三丁基氧化膦-离子液体体系萃取UO2(NO3)2的机理和选择性

doi:10.3866/PKU.WHXB201503202

物理化学学报 >> 2015, Vol. 31 >> Issue (5): 843-851.doi: 10.3866/PKU.WHXB201503202

三丁基氧化膦-离子液体体系萃取UO₂(NO₃)₂的机理和选择性

刘海望, 沈兴海, 陈庆德

北京大学化学与分子工程学院, 放射化学与辐射化学重点学科实验室, 北京分子科学国家实验室, 北京100871

收稿日期:2015-01-13 修回日期:2015-03-19 发布日期:2015-05-08
通讯作者: 沈兴海 E-mail:xshen@pku.edu.cn
基金资助:
国家自然科学基金(91226112)资助项目

Extraction Mechanism and Selectivity of UO₂(NO₃)₂ in Tributylphosphine Oxide-Ionic Liquid System

LIU Hai-Wang, SHEN Xing-Hai, CHEN Qing-De

Beijing National Laboratory for Molecular Sciences, Fundamental Science on Radiochemistry and Radiation Chemistry Laboratory, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Received:2015-01-13 Revised:2015-03-19 Published:2015-05-08
Contact: SHEN Xing-Hai E-mail:xshen@pku.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (91226112).

摘要/Abstract

摘要：

研究了三辛基氧化膦(TOPO)和三丁基氧化膦(TBPO)在离子液体(ILs) 1-烷基-3-甲基咪唑双三氟甲基磺酰亚胺盐(C_nmimNTf₂, n=2, 4, 6, 8)中萃取分离UO₂(NO₃)₂. TOPO-C₂mimNTf₂和TOPO-C₄mimNTf₂体系萃取UO₂(NO₃)₂时会出现三相, 而TBPO萃取UO₂(NO₃)₂的萃合物可以很好地溶解在所有离子液体中. 论文也考察了萃取过程中的萃取剂浓度效应、酸效应、盐效应. 水相加入HNO₃会降低萃取效率. 盐效应证明了萃取是一种阳离子交换机理. 水相中加入NO₃^-能够提高U的萃取, 这说明NO₃^-参与萃取. 选择性研究表明: 除了在高酸度下对Zr 的显著萃取, TBPO-C₄mimNTf₂萃取体系在低酸度下对U呈现较好的选择性; 去除U后, 在低酸度下该体系对三价Nd 仍保持较好的选择性. 通过定量比较离子液体中NO₃^-进入量, 电喷雾质谱(ESI-MS)和紫外光谱表征确定了TBPO-C_nmimNTf₂中萃取机理的差异性. 萃取中存在两种萃合物, 即UO₂(TBPO)₃(NO₃)⁺和UO₂(TBPO)₃²⁺, 其中UO₂(TBPO)₃(NO₃)⁺的比例从C₂mimNTf₂体系到C₈mimNTf₂体系逐渐增加.

关键词: 铀, 离子液体, 萃取三相, 萃取选择性, 萃取机理

Abstract:

The extraction of UO₂(NO₃)₂ from aqueous solution was investigated using trioctylphosphine oxide (TOPO) and tributylphosphine oxide (TBPO) in ionic liquids (ILs) (C_nmimNTf₂, n=2, 4, 6, 8). A third phase was formed in the TOPO-C₂mimNTf₂ and TOPO-C₄mimNTf₂ extraction systems, whereas the extracted species of TBPO-C_nmimNTf₂ (n=2, 4, 6, 8) were well soluble in all ILs. The influence of the concentrations of the extractant, nitric acid, and salt on the extraction efficiency was also investigated. Adding HNO₃ to the aqueous phase decreased the extraction efficiency. The effect of salt indicates the presence of a cation-exchange mechanism in the extraction. The addition of NO₃ - in the aqueous phase increased the extraction efficiency of U, which indicates that NO₃ - participates in the extraction. Selective extraction research indicates that TBPO-C₄mimNTf₂ exhibits good selectivity for U at low acid concentration despite the significant extraction efficiency on Zr at high acid concentration. After removing U, TBPO-C₄mimNTf₂ still showed high selectivity for Nd at low acid concentration. We also confirmed the difference of the extraction mechanisms among TBPO-C_nmimNTf₂ by quantitative measurement of NNO₃ - in ILs, electrospray ionization mass spectroscopy (ESI- MS), and UV spectroscopy. There are two extraction species (UO₂(TBPO)₃(NO₃)⁺ and UO₂(TBPO)₃²⁺) and the proportion of UO₂(TBPO)₃(NO₃)⁺ increases from C₂mimNTf₂ to C₈mimNTf₂.

Key words: Uranium, Ionic liquid, Extraction third phase, Extraction selectivity, Extraction mechanism

刘海望, 沈兴海, 陈庆德. 三丁基氧化膦-离子液体体系萃取UO₂(NO₃)₂的机理和选择性[J]. 物理化学学报, 2015, 31(5), 843-851. doi: 10.3866/PKU.WHXB201503202

LIU Hai-Wang, SHEN Xing-Hai, CHEN Qing-De. Extraction Mechanism and Selectivity of UO₂(NO₃)₂ in Tributylphosphine Oxide-Ionic Liquid System[J]. Acta Phys. -Chim. Sin. 2015, 31(5), 843-851. doi: 10.3866/PKU.WHXB201503202

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201503202

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I5/843

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三丁基氧化膦-离子液体体系萃取UO₂(NO₃)₂的机理和选择性

Extraction Mechanism and Selectivity of UO₂(NO₃)₂ in Tributylphosphine Oxide-Ionic Liquid System

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