用溶剂萃取—沉淀法从废锂离子电池正极材料中回收钴镍锂
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摘要
采用溶剂萃取—化学沉淀法从废锂离子电池正极材料中回收硫酸钴、氢氧化镍和氟化锂,比较了萃取剂P507和Cyanex272对钴、镍的萃取分离性能。试验结果表明:1-1-1型废锂离子电池正极材料浸出液经P204除锰后,用0.5 mol/L P507或0.6 mol/L Cyanex272经两级错流萃取钴,钴萃取率分别为98.21%和99.44%,镍共萃取率分别为24.42%和4.26%,锂共萃取率分别为15.84%和5.11%,Cyanex272对钴镍的萃取分离性能明显优于P507;P507和Cyanex272负载有机相分别用CoSO_4溶液和HAc-NaAc溶液洗脱共萃取的镍和锂,然后用硫酸反萃取钴,反萃取液中Co/Ni质量比分别为3 217(P507)和12 643(Cyanex272),蒸发结晶可得高纯硫酸钴;萃余液中的镍、锂分别用NaOH和HF沉淀,可得氢氧化镍和氟化锂固体。采用此方法,废锂离子电池正极材料中的钴、镍、锂都得到有效回收。
By solvent extraction-chemical precipitation process,the CoSO_4,Ni(OH)_2and LiF were recovered from the leaching solution of spent lithium ion battery cathode material.P507 and Cyanex272 separation performance for cobalt and nickel were compared.After manganese in the leaching solution is removed by solvent extraction using P204,the cobalt is extracted using 0.5 mol/L P507 or 0.6 mol/L Cyanex272 by two-stage cross-flow extraction with extraction rate of 98.21% and 99.44%,respectively and nickel co-extraction rate of 24.42% and 4.26% and lithium co-extraction rate of 15.84% and 5.11%,respectively.The separation performance of Cyanex272 for cobalt and nickel is significantly better than that of P507.The co-extracted nickel and lithium in P507 and Cyanex272 loaded organic phases can be scrubbed using CoSO_4solution and HAc-NaAc solution,respectively.Finally,the cobalt in the scrubbed organic phase can be complete stripped using H_2SO_4 solution.The cobalt/nickel in the stripping solution are 3 217(P507) and 12 643(Cyanex272),the high purity cobalt sulfate solution is obtained.NaOH and HF are used as precipitants to precipitate nickel and lithium in the raffinate in the form of nickel hydroxide and lithium fluoride.Using the method,the cobalt,nickel and lithium can be recovered effectivily.
By solvent extraction-chemical precipitation process,the CoSO_4,Ni(OH)_2and LiF were recovered from the leaching solution of spent lithium ion battery cathode material.P507 and Cyanex272 separation performance for cobalt and nickel were compared.After manganese in the leaching solution is removed by solvent extraction using P204,the cobalt is extracted using 0.5 mol/L P507 or 0.6 mol/L Cyanex272 by two-stage cross-flow extraction with extraction rate of 98.21% and 99.44%,respectively and nickel co-extraction rate of 24.42% and 4.26% and lithium co-extraction rate of 15.84% and 5.11%,respectively.The separation performance of Cyanex272 for cobalt and nickel is significantly better than that of P507.The co-extracted nickel and lithium in P507 and Cyanex272 loaded organic phases can be scrubbed using CoSO_4solution and HAc-NaAc solution,respectively.Finally,the cobalt in the scrubbed organic phase can be complete stripped using H_2SO_4 solution.The cobalt/nickel in the stripping solution are 3 217(P507) and 12 643(Cyanex272),the high purity cobalt sulfate solution is obtained.NaOH and HF are used as precipitants to precipitate nickel and lithium in the raffinate in the form of nickel hydroxide and lithium fluoride.Using the method,the cobalt,nickel and lithium can be recovered effectivily.
引文
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[12] 施丽华,孙水裕,卢创鑫,等.用硫酸-亚硫酸钠从废旧三元锂离子电池材料中浸出镍钴锰锂[J].湿法冶金,2018,37(5):384-387.
[13] 何显达,郭学益,李平,等.从人造金刚石触媒酸洗废液中回收镍、钴和锰[J].湿法冶金,2005,24(3):150-154.
[14] 宋士涛,邓小川,孙建之,等.氢氧化锂的应用与生产方法研究进展[J].海湖盐与化工,2005,34(1):32-35.
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[16] 支红军,唐向阳,刘力,等.电池级高纯氟化锂及其制备方法:103449480[P].2013-12-18.
[2] 徐志刚,季尚军,王朝华,等.溶液中镍钴萃取分离技术研究状况[J].湿法冶金,2018,37(5):344-348.
[3] 兰兴华.镍和钴溶剂萃取进展[J].世界有色金属,2004(9):35-39.
[4] 陈亮,唐新村,张阳,等.从废旧锂离子电池中分离回收钴镍锰[J].中国有色金属学报,2011,21(5):1192-1198.
[5] 夏李斌,谢法正,王瑞祥.P507-Cyanex272协同萃取分离回收废旧镍氢电池中镍钴金属新工艺研究[J].中国有色冶金,2011,40(1):67-69.
[6] NOGUEIRA C A,OLIVEIRA P C,PEDROSA F M.Scrubbing of cadmium and nickel from cyanex 272 loaded with cobalt[J].Solvent Extraction and Ion Exchange,2003,21(5):717-734.
[7] 田磊,常卿卿,李红超,等.从镍氢电池正极酸浸液中萃取分离镍钴[J].湿法冶金,2011,30(4):320-322.
[8] VIROLAINEN S,FINI M F,LAITINEN A,et al.Solvent extraction fractionation of Li-ion battery leachate containing Li,Ni and Co[J].Separation and Purification Technology,2017,179:274-282.
[9] 时美玲.红土矿常压盐酸浸出液中镍钴萃取分离研究[D].秦皇岛:燕山大学,2014.
[10] 张阳,满瑞林,王辉,等.用P507萃取分离钴及草酸反萃制备草酸钴[J].中南大学学报(自然科学版),2011,42(2):317-322.
[11] KANG J,SENANAYAKE G,SOHN J,et al.Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with Cyanex 272[J].Hydrometallurgy,2010,100(3/4):168-171.
[12] 施丽华,孙水裕,卢创鑫,等.用硫酸-亚硫酸钠从废旧三元锂离子电池材料中浸出镍钴锰锂[J].湿法冶金,2018,37(5):384-387.
[13] 何显达,郭学益,李平,等.从人造金刚石触媒酸洗废液中回收镍、钴和锰[J].湿法冶金,2005,24(3):150-154.
[14] 宋士涛,邓小川,孙建之,等.氢氧化锂的应用与生产方法研究进展[J].海湖盐与化工,2005,34(1):32-35.
[15] 刘海霞.氟化锂生产工艺研究进展[J].轻金属,2011(3):11-13.
[16] 支红军,唐向阳,刘力,等.电池级高纯氟化锂及其制备方法:103449480[P].2013-12-18.
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