无水氟化氢和氟化铝工艺研发及工业应用进展

doi:10.19964/j.issn.1006-4990.2022-0649

Abstract

Abstract:

The current situation of fluoride resources and the development of anhydrous hydrogen fluoride（AHF） and anhydrous aluminum fluoride（AAF） process at home and abroad were reviewed.The advantages and disadvantages of AHF and AAF process based on fluorite resources and fluorophosphates were compared for different process route.For the fluorite-AHF route，it was focused on the technological characteristics，key units，energy conservation and emission reduction.For the routes using fluosilicic acid as raw material，the process characteristics and industrial application progress for the routes of direct pyrolysis，acid hydrolysis，ammonolysis，fluoride-acid hydrolysis and wet process were mainly summarized so as to indicate the improvement potential and development trend for each route.Finally，it was introduced the requirements of compound AAF containing lithium and the application of process strengthening equipment such as microchannel reactor in fluorine chemical industry.This review would provide support for the future research and development of inorganic fluorine chemical technology such as key equipment development，energy cascade utilization，energy conservation and emission reduction.

Key words: fluorite, fluosilicic acid, anhydrous hydrogen fluoride, anhydrous aluminum fluoride, fluorine chemical industry

CLC Number:

TQ124.3

YANG Yong, CHEN Haiyang, LI Yukun, FAN Zongliang, LI Guixian, DUAN Zhiqiang, ZHAO Yu, WANG Dongliang. Progress of process development and industrial application for anhydrous hydrogen fluoride and aluminum fluoride[J]. Inorganic Chemicals Industry, 2023, 55(9): 17-25.

Figures/Tables 4

References 50

1	欧健，李天祥，隋岩峰，等.工业含氟废气处理及资源回收的概述［J］.无机盐工业，2021，53（5）：39-46.
	Jian OU， LI Tianxiang， SUI Yanfeng，et al.Review of treatment and resource recovery of industrial fluoride-containing waste gas［J］.Inorganic Chemicals Industry，2021，53（5）：39-46.
2	王傢俊，邓帅，赵睿恺，等.电子级HF吸附法回收的节能降耗潜力分析［J］.化工进展，2021，40（7）：3645-3655.
	WANG Jiajun， DENG Shuai， ZHAO Ruikai，et al.Analysis of energy and consumption reduction in adsorption recovery of electronic HF［J］.Chemical Industry and Engineering Progress，2021，40（7）：3645-3655.
3	郝建堂，张枝芝，王建萍，等.电子级氢氟酸的专利技术分析［J］.河南化工，2018，35（11）：7-10.
	HAO Jiantang， ZHANG Zhizhi， WANG Jianping，et al.Patent technical analysis of electronic grade hydrofluoric acid［J］.Henan Che-mical Industry，2018，35（11）：7-10.
4	LIN Minfa， WU J L， CHANG Kenlin，et al.Recycle of synthetic calcium fluoride and waste sulfuric acid to produce electronic grade hydrofluoric acid［J］.Environmental Science and Pollution Research，2021，28（30）：40633-40639.
5	张小霞.浅议电解铝用氟化铝的发展趋势［J］.河南化工，2021，38（2）：1-4.
	ZHANG Xiaoxia.Discussion on development trend of aluminum fluoride for electrolytic aluminum［J］.Henan Chemical Industry，2021，38（2）：1-4.
6	黄维凤.氟化铝生产工艺综述及实际应用案例［J］.化工设计通讯，2019，45（11）：45-46.
	HUANG Weifeng.Review on the technology of aluminium fluoride production and its practical application［J］.Chemical Engineering Design Communications，2019，45（11）：45-46.
7	COLUMBIUM N.Mineral commodity summaries 2020［R/OL］.（2020-2-31）［2022-2-08］..
8	樊惠，张宗凡，罗康碧，等.人造萤石生产方法及应用进展［J］.无机盐工业，2014，46（2）：14-17.
	FAN Hui， ZHANG Zongfan， LUO Kangbi，et al.Production methods and application progress of artificial fluorite［J］.Inorganic Chemicals Industry，2014，46（2）：14-17.
9	施浩进，丁铁福，杨波，等.氟硅酸制备HF和CaF₂生产方法简述［J］.有机氟工业，2019（3）：54-57.
	SHI Haojin， DING Tiefu， YANG Bo，et al.Review on preparation of HF and CaF₂ by fluorosilicic acid［J］.Organo-Fluorine Industry，2019（3）：54-57.
10	侯屹东.氟硅酸制备氟化钙联产白炭黑研究［D］.昆明：昆明理工大学，2021.
	HOU Yidong.Study on preparation of calcium fluoride and co-production of white carbon black from fluorosilicic acid［D］.Kunming：Kunming University of Science and Technology，2021.
11	HU Xianwei， LI Lin， GAO Bingliang，et al.Thermal decomposition of ammonium hexafluoroaluminate and preparation of aluminum fluoride［J］.Transactions of Nonferrous Metals Society of China，2011，21（9）：2087-2092.
12	韩润林，隋岩，刘小兵，等.一种氟硅酸与碳酸钙快速反应制备高纯萤石的方法. 中国，111533152A［P］.2020-2-14.
13	李世江，侯红军，杨华春，等.一种利用氟硅酸与电石灰制备四氟化硅联产氟化钙的方法. 中国，102701215A［P］.2012-2-03.
14	杜婷婷，邱仕麟，陈开斌，等.电解铝富余氟化物与浓硫酸反应性研究［J］.轻金属，2021（3）：32-36.
	DU Tingting， QIU Shilin， CHEN Kaibin，et al.Study on the reactivity of surplus fluoride and concentrated sulfuric acid in aluminum industry［J］.Light Metals，2021（3）：32-36.
15	LACSON C F Z， LU Mingchun， HUANG Y.Chemical precipitation at extreme fluoride concentration and potential recovery of CaF₂ particles by fluidized-bed homogenous crystallization process［J］.Chemical Engineering Journal，2021，415：128917.
16	牛永生.干法合成氟化铝反应器设计及工艺研究［D］.昆明：昆明理工大学，2013.
	NIU Yongsheng.Study on design and process of reactor for dry synthesis of aluminum fluoride［D］.Kunming：Kunming University of Science and Technology，2013.
17	刘海霞.干法氟化铝和无水氟化铝制备工艺和应用效果对比［J］.无机盐工业，2018，50（9）：10-13.
	LIU Haixia.Comparison on preparation processes and application effects of dry process aluminum fluoride and anhydrous aluminum fluoride［J］.Inorganic Chemicals Industry，2018，50（9）：10-13.
18	张保平.高性能无水氟化铝生产技术研究［J］.化工管理，2022（6）：65-67.
	ZHANG Baoping.Research on the production technology of high-performance anhydrous aluminum fluoride［J］.Chemical Management，2022（6）：65-67.
19	宋德雄.氟化铝生产工艺对比［J］.甘肃科技，2020，36（7）：42-44.
	SONG Dexiong.Production process comparison of aluminum fluoride［J］.Gansu Science and Technology，2020，36（7）：42-44.
20	李飞阔，李志刚，郑学锋.氟硅酸法生产氟化铝的工艺技术比较及发展现状［J］.化肥设计，2014，52（2）：41-44.
	LI Feikuo， LI Zhigang， ZHENG Xuefeng.Process technology comparison of aluminium fluoride produced by fluosilicic acid method and its present developmental situation［J］.Chemical Fertilizer Design，2014，52（2）：41-44.
21	刘欢.无水氟化氢生产装置分离系统的流程模拟与方案对比［D］.北京：北京化工大学，2016.
	LIU Huan.Process simulation and comparison of anhydrous hydrogen fluoride production devices separation［D］.Beijing：Beijing University of Chemical Technology，2016.
22	宋德雄.无水氟化铝生产尾气处理技术研究与实际应用［J］.甘肃科技，2020，36（8）：53-54，32.
	SONG Dexiong.Research and application of tail gas treatment technology in anhydrous aluminum fluoride production［J］.Gansu Science and Technology，2020，36（8）：53-54，32.
23	吴宁宁.影响无水氟化氢生产效率的因素及控制方法［J］.化工管理，2021（9）：96-97.
	WU Ningning.Factors affecting production efficiency of anhydrous hydrogen fluoride and control methods［J］.Chemical Enterprise Management，2021（9）：96-97.
24	谷正彦.无水氟化铝生产分析［J］.轻金属，2020（3）：5-8.
	GU Zhengyan.Production analysis of anhydrous aluminum fluoride［J］.Light Metals，2020（3）：5-8.
25	张永忠.多金属尾矿伴生萤石综合回收利用分析［J］.浙江化工，2021，52（2）：1-4.
	ZHANG Yongzhong.Analysis on comprehensive recovery and utilization of fluorite associated with polymetallic tailings［J］.Zhejiang Chemical Industry，2021，52（2）：1-4.
26	侯利芳.预反应器在氢氟酸生产中的应用［J］.河南化工，2017，34（4）：57-58.
	HOU Lifang.Application of pre-reactor in hydrofluoric acid production［J］.Henan Chemical Industry，2017，34（4）：57-58.
27	黄正梁，杨遥，林王旻，等.一种以萤石粉生产氟化氢的循环流化床系统及方法. 中国，107311109B［P］.2019-2-30.
28	杨遥，陈蜀康，林王旻，等.无水氟化氢生产方法及其设备. 中国，202010999888.X［P］.2020-2-22.
29	YANG Yao， CHEN Cheng， LIU Zhongxuan，et al.Stable operating range and solids residence time of fine fluorite particles in the two-stage fluidized bed［J］.Chemical Engineering and Processing - Process Intensification，2019，142：107558.
30	刘仲玄.细颗粒解聚团流态化及萤石制无水氟化氢新工艺研究［D］.杭州：浙江大学，2018.
	LIU Zhongxuan.Deagglomerate fluidization of fine particles and new process of production of anhydrous hydrogen fluoride with fluorite as raw materials［D］.Hangzhou：Zhejiang University，2018.
31	林王旻.细萤石颗粒的分层流化行为及流化质量的强化方法［D］.杭州：浙江大学，2020.
	LIN Wangmin.Stratified fluidization of fine fluorite particles in fluidized bed and the fluidization enhancement［D］.Hangzhou：Zhejiang University，2020.
32	汤正河，谭蕾.湿法磷酸生产中含氟气体的处理现状及存在问题［J］.云南化工，2008，35（5）：41-42.
	TANG Zhenghe， TAN Lei.Present situation and existing problem on the treatment of fluorine-containing gas in the production of wet-process phosphoric acid［J］.Yunnan Chemical Technology，2008，35（5）：41-42.
33	AWWAD N S， EL-NADI Y A， HAMED M M.Successive processes for purification and extraction of phosphoric acid produced by wet process［J］.Chemical Engineering and Processing：Process Intensification，2013，74：69-74.
34	MATTA S， STEPHAN K， STEPHAN J，et al.Phosphoric acid production by attacking phosphate rock with recycled hexafluosilicic acid［J］.International Journal of Mineral Processing，2017，161：21-27.
35	屈吉艳，杨兴东，陈高祥，等.氟硅酸制备氟化氢工艺综述及利用微通道反应器制备无水氟化氢技术简介［J］.磷肥与复肥，2021，36（3）：27-31.
	QU Jiyan， YANG Xingdong， CHEN Gaoxiang，et al.Review on preparation process of hydrogen fluoride from fluosilicic acid and technology introduction of anhydrous hydrogen fluoride preparation by micro-channel reactor［J］.Phosphate & Compound Fertilizer，2021，36（3）：27-31.
36	GELMBOLDT V O.To the properties of fluorosilicic acid：Evolution of views on the state in aqueous solutions（overview）［J］.Russian Journal of Inorganic Chemistry，2018，63（13）：1746-1751.
37	赵陈，肖飞彪，王志昆.氟硅酸制取氢氟酸研究进展［J］.有机氟工业，2020（3）：32-38.
	ZHAO Chen， XIAO Feibiao， WANG Zhikun.Research progress in the preparation of hydrofluoric acid from fluorosilicic acid［J］.Organo-Fluorine Industry，2020（3）：32-38.
38	DAHLKE T， RUFFINER O， CANT R.Production of HF from H₂SiF₆ ［J］.Procedia Engineering，2016，138：231-239.
39	李勇辉，明大增，李志祥，等.磷肥副产氟硅酸制备氟化氢技术［J］.磷肥与复肥，2010，25（2）：48-51.
	LI Yonghui， MING Dazeng， LI Zhixiang，et al.Preparation technology of hydrogen fluoride from by-product fluosilicic acid in phosphate fertilizer production［J］.Phosphate & Compound Fertilizer，2010，25（2）：48-51.
40	程立静，刘海霞，张小霞.磷肥副产氟硅酸制备高纯氢氟酸新工艺研究［J］.河南化工，2019，36（8）：29-31.
	CHENG Lijing， LIU Haixia， ZHANG Xiaoxia.Study on new technology of preparing high purity hydrofluoric acid from by-product fluosilicic acid in phosphate fertilizer［J］.Henan Chemical Industry，2019，36（8）：29-31.
41	闵蒋兴，周翔.氟硅酸的综合利用［J］.化学工业与工程技术，1999，20（4）：30-33.
	MIN Jiangxing， ZHOU Xiang.Comprehensive utilization of fluosilicic acid［J］.Journal of Chemical Industry & Engineering，1999，20（4）：30-33.
42	薛彦辉，郭婷婷，王坤.氟硅酸钙法制氟化氢联产偏硅酸钠新工艺研究［J］.无机盐工业，2011，43（12）：45-46.
	XUE Yanhui， GUO Tingting， WANG Kun.New technology of copreparing fluorine hydride and sodium metasilicate by hydrofluosilicic acid method［J］.Inorganic Chemicals Industry，2011，43（12）：45-46.
43	希格尼伦·劳伦特.制取氟化钙和纯氟硅酸的原料氟硅酸钙的生产方法. 中国，86105595［P］.1987-2-21.
44	李世江，侯红军，杨华春，等.一种生产氢氟酸、无水硫酸镁的方法. 中国，101134560A ［P］.2008-2-05.
45	郝建堂.氟硅酸、氧化镁制无水氟化氢联产优质硫酸镁工艺研究［J］.无机盐工业，2019，51（8）：40-43.
	HAO Jiantang.Study on producing anhydrous hydrogen fluoride by fluorosilicic acid and magnesium oxide and combined production of high quality magnesium sulfate［J］.Inorganic Chemicals Industry，2019，51（8）：40-43.
46	CHEN Gaoxiang， YANG Xingdong， QU Jiyan，et al.Kinetic study on the preparation of aluminum fluoride based on fluosilicic ac-id［J］.Polish Journal of Chemical Technology，2021，23（3）：10-16.
47	虞云峰，冷慧，刘永成.20 kt/a氟硅酸法氟化铝装置设计及运行状况［J］.磷肥与复肥，2021，36（3）：16-18.
	YU Yunfeng， LENG Hui， LIU Yongcheng.Design and operation of 20 kt/a aluminum fluoride plant by fluosilicic acid process［J］.Phosphate & Compound Fertilizer，2021，36（3）：16-18.
48	侯红军.浅议含锂无水氟化铝的应用［J］.轻金属，2011（12）：34-36.
	HOU Hongjun.Brief discussion of application of anhydrous aluminium fluoride contained lithium［J］.Light Metals，2011（12）：34-36.
49	罗建洪，杨兴东，屈吉艳，等.一种氟硅酸制备无水氟化氢和纳米二氧化硅的方法. 中国，112340703A［P］.2021-2-08.
50	罗建洪，陈高祥，王琳溪，等.一种氟化氢气体处理工艺. 中国，112607708B［P］.2021-2-08.

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[4]	Hao Jiantang. Study on producing anhydrous hydrogen fluoride by fluorosilicic acid and magnesium oxide and combined production of high quality magnesium sulfate [J]. Inorganic Chemicals Industry, 2019, 51(8): 40-43.
[5]	XUE Bing, YANG Bao-Jun, WANG Zhong-Han, GE Li-Xiang. Study on nano precipitated silica from fluosilicic acid wastewater by situ modification [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(1): 58-.
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[7]	ZHANG Guang-Xu, SHI Rui, PENG Yu, DENG Jun. Research on potassium fluosilicate preparation from potassium feldspar [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(3): 57-.
[8]	FAN Hui, ZHANG Zong-Fan, LUO Kang-Bi, LI Heng. Production methods and application progress of artificial fluorite [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(2): 14-.
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Progress of process development and industrial application for anhydrous hydrogen fluoride and aluminum fluoride

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