三丁基氧化膦-离子液体体系萃取UO2(NO3)2的机理和选择性

引用本文: 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 shu

Citation: 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 Physico-Chimica Sinica, 2015, 31(5): 843-851. doi: 10.3866/PKU.WHXB201503202 shu

三丁基氧化膦-离子液体体系萃取UO₂(NO₃)₂的机理和选择性

基金项目:
国家自然科学基金(91226112)资助项目 (91226112)

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:

English

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

1.
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 Date: 13 January 2015
Available Online: 08 May 2015
Fund Project:
国家自然科学基金(91226112)资助项目

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 od 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:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

三丁基氧化膦-离子液体体系萃取UO₂(NO₃)₂的机理和选择性

English

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

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