HF体系中AlF3杂质的溶解度与纯化机理

doi:10.16085/j.issn.1000-6613.2024-0284

摘要/Abstract

摘要：

为了解决现代铍冶金工艺中铍纯度低、铍收得率低以及危废渣量大等难题，本文聚焦铍冶金基础理论，提出了低温解离铍矿+物理纯化含铍化合物的提铍新方法。针对铍矿中含铝氟化物的除杂过程，在HF体系背景下，研究了AlF₃杂质的溶解度规律和纯化机理，从溶解度实验结果来看，AlF₃直接解离出来的Al³⁺浓度和F^-浓度是很低的，在10^-5级别，难以形成AlF $_{6}^{3 -}$ 配合物，所以在H₂O体系中AlF₃的溶解度要低于在HF体系中的溶解度，而在HF-H₂O-AlF₃体系下，会形成F的配位离子，使原本不溶的AlF₃反而有了一定的溶解度。以此为基础，采用低温煅烧的方式破坏H₃AlF₆结构，将H₃AlF₆分解成AlF₃，避免了H₃AlF₆对AlF₃溶解度产生的影响，从而解决了杂质的分离难题。

关键词: 氟化氢体系, 铍冶金, 绿柱石, 氟化铝, 溶解度

Abstract:

In order to solve the problems of low beryllium purity, low beryllium yield and large amount of hazardous waste residue in the modern beryllium metallurgy process, the team focused on the basic theories of beryllium metallurgy and proposed a new beryllium extraction method of low-temperature dissociation of beryllium ores plus physical purification of beryllium-containing compounds. For the decontamination process of aluminum-containing fluorides in beryllium ores, the solubility law and purification mechanism of AlF₃ impurities were investigated in the context of the HF system. From the results of the solubility experiments, the concentration of Al³⁺ and the concentration of F^- from the direct dissociation of AlF₃ were very low, at the level of 10^-5, and it was difficult to form the AlF $_{6}^{3 -}$ complex. Therefore, the solubility of AlF₃ in the H₂O system was lower than that in the HF system, while under the HF-H₂O-AlF₃ system, the ligand ion of F would be formed so that the originally insoluble AlF₃ had certain solubility instead. Based on this, low-temperature calcination was used to destroy the structure of H₃AlF₆ and decompose H₃AlF₆ into AlF₃, avoiding the effect of H₃AlF₆ on the solubility of AlF₃, and thus solving the separation problem of impurities.

Key words: HF system, beryllium metallurgy, beryl, AlF₃, solubility

中图分类号:

TF801

申耀宗, 郭培民, 王磊, 孔令兵, 郭庆, 谢奕斌. HF体系中AlF₃杂质的溶解度与纯化机理[J]. 化工进展, 2025, 44(2): 1157-1162.

SHEN Yaozong, GUO Peimin, WANG Lei, KONG Lingbing, GUO Qing, XIE Yibin. Solubility and purification mechanism of AlF₃ impurities in the HF system[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 1157-1162.

图/表 9

图1 氢氟酸解离铍矿工艺流程图

图2 不同体系下AlF3溶解度的变化趋势

表1 绿柱石矿主要成分

参数	BeO	SiO₂	Al₂O₃	Fe₂O₃	MnO	CaO	MgO	P	F
质量分数/%	10.81	66.44	19.54	1.72	0.32	0.45	0.35	0.15	0.038
物质的量n_i	0.432	1.107	0.192	0.011	0.0045	0.0080	0.0088	0.0048	0.002

图3 AlF3在不同条件下的热力学情况

图4 AlF3分解出来的Al3+浓度与温度关系

图5 利用AlF3浓度得到的AlF3溶解自由能

图6 AlF3的配合物

图7 F-浓度对配物离子AlF63-浓度影响

图8 AlF63-加热分解标准吉布斯自由能

参考文献 33

1	ZHENG Lifang, WANG Xiaogang, YUE Lina, et al. Progress in the application of rare light metal beryllium[J]. Materials Science Forum, 2020, 977: 261-271.
2	朱学红, 冯慧, 张宏伟. 地缘政治视角下铍资源供应风险分析[J]. 中南大学学报(社会科学版), 2023, 29(5): 138-147.
	ZHU Xuehong, FENG Hui, ZHANG Hongwei. Beryllium resource supply risk analysis from the geopolitical perspective[J]. Journal of Central South University (Social Sciences), 2023, 29(5): 138-147.
3	CHEN Zhaoxi, JIN Guangxu, CHEN Kaiyun, et al. Development and experimental study of beryllium window for ITER radial X-ray camera[J]. Fusion Engineering and Design, 2013, 88(12): 3280-3286.
4	邵伟华, 曾永杰, 常学勇, 等. 某含萤石铍矿综合回收铍和萤石的试验研究[J]. 矿产保护与利用, 2023, 43(1): 98-104.
	SHAO Weihua, ZENG Yongjie, CHANG Xueyong, et al. Experimental study on comprehensive recovery of beryllium and fluorite from a fluorite-beryllium ore[J]. Conservation and Utilization of Mineral Resources, 2023, 43(1): 98-104.
5	ROUXEL Baptiste, MISCHLER Stefano, Roland LOGÉ, et al. Wear behaviour of novel copper alloy as an alternative to copper-beryllium[J]. Wear, 2023, 524: 204817.
6	中国有色金属工业协会专家委员会组织. 中国铍业[M]. 北京: 冶金工业出版社, 2015.
	China Nonferrous Metals Industry Association Expert Committee Organization. China beryllium industry[M]. Beijing: Metallurgical Industry Press, 2015.
7	LU Ruilong, HAN Jingtao, LI Zhanhua, et al. Study of the mechanical properties and microstructure of spiral tubes and actuators for controlled extension fabricated with beryllium bronze strips[J]. Materials, 2023, 16(20): 6719.
8	PAVLOV Alexandr, SAGDOLDINA Zhuldyz, ZHILKASHINOVA Almira, et al. Synthesis and investigation of properties of beryllium ceramics modified with titanium dioxide nanoparticles[J]. Materials, 2023, 16(19): 6507.
9	宗国强, 肖吉昌. 氟化物熔盐的制备及其应用进展[J]. 化工进展, 2018, 37(7): 2455-2472.
	ZONG Guoqiang, XIAO Jichang. Advances in the preparation and application of fluoride molten salts[J]. Chemical Industry and Engineering Progress, 2018, 37(7): 2455-2472.
10	贺云鹏. 高纯铍真空热压成型装置设计与研究[D]. 沈阳: 沈阳大学, 2021.
	HE Yunpeng. Design and research of high-purity beryllium vacuum hot pressing device[D]. Shenyang: Shenyang University, 2021.
11	GERASIMOV M F, NIKIFOROV S V. Simulation of the thermoluminescence isothermal decay curves in Al₂O₃-BeO ceramics taking into account the energy distribution of trapping centers[J]. Bulletin of the Russian Academy of Sciences: Physics, 2023, 87(11): 1655-1660.
12	LAZUKINA O P, VOLKOVA E N, MALYSHEV K K, et al. Purity of alkaline-earth metals (according to materials in the exhibition-collection of extrapure substances)[J]. Inorganic Materials, 2021, 57(11): 1167-1172.
13	MATYASOVA V E, KOTSAR’ M L, ANAN’EV A V, et al. Ion-exchange processes in the reprocessing of sulfate solutions and pulps with production of high-purity beryllium compounds[J]. Atomic Energy, 2016, 119(6): 408-413.
14	ZHAO Xu, XIA Hongyang, SU Yucheng, et al. Study on removal of beryllium from uranium beryllium ore wastewater by acid leaching activated carbon and its mechanism[J]. Journal of Radioanalytical and Nuclear Chemistry, 2023, 332(10): 4231-4242.
15	邓伟, 颜世强, 谭洪旗, 等. 我国铍矿资源概况及选矿技术研究现状[J]. 矿产综合利用, 2023(1): 148-154.
	DENG Wei, YAN Shiqiang, TAN Hongqi, et al. General situation of beryllium ore resources and research status of mineral processing technology in China[J]. Multipurpose Utilization of Mineral Resources, 2023(1): 148-154.
16	张森, 鞠楠, 伍月, 等. 铍矿分布特点、主要类型与勘查开发现状[J]. 中国地质, 2023, 50(2): 410-424.
	ZHANG Sen, JU Nan, WU Yue, et al. Distribution characteristics, main types and exploration and development status of beryllium deposit[J]. Geology in China, 2023, 50(2): 410-424.
17	贾福东, 张长青, 化志新, 等. 云南麻花坪钨铍矿床蓝柱石的鉴定特征及成分与成因分析[J]. 光谱学与光谱分析, 2020, 40(10): 3185-3192.
	JIA Fudong, ZHANG Changqing, HUA Zhixin, et al. Identification characteristics, composition and genesis of euclase in mahuaping tungsten-beryllium polymetallic deposit in Yunnan Province, Southwest China[J]. Spectroscopy and Spectral Analysis, 2020, 40(10): 3185-3192.
18	李中. 铍矿石的浸出及回收工艺试验研究[D]. 衡阳: 南华大学, 2015.
	LI Zhong. Study on the experimentalof beryllium ore leaching and recovery process[D]. Hengyang: University of South China, 2015.
19	雷湘. 高氟铍矿石的脱氟试验研究[J]. 湖南有色金属, 2004, 20(1): 21-22, 25.
	LEI Xiang. Research on removing fluorine from beryllium ore containing high fluorine[J]. Hunan Nonferrous Metals, 2004, 20(1): 21-22, 25.
20	李卫. 高氟铍矿石的冶炼工艺研究[D]. 长沙: 中南大学, 2003.
	LI Wei. Study on smelting process of high fluorine beryllium ore[D]. Changsha: Central South University, 2003.
21	肖超, 李婕, 吴海国. 硫酸法提取铍工艺中铝杂质分离的研究现状[J]. 稀有金属与硬质合金, 2013, 41(3): 8-10, 27.
	XIAO Chao, LI Jie, WU Haiguo. The latest research on the aluminum separation during beryllium extraction with sulfuric acid[J]. Rare Metals and Cemented Carbides, 2013, 41(3): 8-10, 27.
22	郭培民, 赵沛, 王磊, 等. 一种从绿柱石中浸出铍的方法: CN112322893A[P]. 2021-02-05.
	GUO Peimin, ZHAO Pei, WANG Lei, et al. A method for leaching beryllium from beryl: CN112322893A[P]. 2021-02-05.
23	郭培民, 王磊, 孔令兵, 等. 一种从含氟化铍混合物中提纯制备氢氧化铍的方法: CN113003591A[P]. 2021-06-22.
	GUO Peimin, WANG Lei, KONG Lingbing, et al. A method for the purification and preparation of beryllium hydroxide from beryllium fluoride-containing mixtures: CN113003591A [P]. 2021-06-22.
24	郭培民, 王磊, 孔令兵, 等. 一种从含氟化铍混合物中提纯制备氟铍化铵的方法: CN112794343B[P]. 2022-12-16.
	GUO Peimin, WANG Lei, KONG Lingbing, et al. A method for the purification and preparation of ammonium beryllium fluoride from beryllium fluoride-containing mixtures: CN112794343B[P]. 2022-12-16.
25	郭培民, 曾志彦, 王磊, 等. 一种金属铍珠及金属铍锭的制备方法: CN113059154B[P]. 2022-09-16.
	GUO Peimin, ZENG Zhiyan, WANG Lei, et al. A preparation method of beryllium metal beads and beryllium metal ingots: CN113059154B[P]. 2022-09-16.
26	刘光启. 化学化工物性数据手册-无机卷[M]. 北京: 化学工业出版社, 2002.
	LIU Guangqi. Handbook of physical properties of chemistry and chemical engineering-inorganic volume[M]. Beijing: Chemical Industry Press, 2002.
27	稀有金属手册编辑委员会. 稀有金属手册.下[M]. 北京: 冶金工业出版社, 1995.
	Editorial Board of the Handbook of Rare Metals. Handbook of rare metals. Next[M]. Beijing: Metallurgical Industry Press, 1995.
28	郭培民, 赵沛. 冶金资源高效利用[M]. 北京: 冶金工业出版社, 2012.
	GUO Peimin, ZHAO Pei. Efficient utilization of metallurgical resources[M]. Beijing: Metallurgical Industry Press, 2012.
29	EVEREST David Anthony. The chemistry of beryllium[M]. Amsterdam: Elsevier Publishing Company, 1964.
30	马进伟, 方浩, 陈茜茜, 等. 基于焓-熵-(火用)平衡的无盖板PV/T系统热力学分析与优化[J]. 化工进展, 2022, 41(4): 1840-1847.
	MA Jinwei, FANG Hao, CHEN Qianqian, et al. Thermodynamic analysis and optimization of unglazed PV/T system based on enthalpy-entropy-exergy equilibrium[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1840-1847.
31	宋昌斌, 李润超. 碳酸锂在水中的溶解度和超溶解度的测定及热力学分析[J]. 化工进展, 2016, 35(8): 2350-2354.
	SONG Changbin, LI Runchao. Measurement and thermodynamic analysis of the solubility and supersolubility of lithium carbonate in water[J]. Chemical Industry and Engineering Progress, 2016, 35(8): 2350-2354.
32	张琳. F^-、Al³⁺、CaF₂络合平衡在废液制冰晶石中的应用[D]. 青岛: 山东科技大学, 2010.
	ZHANG Lin. Application of F^-, Al³⁺, CaF₂ complex balance in making cryolite from waste water[D]. Qingdao: Shandong University of Science and Technology, 2010.
33	申耀宗, 郭培民, 王磊, 等. 氢氟酸解离铍矿新路线中氧化物杂质的浸出热力学[J]. 有色金属(冶炼部分), 2023(10): 42-48.
	SHEN Yaozong, GUO Peimin, WANG Lei, et al. Leaching thermodynamics of oxide impurities in a new route of beryllium ore dissociation by hydrofluoric acid[J]. Nonferrous Metals (Extractive Metallurgy), 2023(10): 42-48.

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HF体系中AlF₃杂质的溶解度与纯化机理

Solubility and purification mechanism of AlF₃ impurities in the HF system

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