TODGA-DHOA体系萃取金属离子 Ⅱ.对Pu(Ⅲ,Ⅳ,Ⅵ)的萃取
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摘要
研究了以N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)和N,N-二己基辛酰胺(DHOA)为萃取剂,正十二烷为稀释剂体系对Pu(Ⅲ)、Pu(Ⅳ)和Pu(Ⅵ)的萃取行为,主要考察了萃取剂浓度、HNO3浓度和NaNO3浓度的影响。结果表明:TODGA和DHOA对Pu(Ⅲ)、Pu(Ⅳ)和Pu(Ⅵ)的萃取分配比大小顺序均为:D(Pu(Ⅲ))>D(Pu(Ⅳ))>D(Pu(Ⅵ)),TODGA/正十二烷体系中加入DHOA时,对Pu(Ⅲ,Ⅳ,Ⅵ)萃取具有一定抑制作用,但在较高酸度范围内(≥3.0mol/L HNO3),不论体系中Pu的价态为何种形式,TODGA均能对其进行有效的回收。TODGA萃取Pu(Ⅲ,Ⅳ,Ⅵ)的方程式分别为:Pu3++3NO-3a+4TODGA。→Pu(NO3)3.4TODGA。Pu4+a+4NO-3a+3TODGA。→Pu(NO3)4.3TODGA。PuO2+2a+2NO-3a+2TODGA。→PuO2(NO3)2.2TODGA。
The recovery of uranium and plutonium from the spent nuclear fuel by Purex reprocess is a well-established technology on an industrial scale.However,about 0.5%Pu enter the raffinate flows(high-level liquid waste).From the disposal of waste and environmental concern,this fraction of Pu must be separated and recovered from HLLW.Recently developed N,N,N′,N′-tetraoctyl diglycolamide(TODGA) has been identified as one of the most promising extractants being considered for the partitioning of trivalent actinides and lanthanides from HLLW solutions.In the present paper,extraction characteristics of TODGA and N,N-dihexyl-octanamide(DHOA),for Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ),from nitric acid solutions were studied.The effects of concentration of the nitric acid,salting-out agents in aqueous phase and the extractant in organic phase on distribution ratios were examined.The results show that Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) are well extracted by TODGA.The order of distribution ratios of Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) ions by TODGA is D(Pu(Ⅲ))>D(Pu(Ⅳ))>D(Pu(Ⅵ)).After adding DHOA to TODGA/dodecane system,the distribution ratios of Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) decrease with increasing of the concentration of DHOA,but the distribution ratios are large enough for recovery of them from aqueous HNO3 solution.The extraction equations of Pu(Ⅲ,Ⅳ,Ⅵ) ions by TODGA are deduced as follows: Pu3++3NO-3a+4TODGA。→Pu(NO3)3·4TODGA。 Pu4+a+4NO-3a+3TODGA。→Pu(NO3)4·3TODGA。 PuO2+2a+2NO-3a+2TODGA。→PuO2(NO3)2·2TODGA。
The recovery of uranium and plutonium from the spent nuclear fuel by Purex reprocess is a well-established technology on an industrial scale.However,about 0.5%Pu enter the raffinate flows(high-level liquid waste).From the disposal of waste and environmental concern,this fraction of Pu must be separated and recovered from HLLW.Recently developed N,N,N′,N′-tetraoctyl diglycolamide(TODGA) has been identified as one of the most promising extractants being considered for the partitioning of trivalent actinides and lanthanides from HLLW solutions.In the present paper,extraction characteristics of TODGA and N,N-dihexyl-octanamide(DHOA),for Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ),from nitric acid solutions were studied.The effects of concentration of the nitric acid,salting-out agents in aqueous phase and the extractant in organic phase on distribution ratios were examined.The results show that Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) are well extracted by TODGA.The order of distribution ratios of Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) ions by TODGA is D(Pu(Ⅲ))>D(Pu(Ⅳ))>D(Pu(Ⅵ)).After adding DHOA to TODGA/dodecane system,the distribution ratios of Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) decrease with increasing of the concentration of DHOA,but the distribution ratios are large enough for recovery of them from aqueous HNO3 solution.The extraction equations of Pu(Ⅲ,Ⅳ,Ⅵ) ions by TODGA are deduced as follows: Pu3++3NO-3a+4TODGA。→Pu(NO3)3·4TODGA。 Pu4+a+4NO-3a+3TODGA。→Pu(NO3)4·3TODGA。 PuO2+2a+2NO-3a+2TODGA。→PuO2(NO3)2·2TODGA。
引文
[1]Nash K L,Lumetta G J.Advanced SeparationTechniques for Nuclear Fuel Reprocessing and Radio-active Waste Treatment[M].England:WoodheadPublishing Series in Energy:Number 2,2011.
[2]Ozawa M,Koma Y,Nomura K,et al.Separationof Actinides and Fission Products in High-LevelLiquid Wastes by the Improved TRUEX Process[J].J Alloys Compd,1998(271-273):538-543.
[3]Rizvi G H,Mathur J N.Stripping of Actinides,Fission and Corrosion Products From LoadedTRUEX Solvent(0.2M CMPO+1.2M TBP inDodecane)Phase Using Potassium Ferrocyanide[J].J Radioanal Nucl Chem,2002,253(1):179-181.
[4]Morita Y,Glatz J P,Kubota M,et al.ActinidePartitioning From HLW in a Continuous DIDPAExtraction Process by Means of Centrifugal Extrac-tors[J].Solvent Extr Ion Exch,1996,14(3):385-400.
[5]Watanabe M,Tatsugae R,Morita Y,et al.Back-Extraction of Tri-and Tetravalent Actinides FromDiisodecylphosphoric Acid(DIDPA)With Hydra-zine Carbonate[J].J Radioanal Nucl Chem,2002,252(1):53-57.
[6]郑华铃.三烷基氧膦萃取流程及其应用前景[J].乏燃料管理及后处理,1995(7/8):1-32.
[7]Zhu Y J,Jiao R Z.Chinese Experience in theRemoval of Actinides From Highly Active Waste byTrialkylphosphine Oxide Extraction[J].Nucl Tech-nol,1994,108(3):361-369.
[8]陈靖,王建晨.从高放废液中去除锕系元素的TRPO流程发展三十年[J].化学进展,2011,23(7):1366-1 371.
[9]宋崇立,Glatz J P,Koch L,等.从高放废液中去除超铀元素的流程热实验[J].清华大学学报(自然科学版),1996,36(6):102-110.
[10]Cuillerdier C,Musikas C,Nigond L.Diamides asActinide Extractants for Various Waste Treatments[J].Sep Sci Technol,1993,28:155-159.
[11]Mahajan G R,Prabhu D R,Manchanda V K,et al.Substituted Malonamides as Extractants for Parti-tioning of Actinides From Nuclear Waste Solutions[J].Waste Management,1998,18:125-133.
[12]Narita H,Yaita T,Tamura K,et al.SolventExtraction of Trivalent Lanthanoid Ions With N,N′-Dimethyl-N,N′-Diphenyl-3-Oxapentanediamide[J].Radiochim Acta,1998,81:223-226.
[13]Narita H,Yaita T,Tamura K,et al.Study on theExtraction of Trivalent Lanthanide Ions With N,N′-Dimethyl-N,N′-Diphenyl-Malonamide and Diglyco-lamide[J].J Radioanal Nucl Chem,1999,239:381-384.
[14]Sasaki Y,Sugo Y,Suzuki S,et al.The NovelExtractants,Diglycolamides,for the Extraction ofLanthanides and Actinides in HNO3-n-DodecaneSystem[J].Solvent Extr Ion Exch,2001,19:91-103.
[15]Tachimori S,Sasaki Y,Suzuki S.Modification ofTODGA n-Dodecane Solvent With a Monoamide forHigh Loading of Lanthanides(Ⅲ)and Actinides(Ⅲ)[J].Solvent Extr Ion Exch,2002,20(6):687-699.
[16]Suzuki H,Sasaki Y,Sugo Y,et al.Extraction andSeparation of Am(Ⅲ)and Sr(Ⅱ)by N,N,N′,N′-Tetraoctyl-3-Oxapentanediamide(TODGA)[J].Radio-chim Acta,2004,92:463-566.
[17]Tachimori S,Suzuki S,Sasaki Y,et al.SolventExtraction of Alkaline Earth Metal Ions by Digly-colic Amides From Nitric Acid Solutions[J].Sol-vent Extr Ion Exch,2003,21(5):707-715.
[18]朱文彬,叶国安,李峰峰,等.TODGA-DHOA体系从硝酸介质中萃取碱土金属[J].核化学与放射化学,2011,33(6):328-334.
[19]朱文彬,叶国安,李峰峰,等,TODGA-DHOA体系萃取金属离子Ⅰ:对Np(Ⅳ,Ⅴ,Ⅵ)的萃取[J].核化学与放射化学,2012,34(5):262-268.
[20]Morita Y,Sasakki Y,Tachimori S.Actinide Sepa-ration by TODGA Extraction[C]∥JAERI-Conf2002-004:255-260.
[21]Magnusson D,Christiansen B,Glatz J-P,et al.Partitioning of Minor Actinides From Purex Raffi-nate by the TODGA Process[C]∥Proceedings ofGlobal 2007.Boise,Idaho,USA,Sep.9-13,2007:713-718.
[22]Modolo G,Asp H,Vijgen H,et al.Demonstrationof a TODGA/TBP Process for Recovery of Triva-lent Actinides and Lanthanides From a Purex Raffi-nate[C]∥Proceedings of Global 2007.Boise,Idaho,USA,Sep.9-13,2007:1 111-1 116.
[2]Ozawa M,Koma Y,Nomura K,et al.Separationof Actinides and Fission Products in High-LevelLiquid Wastes by the Improved TRUEX Process[J].J Alloys Compd,1998(271-273):538-543.
[3]Rizvi G H,Mathur J N.Stripping of Actinides,Fission and Corrosion Products From LoadedTRUEX Solvent(0.2M CMPO+1.2M TBP inDodecane)Phase Using Potassium Ferrocyanide[J].J Radioanal Nucl Chem,2002,253(1):179-181.
[4]Morita Y,Glatz J P,Kubota M,et al.ActinidePartitioning From HLW in a Continuous DIDPAExtraction Process by Means of Centrifugal Extrac-tors[J].Solvent Extr Ion Exch,1996,14(3):385-400.
[5]Watanabe M,Tatsugae R,Morita Y,et al.Back-Extraction of Tri-and Tetravalent Actinides FromDiisodecylphosphoric Acid(DIDPA)With Hydra-zine Carbonate[J].J Radioanal Nucl Chem,2002,252(1):53-57.
[6]郑华铃.三烷基氧膦萃取流程及其应用前景[J].乏燃料管理及后处理,1995(7/8):1-32.
[7]Zhu Y J,Jiao R Z.Chinese Experience in theRemoval of Actinides From Highly Active Waste byTrialkylphosphine Oxide Extraction[J].Nucl Tech-nol,1994,108(3):361-369.
[8]陈靖,王建晨.从高放废液中去除锕系元素的TRPO流程发展三十年[J].化学进展,2011,23(7):1366-1 371.
[9]宋崇立,Glatz J P,Koch L,等.从高放废液中去除超铀元素的流程热实验[J].清华大学学报(自然科学版),1996,36(6):102-110.
[10]Cuillerdier C,Musikas C,Nigond L.Diamides asActinide Extractants for Various Waste Treatments[J].Sep Sci Technol,1993,28:155-159.
[11]Mahajan G R,Prabhu D R,Manchanda V K,et al.Substituted Malonamides as Extractants for Parti-tioning of Actinides From Nuclear Waste Solutions[J].Waste Management,1998,18:125-133.
[12]Narita H,Yaita T,Tamura K,et al.SolventExtraction of Trivalent Lanthanoid Ions With N,N′-Dimethyl-N,N′-Diphenyl-3-Oxapentanediamide[J].Radiochim Acta,1998,81:223-226.
[13]Narita H,Yaita T,Tamura K,et al.Study on theExtraction of Trivalent Lanthanide Ions With N,N′-Dimethyl-N,N′-Diphenyl-Malonamide and Diglyco-lamide[J].J Radioanal Nucl Chem,1999,239:381-384.
[14]Sasaki Y,Sugo Y,Suzuki S,et al.The NovelExtractants,Diglycolamides,for the Extraction ofLanthanides and Actinides in HNO3-n-DodecaneSystem[J].Solvent Extr Ion Exch,2001,19:91-103.
[15]Tachimori S,Sasaki Y,Suzuki S.Modification ofTODGA n-Dodecane Solvent With a Monoamide forHigh Loading of Lanthanides(Ⅲ)and Actinides(Ⅲ)[J].Solvent Extr Ion Exch,2002,20(6):687-699.
[16]Suzuki H,Sasaki Y,Sugo Y,et al.Extraction andSeparation of Am(Ⅲ)and Sr(Ⅱ)by N,N,N′,N′-Tetraoctyl-3-Oxapentanediamide(TODGA)[J].Radio-chim Acta,2004,92:463-566.
[17]Tachimori S,Suzuki S,Sasaki Y,et al.SolventExtraction of Alkaline Earth Metal Ions by Digly-colic Amides From Nitric Acid Solutions[J].Sol-vent Extr Ion Exch,2003,21(5):707-715.
[18]朱文彬,叶国安,李峰峰,等.TODGA-DHOA体系从硝酸介质中萃取碱土金属[J].核化学与放射化学,2011,33(6):328-334.
[19]朱文彬,叶国安,李峰峰,等,TODGA-DHOA体系萃取金属离子Ⅰ:对Np(Ⅳ,Ⅴ,Ⅵ)的萃取[J].核化学与放射化学,2012,34(5):262-268.
[20]Morita Y,Sasakki Y,Tachimori S.Actinide Sepa-ration by TODGA Extraction[C]∥JAERI-Conf2002-004:255-260.
[21]Magnusson D,Christiansen B,Glatz J-P,et al.Partitioning of Minor Actinides From Purex Raffi-nate by the TODGA Process[C]∥Proceedings ofGlobal 2007.Boise,Idaho,USA,Sep.9-13,2007:713-718.
[22]Modolo G,Asp H,Vijgen H,et al.Demonstrationof a TODGA/TBP Process for Recovery of Triva-lent Actinides and Lanthanides From a Purex Raffi-nate[C]∥Proceedings of Global 2007.Boise,Idaho,USA,Sep.9-13,2007:1 111-1 116.