水中铟(Ⅲ)的分离富集及资源化回用研究进展

doi:10.16085/j.issn.1000-6613.2015.07.034

摘要/Abstract

摘要： 我国铟资源在世界上处于绝对的优势地位, 但国内生产工艺水平低, 导致大量原生铟在生产加工过程中流失, 严重阻碍我国高新技术产业的发展。而铟具有很好的再生性, 国内外不少学者对铟的富集回用做出研究。文章回顾了传统分离富集法, 主要包括沉淀法、离子交换法和溶剂萃取法等, 简述了各个方法的优缺点及未来的发展趋势, 并着重分析了目前分离富集铟的新型方法:液膜法、萃淋树脂法、螯合树脂法、溶剂微胶囊法、浮选法及纳米技术等。指出在合适的条件下, 运用这些技术可对铟进行有效地分离回收, 并对分离富集铟的技术发展作出展望:加强这些技术所使用分离材料的稳定性、分离机理以及传质模型的研究, 以期发展出具有低能耗、低成本的优势技术。

关键词: 铟, 分离, 富集, 溶剂萃取, 纳米材料

Abstract: This article described the traditional methods of separation and enrichment for indium, including precipitation, ion exchange process, solvent extraction, etc, and the advantages and disadvantages of each method and the development trend in future research. The article focused on the analysis of liquid membrane method, levextrel resin method, chelating resin method, solvent microencapsule method, flotation, nanotechnology and other new technologies. The indium can be effectively separated under proper conditions. More study is needed to improve stability of separation materials, separation mechanism and mass transfer mathematical models, in order to develop techniques for waste water containing indium(Ⅲ) with low energy consumption and low cost .

Key words: indium, separation, enrichment, solvent extraction, nanomaterials

中图分类号:

TQ085⁺.4

陈文, 张亚雷, 周雪飞, 代朝猛. 水中铟(Ⅲ)的分离富集及资源化回用研究进展[J]. 化工进展, 2015, 34(07): 2009-2015.

CHEN Wen, ZHANG Yalei, ZHOU Xuefei, DAI Chaomeng. Research advancement on separation and enrichment of resource reusing of indium(Ⅲ) in water environment[J]. Chemical Industry and Engineering Progree, 2015, 34(07): 2009-2015.

参考文献

[1] 王顺昌, 齐守智. 铟的资源、应用和市场[J]. 世界有色金属, 2000(12):22-24.
[2] 俞小花, 谢刚. 有色冶金过程中铟的回收[J]. 有色金属:冶炼部分, 2006(1):37-39.
[3] 冉俊铭, 伍永田, 易健宏. 铟产业发展现状及展望[J]. 世界有色金属, 2008(1):26-28.
[4] Brown R D, Blossom J W, Smith G R. Mineral Commodity Summaries (Gallium, Germanium, Indium, Rhenium, Selenium, Tellurium and Thallium)[G]//US Geo Logical Survey, 2008:64-117.
[5] 邹家炎. 铟的提取、应用和新产品开发[J]. 广东有色金属学报, 2002(12):16-20.
[6] 巴·依·费多洛夫, 拉·哈·阿克楚林(俄)编. 铟化学手册[M]. 张启运, 许克敏译. 北京:北京大学出版社, 2005:4-7.
[7] 洪托, 秦德先, 刘方成, 等. 铟市场形势及中国铟资源特点[J]. 云南地理环境研究, 2004, 16(3):27-28.
[8] 伍赠玲. 铟的资源、应用与分离回收技术研究进展[J]. 铜业工程, 2011(1):25-26.
[9] 蘇憶安. 化学混凝法去除水中钼、铟之研究[D]. 台湾:淡江大学, 2012.
[10] 俞小花, 谢刚, 王吉坤, 等. 从含铟加压浸出液中和沉淀铟[J]. 有色金属, 2008, 60(1):71-73.
[11] 周存, 何静, 唐谟堂, 等. 锌焙砂还原浸出液中和沉铟及净化工艺研究[J]. 化学工程与装备, 2010(2):5-8.
[12] Tulenin S S, Bakhteev S A, Yusupov R A, et al. Diagrams of the formation of In₂S₃ and In₂Se₃ films on vitroceramic upon precipitation, according to potentiometric titration[J]. Russian Journal of Physical Chemistry A, 2013, 87:1771-1777.
[13] 李明愉, 曾庆轩, 李建博, 等. 强酸性阳离子交换纤维吸附铟的热力学[J]. 中国有色金属学报, 2012, 22(10):2846-2847.
[14] Mihalyi R M, Beyer H K, Mavrodinova V, et al. Study of the reductive solid-state ion exchange of indium into an NH₄-beta zeolite[J]. Microporous and Mesoporous Materials, 1998, 24:143-151.
[15] Fortes M C B, Martins A H, Benedetto J S. Indium adsorption onto ion exchange polymeric resins[J]. Minerals Engineering, 2003, 16:659-663.
[16] Adya V C, Thulasidas S K, Kumar M, et al. Determination of In and Ga in plutonium oxide matrix by ICP-AES after chemical separation[J]. Radiochimica Acta , 2011, 99(9):581-585.
[17] 高远, 王继民, 吴昊. N₅₀₃萃取分离铁铟的研究[J]. 材料研究与应用, 2011, 5(1):62-66.
[18] 朱薇, 肖连生, 肖超, 等. N₂₃₅萃取镍钼矿硫酸浸出液中钼的研究[J]. 稀有金属与硬质合金, 2010, 38(1):1-4.
[19] 刘厚凡, 史爱芹, 周新木, 等. 硫酸体系中P₅₀₇对铟锌猛的萃取分离研究[J]. 无机盐工业, 2010, 42(3):20-22.
[20] 王瑞永, 黄中省. D2EHPA萃取分离锌和镍试验研究[J]. 有色冶金设计与研究, 2013, 36(6):18-22.
[21] 孙进贺, 贾永忠, 景燕, 等. P₂₀₄-Cyanex923磺化煤油用于铟的萃取和反萃取研究[J]. 有色金属:冶炼部分, 2011(1):26-29.
[22] Virolainen Sami, Ibana Don, Paatero Erkki. Recovery of indium from indium tin oxide by solvent extraction[J]. Hydrometallurgy, 2011, 107 :56-61.
[23] 刘祥宣, 王煊军. H₂SO₄介质中P5708萃取铟、铁热力学平衡研究[J]. 有色金属, 2001(3):36-39.
[24] Jiang Jibo, Liang Duoqiang, Zhong Qingdong. Precipitation of indium using sodium tripolyphosphate[J]. Hydrometallurgy, 2011, 106:165-169.
[25] 郑子恩, 赵婷. InCl₃富铟溶液的置换及置换后液的处理工艺[J]. 矿冶工程, 2012, 32(4):87-89.
[26] Chou Weilung, Huang Yen-Hsiang. Electrochemical removal of indium ions from aqueous solution using iron electrodes[J]. Journal of Hazardous Materials , 2009, 172:46-3.
[27] 孙创, 冯权莉, 王学谦, 等. 液膜分离技术在废水处理中的应用与展望[J]. 化工新型材料, 2014, 42(6):210-212.
[28] 冯海波, 贾悦, 吕晓龙, 等. 中空纤维支撑液膜萃取法提铟工艺比较研究[J]. 水处理技术, 2012, 38(8):96-100.
[29] 贾悦, 吕晓龙, 周文佳, 等. 支撑液膜超滤耦合工艺提取稀散金属铟[C]//第四届全国膜分离技术在冶金工业中应用研讨会论文集, 2014.
[30] 吴小宁, 姚秉华, 冯晋阳. N503-煤油-KSCN 分散支撑液膜体系中Pd(Ⅱ)的传输研究[J]. 稀有金属材料与工程, 2012, 41(1):78-81.
[31] Kim Sangil, Fornasiero Francesco, Park Hyung Gyu, et al. Fabrication of flexible, aligned carbon nanotube/polymer composite membranes by in-situ polymerization[J]. Journal of Membrane Science, 2014, 460:91-98.
[32] 沈江南, 阮慧敏, 吴东柱, 等. 离子液体支撑液膜的研究及应用进展[J]. 化工进展, 2009, 28(12):2092-2098.
[33] Kazuo Kondo, Michiaki Matsumoto. Separation and concentration of indium (Ⅲ) by an emulsion liquid membrane containing diisostearylphosphoric acid as a mobile carrier[J]. Separation and Purification Technology, 1998, 13 :109- 115.
[34] 毛磊, 万静, 许利军, 等. 用乳状液膜萃取瓦斯灰酸浸液中的铟[J]. 有色金属:冶炼部分, 2009(4):23-25.
[35] 何飞, 胡耀强, 陈亚文, 等. W/O/W型乳状液膜溶胀研究进展[J]. 应用化工, 2010, 39(12):1914-1917.
[36] 刘长洪, 刘代俊, 曹来宗. 乳状液膜用表面活性剂的合成及其在液膜体系中的稳定性研究[J]. 化学工业及工程技术, 2008, 29(1):1-3.
[37] 冯军香, 屈撑囤, 张宁生, 等. 表面活性剂对乳状液膜稳定性的影响[J]. 油田化学, 2012, 29(1):106-110.
[38] 朱山东. 流动载体对乳状液膜分离效果的影响[D]. 武汉:中南民族大学, 2012.
[39] Kabay N, Cortina J L, Trochimczuk A, et al. Solvent-impregnated resins(sirs)-methods of preparation and their applications[J]. Reactive and Functional Polymers, 2010, 70(8):484-496.
[40] Yuan Yanxu, Liu Junshen, Zhou Baoxue, et al. Synthesis of coated solvent impregnated resin for the adsorption of indium (Ⅲ)[J]. Hydrometallurgy, 2010, 101:148-155.
[41] Birendra BA, Manju G, Hidetaka K, et al. Solid phase extraction, preconcentration and separation of indium with methylene crosslinked calix[4]- and calix[6]arene carboxylic acid resins[J]. Chemical Engineering Science, 2012, 78:144-154.
[42] 刘军深, 袁延旭. P₅₀₇萃淋树脂在盐酸介质中吸附铟(Ⅲ)的性能[J]. 稀有金属与硬质合金, 2008(4):1-4.
[43] 袁延旭, 刘军深, 王海燕. 浸渍树脂自盐酸介质中吸附铟(Ⅲ)的性能[J]. 材料研究与应用, 2009, 3(2):93-96.
[44] 高学珍, 刘军深, 李海梅, 等. 包覆型浸渍树脂在硫酸介质中吸附铟(Ⅲ)的机理[J]. 稀有金属与硬质合金, 2012, 40(4):4-6.
[45] Liu J S, Chen H, Chen X Y, et al. Extraction and separation of In(Ⅲ), Ga(Ⅲ) and Zn(Ⅱ) from sulfate solution using extraction resin[J]. Hydrometallurgy, 2006, 82(3-4):137-143.
[46] 龚福忠, 王旭刚, 曹欣欣, 等. 表面活性剂改性P₅₀₇浸渍树脂吸附In(Ⅲ)的性能研究[J]. 离子交换与吸附, 2012, 28(6):506-515.
[47] 刘军深, 李桂华. 螯合树脂法分离回收镓和铟的研究进展[J]. 稀有金属与硬质合金, 2005, 33(4):42-45.
[48] Saberyan K, Zolfonoun E, Shamsipur M, et al. Amberlite XAD-4 impregnated with a new pentadentate Schiff base:a chelating collector for separation and preconcentration of trace amounts of gallium(Ⅲ) and indium(Ⅲ)[J]. Acta Chimica Slovenice, 2010, 57(1):222-229.
[49] Miyazaki, A, Kimura A, Tao H. Determination of indium in sea water around Japan and in the Pacific Ocean by ICP-MS after preconcentration using Chelex-100 chelating resin[J]. Bunseki Kagaku, 2008, 57(7):555-561.
[50] Liu Huiming, Chang Chingyao, Wu Chiachan, et al. Determination of trace indium in urine after preconcentration with a chelating-resin-packed minicolumn[J]. J. Sep. Sci., 2012, 35:846-852.
[51] 杨伟伟, 骆广生, 龚行楚, 等. 溶剂微胶囊——现代萃取技术发展的核心之一[J]. 化工进展, 2004, 23(1):24-27.
[52] 杨伟伟, 骆广生, 伍方昱, 等. 溶剂挥发法制备萃取剂微胶囊[J]. 高分子学报, 2005(2):207-212.
[53] Kamio Eiji, Matsumoto Michiaki, Valenzuela Fernando, et al. Sorption behavior of Ga(Ⅲ) and In(Ⅲ) into a microcapsule containing long-chain alkylphosphonic acid monoester[J]. Industrial and Engineering Chemistry Research, 2005, 44:2266-2272.
[54] 李海梅, 刘军深, 袁延旭, 等. P₅₀₇聚砜微胶囊的合成及吸附铟的性能[C]//中国化学会第15届反应性高分子学术讨论会. 烟台, 2010.
[55] Luong H V Thanh, Liu Jhy-Chern. Flotation separation of soluble and colloidal indium from aqueous solution[J]. Industrial & Engineering Chemistry Research, 2014, 53(3):1242-1248.
[56] Zhang Lei, Wang Yingnan, Guo Xingjia, et al. Separation and preconcentration of trace indium(Ⅲ) from environmental samples with nanometer-size titanium dioxide[J]. Hydrometallurgy, 2009, 95:92-95.
[57] Kwak Noh-Seok, Park Hui-Man, Hwang Taek Sung. Preparation of ion-exchangeable nanobeads using suspension polymerization and their sorption properties for indium in aqueous solution[J]. Chemical Engineering Journal, 2012, 191:579-587.
[58] Seol Kima Ah, Kamala-Kannan Seralathan, Lee Kui-Jae, et al. Removal of Pb(Ⅱ) from aqueous solution by a zeolite-nanoscalezero- valent iron composite[J]. Chemical Engineering Journal, 2013, 217:54-60.