磷酸铁锂废料中磷、铁、锂的综合回收
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摘要
采用氢氧化钠溶液除去经前处理后的废旧磷酸铁锂电池、极片或边角料粉料中的铝,采用盐酸浸出-双氧水氧化-纯碱调p H值工艺,得到二水磷酸铁和氯化锂溶液。二水磷酸铁经洗涤后与氢氧化钠反应得到氢氧化铁产品和磷酸三钠水溶液,磷酸三钠水溶液蒸发结晶得到十二水磷酸三钠产品。氯化锂溶液经进一步除杂和蒸发后与碳酸钠反应得到碳酸锂产品。重点研究了磷酸铁的沉淀以及由磷酸铁制备磷酸三钠的工艺。制得的产品十二水磷酸三钠达到了工业级要求,主含量高达99.03%。实现了磷、铁、锂的全部综合回收。
The pretreated spent lithium iron phosphate batteries,electrode plate or scrap powder was firstly processed with sodium hydroxide solution to remove aluminum,then subjected to a process consisting of leaching with hydrochloric acid,oxidation with hydrogen peroxide and adjusting the p H value with soda,with the iron phosphate and lithium chloride solution obtained. The iron phosphate after washing reacted with sodium hydrogen solution to give ferric hydroxide and trisodium phosphate solution. Trisodium phosphate solution went through the evaporation crystallization process,yielding a trisodium phosphate product. While previously obtained lithium chloride solution,after further purification and evaporation,was reacted with sodium carbonate to yield a lithium carbonate product. The precipitation of ferric phosphate and the process for preparing trisodium phosphate from ferric phosphate were the focuses of the study.It is shown that the obtained sodium phosphate tribasic dodecahydrate has reached the industrial grade requirement,with the main content as high as 99. 03%,thus the comprehensive recovery of phosphorus,iron and lithium can be realized.
The pretreated spent lithium iron phosphate batteries,electrode plate or scrap powder was firstly processed with sodium hydroxide solution to remove aluminum,then subjected to a process consisting of leaching with hydrochloric acid,oxidation with hydrogen peroxide and adjusting the p H value with soda,with the iron phosphate and lithium chloride solution obtained. The iron phosphate after washing reacted with sodium hydrogen solution to give ferric hydroxide and trisodium phosphate solution. Trisodium phosphate solution went through the evaporation crystallization process,yielding a trisodium phosphate product. While previously obtained lithium chloride solution,after further purification and evaporation,was reacted with sodium carbonate to yield a lithium carbonate product. The precipitation of ferric phosphate and the process for preparing trisodium phosphate from ferric phosphate were the focuses of the study.It is shown that the obtained sodium phosphate tribasic dodecahydrate has reached the industrial grade requirement,with the main content as high as 99. 03%,thus the comprehensive recovery of phosphorus,iron and lithium can be realized.
引文
[1]王英东,杨敬增,张承龙,等.退役动力磷酸铁锂电池梯次利用的情况分析与建议[J].再生资源与循环经济,2017,10(4):23-27.
[2]杨见青,关杰,梁波,等.我国废弃磷酸铁锂电池的资源化研究[J].环境工程,2017,35(2):127-132.
[3]李肖肖,王楠,郭盛昌,等.废旧动力锂离子电池回收的研究进展[J].电池,2017,47(1):52-55.
[4]曹利娜,宫璐,刘成士,等.废旧锂离子电池回收技术研究进展[J].电源技术,2015,39(9):2014-2016.
[5]孙永辉,范小明,张卫新,等.废旧磷酸铁锂电池的回收及利用[J].安徽化工,2016,42(6):87-94.
[6]韩小云,徐金球.沉淀法回收废旧磷酸铁锂电池中的铁和锂[J].广东化工,2017,44(4):12-16.
[7]戴长松,郑茹娟,刘元龙,等.磷酸铁锂电池中回收电池级磷酸铁及利用废旧磷酸铁锂电池制备磷酸铁锂正极材料的方法:中国,CN104953200A[P].2015-09-30.
[8]许开华,张云河,闫梨.一种废旧磷酸铁锂正极材料的回收方法:中国,CN106384855A[P].2017-02-08.
[9]许开华,张云河.一种磷酸铁锂废料的资源回收方法:中国,CN106629646A[P].2017-05-10.
[10]马小路.一种采用报废磷酸铁锂电池制备碳酸锂的方法:中国,CN106129519A[P].2016-11-16.
[11]曹乃珍,高洁,周梅,等.酸浸法回收处理废旧磷酸铁锂正极材料的方法:中国,CN106684485A[P].2017-05-17.
[12]胡简,郭永兴,祝宏帅,等.一种从失效磷酸铁锂电池正极材料中选择性浸出锂的方法:中国,CN106532172A[P].2015-09-30.
[13]刘秀兰,迟忠君,李香龙,等.锂元素的回收:中国,CN105119024A[P].2015-12-02.
[14]梁立君.废旧锂离子电池正极材料Li Fe PO4的回收及合成的研究[D].大连:大连交通大学环境与化学工程学院,2012.
[2]杨见青,关杰,梁波,等.我国废弃磷酸铁锂电池的资源化研究[J].环境工程,2017,35(2):127-132.
[3]李肖肖,王楠,郭盛昌,等.废旧动力锂离子电池回收的研究进展[J].电池,2017,47(1):52-55.
[4]曹利娜,宫璐,刘成士,等.废旧锂离子电池回收技术研究进展[J].电源技术,2015,39(9):2014-2016.
[5]孙永辉,范小明,张卫新,等.废旧磷酸铁锂电池的回收及利用[J].安徽化工,2016,42(6):87-94.
[6]韩小云,徐金球.沉淀法回收废旧磷酸铁锂电池中的铁和锂[J].广东化工,2017,44(4):12-16.
[7]戴长松,郑茹娟,刘元龙,等.磷酸铁锂电池中回收电池级磷酸铁及利用废旧磷酸铁锂电池制备磷酸铁锂正极材料的方法:中国,CN104953200A[P].2015-09-30.
[8]许开华,张云河,闫梨.一种废旧磷酸铁锂正极材料的回收方法:中国,CN106384855A[P].2017-02-08.
[9]许开华,张云河.一种磷酸铁锂废料的资源回收方法:中国,CN106629646A[P].2017-05-10.
[10]马小路.一种采用报废磷酸铁锂电池制备碳酸锂的方法:中国,CN106129519A[P].2016-11-16.
[11]曹乃珍,高洁,周梅,等.酸浸法回收处理废旧磷酸铁锂正极材料的方法:中国,CN106684485A[P].2017-05-17.
[12]胡简,郭永兴,祝宏帅,等.一种从失效磷酸铁锂电池正极材料中选择性浸出锂的方法:中国,CN106532172A[P].2015-09-30.
[13]刘秀兰,迟忠君,李香龙,等.锂元素的回收:中国,CN105119024A[P].2015-12-02.
[14]梁立君.废旧锂离子电池正极材料Li Fe PO4的回收及合成的研究[D].大连:大连交通大学环境与化学工程学院,2012.