	0.71	6.63	16.64	9.36	0.00	1.30	Hy+NN+KN+Nit
12,B₂	1.37	5.91	18.78	2.82	0.00	1.24	Hy+KN+Sy+Car
13,B₃	0.42	7.72	18.03	9.67	0.00	0.43	Hy+KN+Car+Nit
14,B₄	0.15	8.36	20.34	8.52	0.00	0.45	Hy+Car+Nit+M₈
15,B₅	0.00	4.79	14.02	8.39	1.15	3.69	Hy+Eps+S₁₀+NN
16,B₆	0.00	8.24	18.76	9.86	0.54	0.50	Hy+Eps+Nit+NN
17,B₇	0.00	8.50	19.97	8.82	0.77	0.51	Hy+Eps+M₈+Nit
18,B₈^①	2.03	0.00	9.81	17.34	0.24	11.71	Hy+NN+S₁₀+KN
19,B₉^①	4.13	0.00	14.34	4.97	0.29	8.86	Hy+S₁₀+Sy+KN
20,B₁₀^①	1.72	4.12	16.07	0.00	2.37	2.76	Hy+Eps+S₁₀+Sy
21,B₁₁^①	0.84	6.45	19.45	0.00	0.93	0.37	Hy+Eps+Car+Sy
22,B₁₂^①	0.04	8.57	24.92	0.00	0.57	0.21	Hy+Eps+Car+M₈
23,C₁	0.37	7.70	17.45	11.04	0.79	1.00	Hy+Eps+Nit+NN+KN
24,C₂	0.29	7.40	19.28	4.99	0.60	0.46	Hy+Eps+Sy+Car+KN
25,C₃	0.09	8.36	19.98	8.78	0.76	0.70	Hy+Eps+Nit+Car+KN
26,C₄	0.09	8.56	19.62	9.00	0.55	0.08	Hy+Eps+M₈+Car+Nit
27,C₅	0.84	5.83	15.14	8.84	0.81	1.97	Hy+Eps+NN+S₁₀+KN
28,C₆	1.28	6.22	18.62	2.81	0.89	1.03	Hy+Eps+Sy+S₁₀+KN
29	0.67	7.14	17.09	9.90	0.61	1.14	Hy+NN+KN+Nit
30	1.07	6.37	18.75	3.27	0.93	1.15	Hy+KN+Sy+Car
31	0.62	6.96	19.59	4.22	0.78	1.12	Hy+KN+Sy+Car
32	0.10	8.48	19.74	9.01	0.58	0.33	Hy+KN+Car+Nit
33	0.10	8.39	19.66	8.68	1.21	0.61	Hy+Car+Nit+M₈
34	0.09	8.35	20.12	8.83	0.69	0.80	Hy+Car+Nit+M₈
35	2.09	1.63	10.38	16.52	0.33	8.71	Hy+NN+S₁₀+KN
36	1.01	4.71	13.87	9.37	1.20	3.54	Hy+NN+S₁₀+KN
37	0.91	5.03	14.07	8.96	1.37	3.06	Hy+NN+Eps+S₁₀
38	0.84	5.65	15.05	8.72	0.83	2.20	Hy+NN+Eps+S₁₀
39	1.52	5.40	17.06	2.92	1.28	1.65	Hy+Eps+S₁₀+Sy
40	0.10	8.35	19.86	8.66	0.62	0.52	Hy+NN+Eps+Nit
41	0.27	7.59	20.61	3.26	0.74	0.41	Hy+Eps+Car+Sy
42	0.10	7.98	21.92	3.75	0.60	0.73	Hy+Eps+Car+Sy
43	0.05	8.38	21.66	4.24	0.60	0.01	Hy+Eps+Car+Sy
44	0.07	8.31	20.46	6.32	0.56	0.13	Hy+Eps+Car+Sy
45	0.05	8.26	21.84	3.29	0.68	0.05	Hy+Eps+Car+M₈
46	0.03	8.71	23.37	3.70	0.71	0.37	Hy+Eps+Car+M₈
47	0.05	8.45	21.03	6.66	0.73	0.44	Hy+Eps+Car+M₈
48	0.09	8.39	19.29	8.62	0.56	0.05	Hy+Eps+Nit+M₈
49	0.09	8.49	19.51	8.60	0.65	0.03	Hy+Eps+Nit+M₈
50	3.61	1.32	15.13	4.15	0.54	7.00	Hy+Sy+KN+S₁₀
51	3.12	2.27	14.84	3.76	0.84	5.29	Hy+Sy+KN+S₁₀

卤水样品	组分/%(质量)
卤水样品	K⁺	Mg²⁺	Cl^-	NO₃^-	SO₄^2-	Na⁺	H₂O
1^#	0.270	0.194	14.90	0.824	1.831	10.32	71.66
2^#	0.291	0.115	14.81	1.275	1.505	10.41	71.60

卤水样品	组分/%(质量)
卤水样品	K⁺	Mg²⁺	Cl^-	NO₃^-	SO₄^2-	Na⁺	H₂O
1^#	0.270	0.194	14.90	0.824	1.831	10.32	71.66
2^#	0.291	0.115	14.81	1.275	1.505	10.41	71.60

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Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃

-15℃下Na⁺， K⁺， Mg²⁺//Cl^-， NO₃^-， SO₄^2--H₂O体系相平衡研究

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