钙芒硝石膏深度提纯工艺的研究

doi:10.19964/j.issn.1006-4990.2022-0075

摘要/Abstract

摘要：

钙芒硝石膏是工业上采用溶浸法生产元明粉的副产尾矿，与脱硫石膏和磷石膏等工业副产石膏相比其杂质含量高、纯度低、利用价值低。采用酸浸-重结晶工艺对钙芒硝石膏进行提纯，通过酸浸去除钙芒硝石膏中的酸溶性杂质，并将二水硫酸钙（DH）脱水转化为无水硫酸钙（AH），然后控制水化条件，使AH水化为大尺寸的DH晶体，并与小尺寸的酸不溶性杂质分离开来，得到高纯度的二水石膏。研究了硫酸浓度、水化激发剂、液固质量比、反应时间等对石膏提纯的影响。研究结果表明：常压下，在硫酸酸洗液质量分数为35%、反应温度为80 ℃、石膏与硫酸溶液固液质量比为1∶5、酸洗时间为2 h时能有效去除钙芒硝石膏中的酸溶性杂质；在水化硫酸质量分数为5%、硫酸钾质量分数为1.74%、反应温度为25 ℃、固液质量比为1∶6、陈化时间为18 h时能有效去除钙芒硝石膏中酸不溶性杂质，提纯后的石膏纯度可达97%以上。

关键词: 钙芒硝石膏, 石膏提纯, 重结晶

Abstract:

Glauberite gypsum is the by-product tailings produced by leaching sodium sulfate in the industry.Compared with industrial by-product gypsum such as desulfurized gypsum and phosphogypsum，it has higher impurity content，lower purity and utilization value.Glauberite gypsum was purified by acid leaching-recrystallization process，the acid-soluble impurities in Glauberite gypsum were removed by acid leaching and dihydrate calcium sulfate（DH） was converted into anhydrous calcium sulfate（AH）.Then hydration conditions were controlled to hydrate AH into large-size DH crystals separated from small-sized acid-insoluble impurities to obtain high-purity dihydrate gypsum.The effects of sulfuric acid concentration，hydration activator，liquid-solid ratio and reaction time on purified gypsum were studied.The research results showed that under normal pressure，when the mass fraction of sulfuric acid pickling solution was 35%，the reaction temperature was 80 ℃，the solid-liquid ratio of gypsum and sulfuric acid solution was 1∶5，and the pickling time was 2 h，it could effectively remove acid-soluble impurities in glauberite gypsum.When mass fraction of hydrate sulfuric acid was 5%，mass fraction of potassium sulfate was 1.74%，reaction temperature was 25 ℃，solid-liquid ratio was 1∶6，aging time was 18 h，it could effectively remove acid-insoluble impurities in glauberite gypsum，and the purity of purified gypsum could reach more than 97%.

Key words: glauberite gypsum, gypsum purification, recrystallization

中图分类号:

X781

尹会斌,李军,郑卓超. 钙芒硝石膏深度提纯工艺的研究[J]. 无机盐工业, 2022, 54(11): 104-111.

YIN Huibin,LI Jun,ZHENG Zhuochao. Research on deep purification process of glauberite gypsum[J]. Inorganic Chemicals Industry, 2022, 54(11): 104-111.

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组成	w（CaO）/%	w （SO₃）/ %	w （SiO₂）/ %	w （CO₂）/ %	w （MgO）/ %	w （Al₂O₃）/ %	w （Fe₂O₃）/ %	w （SrO）/ %	w （K₂O）/ %	w （Na₂O）/ %	w （TiO₂）/ %	w （MnO₂）/ %	w （P₂O₅）/ %	LOI/ %	总计/ %
MG₁	27.54	35.10	6.59	9.10	2.38	2.02	1.08	0.47	0.42	0.23	0.13	0.03	0.03	14.89	100.01
MG₂	27.27	39.91	7.63	5.33	0.47	1.79	0.43	0.47	0.43	0.10	0.13	—	—	16.03	99.99
MG₃	27.39	40.20	7.59	5.06	0.30	1.59	0.32	0.46	0.39	0.13	0.13	—	0.02	16.41	99.99
MG₄	34.71	47.53	13.85	—	0.34	1.79	0.12	0.58	—	0.21	0.17	—	—	0.72	100.02

组成	w （CaO）/ %	w （SO₃）/ %	w （SiO₂）/ %	w （CO₂）/ %	w （MgO）/ %	w （Al₂O₃）/ %	w （Fe₂O₃）/ %	w （SrO）/ %	w （K₂O）/ %	w （Na₂O）/ %	w （TiO₂）/ %	LOI/ %	总量 %
MG₅	27.80	40.75	8.04	4.44	0.33	1.75	0.37	0.49	0.41	0.15	0.12	15.36	100.01
MG₆	31.09	45.24	10.45	5.28	0.35	2.04	0.27	0.56	0.45	0.15	0.16	3.96	100.00
MG₄	34.71	47.53	13.85	—	0.34	1.79	0.12	0.58	—	0.21	0.17	0.72	100.02
MG₇	34.61	48.10	13.63	—	0.34	1.64	0.13	0.58	—	0.19	0.14	0.71	100.07

组成	w（石膏）/%	w（酸不溶性杂质）/%	组成	w（石膏）/%	w（酸不溶性杂质）/%
CaO	32.79	7.26	K₂O	—	3.16
SO₃	46.98	12.64	Na₂O	—	0.55
SiO₂	0.25	62.66	TiO₂	—	0.93
CO₂	—	—	MnO₂	—	—
MgO	—	0.57	P₂O₅	—	0.08
Al₂O₃	—	10.96	LOI	19.50	0.00
Fe₂O₃	—	1.01	总计	99.95	100.53
SrO	0.43	0.71

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