硫酸镁型光卤石转化钾盐镁矾的过程机制与动态规律

doi:10.11949/0438-1157.20220510

摘要/Abstract

摘要：

硫酸镁的存在影响光卤石矿加工的钾盐收率和产品质量。通过对一里坪盐湖硫酸镁型光卤石进行等温不完全分解实验，研究了钾盐分解转化机制和动态特征，并建立了钾盐转化过程的动态模型。结果表明：（1）硫酸镁型光卤石在加水过程迅速分解，而经过3~4 h诱导期，氯化钾与硫酸镁会逐渐转化为钾盐镁矾，经过50 h系统达到平衡，总钾量的近55%转化为钾盐镁矾，约20%溶于分解液，仅25%以固相氯化钾存在；（2）转化过程中，如有硫酸镁水合物存在，会出现“固、液相点不动的介稳态”假象，而实际上是氯化钾和硫酸镁水合物转化为钾盐镁矾的动态过程，当固相硫酸镁水合物缺失，液相点会向氯化钠、氯化钾、钾盐镁矾、光卤石的四盐共饱点移动；（3）钾盐镁矾生成的动力学方程的反应推动力（离子活度积与共饱点活度积之差）级数为1.5，产物存量的影响指数为2/3，反应速率常数为3.907×10^-4 mol^1/3·min^-1，动力学方程与全组分物料方程构成了动态模型，可量化表达转化过程中任意时刻固液混合体系的状态。这一研究结果对改善盐湖钾资源利用过程具有重要指导意义。

关键词: 硫酸镁亚型盐湖, 光卤石, 钾盐镁矾, 相平衡, 多相反应, 动力学模型

Abstract:

The existence of magnesium sulfate affects the potassium salt yield and product quality of carnallite (Car) processing. In this study, the incomplete decomposition experiments of magnesium sulfate Car in Yiliping salt lake was carried out at 25℃, the decomposition and formation mechanism, and the dynamic behavior of potassium salts were studied. The results show that: (1) Magnesium sulfate type Car will decomposes rapidly when water added, and after 3—4 h of induction period, potassium chloride and magnesium sulfate will gradually converts into kainite (Kai), although there is no Kai phase area on the metastable phase diagram. When phase equilibria achieved after 50 h, nearly 55% of the total potassium converts into Kai, about 20% dissolves in decomposition solution, and only 25% exists as solid potassium chloride. (2) During the conversion process, if there is magnesium sulfate hydrate, the illusion of “metastable state with fixed solid and liquid points” will appear, In fact, it is the dynamic process of the conversion of potassium chloride and magnesium sulfate hydrate into kaleite. When the solid phase magnesium sulfate hydrate is absent, the liquid point will move to the tetrasalt co-saturation point of sodium chloride, potassium chloride, kaleite, and carnallite. (3) In the kinetic equation of Kai formation, the order of the reaction driving force (the difference between the ionic activity products at invariable point and process point) is 1.5, the influence index of the product stock is 2/3, and the reaction rate constant is 3.907×10^-4 mol^1/3·min^-1. The kinetic equation and the full-component material equation constitute a dynamic model, which can quantitatively express the state of the solid-liquid mixing system at any time during the transformation process. These results have important guiding significance for improving the utilization process of potassium resources in salt lakes.

Key words: magnesium sulfate subtype salt lake, carnallite, kainite, phase equilibria, multiphase reaction, kinetic modeling

中图分类号:

TQ 443

周桓, 张梦丽, 郝晴, 吴思, 李杰, 徐存兵. 硫酸镁型光卤石转化钾盐镁矾的过程机制与动态规律[J]. 化工学报, 2022, 73(9): 3841-3850.

Huan ZHOU, Mengli ZHANG, Qing HAO, Si WU, Jie LI, Cunbing XU. Process mechanism and dynamic behaviors of magnesium sulfate type carnallite converting into kainite[J]. CIESC Journal, 2022, 73(9): 3841-3850.

图/表 11

图1 五元体系25℃平衡相图[14]与“介稳相图”[17]比较

Fig.1 Comparison between the 25℃ equilibrium phase diagram[14] and “metastable phase diagram” [17] of quinary system

表1 硫酸镁型光卤石矿组成

Table 1 Composition of magnesium sulfate type carnallite

盐类	组成/%
盐类	25℃	15℃	一里坪矿样一	一里坪矿样二
KCl·MgCl₂·6H₂O	63.54	68.62	56.42	36.48
MgSO₄·7H₂O	33.12	22.97	25.98	30.98
KCl·MgSO₄·2.75H₂O	—	—	—	4.08
KCl	—	—	—	13.38
NaCl	3.34	8.41	4.68	9.87
其他	—	—	12.92	5.21

图2 硫酸镁型盐田光卤石矿组成点与分解液相点

Fig.2 Composition points of magnesium sulfate type carnallite ore points and decomposition liquid

图3 硫酸镁型光卤石转化钾盐镁矾的反应机制

Fig.3 Conversion mechanism of magnesium sulfate type carnallite convert to kainite

图4 硫酸镁型光卤石转化钾盐镁矾的相图分析

Fig.4 Phase diagram analysis of magnesium sulfate type carnallite convert into kainite

表2 25℃光卤石矿加水转化钾盐镁矾过程的固液相离子浓度

Table 2 Solid and liquid ion concentrations of kainite converted from carnallite ore with water at 25℃

时间/min	液相化学组成/%						湿固相化学组成/%
时间/min	Na⁺	K⁺	Mg²⁺	Cl^-	$S O 4 2 -$	H₂O	Na⁺	K⁺	Mg²⁺	Cl^-	$S O 4 2 -$	H₂O
0	3.50	9.08	8.46	30.19	11.00	37.78	5.30	10.50	7.18	28.87	13.25	34.90
5	0.07	2.42	7.00	18.81	5.29	66.41	5.14	10.45	7.20	28.60	13.31	35.30
10	0.30	2.46	7.03	18.98	5.72	65.50	4.97	9.67	7.11	27.97	12.47	37.82
20	0.47	2.34	6.98	19.23	5.38	65.61	4.42	10.28	7.12	27.96	12.14	38.06
30	0.28	2.38	6.94	18.98	5.22	66.19	4.33	9.68	7.28	27.74	12.11	38.86
60	0.09	2.33	7.10	19.14	5.18	66.16	4.10	10.25	7.14	27.39	12.27	38.85
120	0.31	2.36	7.05	19.39	5.13	65.76	5.00	10.03	7.10	27.87	13.09	36.91
240	0.40	2.32	7.05	19.41	5.24	65.58	4.12	10.26	7.31	27.76	12.52	38.03
360	0.42	2.28	7.00	19.30	5.20	65.79	3.84	10.79	7.32	27.96	12.32	37.77
480	0.46	2.25	6.96	19.18	5.26	65.89	3.88	11.06	7.29	28.70	11.63	37.44
600	0.47	2.25	6.96	19.30	5.09	65.93	4.21	11.35	7.12	28.23	12.62	36.46
720	0.45	2.21	6.93	19.20	5.02	66.19	4.51	10.43	7.07	27.73	12.61	37.64
900	0.47	2.19	6.90	19.20	4.93	66.31	4.16	10.33	7.16	27.71	12.13	38.51
1080	0.49	2.25	6.95	19.23	5.22	65.85	4.48	10.61	7.13	28.10	12.51	37.17
1260	0.52	2.29	6.96	19.23	5.37	65.63	5.44	10.07	7.09	28.59	13.05	35.75
1440	0.47	2.29	6.92	19.15	5.21	65.95	5.78	10.92	7.12	29.79	13.27	33.11
1620	0.35	2.26	6.98	19.20	5.10	66.10	4.80	10.89	7.43	27.79	15.13	33.96
1823^①	0.36	2.19	6.96	19.32	4.78	66.39	—	—	—	—	—	—
1920	0.38	1.90	6.88	19.80	3.48	67.57	5.31	11.22	7.25	29.45	13.64	33.13
2220	0.34	1.90	6.72	19.94	2.59	68.50	5.73	11.95	7.76	30.09	16.55	27.92
2400	0.35	1.93	6.65	19.92	2.39	68.76	5.49	11.90	7.38	30.33	14.15	30.76
2700	0.38	1.92	6.68	20.18	2.22	68.62	4.98	11.95	7.64	30.91	13.40	31.13
3000	0.50	1.92	6.56	20.10	2.10	68.82	5.30	10.50	7.18	28.87	13.25	34.90

表2 25℃光卤石矿加水转化钾盐镁矾过程的固液相离子浓度

Table 2 Solid and liquid ion concentrations of kainite converted from carnallite ore with water at 25℃

时间/min	液相化学组成/%						湿固相化学组成/%
时间/min	Na⁺	K⁺	Mg²⁺	Cl^-	$S O 4 2 -$	H₂O	Na⁺	K⁺	Mg²⁺	Cl^-	$S O 4 2 -$	H₂O
0	3.50	9.08	8.46	30.19	11.00	37.78	5.30	10.50	7.18	28.87	13.25	34.90
5	0.07	2.42	7.00	18.81	5.29	66.41	5.14	10.45	7.20	28.60	13.31	35.30
10	0.30	2.46	7.03	18.98	5.72	65.50	4.97	9.67	7.11	27.97	12.47	37.82
20	0.47	2.34	6.98	19.23	5.38	65.61	4.42	10.28	7.12	27.96	12.14	38.06
30	0.28	2.38	6.94	18.98	5.22	66.19	4.33	9.68	7.28	27.74	12.11	38.86
60	0.09	2.33	7.10	19.14	5.18	66.16	4.10	10.25	7.14	27.39	12.27	38.85
120	0.31	2.36	7.05	19.39	5.13	65.76	5.00	10.03	7.10	27.87	13.09	36.91
240	0.40	2.32	7.05	19.41	5.24	65.58	4.12	10.26	7.31	27.76	12.52	38.03
360	0.42	2.28	7.00	19.30	5.20	65.79	3.84	10.79	7.32	27.96	12.32	37.77
480	0.46	2.25	6.96	19.18	5.26	65.89	3.88	11.06	7.29	28.70	11.63	37.44
600	0.47	2.25	6.96	19.30	5.09	65.93	4.21	11.35	7.12	28.23	12.62	36.46
720	0.45	2.21	6.93	19.20	5.02	66.19	4.51	10.43	7.07	27.73	12.61	37.64
900	0.47	2.19	6.90	19.20	4.93	66.31	4.16	10.33	7.16	27.71	12.13	38.51
1080	0.49	2.25	6.95	19.23	5.22	65.85	4.48	10.61	7.13	28.10	12.51	37.17
1260	0.52	2.29	6.96	19.23	5.37	65.63	5.44	10.07	7.09	28.59	13.05	35.75
1440	0.47	2.29	6.92	19.15	5.21	65.95	5.78	10.92	7.12	29.79	13.27	33.11
1620	0.35	2.26	6.98	19.20	5.10	66.10	4.80	10.89	7.43	27.79	15.13	33.96
1823^①	0.36	2.19	6.96	19.32	4.78	66.39	—	—	—	—	—	—
1920	0.38	1.90	6.88	19.80	3.48	67.57	5.31	11.22	7.25	29.45	13.64	33.13
2220	0.34	1.90	6.72	19.94	2.59	68.50	5.73	11.95	7.76	30.09	16.55	27.92
2400	0.35	1.93	6.65	19.92	2.39	68.76	5.49	11.90	7.38	30.33	14.15	30.76
2700	0.38	1.92	6.68	20.18	2.22	68.62	4.98	11.95	7.64	30.91	13.40	31.13
3000	0.50	1.92	6.56	20.10	2.10	68.82	5.30	10.50	7.18	28.87	13.25	34.90

表3 25℃光卤石矿加水转化钾盐镁矾过程的盐类组成和母液量

Table 3 Salt composition and mother liquor amount in the process of kainite converted from carnallite ore at 25℃

时间/min	固、液相质量（盐的质量和干基质量百分比）/%
时间/min	Car		Kai		Eps		KCl		NaCl		母液
0	603.46	61.01	0	0	283.87	28.70	12.15	1.23	89.59	9.06	0
5	273.08	42.69	0	0	204.28	31.94	73.77	11.53	88.51	13.84	586.44
10	264.99	42.79	0	0	194.74	31.45	74.48	12.03	85.01	13.73	606.86
20	267.71	42.71	0	0	201.17	32.09	75.48	12.04	82.49	13.16	599.23
30	276.56	43.17	0	0	205.46	32.07	73.28	11.44	85.36	13.32	585.43
60	256.37	40.85	0	0	204.37	32.56	78.72	12.54	88.2	14.05	598.42
120	257.12	41.15	0	0	204.76	32.77	78.00	12.48	84.9	13.59	601.30
240	256.37	41.29	0.10	0.02	202.44	32.60	78.54	12.65	83.47	13.44	605.27
360	268.45	42.38	0.43	0.07	204.96	32.36	76.2	12.03	83.37	13.16	592.67
480	267.91	42.35	1.32	0.21	203.95	32.24	76.04	12.02	83.36	13.18	593.49
600	266.79	42.29	3.20	0.51	201.83	31.99	75.69	12.00	83.34	13.21	595.23
720	264.77	42.18	6.58	1.05	198.01	31.54	75.07	11.96	83.31	13.27	598.34
900	259.89	41.90	14.76	2.38	188.77	30.44	73.56	11.86	83.23	13.42	605.88
1080	251.49	41.42	28.81	4.74	172.88	28.47	70.96	11.69	83.10	13.68	618.84
1260	238.72	40.63	50.18	8.54	148.72	25.31	67.02	11.41	82.89	14.11	638.55
1440	220.61	39.42	80.48	14.38	114.47	20.46	61.42	10.98	82.59	14.76	666.49
1620	194.5	37.46	124.18	23.91	65.08	12.53	53.35	10.27	82.17	15.82	706.79
1823^①	160.10	34.34	181.76	38.99	0.00	0.00	42.72	9.16	81.61	17.51	759.88
1920	145.29	29.89	215.93	44.42	0.00	0.00	42.43	8.73	82.45	16.96	739.93
2220	155.11	30.39	238.20	46.66	0.00	0.00	33.78	6.62	83.37	16.33	717.47
2400	161.6	31.27	240.84	46.60	0.00	0.00	31.13	6.02	83.30	16.12	710.39
2700	150.69	29.58	242.77	47.66	0.00	0.00	33.29	6.53	82.67	16.23	717.49
3000	165.28	31.84	243.71	46.95	0.00	0.00	29.54	5.69	80.54	15.52	707.01

图5 硫酸镁型光卤石矿加水转化过程液相组成变化

Fig.5 The liquid composition change in magnesium sulfate type carnallite ore decompose process

图6 光卤石矿加水转化钾盐镁矾过程的固相XRD谱图

Fig.6 XRD pattern of solid phase during carnallite ore decompose process

图7 钾盐镁矾析出的过程推动力随时间的变化

Fig.7 Driving force changes of potassium magnesium alum precipitation process with time

图8 硫酸镁亚型光卤石分解过程盐类变化规律

Fig.8 Salts conversion behaviors in carnallite decomposition process

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