废旧三元锂离子电池正极材料的淀粉还原浸出工艺及其动力学
|
摘要
根据淀粉在稀酸或加热条件下可水解为还原性单糖的性质,以淀粉作为还原剂,采用酸浸出方法对从废旧三元锂离子电池正极材料中回收Li、Ni、Co、Mn的浸出工艺进行研究;分别考察酸度、淀粉浓度、固液比、浸出温度和浸出时间对4种有价金属浸出率的影响。结果表明:在最佳条件即2mol/LH_2SO_4、4g/L淀粉、固液比50g/L、浸出温度80℃、浸出时间120min时,Li、Ni、Co、Mn的浸出率分别达到98.55%、97.6%、96.73%以及91.92%。此外,基于对数定律方程对浸出动力学参数进行了拟合,表现出较好的线性相关度,计算得出Li、Ni、Co、Mn的表观活化能分别为14.8、21.3、24以及26.4kJ/mol。浸出渣的XRD谱和SEM像显示其主要物相为C和MnO2。
Based on the properties that starch can be hydrolyzed into reduced monosaccharide under dilute acid or heating conditions, starch was used as a reducing agent by acid leaching method for recovering Li, Ni, Co, Mn from cathode materials of spent ternary lithium ion battery. The effects of acid concentration, starch concentration, solid to liquid ratio, leaching temperature and leaching time on the leaching rate of four valuable metals were investigated. The results show that the leaching rates of Li, Ni, Co and Mn reach 98.55%, 97.6%, 96.73% and 91.92%, respectively under the optimum conditions of 2 mol/L H_2SO_4, 4 g/L starch, solid-liquid ratio at 50 g/L, leaching temperature at 80 ℃ and leaching time at 120 min. In addition, a good linear correlation is shown by fitting the kinetic parameters of leaching based on the logarithmic law equation, and the apparent activation energies of Li, Ni, Co and Mn are 14.8 kJ/mol, 21.3 k J/mol, 24 kJ/mol and 26.4 kJ/mol, respectively. The analysis results of XRD and SEM show that the main phases of the leaching residue was C and MnO_2.
Based on the properties that starch can be hydrolyzed into reduced monosaccharide under dilute acid or heating conditions, starch was used as a reducing agent by acid leaching method for recovering Li, Ni, Co, Mn from cathode materials of spent ternary lithium ion battery. The effects of acid concentration, starch concentration, solid to liquid ratio, leaching temperature and leaching time on the leaching rate of four valuable metals were investigated. The results show that the leaching rates of Li, Ni, Co and Mn reach 98.55%, 97.6%, 96.73% and 91.92%, respectively under the optimum conditions of 2 mol/L H_2SO_4, 4 g/L starch, solid-liquid ratio at 50 g/L, leaching temperature at 80 ℃ and leaching time at 120 min. In addition, a good linear correlation is shown by fitting the kinetic parameters of leaching based on the logarithmic law equation, and the apparent activation energies of Li, Ni, Co and Mn are 14.8 kJ/mol, 21.3 k J/mol, 24 kJ/mol and 26.4 kJ/mol, respectively. The analysis results of XRD and SEM show that the main phases of the leaching residue was C and MnO_2.
引文
[1]VIKSTR?M H,DAVIDSSON S,H??K M.Lithium availability and future production outlooks[J].Applied Energy,2013,110:252-266.
[2]卢毅屏,夏自发,冯其明,龙涛,欧乐明,张国范.废锂离子电池中集流体与活性物质的分离[J].中国有色金属学报,2007,17(6):997-1001.LU Yi-ping,XIA Zi-fa,FENG Qi-ming,LONG Tao,OULe-ming,ZHANG Guo-fan.Separation of current collectors and active materials from spent lithium-ion secondary batteries[J].The Chinese Journal of Nonferrous Metals,2007,17(6):997-1001.
[3]FOUAD O A,FARGHALY F I,BAHGAT M.A novel approach for synthesis of nanocrystallineγ-LiAlO2,from spent lithium-ion batteries[J].Journal of Analytical&Applied Pyrolysis,2007,78(1):65-69.
[4]KANG J,SENANAYAKE G,SOHN J,SHIN S M.Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with cyanex 272[J].Hydrometallurgy,2010,96(3):168-171.
[5]MESHRAM P,PANDEY B D,MANKHAND T R.Extraction of lithium from primary and secondary sources by pre-treatment,leaching and separation:A comprehensive review[J].Hydrometallurgy,2014,150:192-208.
[6]常伟,满瑞林,尹晓莹,张建.电化学还原技术从废旧锂离子电池中浸出LiCoO2[J].中国有色金属学报,2014,24(3):787-792.CHANG Wei,MAN Rui-lin,YIN Xiao-ying,ZHANG Jian.Leaching LiCoO2 from spent lithium-ion batteries by electrochemical reduction[J].The Chinese Journal of Nonferrous Metals,2014,24(3):787-792.
[7]GRANATA G,MOSCARDINI E,PAGNANELLI F,TRABUCCO F,TORO L.Product recovery from Li-ion battery wastes coming from an industrial pre-treatment plant:Lab scale tests and process simulations[J].Journal of Power Sources,2012,206(1):393-401.
[8]ZOU H,GRATZ E,APELIAN D,WANG Y.A novel method to recycle mixed cathode materials for lithium ion batteries[J].Green Chemistry,2012,15(5):1183-1191.
[9]PINNA E G,RUIZ M C,OJEDA M W,RODRIGUEZ M H.Cathodes of spent Li-ion batteries:Dissolution with phosphoric acid and recovery of lithium and cobalt from leach liquors[J].Hydrometallurgy,2016,167:66-71.
[10]MESHRAM P,PANDEY B D,MANKHAND T R.Hydrometallurgical processing of spent lithium ion batteries(LIBs)in the presence of a reducing agent with emphasis on kinetics of leaching[J].Chemical Engineering Journal,2015,281:418-427.
[11]周旭,朱曙光,次西拉姆,贺文智,李光明,黄菊文.废锂离子电池负极材料的机械分离与回收[J].中国有色金属学报,2011,21(12):3082-3086.ZHOU Xu,ZHU Shu-guang,CIXI La-mu,HE Wen-zhi,LIGuang-ming,HUANG Ju-we.Mechanical separation and recovery process of anode materials from spent lithium-ion batteries[J].The Chinese Journal of Nonferrous Metals,2011,21(12):3082-3086.
[12]LI L,GE J,WU F,CHEN R,CHEN S,WU B.Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant[J].Journal of Hazardous Materials,2010,176(1):288-293.
[13]LI L,GE J,CHEN R,WU F,CHEN S,ZHANG X.Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J].Waste Management,2010,30(12):2615-2621.
[14]陈亮,唐新村,张阳,瞿毅,王志敏.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.CHEN Liang,TANG Xin-cun,ZHANG Yang,QU Yi,WANGZhi-min.Separation and recovery of Ni,Co and Mn from spent lithium-ion batteries[J].The Chinese Journal of Nonferrous Metals,2011,21(5):1192-1198.
[15]ZENG X,LI J,SHEN B.Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J].Journal of Hazardous Materials,2015,295:112-118.
[16]YANG Y,XU S,HE Y.Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes[J].Waste Management,2017,64:219-227.
[17]姚路.废旧锂离子电池正极材料回收再利用研究[D].新乡:河南师范大学,2016.YAO Lu.Study on recycling of cathode material from waste lithium ion batteries[D].Xinxiang:Henan Normal University,2016.
[18]孙秀萍.酸水解淀粉制备淀粉微晶及其结晶结构与性质的研究[D].天津:天津大学,2003.Study on the preparation of starch microcrystalline by acid hydrolysis of starch and the crystalline structure and properties of starch microcrystalline[D].Tianjing:Tianjing University,2003.
[19]KAMBLE M P,YADAV G D.Kinetic resolution of(R,S)-α-tetralol by immobilized Candida antarctica lipase B:Comparison of packed bed over stirred tank batch bioreactor[J].Industrial&Engineering Chemistry Research,2017,56(7):1750-1757.
[20]贺凤,满瑞林,刘琦,孙祖梅,徐娟,张建.燕麦秸秆酸浸回收废旧锂电池中Co的动力学[J].中国有色金属学报,2015,25(4):1103-1108.HE Feng,MAN Rui-lin,LIU Qi,SUN Zu-mei,XU Juan,ZHANG Jian.Kinetics of acid leaching cobalt from waste lithium-ion batteries using oat straw[J].The Chinese Journal of Nonferrous Metals,2015,25(4):1103-1108.
[21]SUN L,QIU K.Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries[J].Waste Management,2012,32(8):1575-1582.
[22]徐筱群,满瑞林,张建,刘琦,徐娟,孙祖梅.电解剥离-生物质酸浸回收废旧锂电池[J].中国有色金属学报,2014,24(10):2576-2581.XU Xiao-qun,MAN Rui-lin,ZHANG Jian,LIU Qi,XU Juan,SUN Zu-mei.Electrolytic stripping-biomass acid leachingrecycling spent Li-ion battery[J].The Chinese Journal of Nonferrous Metals,2014,24(10):2576-2581.
[23]LI L,BIAN Y,ZHANG X,GUAN Y,FAN E,WU F.Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching[J].Waste Management,2018,71:362-371.
[24]RENDóNANGELES J C,MATAMOROSVELOZA Z,VELOZAA M,PEREZGARIBAY R,RODRIGUEZGALICIA J L,KAZUMICHI Y.Facile synthesis of perovskite-structured powders using barite-celestite ore under hydrothermal alkaline conditions[J].Industrial&Engineering Chemistry Research,2017,56(36):9942-9952.
[2]卢毅屏,夏自发,冯其明,龙涛,欧乐明,张国范.废锂离子电池中集流体与活性物质的分离[J].中国有色金属学报,2007,17(6):997-1001.LU Yi-ping,XIA Zi-fa,FENG Qi-ming,LONG Tao,OULe-ming,ZHANG Guo-fan.Separation of current collectors and active materials from spent lithium-ion secondary batteries[J].The Chinese Journal of Nonferrous Metals,2007,17(6):997-1001.
[3]FOUAD O A,FARGHALY F I,BAHGAT M.A novel approach for synthesis of nanocrystallineγ-LiAlO2,from spent lithium-ion batteries[J].Journal of Analytical&Applied Pyrolysis,2007,78(1):65-69.
[4]KANG J,SENANAYAKE G,SOHN J,SHIN S M.Recovery of cobalt sulfate from spent lithium ion batteries by reductive leaching and solvent extraction with cyanex 272[J].Hydrometallurgy,2010,96(3):168-171.
[5]MESHRAM P,PANDEY B D,MANKHAND T R.Extraction of lithium from primary and secondary sources by pre-treatment,leaching and separation:A comprehensive review[J].Hydrometallurgy,2014,150:192-208.
[6]常伟,满瑞林,尹晓莹,张建.电化学还原技术从废旧锂离子电池中浸出LiCoO2[J].中国有色金属学报,2014,24(3):787-792.CHANG Wei,MAN Rui-lin,YIN Xiao-ying,ZHANG Jian.Leaching LiCoO2 from spent lithium-ion batteries by electrochemical reduction[J].The Chinese Journal of Nonferrous Metals,2014,24(3):787-792.
[7]GRANATA G,MOSCARDINI E,PAGNANELLI F,TRABUCCO F,TORO L.Product recovery from Li-ion battery wastes coming from an industrial pre-treatment plant:Lab scale tests and process simulations[J].Journal of Power Sources,2012,206(1):393-401.
[8]ZOU H,GRATZ E,APELIAN D,WANG Y.A novel method to recycle mixed cathode materials for lithium ion batteries[J].Green Chemistry,2012,15(5):1183-1191.
[9]PINNA E G,RUIZ M C,OJEDA M W,RODRIGUEZ M H.Cathodes of spent Li-ion batteries:Dissolution with phosphoric acid and recovery of lithium and cobalt from leach liquors[J].Hydrometallurgy,2016,167:66-71.
[10]MESHRAM P,PANDEY B D,MANKHAND T R.Hydrometallurgical processing of spent lithium ion batteries(LIBs)in the presence of a reducing agent with emphasis on kinetics of leaching[J].Chemical Engineering Journal,2015,281:418-427.
[11]周旭,朱曙光,次西拉姆,贺文智,李光明,黄菊文.废锂离子电池负极材料的机械分离与回收[J].中国有色金属学报,2011,21(12):3082-3086.ZHOU Xu,ZHU Shu-guang,CIXI La-mu,HE Wen-zhi,LIGuang-ming,HUANG Ju-we.Mechanical separation and recovery process of anode materials from spent lithium-ion batteries[J].The Chinese Journal of Nonferrous Metals,2011,21(12):3082-3086.
[12]LI L,GE J,WU F,CHEN R,CHEN S,WU B.Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant[J].Journal of Hazardous Materials,2010,176(1):288-293.
[13]LI L,GE J,CHEN R,WU F,CHEN S,ZHANG X.Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries[J].Waste Management,2010,30(12):2615-2621.
[14]陈亮,唐新村,张阳,瞿毅,王志敏.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.CHEN Liang,TANG Xin-cun,ZHANG Yang,QU Yi,WANGZhi-min.Separation and recovery of Ni,Co and Mn from spent lithium-ion batteries[J].The Chinese Journal of Nonferrous Metals,2011,21(5):1192-1198.
[15]ZENG X,LI J,SHEN B.Novel approach to recover cobalt and lithium from spent lithium-ion battery using oxalic acid[J].Journal of Hazardous Materials,2015,295:112-118.
[16]YANG Y,XU S,HE Y.Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes[J].Waste Management,2017,64:219-227.
[17]姚路.废旧锂离子电池正极材料回收再利用研究[D].新乡:河南师范大学,2016.YAO Lu.Study on recycling of cathode material from waste lithium ion batteries[D].Xinxiang:Henan Normal University,2016.
[18]孙秀萍.酸水解淀粉制备淀粉微晶及其结晶结构与性质的研究[D].天津:天津大学,2003.Study on the preparation of starch microcrystalline by acid hydrolysis of starch and the crystalline structure and properties of starch microcrystalline[D].Tianjing:Tianjing University,2003.
[19]KAMBLE M P,YADAV G D.Kinetic resolution of(R,S)-α-tetralol by immobilized Candida antarctica lipase B:Comparison of packed bed over stirred tank batch bioreactor[J].Industrial&Engineering Chemistry Research,2017,56(7):1750-1757.
[20]贺凤,满瑞林,刘琦,孙祖梅,徐娟,张建.燕麦秸秆酸浸回收废旧锂电池中Co的动力学[J].中国有色金属学报,2015,25(4):1103-1108.HE Feng,MAN Rui-lin,LIU Qi,SUN Zu-mei,XU Juan,ZHANG Jian.Kinetics of acid leaching cobalt from waste lithium-ion batteries using oat straw[J].The Chinese Journal of Nonferrous Metals,2015,25(4):1103-1108.
[21]SUN L,QIU K.Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries[J].Waste Management,2012,32(8):1575-1582.
[22]徐筱群,满瑞林,张建,刘琦,徐娟,孙祖梅.电解剥离-生物质酸浸回收废旧锂电池[J].中国有色金属学报,2014,24(10):2576-2581.XU Xiao-qun,MAN Rui-lin,ZHANG Jian,LIU Qi,XU Juan,SUN Zu-mei.Electrolytic stripping-biomass acid leachingrecycling spent Li-ion battery[J].The Chinese Journal of Nonferrous Metals,2014,24(10):2576-2581.
[23]LI L,BIAN Y,ZHANG X,GUAN Y,FAN E,WU F.Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching[J].Waste Management,2018,71:362-371.
[24]RENDóNANGELES J C,MATAMOROSVELOZA Z,VELOZAA M,PEREZGARIBAY R,RODRIGUEZGALICIA J L,KAZUMICHI Y.Facile synthesis of perovskite-structured powders using barite-celestite ore under hydrothermal alkaline conditions[J].Industrial&Engineering Chemistry Research,2017,56(36):9942-9952.