使用P204从甲基磺酸溶液中萃取铟的研究
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摘要
以粗铅电解后液的甲基磺酸溶液为原料,使用萃取剂P204从甲基磺酸溶液中萃取铟。考察萃取剂体积分数、水相组成、搅拌时间、温度、相比等因素对铟萃取率的影响,模拟理论级数的逆流萃取。研究结果表明:在萃取剂体积分数为55%,甲基磺酸浓度为0.52～1.04mol/L,水相pH为0.5～2.0,搅拌时间为1.5min,温度为20～30℃,水相和有机相体积比为4:1的最优条件下,铟的平均萃取率达到98%以上;经过2级逆流萃取,铟萃取率达到99%;通过斜率法和红外光谱技术得到萃合物的分子式及萃取反应式,证实P204中的羟基—OH参加成键,并与游离的铟离子发生取代反应。
Indium was extracted from methanesulfonic acid solution after crude lead electrolysis using P204 as an extractant. The effects of extractant concentration, composition of aqueous phase, agitation time, temperature and phase ratio on the extraction rate of indium were investigated. The countercurrent extraction of theoretical series was simulated.The results show that the average extraction ratio of indium is larger than 98% under the following optimum conditions:volume fraction of extractant P204 is 55%, methanesulfonic acid concentration is 0.52-1.04 mol/L, pH is 0.5-2.0,agitation time is 1.5 min, temperature is 20-30 ℃, and volume ratio of equeous phase to organic phase is 4:1. After2-stage counter current extraction, the indium extraction rate reaches 99%. Molecular formula and extraction reaction formula of extracted species are obtained by slope method and infrared spectroscopy. It is demonstrated that the hydroxyl group —OH in P204 participates in bonding and undergoes a substitution reaction with free indium ions.
Indium was extracted from methanesulfonic acid solution after crude lead electrolysis using P204 as an extractant. The effects of extractant concentration, composition of aqueous phase, agitation time, temperature and phase ratio on the extraction rate of indium were investigated. The countercurrent extraction of theoretical series was simulated.The results show that the average extraction ratio of indium is larger than 98% under the following optimum conditions:volume fraction of extractant P204 is 55%, methanesulfonic acid concentration is 0.52-1.04 mol/L, pH is 0.5-2.0,agitation time is 1.5 min, temperature is 20-30 ℃, and volume ratio of equeous phase to organic phase is 4:1. After2-stage counter current extraction, the indium extraction rate reaches 99%. Molecular formula and extraction reaction formula of extracted species are obtained by slope method and infrared spectroscopy. It is demonstrated that the hydroxyl group —OH in P204 participates in bonding and undergoes a substitution reaction with free indium ions.
引文
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[18]马荣骏.萃取冶金[M].北京:冶金工业出版社,2009:58-114.MA Rongjun.Extraction metallurgy[M].Beijing:Metallurgical Industry Publishing House,2009:58-114.
[19]刘兴芝,房大维,李俊,等.P204萃取铟的热力学研究[J].材料研究与应用,2005,15(1):4-7.LIU Xingzhi,FANG Dawei,LI Jun,et al.Study on thermodynamics of solvent extraction of indium with P204[J].Materials Research and Application,2005,15(1):4-7.
[2]SARKAR M B,MONDAL A,CHOUDHURI B.Presence of capacitive memory in indium doped TiO2,alloy thin film[J].Journal of Alloys and Compounds,2016,654(5):529-533.
[3]林丰,李建武.浅析中国铟资源特点及产业现状[J].地质论评,2016,62(Z1):9-10.LIN Feng,LI Jianwu.Analyses on the resources characteristics and industrial present situation of indium in China[J].Geological Review,2016,62(Z1):9-10.
[4]ZHANG Qian,ZHAN Xinzhi,PAN Jiayong,et al.Geochemical enrichment and mineralization of indium[J].Acta Geochimica,1998,17(3):221-225.
[5]ALFANTAZI A M,MOSKALYK R R.Processing of indium:a review[J].Minerals Engineering,2003,16(8):687-694.
[6]SAWAI H,RAHMAN I M M,TSUKAGOSHI Y,et al.Selective recovery of indium from lead-smelting dust[J].Chemical Engineering Journal,2015,277(1):219-228.
[7]袁铁锤,陶政修,周科朝.提高含铟锌精矿中锌铟回收率的方法[J].中南大学学报(自然科学版),2006,37(5):874-877.YUAN Tiechui,TAO Zhengxiu,ZHOU Kechao.Methods for improving recovery of zinc and indium from indium-contained zinc concentrate[J].Journal of Central South University(Science and Technology),2006,37(5):874-877.
[8]ZHANG Yuhui,JIN Bingjie,MA Baozhong,et al.Separation of indium from lead smelting hazardous dust via leaching and solvent extraction[J].Journal of Environmental Chemical Engineering,2017,5(3):2182-2188.
[9]罗虹霖.氧化锌烟尘提取铟的工艺研究[J].稀有金属与硬质合金,2017(1):17-22.LUO Honglin.Technological research on indium recovery from zinc oxide flue dust[J].Rare Matals and Cemented Carbides,2017(1):17-22.
[10]LI Xingbin,DENG Zhigan,LI Cunxiong,et al.Direct solvent extraction of indium from a zinc residue reductive leach solution by D2EHPA[J].Hydrometallurgy,2015,156:1-5.
[11]VIROLAINEN S,IBANA D,PAATERO E.Recovery of indium from indium tin oxide by solvent extraction[J].Hydrometallurgy,2011,107(1):56-61.
[12]郭小东,魏昶,李兴彬,等.次氧化锌酸性浸出液中萃取分离铟的工艺[J].中国有色金属学报,2017,27(12):2590-2597.GUO Xiaodong,WEI Chang,LI Xingbin,et al.Solvent extraction and separation of indium from leaching solution of zinc oxide[J].The Chinese Journal of Nonferrous Metals,2017,27(12):2590-2597.
[13]邱伟明,奚长生,丘秀珍,等.从冶锌工业废渣中提取镓和铟[J].有色金属(冶炼部分),2017(5):28-32.QIU Weiming,XI Changsheng,QIU Xiuzhen,et al.Extraction of gallium and indium from zinc residues[J].Nonferrous Metals(Extractive Metallurgy),2017(5):28-32.
[14]BALAJI R,MALATHY P,罗慧梅.甲基磺酸在电镀相关金属精饰领域的应用[J].电镀与涂饰,2004,23(5):40-45.BALAJI R,MALATHY P,LUO Huimei.Methanesulphonic acid in electroplating related metal finishing industries[J].Electroplating and Finishing,2004,23(5):40-45.
[15]JIN B,DREISINGER D B.A green electrorefining process for production of pure lead from methanesulfonic acid medium[J].Separation and Purification Technology,2016,170(1):199-207.
[16]杨声海,吴彦增,孙彦伟,等.甲基磺酸体系电沉积铅过程中阳极反应的电化学研究[J].湿法冶金,2018,37(5):356-361.YANG Shenghai,WU Yanzeng,SUN Yanwei,et al.Electrochemistry of anodic reactions in MSA system during electrowinning of lead[J].Hydrometallurgy of China,2018,37(5):356-361.
[17]李有刚,甘红祥,陆宾,等.甲基磺酸体系铅选择性浸出动力学研究[J].大众科技,2017,19(12):9-11.LI Yougang,GAN Hongxiang,LU Bin,et al.Methylsulfonic acid system lead selective leaching dynamics research[J].Popular Science and Technology,2017,19(12):9-11.
[18]马荣骏.萃取冶金[M].北京:冶金工业出版社,2009:58-114.MA Rongjun.Extraction metallurgy[M].Beijing:Metallurgical Industry Publishing House,2009:58-114.
[19]刘兴芝,房大维,李俊,等.P204萃取铟的热力学研究[J].材料研究与应用,2005,15(1):4-7.LIU Xingzhi,FANG Dawei,LI Jun,et al.Study on thermodynamics of solvent extraction of indium with P204[J].Materials Research and Application,2005,15(1):4-7.