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化学进展 2011, Vol. 23 Issue (7): 1338-1344 前一篇   后一篇

• 放射化学专辑 •

二烃基二硫代膦酸萃取分离三价锕系与镧系元素研究

陈靖*, 王芳, 何喜红, 盘登芳   

  1. 清华大学核能与新能源技术研究院 北京 100084
  • 收稿日期:2011-03-01 修回日期:2011-04-01 出版日期:2011-07-24 发布日期:2012-03-15
  • 通讯作者: e-mail:jingxia@tsinghua.edu.cn E-mail:jingxia@tsinghua.edu.cn
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Studies on Separating Trivalent Actinides from Lanthanides by Dialkyldithiophosphinic Acid Extraction

Chen Jing*, Wang Fang, He Xihong, Pan Dengfang   

  1. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China
  • Received:2011-03-01 Revised:2011-04-01 Online:2011-07-24 Published:2012-03-15

三价锕系与镧系元素的有效分离是实现“分离-嬗变”先进燃料循环的关键环节之一。然而,由于三价锕系与镧系元素的物理化学性质极为接近,其有效分离一直是分离领域的难题之一。在溶剂萃取分离法中,含S、N等软配体的萃取剂表现出良好的分离性能。1995年,商业试剂Cyanex 301被发现能够从常量镧系元素中有效分离三价锕系元素,随后发现其纯化产品二(2,4,4-三甲基戊基)二硫代膦酸对示踪量和常量的镧系元素中的三价锕系都具有非常好的萃取分离效果,并提出了分离工艺,进行了热实验验证。机理研究结果表明,二(2,4,4-三甲基戊基)二硫代膦与三价锕系或镧系元素形成的配合物中以八配位的立方体为主。烃基换成苯基或氯苯等基团之后,没有分离效果,但在磷酸三烃基酯等中性萃取剂协萃条件下,具有一定的分离效果。最近发现烃基换成o-三氟甲基苯基后,可以获得非常好的分离效果。虽然二烃基二硫代膦酸的稳定性还期望进一步提高,对其萃取分离机理的认识还有待深入,但是由于其卓越的分离性能,在三价锕系与镧系元素分离应用中具有良好的应用前景。

关键词： 锕系, 镧系, 萃取分离, 二烃基二硫代膦酸

The effective separation of trivalent actinides from lanthanides is one of key steps to realizing the advanced nuclear fuel cycle based on “partitioning-transmutation”. However, their effective separation is always one of difficulties in the separation field because of the very similar physical and chemical properties between trivalent actinides and lanthanides. In the separation by solvent extraction, ligands containing soft donor S, N show good performance to separate trivalent actinides from lanthanides. In 1995, Cyanex 301, a commercial reagent, was found to be able to separate trivalent actinides from macro amount of lanthanides, and then the purified product bis(2,4,4-trimethylpentyl)dithiophosphinic acid was proven to have remarkable ability to separate actinides from both micro and macro amount of lanthanides. The separation process was studied and demonstrated by hot test. The dominant complex in extraction is of cubic structure with a coordination number of 8. The phenyl, chlorophenyl-substituted compounds had no separation ability, but achieved a good separation performance with the synergistic extraction of neutral extractants such as trialkylphosphate. Recently, o-trifluoromethylphenyl- substituted extractant compound was proven to have an excellent separation performance. Although the improvement in stability is desired and the further investigation to the separation mechanism is needed, dialkyldithiophosphinic acids are promising reagents for trivalent actinides/lanthanides separation because of the outstanding separation performance.

Contents
1 Introduction
2 Separation of trivalent actinides from lanthanides
3 Separation of trivalent actinides from lanthanides by Cyanex 301 extraction
4 Separation of trivalent actinides from lanthanides by dialkyldithiophosphinic acids extraction
5 Future of dialkyldithiophosphinic acid-based separation technology

Key words: actinides, lanthanides, extraction separation, dialkyldithiophosphinic acid

中图分类号: 

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