溶剂萃取法分离锂同位素研究进展
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摘要
锂同位素(6Li和7Li)在原子能工业中占据着重要的地位。在众多锂同位素的分离方法和体系中,溶剂萃取法是一种具有较高分离系数,并最有望实现无毒、高效分离的工业生产方法。阐述了溶剂萃取法分离锂同位素的原理,综述了醇类与酮类、烷基膦与膦酸脂类、冠醚类及其它溶剂萃取体系在锂同位素分离中的研究现状及趋势,并展望了溶剂萃取法在锂同位素分离和未来青海、西藏盐湖锂资源高值化利用中的潜在应用前景。
The two naturally occurring isotopes of lithium(6Li and7Li) occupy important roles in the atomic energy industry. Among the methods for the separation of lithium isotopes,solvent extraction is a method which not only have a higher isotope separation factor,but also is the most promising method expected to achieve industrial production with nontoxicity and higher efficient. Hence,in this paper,we simply illustrate the method of solvent extraction separation of lithium isotopes,and summarizes the alcohols and ketones,the alkylphosphines and phosphonates,the crown ethers and the other solvent extraction systems in the separation of lithium isotope. We also prospect its potential applications in separation of lithium isotopes and to develop a high-value utilization of lithium resources in salt lakes of Qinghai and Tibet.
The two naturally occurring isotopes of lithium(6Li and7Li) occupy important roles in the atomic energy industry. Among the methods for the separation of lithium isotopes,solvent extraction is a method which not only have a higher isotope separation factor,but also is the most promising method expected to achieve industrial production with nontoxicity and higher efficient. Hence,in this paper,we simply illustrate the method of solvent extraction separation of lithium isotopes,and summarizes the alcohols and ketones,the alkylphosphines and phosphonates,the crown ethers and the other solvent extraction systems in the separation of lithium isotope. We also prospect its potential applications in separation of lithium isotopes and to develop a high-value utilization of lithium resources in salt lakes of Qinghai and Tibet.
引文
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[2]Xiang Y,Zhu Z,Xiang X.Problems of Lithium Isotope Research in Salt Lake Study[J].Acta Geologica Sinica(English Edition),2014,88(s1):165-166.
[3]National Research Council(US).Committee on Separations Technology,Transmutation Systems.Nuclear wastes:technologies for separations and transmutation[M].National Academies Press,1996.
[4]陈耀焕.溶剂萃取分离锂同位素概况[J].稀有金属,1983,(4):79-87.
[5]李廷伍.化学交换法分离锂同位素[J].原子能科学技术,1990:87-90.
[6]顾志国,李在均,杨杰.锂同位素分离[J].化学进展,2011,(9):1892-1905.
[7]刘华,黄祚刚,文珂,等.多齿络合法分离锂同位素的冠醚化学[J].有机化学,2013,34(2):316-324.
[8]Bigeleisen J,Mayer M G.Calculation of equilibrium constants for isotopic exchange reactions[J].The Journal of Chemical Physics,1947,15(5):261-267.
[9]Betts R H,Bron J.A Discussion of Partial Isotope Separation by Means of Solvent Extraction[J].Separation Science,1977,12(6):635-639.
[10]姜延林,张心祥,钱建华,等.锂盐-冠醚络合物化学交换体系中的同位素效应[J].原子能科学技术,1986,(1):2-8.
[11]Deb A K S,Ali S M,Shenoy K T,et al.Nano Cavity Induced Isotope Separation of Zinc:Density Functional Theoretical Modeling[J].Journal of Chemical&Engineering Data,2014,59(8):2472-2484.
[12]Taylor T I,Urey H C.On the electrolytic and chemical exchange methods for the separation of the lithium isotopes[J].The Journal of Chemical Physics,1937,5(7):597-598.
[13]Drury J S.United States Atomic Energy Commission,1951,Y-785.
[14]Martin F S,Holt R J W.Liquid-liquid extraction in inorganic chemistry[J].Q.Rev.Chem.Soc.,1959,13(4):327-352.
[15]Lee D A.Isotope Effect in chemistry Processes,Advance in Chemistry,Series,1969,89,57.
[16]许庆仁.从氯化镁饱和溶液中萃取锂的研究[J].有机化学,1979,(1):13-33.
[17]Pedersen C J.Cyclic polyethers and their complexes with metal salts[J].Journal of the American Chemical Society,1967,89(26):7017-7036.
[18]Jepson B E,Cairns G A.Lithium isotope effects in chemical exchange with(2,2,1)cryptand[R].Mound Facility,Miamisburg,OH(USA),1979.
[19]支克正,窦富全,朱建华,等.冠醚分离锂同位素研究Ⅰ.锂盐-穴醚两相交换体系的锂同位素效应[J].原子能科学技术,1982,(6):686-690.
[20]方胜强,支克正,傅立安,等.用冠醚C(401)分离锂同位素[J].兰州大学学报:自然科学版,1982,18(4):187.
[21]支克正,窦富全,杨坤山,等.冠醚分离锂同位素研究Ⅱ.锂盐-冠醚两相交换体系的锂同位素效应[J].原子能科学技术,1983,(3):347-352,339.
[22]Nishizawa K,Ishino S,Watanabe H,et al.Lithium isotope separation by liquid-liquid extraction using benzo-15-crown-5[J].Journal of Nuclear Science and Technology,1984,21(9):694-701.
[23]方胜强,傅立安,张复昇,等.4,4’-二叔丁基二苯并-30-冠-10与硫氰酸锂络合过程中锂的同位素效应[J].核化学与放射化学,1984,(1):40.
[24]方胜强,支克正,傅立安等.4-叔丁基苯并-15-冠-5液-液萃取法分离锂同位素[J].核化学与放射化学,1987,(3):142-147.
[25]Nishizawa K,Takano T,Ikeda I,et al.Extractive separation of lithium isotopes by crown ethers[J].Separation Science and Technology,1988,23(4-5):333-345.
[26]Nishizawa K,Takano T.Extractive separation of lithium isotopes using benzo-15-crown-5.Effect of salt concentration[J].Separation Science and Technology,1988,23(6-7):751-757.
[27]傅立安,方胜强,姚钟麒,等.多醚液-液萃取体系中各种因素对锂的热力学同位素效应的影响[J].核化学与放射化学,1989,11(3):142-420.
[28]方胜强,傅立安.多醚萃取体系中锂的同位素效应-盐浓效应[J].同位素,1991,(3):166-173.
[29]方胜强,高志昌.对甲苯氧基联苯桥联双苯并-15-冠-5分离锂同位素的能力[J].核化学与放射化学,1992,14(2):111-113.
[30]方胜强,傅立安.冠醚萃取体系中锂的同位素效应-混合锂盐效应[J].同位素,1994,(3):168-171.
[31]Fang S,Fu L.Extractive separation of lithium isotopes by 4-tert-butylbenzo-15-crown-5[J].Journal of radioanalytical and nuclear chemistry,1994,187(1):25-32.
[32]金建南,王全基,孟明礼,等.用开链冠醚PAIV溶剂萃取分离锂同位素[J].四川大学学报:自然科学版,1999,(36):903-906.
[33]Davoudi M,Mallah M H.Enrichment of 6 Li using dispersive liquid-liquid microextraction as a highly efficient technique[J].Annals of Nuclear Energy,2013,(62):499-503.
[34]Sun X L,Zhou W,Gu L.,et al.Liquid-liquid extraction to lithium isotope separation based on room-temperature ionic liquids containing 2,2’-binaphthyldiyl-17-crown-5[J].Journal of Nuclear Science and Technology,2015,52(3):332-341.
[35]陈耀焕,严金英,吴甫炳,等.溶剂萃取分离锂同位素研究Ⅰ.苏丹Ⅰ-中性配位体协萃体系萃取分离锂同位素效应[J].原子能科学技术,1987,(4):433-440.
[36]陈耀焕,严金英,李永坤,等.溶剂萃取分离锂同位素研究Ⅱ.苏丹Ⅰ-中性配位体协萃体系萃取分离锂同位素效应探讨[J].原子能科学技术,1987,(5):536-544.
[37]Grote Z,Wizemann H.D,Scopelliti R,et al.Lithium Isotope Separation by 12-Metallacrown-3 Complexes[J].Zeitschrift für anorganische und allgemeine Chemie,2007,633(5-6):858-864.
[38]Xu J J,Li Z J,Gu Z G,et al.Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent[J].Journal of Radioanalytical and Nuclear Chemistry,2013,295(3):2103-2110.
[39]周文.锂同位素萃取分离新体系的研究[D].无锡:江南大学,2014.
[40]中国科学院上海有机化学研究所.一种用于分离锂同位素的萃取剂及其应用:中国.103801194A[P].2014-05-21.
[2]Xiang Y,Zhu Z,Xiang X.Problems of Lithium Isotope Research in Salt Lake Study[J].Acta Geologica Sinica(English Edition),2014,88(s1):165-166.
[3]National Research Council(US).Committee on Separations Technology,Transmutation Systems.Nuclear wastes:technologies for separations and transmutation[M].National Academies Press,1996.
[4]陈耀焕.溶剂萃取分离锂同位素概况[J].稀有金属,1983,(4):79-87.
[5]李廷伍.化学交换法分离锂同位素[J].原子能科学技术,1990:87-90.
[6]顾志国,李在均,杨杰.锂同位素分离[J].化学进展,2011,(9):1892-1905.
[7]刘华,黄祚刚,文珂,等.多齿络合法分离锂同位素的冠醚化学[J].有机化学,2013,34(2):316-324.
[8]Bigeleisen J,Mayer M G.Calculation of equilibrium constants for isotopic exchange reactions[J].The Journal of Chemical Physics,1947,15(5):261-267.
[9]Betts R H,Bron J.A Discussion of Partial Isotope Separation by Means of Solvent Extraction[J].Separation Science,1977,12(6):635-639.
[10]姜延林,张心祥,钱建华,等.锂盐-冠醚络合物化学交换体系中的同位素效应[J].原子能科学技术,1986,(1):2-8.
[11]Deb A K S,Ali S M,Shenoy K T,et al.Nano Cavity Induced Isotope Separation of Zinc:Density Functional Theoretical Modeling[J].Journal of Chemical&Engineering Data,2014,59(8):2472-2484.
[12]Taylor T I,Urey H C.On the electrolytic and chemical exchange methods for the separation of the lithium isotopes[J].The Journal of Chemical Physics,1937,5(7):597-598.
[13]Drury J S.United States Atomic Energy Commission,1951,Y-785.
[14]Martin F S,Holt R J W.Liquid-liquid extraction in inorganic chemistry[J].Q.Rev.Chem.Soc.,1959,13(4):327-352.
[15]Lee D A.Isotope Effect in chemistry Processes,Advance in Chemistry,Series,1969,89,57.
[16]许庆仁.从氯化镁饱和溶液中萃取锂的研究[J].有机化学,1979,(1):13-33.
[17]Pedersen C J.Cyclic polyethers and their complexes with metal salts[J].Journal of the American Chemical Society,1967,89(26):7017-7036.
[18]Jepson B E,Cairns G A.Lithium isotope effects in chemical exchange with(2,2,1)cryptand[R].Mound Facility,Miamisburg,OH(USA),1979.
[19]支克正,窦富全,朱建华,等.冠醚分离锂同位素研究Ⅰ.锂盐-穴醚两相交换体系的锂同位素效应[J].原子能科学技术,1982,(6):686-690.
[20]方胜强,支克正,傅立安,等.用冠醚C(401)分离锂同位素[J].兰州大学学报:自然科学版,1982,18(4):187.
[21]支克正,窦富全,杨坤山,等.冠醚分离锂同位素研究Ⅱ.锂盐-冠醚两相交换体系的锂同位素效应[J].原子能科学技术,1983,(3):347-352,339.
[22]Nishizawa K,Ishino S,Watanabe H,et al.Lithium isotope separation by liquid-liquid extraction using benzo-15-crown-5[J].Journal of Nuclear Science and Technology,1984,21(9):694-701.
[23]方胜强,傅立安,张复昇,等.4,4’-二叔丁基二苯并-30-冠-10与硫氰酸锂络合过程中锂的同位素效应[J].核化学与放射化学,1984,(1):40.
[24]方胜强,支克正,傅立安等.4-叔丁基苯并-15-冠-5液-液萃取法分离锂同位素[J].核化学与放射化学,1987,(3):142-147.
[25]Nishizawa K,Takano T,Ikeda I,et al.Extractive separation of lithium isotopes by crown ethers[J].Separation Science and Technology,1988,23(4-5):333-345.
[26]Nishizawa K,Takano T.Extractive separation of lithium isotopes using benzo-15-crown-5.Effect of salt concentration[J].Separation Science and Technology,1988,23(6-7):751-757.
[27]傅立安,方胜强,姚钟麒,等.多醚液-液萃取体系中各种因素对锂的热力学同位素效应的影响[J].核化学与放射化学,1989,11(3):142-420.
[28]方胜强,傅立安.多醚萃取体系中锂的同位素效应-盐浓效应[J].同位素,1991,(3):166-173.
[29]方胜强,高志昌.对甲苯氧基联苯桥联双苯并-15-冠-5分离锂同位素的能力[J].核化学与放射化学,1992,14(2):111-113.
[30]方胜强,傅立安.冠醚萃取体系中锂的同位素效应-混合锂盐效应[J].同位素,1994,(3):168-171.
[31]Fang S,Fu L.Extractive separation of lithium isotopes by 4-tert-butylbenzo-15-crown-5[J].Journal of radioanalytical and nuclear chemistry,1994,187(1):25-32.
[32]金建南,王全基,孟明礼,等.用开链冠醚PAIV溶剂萃取分离锂同位素[J].四川大学学报:自然科学版,1999,(36):903-906.
[33]Davoudi M,Mallah M H.Enrichment of 6 Li using dispersive liquid-liquid microextraction as a highly efficient technique[J].Annals of Nuclear Energy,2013,(62):499-503.
[34]Sun X L,Zhou W,Gu L.,et al.Liquid-liquid extraction to lithium isotope separation based on room-temperature ionic liquids containing 2,2’-binaphthyldiyl-17-crown-5[J].Journal of Nuclear Science and Technology,2015,52(3):332-341.
[35]陈耀焕,严金英,吴甫炳,等.溶剂萃取分离锂同位素研究Ⅰ.苏丹Ⅰ-中性配位体协萃体系萃取分离锂同位素效应[J].原子能科学技术,1987,(4):433-440.
[36]陈耀焕,严金英,李永坤,等.溶剂萃取分离锂同位素研究Ⅱ.苏丹Ⅰ-中性配位体协萃体系萃取分离锂同位素效应探讨[J].原子能科学技术,1987,(5):536-544.
[37]Grote Z,Wizemann H.D,Scopelliti R,et al.Lithium Isotope Separation by 12-Metallacrown-3 Complexes[J].Zeitschrift für anorganische und allgemeine Chemie,2007,633(5-6):858-864.
[38]Xu J J,Li Z J,Gu Z G,et al.Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent[J].Journal of Radioanalytical and Nuclear Chemistry,2013,295(3):2103-2110.
[39]周文.锂同位素萃取分离新体系的研究[D].无锡:江南大学,2014.
[40]中国科学院上海有机化学研究所.一种用于分离锂同位素的萃取剂及其应用:中国.103801194A[P].2014-05-21.
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