N,N′-二甲基-N,N′-二辛基-3-氧杂-戊二酰胺对Np(Ⅳ,Ⅴ,Ⅵ)的萃取行为

    Extraction of Np(Ⅳ,Ⅴ,Ⅵ) With N,N′-Dimethyl-N,N′-Dioctyl-3-Oxa-Glutaramide

    • 摘要: 237Np半衰期较长,具有较高的生物毒性,使其成为高放废液非α化过程中重点关注的核素之一。本工作采用新型的N,N′-二甲基-N,N′-二辛基-3-氧杂-戊二酰胺(DMDODGA)为萃取剂,研究了萃取剂浓度、水相初始硝酸浓度和温度等因素对DMDODGA萃取Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的影响。结果表明:随着DMDODGA浓度和水相初始硝酸浓度的增加,Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的分配比均增大。萃取剂浓度小于0.005 mol/L时,DMDODGA与Np(Ⅳ)生成1∶2型萃合物;萃取剂浓度大于0.005 mol/L时,DMDODGA与Np(Ⅳ)生成1∶3型萃合物。萃取剂浓度在0.1~1.0 mol/L范围内,DMDODGA与Np(Ⅴ)、Np(Ⅵ)均生成1∶2型萃合物。DMDODGA萃取Np(Ⅳ)、Np(Ⅴ)、Np(Ⅵ)的ΔH分别为-59.55、-22.02、-31.40 kJ/mol,3个反应均为放热反应,降低温度有利于反应的正向进行。

       

      Abstract: 237Np is one of the key nuclides in non-α process of high level liquid waste because of long half-life and high biotoxicity. In this work, the effects of extractant concentration, initial nitric acid concentration and temperature were studied for Np(Ⅳ), Np(Ⅴ), Np(Ⅵ) extraction process. The result shows that the increasement of concentration of N,N′-dimethyl-N, N′-dioctyl-3-oxa-glutaramide(DMDODGA) and initial nitric acid can enhance the distribution ratios of Np(Ⅳ), Np(Ⅴ), Np(Ⅵ). When the concentration of DMDODGA is lower than 0.005 mol/L, 1∶2-type complexe is found for Np(Ⅳ). When the concentration of DMDODGA is higher than 0.005 mol/L, 1∶3-type complexe is found for Np(Ⅳ). 1∶2-type complexe is found for Np(Ⅴ) and Np(Ⅵ), when the concentration of DMDODGA is in the range of 0.1-1.0 mol/L. The extractions between DMDODGA and Np(Ⅳ), Np(Ⅴ), Np(Ⅵ) are exothermic reactions. The enthalpy changes are -5955 kJ/mol, -22.02 kJ/mol and -31.40 kJ/mol, respectively. The decrease of temperature is benefit for the reaction.

       

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