萃取法从废旧锂离子电池正极材料浸出液中提取锂
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摘要
废旧锂离子电池正极材料浸出后,溶液中的镍、钴等有价金属十分容易回收,但一直没有很好的方法来回收锂.实际上,这种浸出液和盐湖卤水都为锂盐溶液,所不同的只是盐湖卤水中锂的浓度往往要低一些,并有大量的氯化钠、氯化镁伴生,因此可将废旧锂离子电池浸出液看做一种特殊的"盐湖卤水",并进一步调整其Cl~-的浓度,进而成功地采用盐湖提锂中常用的萃取法.该方法以磷酸三丁酯(TBP)为萃取剂,磺化煤油为稀释剂,在三氯化铁(FeCl_3)存在的条件下,实现选择性提取锂.TBP首先与FeCl_3-NaCl的酸性溶液接触,形成了锂的专属萃取剂;并将浸出液中氯化钠的浓度进一步调整到250 g/L,在相比(V_O/V_A)为3,温度为室温条件下萃取5 min,锂的单级萃取率可达到75%左右,而Ni~(2+)、Co~(2+)、Mn~(2+)几乎没有被萃取.根据平衡等温线,通过4级逆流萃取,锂的萃取率可达到99%.
After the cathode materials of spent lithium-ion battery have been leached, valuable metals such as nickel and cobalt in solution are easily recycled, but there's been no good way to recycle lithium. In fact, this leaching solution is similar to Salt Lake Brine, the difference is that the concentration of lithium in the Brine is lower, and there is a large amount of sodium chloride, magnesium chloride associated in the Brine. We can treat the leaching solution as a special "Salt Lake Brine", adjusting its chlorine concentration, and then the widely accepted method for extracting lithium from Salt Lake Brine can be successfully applied. With tributyl phosphate(TBP) used as the extractant, sulfonated kerosene as the diluent and ferric chloride(FeCl_3) as the co-extractant, lithium is selectively extracted. TBP firstly reacts with the acidic solution of FeCl_3-NaCl to form the exclusive extractant for lithium. Then adjust the concentration of NaCl in the leaching solution to more than 250 g/L and conduct the extraction experiment for 5 minutes at room temperature with the organic/aqueous volume ratio(O/A) of 3. It turns out that the extraction rate of single-stage lithium stands at 75 %,while Ni~(2+), Co~(2+)and Mn~(2+)are hardly extracted. According to the equilibrium isotherm, extraction rate of lithium can reach 99 % through four-stage countercurrent extraction.
After the cathode materials of spent lithium-ion battery have been leached, valuable metals such as nickel and cobalt in solution are easily recycled, but there's been no good way to recycle lithium. In fact, this leaching solution is similar to Salt Lake Brine, the difference is that the concentration of lithium in the Brine is lower, and there is a large amount of sodium chloride, magnesium chloride associated in the Brine. We can treat the leaching solution as a special "Salt Lake Brine", adjusting its chlorine concentration, and then the widely accepted method for extracting lithium from Salt Lake Brine can be successfully applied. With tributyl phosphate(TBP) used as the extractant, sulfonated kerosene as the diluent and ferric chloride(FeCl_3) as the co-extractant, lithium is selectively extracted. TBP firstly reacts with the acidic solution of FeCl_3-NaCl to form the exclusive extractant for lithium. Then adjust the concentration of NaCl in the leaching solution to more than 250 g/L and conduct the extraction experiment for 5 minutes at room temperature with the organic/aqueous volume ratio(O/A) of 3. It turns out that the extraction rate of single-stage lithium stands at 75 %,while Ni~(2+), Co~(2+)and Mn~(2+)are hardly extracted. According to the equilibrium isotherm, extraction rate of lithium can reach 99 % through four-stage countercurrent extraction.
引文
[1]王光旭,李佳,许振明.废旧锂离子电池中有价金属回收工艺的研究进展[J].材料导报,2015,29(7):113-123.
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[3]宗毅,熊道陵,王露琦,等.废旧锂电池废料除铝及回收铝工艺研究[J].有色金属科学与工程,2018,9(5):26-32.
[4]SONG Y,ZHAO Z.Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques[J].Separation and Purification Technology,2018,206:335-342.
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[8]吴越,裴锋,贾路路,等.废旧锂离子电池中有价金属的回收技术进展[J].稀有金属,2013,37(2):320-329.
[9]朱显峰,赵瑞瑞,常毅,等.废旧锂离子电池三元正极材料酸浸研究[J].电池,2017,47(2):105-108.
[10]张阳,满瑞林,王辉,等.综合回收废旧锂电池中有价金属的研究[J].稀有金属,2009,33(6):931-935.
[11]叶帆.盐湖卤水萃取提锂及其机理研究[D].上海:华东理工大学,2011.
[12]VIROLAINEN S,FINI M F,LAITINEN A,et al.Solvent extraction fractionation of Li-ion battery leachate containing Li,Ni,and Co[J].Separation&Purification Technology,2017,179:274-282.
[13]黄师强,崔荣旦,张淑珍,等.磷酸三丁酯从大柴旦盐湖卤水萃取锂的研究[J].盐湖研究,1980(增刊1):14-24.
[14]贾旭宏,李丽娟,曾忠民,等.磷酸三丁酯萃取体系从盐湖卤水中提取锂[J].无机盐工业,2011,43(8):29-32.
[15]祝茂忠.溶剂萃取法提取盐湖卤水中锂的研究[J].化工矿物与加工,2016(8):27-30.
[16]孙锡良,陈白珍,徐徽,等.从盐湖卤水中萃取锂[J].中南大学学报(自然科学版),2007,38(2):262-266.
[17]JI L,HU Y,LI L,et al.Lithium extraction with a synergistic system of dioctyl phthalate and tributyl phosphate in kerosene and FeCl3[J].Hydrometallurgy,2016,162:71-78.
[18]XIANG W,LIANG S,ZHOU Z,et al.Extraction of lithium from salt lake brine containing borate anion and high concentration of magnesium[J].Hydrometallurgy,2016,166:9-15.
[19]LEE M S.Use of the bromley equation for the analysis of ionic equilibria in mixed ferric and ferrous chloride solutions at 25°C[J].Metallurgical&Materials Transactions B,2006,37(2):173-179.
[20]XIANG W,LIANG S,ZHOU Z,et al.Lithium recovery from salt lake brine by counter-current extraction using tributyl phosphate/FeCl3in methyl isobutyl ketone[J].Hydrometallurgy,2017,171:27-32.
[21]柳培.磷酸三丁酯萃取锂的研究[J].浙江化工,2013,44(1):22-25.
[22]SONG J,HUANG T,QIU H,et al.Recovery of lithium from salt lake brine of high Mg/Li ratio using Na[FeCl4*2TBP]as extractant:Thermodynamics,kinetics and processes[J].Hydrometallurgy,2017,173:63-70.
[2]李金辉,郑顺,熊道陵,等.废旧锂离子电池正极材料有价资源回收方法[J].有色金属科学与工程,2013,4(4):29-35.
[3]宗毅,熊道陵,王露琦,等.废旧锂电池废料除铝及回收铝工艺研究[J].有色金属科学与工程,2018,9(5):26-32.
[4]SONG Y,ZHAO Z.Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques[J].Separation and Purification Technology,2018,206:335-342.
[5]施平川.废旧三元锂离子电池正极材料的回收技术研究[D].北京:北京理工大学,2015.
[6]KIM S,KIM J,KIM S,et al.Electrochemical lithium recovery and organic removal from industrial wastewater of a battery recycling plant[J].Environmental Science Water Research&Technology,2017,4(2):175-182.
[7]徐源来,徐盛明,池汝安,等.废旧锂离子电池正极材料回收工艺研究[J].武汉工程大学学报,2008,30(4):46-50.
[8]吴越,裴锋,贾路路,等.废旧锂离子电池中有价金属的回收技术进展[J].稀有金属,2013,37(2):320-329.
[9]朱显峰,赵瑞瑞,常毅,等.废旧锂离子电池三元正极材料酸浸研究[J].电池,2017,47(2):105-108.
[10]张阳,满瑞林,王辉,等.综合回收废旧锂电池中有价金属的研究[J].稀有金属,2009,33(6):931-935.
[11]叶帆.盐湖卤水萃取提锂及其机理研究[D].上海:华东理工大学,2011.
[12]VIROLAINEN S,FINI M F,LAITINEN A,et al.Solvent extraction fractionation of Li-ion battery leachate containing Li,Ni,and Co[J].Separation&Purification Technology,2017,179:274-282.
[13]黄师强,崔荣旦,张淑珍,等.磷酸三丁酯从大柴旦盐湖卤水萃取锂的研究[J].盐湖研究,1980(增刊1):14-24.
[14]贾旭宏,李丽娟,曾忠民,等.磷酸三丁酯萃取体系从盐湖卤水中提取锂[J].无机盐工业,2011,43(8):29-32.
[15]祝茂忠.溶剂萃取法提取盐湖卤水中锂的研究[J].化工矿物与加工,2016(8):27-30.
[16]孙锡良,陈白珍,徐徽,等.从盐湖卤水中萃取锂[J].中南大学学报(自然科学版),2007,38(2):262-266.
[17]JI L,HU Y,LI L,et al.Lithium extraction with a synergistic system of dioctyl phthalate and tributyl phosphate in kerosene and FeCl3[J].Hydrometallurgy,2016,162:71-78.
[18]XIANG W,LIANG S,ZHOU Z,et al.Extraction of lithium from salt lake brine containing borate anion and high concentration of magnesium[J].Hydrometallurgy,2016,166:9-15.
[19]LEE M S.Use of the bromley equation for the analysis of ionic equilibria in mixed ferric and ferrous chloride solutions at 25°C[J].Metallurgical&Materials Transactions B,2006,37(2):173-179.
[20]XIANG W,LIANG S,ZHOU Z,et al.Lithium recovery from salt lake brine by counter-current extraction using tributyl phosphate/FeCl3in methyl isobutyl ketone[J].Hydrometallurgy,2017,171:27-32.
[21]柳培.磷酸三丁酯萃取锂的研究[J].浙江化工,2013,44(1):22-25.
[22]SONG J,HUANG T,QIU H,et al.Recovery of lithium from salt lake brine of high Mg/Li ratio using Na[FeCl4*2TBP]as extractant:Thermodynamics,kinetics and processes[J].Hydrometallurgy,2017,173:63-70.
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