分子识别技术在金属分离回收中的应用研究进展
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摘要
分子识别技术(Molecular Recognition Technology,MRT)是近年来基于超分子化学领域蓬勃发展起来的一种高选择性的分离技术。在冶金和环境治理领域,分子识别技术能有效分离及纯化金属。该技术主要由填充于分离柱上的分子识别材料(商品名SuperLig)完成分离。当携带目标离子的母液通过分子识别柱时,目标离子被选择性吸附,然后经过洗脱过程回收,最终被富集到少量的洗脱液中而再生。该处理过程环保而经济。综述了分子识别技术的发展、基本原理及其在冶金和环境治理领域分离、纯化和回收金属离子的应用研究进展,同时介绍了该技术在分离和回收核废料液中如铯、锝、锶和镭等放射性元素及矿山酸性废水中重金属的应用,并探讨了该技术的发展前景。
This paper is inclined to provide a summary overview enlightening the advancement and fundamental theory of Molecular Recognition Technology,MRT for short.In operation,the MRT system consists of the bound ligand material,brand-named SuperLig,packed into the fixed bed column.As a matter of fact,MRT is a highly selective separation technology which is founded on the theory of supra-molecular chemistry in recent years.The application of MRT has proved to be an effective treatment process for metal purification by removing the trace impurities in many hydrometallurgical circuits as well as in environmental treatment operations,by which the solution of a mixture of the target metal ion is passed through the column.And,when the target metal ion is removed selectively by means of the SuperLig product,the column can then be washed over to remove the residual feed solution,with the target metal ion recovered with a minimal quantity of affluent.In doing so,the result remains in a highly pure and concentrated product that can be preserved for its value or safe disposal.In addition,the process proves to be highly eco-environment-friendly with no organic solvents being left.Furthermore,this paper has provided a review of some examples of applications of MRT to the separation,purification and recovery of target elements and ions in metallurgical industry by removing the trace impurities and recovery of the trace metal impurities in a concentrated form in an environment-friendly manner.In the paper,we have also discussed some additional separations of interest from the pollution control,including the separation and recovery of Cs,Tc,Sr and Ra from the radioactive and mixed waste solutions and heavy metals from an acid mine drainage.And,finally,mention has also been done as to the development and extended application prospects of the technology in the future decades.
This paper is inclined to provide a summary overview enlightening the advancement and fundamental theory of Molecular Recognition Technology,MRT for short.In operation,the MRT system consists of the bound ligand material,brand-named SuperLig,packed into the fixed bed column.As a matter of fact,MRT is a highly selective separation technology which is founded on the theory of supra-molecular chemistry in recent years.The application of MRT has proved to be an effective treatment process for metal purification by removing the trace impurities in many hydrometallurgical circuits as well as in environmental treatment operations,by which the solution of a mixture of the target metal ion is passed through the column.And,when the target metal ion is removed selectively by means of the SuperLig product,the column can then be washed over to remove the residual feed solution,with the target metal ion recovered with a minimal quantity of affluent.In doing so,the result remains in a highly pure and concentrated product that can be preserved for its value or safe disposal.In addition,the process proves to be highly eco-environment-friendly with no organic solvents being left.Furthermore,this paper has provided a review of some examples of applications of MRT to the separation,purification and recovery of target elements and ions in metallurgical industry by removing the trace impurities and recovery of the trace metal impurities in a concentrated form in an environment-friendly manner.In the paper,we have also discussed some additional separations of interest from the pollution control,including the separation and recovery of Cs,Tc,Sr and Ra from the radioactive and mixed waste solutions and heavy metals from an acid mine drainage.And,finally,mention has also been done as to the development and extended application prospects of the technology in the future decades.
引文
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[11]BRADSHAW JS,KRAKOWIAKK E,TARBET B J,et al.New n-itrogen-containing macrocyclic ligands covalently attached to silica geland their use in separating metal cations[J].Solvent Extraction andIon Exchange,1989,7(5):855-864.
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[13]IZATT S R,BRUENING R L,IZATT N E,et al.An update on theapplication ofmolecular recognition technology(MRT)for Ni/Cu/Cohydrometallurgical process separations and for the purification of cobaltstreams[C]//PAUL F.Proc of the Fifth Southern African Conferenceon Base Metals.Botswana:The Southern African Institute of Miningand Metallurgy,2009:323-340.
[14]DEVENTER J V,PREEZ R D,SCOTT S,et al.Cadmium removalfrom cobalt electrolyte[C]//PAUL F.Proc of the Fourth SouthernAfrican Conference on Base Metals.Namibia:The Southern African In-stitute ofMining and Metallurgy,2007:377-392.
[15]LI Weimin(李卫民).Commercial MRT bismuth removal plant at LS-Nikko copper Inc.refinery[J].ChinaNonferrous Metallurgy(中国有色冶金),2008(1):1-5.
[16]LI Weimin(李卫民).Recent advances in the application ofmolecularrecognition technology(MRT)in copper industry[J].China Nonfer-rous Metallurgy(中国有色冶金),2007(4):1-6.
[17]LIWeimin(李卫民).A new molecular recognition technology applica-tion for bismuth removal and recovery[J].ChinaNonferrous Metallur-gy(中国有色冶金),2008(2):1-5.
[18]IZATT S R,BRUENING RL,IZATT N E,et al.The Application ofmolecular recognition technology for removal of impurities from cobaltfeed streams in the production of high purity cobalt and cobalt chem-icals[C]//ALAN T.Proc of Alta 2008 Nickel/Cobalt Conference.Australia:ALTA Metallurgical Services,2008.
[19]IZATT S R,IZATT N E,BRUENING RL.Review ofselective sepa-rations of Cobalt,Uranium,Zinc,Nickel and associated contaminantsfrom various process streams[C]//PAUL F.Proc of the Sixth South-ern African Conference on Base Metals.Phalaborwa:The SouthernAfrican Institute ofMining and Metallurgy,2011.
[20]FISHER K G.Cobalt processing developments[C]//PAUL F.Procof the Sixth Southern African Conferenceon Base Metals.Phalaborwa:The Southern African Institute of Mining and Metallurgy,2011:237-258.
[21]BELANGER S,MALONEM,IZATT N E,et al.Selective removal ofnickel from cadmium and zinc-rich sulphate electrolyte in the zinc in-dustry[C]//COURTNEY A Y.Hydrometallurgy 2008 Proceedings ofthe Sixth International Symposium.Colorado:The Society forMining,Metallurgy and Exploration,Inc,2008.
[22]TONDER G J V,CILLIERS P J,MEYER E,et al.Molecular recog-nition technology(MRT)pilot plant at the Zincor ofSouth Africa elec-trolytic zinc refinery,removing cobalt and nickel from the main purif-ication impure solution stream without using arsenic trioxide[C]//PAUL F.Proc of Copper,Cobalt,Nickel and ZincRecovery ZimbabweConference.Zimbabwe:The Southern African Institute of Mining andMetallurgy,2001:11-17.
[23]MANZIEK L.32nd annual conference of precious metals[J].Plat-inum Metals Reviews,2009,53(1):40-44.
[24]SEYMOUR R.34nd annual conference of precious metals[J].Plat-inum Metals Reviews,2011,55(1):54-58.
[25]YU Jianmin(余建民).The separation and refining technology of pre-cious metals(贵金属分离与精炼工艺学)[M].Beijing:ChemicalIndustry Press,2006:79.
[26]YU Jianmin(余建民).Solvent extraction chemistry of precious metals(贵金属萃取化学)[M].Beijing:Chemical Industry Press,2010:426-446.
[27]NEILL B.MRT-proven technology for processing metals in solutions[J].Bateman Globe,2000(16):7.
[28]HE Xiaotang(贺小塘),HAN Shouli(韩守礼),WU Xilong(吴喜龙),et al.Application ofmolecular recognition technology in platinumgroup metals refining process[J].Precious Metals(贵金属),2010,31(1):53-56.
[29]NEILL B.Micro PGM refinery for harmony mines[J].BatemanGlobe,2002(26):8.
[30]FISKUM S K,ARM S T,BLANCHARD D L.Small column ion ex-change testing ofSuperLig 644for removal of 137Csfrom hanford wastetank 241-AP-101 diluted feed(envelope A)[M].Richland:Bat-telle Pacific Northwest Division,2002.
[31]JOHN P C.Characterization of theIBC technologies SuperLig 620 sol-id phase extraction resin with applicationsfor automated process monitor-ing[D].Carolina:Environmental Engineering andScience ofClemsonUniversity,2007.
[32]IZATT S R,BRUENINGRL,KRAKOWIAKKE.Theselectivesep-aration of anions and cations in nuclearwaste using commercially avai-lable molecular recognition technology(MRT)products[C]//BRUEN-ING R L.Proc of WasteManagement Symposium Conference.Wiscon-sin:WM Symposia Inc,2003.
[33]IZATT S R,BRUENING R L,IZATT N E,et al.The application ofmolecular recognition technology(MRT)in the nuclear power cycle:from uranium mining and refining to power plant waste separation andrecovery,as well as element analysis and isotope purification-9075[C]//IZATT S R.Proc of WasteManagement Symposium Conference.Wisconsin:WM Symposia Inc,2009.
[2]FRENSDORFF H K.Stability constants of cyclic polyether complexeswith univalent cations[J].Journal of the American Chemical Society,1971,93(3):600-606.
[3]IZATT RM,BRADSHAW J S,NIELSEN S A,et al.Thermodynamicand kinetic data for cation-macrocycle interaction[J].Chemical Re-views,1985,85(4):271-339.
[4]IZATT RM,BRADSHAW J S,BRUENING R L,et al.Solid phaseextraction of ions using molecular recognition technology[J].Pure andApplied Chemistry,1995,67(7):1069-1074.
[5]IZATT N E,BRUENING R L,KRAKOWIAK K E,et al.Contribu-tions of professor ReedM Izatt to molecular recognition technology:fromlaboratory to commercial application[J].Industrial&EngineeringChemistry Research,2000,39(10):3405-3411.
[6]IZATT R M,BRADSHAW J S,BRUENING R L.Ion separation inmembrane and solid phase extraction systems[M]//DAVID N R.Supramolecular materials and technologies.New York:John Wiley&Sons Inc,1999:225-243.
[7]IZATT S R,IZATT N E,BRUENING R L.Metal separations of inter-est to the Chinese metallurgical industry[J].Journal of Rare Earths,2010,28(1):22-29.
[8]IZATT RM,PAWLAK K,BRADSHAW J S.Thermodynamic and k-inetic data for macrocycle interaction with cations,anions and neutralmolecules[J].Chemical Reviews,1995,95(7):2529-2586.
[9]IZATT R M.Review of selective ion separations at BYU using liquidmembrane and solid phase extraction procedures[J].Journal of Inclu-sion Phenomena and Macrocyclic Chemistry,1997,29(3/4):197-220.
[10]IZATT RM,BRADSHAW JS,BRUENING RL.Accomplishment ofdifficult chemical separations using solid phase extraction[J].Pureand Applied Chemistry,1996,68(6):1237-1241.
[11]BRADSHAW JS,KRAKOWIAKK E,TARBET B J,et al.New n-itrogen-containing macrocyclic ligands covalently attached to silica geland their use in separating metal cations[J].Solvent Extraction andIon Exchange,1989,7(5):855-864.
[12]BRADSHAW J S,BRUENING R L,KRAKOWIAK K E,et al.Preparation of silica ge-l bound macrocycle and their cation-bindingproperties[J].Journal of the Chemical Society,Chemical Communi-cations,1988,1(12):812-814.
[13]IZATT S R,BRUENING R L,IZATT N E,et al.An update on theapplication ofmolecular recognition technology(MRT)for Ni/Cu/Cohydrometallurgical process separations and for the purification of cobaltstreams[C]//PAUL F.Proc of the Fifth Southern African Conferenceon Base Metals.Botswana:The Southern African Institute of Miningand Metallurgy,2009:323-340.
[14]DEVENTER J V,PREEZ R D,SCOTT S,et al.Cadmium removalfrom cobalt electrolyte[C]//PAUL F.Proc of the Fourth SouthernAfrican Conference on Base Metals.Namibia:The Southern African In-stitute ofMining and Metallurgy,2007:377-392.
[15]LI Weimin(李卫民).Commercial MRT bismuth removal plant at LS-Nikko copper Inc.refinery[J].ChinaNonferrous Metallurgy(中国有色冶金),2008(1):1-5.
[16]LI Weimin(李卫民).Recent advances in the application ofmolecularrecognition technology(MRT)in copper industry[J].China Nonfer-rous Metallurgy(中国有色冶金),2007(4):1-6.
[17]LIWeimin(李卫民).A new molecular recognition technology applica-tion for bismuth removal and recovery[J].ChinaNonferrous Metallur-gy(中国有色冶金),2008(2):1-5.
[18]IZATT S R,BRUENING RL,IZATT N E,et al.The Application ofmolecular recognition technology for removal of impurities from cobaltfeed streams in the production of high purity cobalt and cobalt chem-icals[C]//ALAN T.Proc of Alta 2008 Nickel/Cobalt Conference.Australia:ALTA Metallurgical Services,2008.
[19]IZATT S R,IZATT N E,BRUENING RL.Review ofselective sepa-rations of Cobalt,Uranium,Zinc,Nickel and associated contaminantsfrom various process streams[C]//PAUL F.Proc of the Sixth South-ern African Conference on Base Metals.Phalaborwa:The SouthernAfrican Institute ofMining and Metallurgy,2011.
[20]FISHER K G.Cobalt processing developments[C]//PAUL F.Procof the Sixth Southern African Conferenceon Base Metals.Phalaborwa:The Southern African Institute of Mining and Metallurgy,2011:237-258.
[21]BELANGER S,MALONEM,IZATT N E,et al.Selective removal ofnickel from cadmium and zinc-rich sulphate electrolyte in the zinc in-dustry[C]//COURTNEY A Y.Hydrometallurgy 2008 Proceedings ofthe Sixth International Symposium.Colorado:The Society forMining,Metallurgy and Exploration,Inc,2008.
[22]TONDER G J V,CILLIERS P J,MEYER E,et al.Molecular recog-nition technology(MRT)pilot plant at the Zincor ofSouth Africa elec-trolytic zinc refinery,removing cobalt and nickel from the main purif-ication impure solution stream without using arsenic trioxide[C]//PAUL F.Proc of Copper,Cobalt,Nickel and ZincRecovery ZimbabweConference.Zimbabwe:The Southern African Institute of Mining andMetallurgy,2001:11-17.
[23]MANZIEK L.32nd annual conference of precious metals[J].Plat-inum Metals Reviews,2009,53(1):40-44.
[24]SEYMOUR R.34nd annual conference of precious metals[J].Plat-inum Metals Reviews,2011,55(1):54-58.
[25]YU Jianmin(余建民).The separation and refining technology of pre-cious metals(贵金属分离与精炼工艺学)[M].Beijing:ChemicalIndustry Press,2006:79.
[26]YU Jianmin(余建民).Solvent extraction chemistry of precious metals(贵金属萃取化学)[M].Beijing:Chemical Industry Press,2010:426-446.
[27]NEILL B.MRT-proven technology for processing metals in solutions[J].Bateman Globe,2000(16):7.
[28]HE Xiaotang(贺小塘),HAN Shouli(韩守礼),WU Xilong(吴喜龙),et al.Application ofmolecular recognition technology in platinumgroup metals refining process[J].Precious Metals(贵金属),2010,31(1):53-56.
[29]NEILL B.Micro PGM refinery for harmony mines[J].BatemanGlobe,2002(26):8.
[30]FISKUM S K,ARM S T,BLANCHARD D L.Small column ion ex-change testing ofSuperLig 644for removal of 137Csfrom hanford wastetank 241-AP-101 diluted feed(envelope A)[M].Richland:Bat-telle Pacific Northwest Division,2002.
[31]JOHN P C.Characterization of theIBC technologies SuperLig 620 sol-id phase extraction resin with applicationsfor automated process monitor-ing[D].Carolina:Environmental Engineering andScience ofClemsonUniversity,2007.
[32]IZATT S R,BRUENINGRL,KRAKOWIAKKE.Theselectivesep-aration of anions and cations in nuclearwaste using commercially avai-lable molecular recognition technology(MRT)products[C]//BRUEN-ING R L.Proc of WasteManagement Symposium Conference.Wiscon-sin:WM Symposia Inc,2003.
[33]IZATT S R,BRUENING R L,IZATT N E,et al.The application ofmolecular recognition technology(MRT)in the nuclear power cycle:from uranium mining and refining to power plant waste separation andrecovery,as well as element analysis and isotope purification-9075[C]//IZATT S R.Proc of WasteManagement Symposium Conference.Wisconsin:WM Symposia Inc,2009.