湿法磷酸净化脱砷的研究现状

doi:10.16085/j.issn.1000-6613.2020-0047

摘要/Abstract

摘要：

随着食品、医药及电子行业的不断发展，磷酸及磷酸盐的市场需求量不断增大，并且对磷酸的品质要求也越来越高，尤其是对湿法磷酸中砷杂质的要求，湿法磷酸中砷的含量将直接影响其在磷精细化工领域的应用，因此湿法磷酸中砷的高效、安全去除是亟待解决的一大难题。本文主要对湿法净化磷酸脱砷技术的研究情况进行综述，比较了几种湿法净化磷酸脱砷工艺的优缺点，介绍了较常见的化学沉淀法、结晶法，以及新兴的电沉积法、垂直区域熔融法和微反应器脱砷工艺的应用前景，并指出这些新兴的脱砷工艺将成为今后湿法磷酸的净化脱砷的发展方向，如能解决将这些脱砷工艺在实际中的问题，将会对磷酸工业的发展提供一个更有力的支持。

关键词: 湿法磷酸, 脱砷, 纯化, 安全, 化学反应

Abstract:

With the continuous development of the food, pharmaceutical and electronics industries, the market demand for phosphoric acid and phosphate is increasing, and the quality requirements for phosphoric acid are also increasing, Especially the requirements for arsenic impurities in wet process phosphoric acid, the content of arsenic in wet process phosphoric acid will directly affect its application in the field of phosphorus fine chemicals. Therefore, the efficient and safe removal of arsenic in wet-process phosphoric acid is a major problem to be solved urgently. The article mainly reviews the research progress of wet purification of phosphoric acid and arsenic removal technology, compares the advantages and disadvantages of several wet purification of phosphoric acid and arsenic removal technology, introduces the application prospects of common chemical precipitation methods, crystallization methods, and emerging electrodeposition methods, vertical zone melting methods, and arsenic removal in microreactor processes. And pointed out that these emerging arsenic removal processes will become the future development direction of purification and arsenic removal of wet-process phosphoric acid. If the practical problems of these arsenic removal processes can be solved, this will provide a stronger support for the development of the phosphoric acid industry.

Key words: wet process phosphoric acid, arsenic removal, purification, safety, chemical reaction

中图分类号:

O613.63

饶轶晟, 杨晓健, 张红, 胡国涛. 湿法磷酸净化脱砷的研究现状[J]. 化工进展, 2020, 39(S1): 219-224.

Yisheng RAO, Xiaojian YANG, hong ZHANG, Guotao HU. Research status of removal of arsenic by wet process phosphoric acid[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 219-224.

图/表 1

参考文献 28

1	白锡柱, 曾寿智. 磷酸生产技术开发的进展[J]. 硫磷设计与粉体工程, 2006(5): 1-5.
	BAI Xizhu, ZENG Shouzhi. Progress in development of phosphoric acid production technology[J]. Phosphorus Design and Powder Engineering, 2006(5): 1-5.
2	莫笑萍, 胡山鹰, 沈静珠. 我国磷资源产业的发展[J]. 化工矿物与加工, 2005, 34(8): 1-4.
	MO Xiaoping, HU Shanying, SHEN Jingzhu. Development of China's phosphorus resources industry[J]. Chemical Minerals and Processing, 2005, 34 (8): 1-4.
3	陈嘉甫, 谭光熏. 磷酸盐的生产与应用[M]. 成都: 成都科技大学出版社, 1989: 560-575.
	CHEN Jiapu, TAN Guangxun. Production and application of phosphate[M]. Chengdu: Chengdu University of Science and Technology Press, 1989: 560-575.
4	毛常明, 刘晶晶, 尹进华, 等. 湿法磷酸的工艺研究进展[J]. 河北化工, 2005(4): 14-16.
	MAO Changming, LIU Jingjing, YIN Jinhua, et al. Research progress of wet phosphoric acid process[J]. Hebei Chemical Industry, 2005 (4): 14-16.
5	路超, 张伟, 刘杰, 等. 氧化-沉淀法净化湿法磷酸的研究[J]. 无机盐工业, 2011, 43(9): 49-51.
	LU Chao, ZHANG Wei, LIU Jie, et al. Study on purification of wet process phosphoric acid by oxidation-precipitation method[J]. Inorganic Chemicals Industry, 2011, 43(9): 49-51.
6	岳海荣, 应建康. 络合沉淀法脱除湿法磷酸中铝镁杂质的统计分析[J]. 无机盐工业, 2009, 41(6): 51-53.
	YUE Hairong, YING Jiankang. Statistical analysis of removal of aluminum and magnesium impurities in wet-process phosphoric acid by complex precipitation method[J]. Inorganic Chemicals Industry, 2009, 41 (6): 51-53.
7	陈敏. 湿法磷酸化学沉淀法除镁工艺[J]. 当代化工研究, 2016(2): 41-42.
	CHEN Min. Process of magnesium removal by wet phosphoric acid chemical precipitation[J]. Modern Chemical Research, 2016(2): 41-42.
8	钟本和, 陈亮, 李军, 等. 溶剂萃取法净化湿法磷酸的新进展[J]. 化工进展, 2005, 24(6): 22-28.
	ZHONG Benhe, CHEN Liang, LI Jun, et al. New progress in purification of wet-process phosphoric acid by solvent extraction[J]. Chemical Industry and Engineering Process, 2005, 24(6): 22-28.
9	侯长军, 党洁修. 结晶法净化湿法磷酸生产Na₂HPO₄·12H₂O工艺研究[J]. 四川理工学院学报（自然版）, 1995,18(4):76-81.
	HOU Changjun, DANG Jiexiu. Study on the technology of crystallization purification of wet process phosphoric acid to produce Na₂HPO₄·12H₂O[J]. Journal of Sichuan University of Science Engineering (Science Edition), 1995,18(4):76-81.
10	熊祥祖, 王威, 李志保, 等. 离子交换树脂脱除湿法磷酸中金属杂质的研究[J]. 武汉工程大学学报, 2009, 31(7): 26-29.
	XIONG Xiangzu, WANG Wei, LI Zhibao, et al. Study on removal of metal impurities in wet phosphoric acid by ion exchange resin[J]. Journal of Wuhan University of Technology, 2009, 31(7): 26-29.
11	崔英德, 易国斌, 康正, 等. 两步法净化湿法磷酸及食品级磷酸氢钙的制备[J]. 精细化工, 2001, 18(5): 265-267.
	CUI Yingde, YI Guobin, KANG Zheng, et al. Two-step purification of wet-process phosphoric acid and preparation of food-grade calcium hydrogen phosphate[J]. Fine Chemical Industry, 2001, 18(5): 265-267.
12	孟永涛, 乔文岑, 戴贺朋, 等. 湿法磷酸净化预处理的实验研究[J]. 广州化工, 2014, 42(5): 67-69.
	MENG Yongtao, QIAO Wencen, DAI Hepeng, et al. Experimental study on purification and pretreatment of wet-process phosphoric acid[J]. Guangzhou Chemical Industry, 2014, 42(5): 67-69.
13	李白玉, 李天祥, 刘佳, 等. 用湿法磷酸预净化重结晶制工业磷酸试验总结[J]. 磷硫设计和粉体工程, 2008(6): 5-8.
	LI Baiyu, LI Tianxiang, LIU Jia, et al. Test summary of industrial phosphoric acid produced by repurification and recrystallization with wet phosphoric acid[J]. Phosphorus and Sulfur Design and Powder Engineering, 2008(6): 5-8.
14	李兴平, 刘阳, 刘伟, 等. 湿法磷酸脱砷实验研究[J]. 山东化工, 2017,46(21): 188-189.
	LI Xingping, LIU Yang, LIU Wei, et al. Experimental study on arsenic removal by wet process phosphoric acid[J]. Shandong Chemical Industry, 2017, 46(21): 188-189.
15	李瑞英. 低砷磷酸产品开发的技术探讨[J]. 磷酸盐工业, 2003(1): 20-23.
	LI Ruiying. Discussion on the technology of low arsenic phosphoric acid product development[J]. Phosphate Industry, 2003(1): 20-23.
16	张晖, 何宾宾, 傅英, 等. 脱除湿法浓磷酸中重金属的实验研究[J]. 磷肥与复肥, 2016, 31(6): 24-25.
	ZHANG Hui, HE Binbin, FU Ying, et al. Experimental study on removal of heavy metals from concentrated phosphoric acid by wet method[J]. Phosphate and Compound Fertilizers, 2016, 31(6): 24-25.
17	PENG Xianjia, CHEN Jingyi, KONG Linghao, et al. Removal of arsenic from strongly acidic wastewater using phosphorus pentasulfide as precipitant: UV-light promoted sulfuration reaction and particle aggregation[J]. Environmental Science & Technology, 2018, 52: 4794-4801.
18	蒋丽红, 林庆友, 陈艳, 等. 氢氧化钙脱除湿法磷酸中砷的研究[J]. 化工科技, 2004, 12(1): 22-25.
	JIANG Lihong, LIN Qingyou, CHEN Yan, et al. Study on removal of arsenic from wet-process phosphoric acid by calcium hydroxide[J]. Chemical Technology, 2004, 12(1): 22-25.
19	蒋丽红, 超声兰. 碳酸钙脱除湿法磷酸中硫、氟、砷的研究[J]. 化肥设计, 2000, 38(6): 12-14.
	JIANG Lihong, CHAO Shenglan. Study on removal of sulfur, fluorine and arsenic from wet phosphoric acid by calcium carbonate[J]. Chemical Fertilizer Design, 2000, 38(6): 12-14.
20	刘飞, 李天祥, 解田, 等. 湿法磷酸净化酸的提纯工艺研究[J]无机盐工业, 2016, 48(2): 42-44.
	LIU Fei, LI Tianxiang, XIE Tian, et al. Study on the purification process of purifying acid by wet process phosphoric acid[J]. Inorganic Chemicals Industry, 2016, 48(2): 42-44.
21	孟文祥, 吴松, 陶志. 以湿法工业级磷酸生产电子级磷酸的脱砷技术[J]. 磷肥与复肥, 2014, 29(1): 47-48.
	MENG Wenxiang, WU Song, TAO Zhi. Arsenic removal technology for producing electronic grade phosphoric acid from wet industrial grade phosphoric acid[J]. Phosphate and Compound Fertilizers, 2014, 29(1): 47-48.
22	陈爱梅. 熔融悬浮结晶法提纯湿法磷酸[J]. 化学工程, 2012, 40(8): 52-56.
	CHEN Aimei. Purification of wet process phosphoric acid by melt suspension crystallization[J]. Chemical Engineering, 2012, 40(8): 52-56.
23	BISANG J M, BOGADO F, RIVERA M O, et al. Electrochemical removal of arsenic from technical grade phosphoricacid[J]．Journal of Applied Electrochemistry, 2004, 34(4): 375-381．
24	彭想军. 磁场作用下工业级磷酸中砷电沉积工艺研究[D]. 武汉: 武汉工程大学, 2008.
	PENG Xiangjun. Research on electrodeposition of arsenic in industrial grade phosphoric acid under magnetic field [D]. Wuhan: Wuhan Engineering University, 2008.
25	REN Yongsheng, DUAN Xiaoxiao, WANG Baoming, et al. Numerical and experimental investigation of arsenic removal process from phosphoric acid by vertical zone melting technique[J]. Industrial & Engineering Chemistry Research, 2012, 51(10):4035-4040.
26	黄照昊, 罗康碧, 李沪萍, 等. 湿法磷酸脱除阳离子杂质的研究进展[J]. 化工科技, 2017, 25(2): 57-61.
	HUANG Zhaohao, LUO Kangbi, LI Huping, et al. Research progress on removal of cationic impurities by wet process phosphoric acid[J]. Chemical Technology, 2017, 25 (2): 57-61.
27	叶楷, 李沪萍, 罗康碧, 等. 湿法磷酸净化脱氟、硫、砷的研究进展[J]. 化工科技, 2017, 25(4): 59-64.
	YE Kai, LI Huping, LUO Kangbi, et al. Research progress in purification of defluorination, sulfur, and arsenic by wet-process phosphoric acid[J]. Chemical Technology, 2017, 25 (4): 59-64.
28	彭想军, 田琦峰, 袁华, 等. 工业级磷酸中砷的电化学沉积工艺研究[C]//全国化学工程与生物化工年会, 西安, 2008.
	PENG Xiangjun, TIAN Qifeng, YUAN Hua, et al. Study on the electrochemical deposition process of arsenic in industrial grade phosphoric acid [C]// National Conference of Chemical Engineering and Biochemical Engineering, Xiʹan, 2008.

净化脱砷方法	优点	缺点	应用状况
硫化物沉淀法	操作简单，容易控制，投资小、成本低	净化深度不够，引入其他杂质离子，耗能高安全风险较大	广泛应用到实际生产中
混凝沉淀法	成本低、适合大量低砷溶液	污染较大，耗能高，可控性也较差	当前的研究较少
结晶法	工艺操作简单、条件温和、耗能低，脱砷效果较好	必须进行多次结晶，且母液与纯晶体难以分离，不适宜大规模生产	目前尚未应用到工业生产中
电化学沉积法	无污染、耗能低、高效、易控制	电流效率不高，易析出AsH₃	仅停留在实验室研究阶段
垂直区域熔融法	方法操作简单、高效、环保	控制过程中砷的重新分布较难	仅仅是理论数据模型
微反应器脱砷法	高效、安全性更高、降低污染	过程控制要求高	尚未应用

净化脱砷方法	优点	缺点	应用状况
硫化物沉淀法	操作简单，容易控制，投资小、成本低	净化深度不够，引入其他杂质离子，耗能高安全风险较大	广泛应用到实际生产中
混凝沉淀法	成本低、适合大量低砷溶液	污染较大，耗能高，可控性也较差	当前的研究较少
结晶法	工艺操作简单、条件温和、耗能低，脱砷效果较好	必须进行多次结晶，且母液与纯晶体难以分离，不适宜大规模生产	目前尚未应用到工业生产中
电化学沉积法	无污染、耗能低、高效、易控制	电流效率不高，易析出AsH₃	仅停留在实验室研究阶段
垂直区域熔融法	方法操作简单、高效、环保	控制过程中砷的重新分布较难	仅仅是理论数据模型
微反应器脱砷法	高效、安全性更高、降低污染	过程控制要求高	尚未应用

[1]	徐晨阳, 都健, 张磊. 基于图神经网络的化学反应优劣评价[J]. 化工进展, 2023, 42(S1): 205-212.
[2]	吕程远, 张函, 杨明旺, 杜健军, 樊江莉. 生物成像用二氧杂环丁烷余辉发光体系的研究进展[J]. 化工进展, 2023, 42(8): 4108-4122.
[3]	郭晋, 张耕, 陈国华, 朱鸣, 谭粤, 李蔚, 夏莉, 胡昆. 车载液氢气瓶设计技术的研究进展[J]. 化工进展, 2023, 42(8): 4221-4229.
[4]	汪嘉欣, 潘勇, 熊欣怡, 万晓月, 王建超. 甲苯一步催化硝化制备二硝基甲苯反应过程及危险性[J]. 化工进展, 2023, 42(7): 3420-3430.
[5]	单雪影, 张濛, 张家傅, 李玲玉, 宋艳, 李锦春. 阻燃型环氧树脂的燃烧数值模拟[J]. 化工进展, 2023, 42(7): 3413-3419.
[6]	吴展华, 盛敏. 绝热加速量热仪在反应安全风险评估应用中的常见问题[J]. 化工进展, 2023, 42(7): 3374-3382.
[7]	乔旭, 张竹修. 化工本征安全技术发展路径的思考与探索[J]. 化工进展, 2023, 42(7): 3319-3324.
[8]	孙鲁芹, 卢会霞, 王建友. 电渗析/超滤内在耦合过程分离蛋清中溶菌酶[J]. 化工进展, 2023, 42(5): 2262-2271.
[9]	闫兴清, 戴行涛, 喻健良, 李岳, 韩冰, 胡军. 高压氢气泄漏射流研究进展[J]. 化工进展, 2023, 42(3): 1118-1128.
[10]	陈韶云, 周贤太, 纪红兵. 金属卟啉/碳纳米管仿生催化剂的制备及其在Baeyer-Villiger氧化反应中的催化机理[J]. 化工进展, 2023, 42(3): 1332-1340.
[11]	张艺璇, 胡伟, 刘梦瑶, 鞠敬鸽, 赵义侠, 康卫民. 聚合物电解质在锌离子电池中的研究进展[J]. 化工进展, 2023, 42(3): 1397-1410.
[12]	王哲, 余颖, 石永杰, 杨顺, 陈久洲, 崔希利, 邢华斌. 尿素包合法分离费托轻质油中的正构烃[J]. 化工进展, 2023, 42(2): 677-683.
[13]	邱沫凡, 蒋琳, 刘荣正, 刘兵, 唐亚平, 刘马林. 气固流化床化学反应数值模拟中颗粒尺度模型研究进展[J]. 化工进展, 2023, 42(10): 5047-5058.
[14]	马文杰, 姚卫棠. 共价有机框架（COFs）在锂离子电池中的应用[J]. 化工进展, 2023, 42(10): 5339-5352.
[15]	齐亚兵, 贾宏磊. 熔融结晶技术分离纯化有机化合物的研究进展[J]. 化工进展, 2023, 42(1): 373-385.