Research progress on preparation of α-hemihydrate gypsum from industrial by-product gypsum

doi:10.16085/j.issn.1000-6613.2024-0456

Abstract

Abstract:

With the rapid development of industry, the emission of industrial by-product gypsum has increased sharply. At present, the stacking-landfill-based treatment method not only wastes a lot of resources, but also seriously pollutes the ecological environment. Therefore, large-scale consumption of industrial by-product gypsum is imminent. Among the gypsum phases, α‍-hemihydrate gypsum has excellent properties which has been widely applied in various practical projects. Using industrial by-product gypsum to prepare α‍-hemihydrate gypsum, realizing the high value-added utilization of gypsum, has great application value. Whereas, the pretreatment method of industrial by-product gypsum, the preparation method of α‍-hemihydrate gypsum as well as the crystal form regulation are important influencing factors for the preparation of α‍‍-hemihydrate gypsum. Based on this, in this paper the industrial sources of α‍-hemihydrate gypsum and the key technologies of preparation at home and abroad were reviewed. The effects of pretreatment methods such as physical and chemical methods on the purification of industrial by-product gypsum were summarized, the crystallization mechanism of α‍-hemihydrate gypsum was discussed, and different preparation methods were compared and evaluated. The crystal form control methods such as stirring and ball milling were reviewed, the effect of crystal modifier on the crystal form of α‍-hemihydrate gypsum was analyzed, and the crystal transformation mechanism was pointed out.

Key words: industrial by-product gypsum, α?-hemihydrate gypsum, pretreatment, preparation method, crystalline control

摘要：

伴随着工业的快速发展，工业副产石膏的排放量激增，目前其以堆积填埋为主的处理方式不仅浪费了大量资源，还严重污染了生态环境。因此，大规模消纳工业副产石膏迫在眉睫。石膏物相中，α型半水石膏具有优异的性能，广泛应用于各种实际工程。利用工业副产石膏制备α型半水石膏，实现石膏的高附加值利用，具有巨大的应用价值。其中，工业副产石膏的预处理方式、α型半水石膏的制备方法及其晶型调控，是制备α型半水石膏的重要影响因素。基于此，本文针对国内外α型半水石膏的工业化来源及其制备的关键技术展开了综述：归纳了物理法及化学法等预处理方式对工业副产石膏净化与提纯的影响；讨论了α型半水石膏的结晶机理，对比分析与评估了不同的制备方法；梳理了搅拌、球磨等晶型调控方法，重点分析了转晶剂对α型半水石膏晶型的影响，并指出其转晶机制。

关键词: 工业副产石膏, α型半水石膏, 预处理, 制备方法, 晶型调控

CLC Number:

TQ177.3⁺7

CAO Yonggang, ZHANG Zilong, LI Zehao, LI Zeyou, GU Yin, XUE Kui, WANG Jialiang, HUANG Wei. Research progress on preparation of α-hemihydrate gypsum from industrial by-product gypsum[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1505-1519.

曹涌钢, 张子龙, 李泽皓, 李泽佑, 谷音, 薛葵, 王佳亮, 黄伟. 工业副产石膏制备α型半水石膏的研究进展[J]. 化工进展, 2025, 44(3): 1505-1519.

Figures/Tables 21

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工业副产石膏	SO₃	CaO	Fe₂O₃	S_iO₂	Al₂O₃	MgO	P₂O₅	F	Na₂O	K₂O	结晶水	其他
脱硫石膏^[27]	42.30	36.21	0.32	0.65	0.25	0.10	—	—	—	0.03	19.62	0.52
脱硫石膏^[28]	41.92	31.51	0.32	2.69	0.35	0.06	—	—	0.03	0.05	17.30	—
脱硫石膏^[29]	42.63	36.87	0.31	0.73	0.31	0.11	—	—	—	0.04	14.95	—
磷石膏^[5]	40.86	29.82	0.14	9.43	0.24	0.06	1.17	0.52	—	—	—	—
磷石膏^[30]	41.39	30.32	0.15	6.41	0.47	0.04	0.58	0.36	0.07	0.05	20.16	—
磷石膏^[31]	36.96	26.77	0.12	13.90	0.68	0.69	1.58	0.52	—	0.15	18.89	0.01
钛石膏^[32]	38.16	34.49	11.44	3.27	1.10	0.29	0.03	—	—	0.21	—	—
钛石膏^[26]	38.82	28.30	18.11	4.20	1.99	1.52	—	—	1.41	—	—	2.22
氟石膏^[33]	47.81	44.49	0.68	0.66	0.56	0.31	—	3.53	1.88	—	—	—
柠檬石膏^[34]	44.71	31.06	0.15	1.88	1.03	0.17	—	—	—	0.08	19.50	—
芒硝石膏^[35]	38.36	29.78	2.66	17.09	5.45	3.56	—	—	0.59	1.16	—	1.35
盐石膏^[36]	55.45	40.64	0.01	0.35	0.01	0.61	—	—	0.88	0.06	—	—
硼石膏^[37]	32.17	37.33	1.08	13.13	2.39	3.10	—	—	—	—	—	—

工业副产石膏	SO₃	CaO	Fe₂O₃	S_iO₂	Al₂O₃	MgO	P₂O₅	F	Na₂O	K₂O	结晶水	其他
脱硫石膏^[27]	42.30	36.21	0.32	0.65	0.25	0.10	—	—	—	0.03	19.62	0.52
脱硫石膏^[28]	41.92	31.51	0.32	2.69	0.35	0.06	—	—	0.03	0.05	17.30	—
脱硫石膏^[29]	42.63	36.87	0.31	0.73	0.31	0.11	—	—	—	0.04	14.95	—
磷石膏^[5]	40.86	29.82	0.14	9.43	0.24	0.06	1.17	0.52	—	—	—	—
磷石膏^[30]	41.39	30.32	0.15	6.41	0.47	0.04	0.58	0.36	0.07	0.05	20.16	—
磷石膏^[31]	36.96	26.77	0.12	13.90	0.68	0.69	1.58	0.52	—	0.15	18.89	0.01
钛石膏^[32]	38.16	34.49	11.44	3.27	1.10	0.29	0.03	—	—	0.21	—	—
钛石膏^[26]	38.82	28.30	18.11	4.20	1.99	1.52	—	—	1.41	—	—	2.22
氟石膏^[33]	47.81	44.49	0.68	0.66	0.56	0.31	—	3.53	1.88	—	—	—
柠檬石膏^[34]	44.71	31.06	0.15	1.88	1.03	0.17	—	—	—	0.08	19.50	—
芒硝石膏^[35]	38.36	29.78	2.66	17.09	5.45	3.56	—	—	0.59	1.16	—	1.35
盐石膏^[36]	55.45	40.64	0.01	0.35	0.01	0.61	—	—	0.88	0.06	—	—
硼石膏^[37]	32.17	37.33	1.08	13.13	2.39	3.10	—	—	—	—	—	—

杂质种类	存在形式	危害
磷类^[38]	H₃PO₄、H₂PO₄^-、HPO₂^-、Ca₃(PO₄)₂	延长凝结时间，降低产物强度
氟类^[39]	NaF、CaF₂、Na₂SiF₆	可溶性氟会减小凝结时间并降低产物强度，难溶氟对石膏无影响
有机物类^[38]	C₅H₁₀O₃、C₂H₃SN、C₆H₁₄O、C₇H₁₆O₂	削弱晶体间的结合，降低产物强度
其他^[40]	碱金属盐杂质	引发粉化、泛霜

杂质种类	存在形式	危害
磷类^[38]	H₃PO₄、H₂PO₄^-、HPO₂^-、Ca₃(PO₄)₂	延长凝结时间，降低产物强度
氟类^[39]	NaF、CaF₂、Na₂SiF₆	可溶性氟会减小凝结时间并降低产物强度，难溶氟对石膏无影响
有机物类^[38]	C₅H₁₀O₃、C₂H₃SN、C₆H₁₄O、C₇H₁₆O₂	削弱晶体间的结合，降低产物强度
其他^[40]	碱金属盐杂质	引发粉化、泛霜

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