N,N'-二乙基-N,N'-二(丙氧基苯基)-2,6-吡啶二酰胺对铀酰离子的选择性络合萃取

doi:10.7503/cjcu20150160

摘要/Abstract

摘要：

研究了新型萃取剂N,N'-二乙基-N,N'-二(丙氧基苯基)-2,6-吡啶二酰胺(1a~1c)对铀酰离子(U $O 2 2 +$ )的络合萃取. 结果表明, 当不加硝酸或硝酸浓度为6 mol/L时, 化合物1a对U $O 2 2 +$ 的萃取率分别高达99%和94%. 在6 mol/L HNO₃的高酸度条件下, 化合物1a能实现U $O 2 2 +$ 和镧系元素(La, Eu及Yb)的选择性分离[分离比SF_{U(Ⅵ)/Ln(Ⅲ)}>20]; 而化合物1b和1c则可以实现U $O 2 2 +$ 和轻镧系元素(La, Eu)之间的分离. 双对数图(lg-lg plot)实验结果表明, 化合物1a~1c与U $O 2 2 +$ 的萃合比在1~2之间, 表明同时存在2∶1和1∶1两种比例的萃合物. 核磁共振波谱和红外光谱数据证明吡啶氮和羰基氧参与了对U $O 2 2 +$ 的配位.

关键词: 吡啶二酰胺, 铀酰离子, 络合萃取, 选择性

Abstract:

To acquire a more efficent and selective dipicolinamide, the affinity of three novel diamide derivatives of dipicolinic acids N,N'-diethyl-N,N'-bis(propoxyphenyl)-2,6-dipicolinamide(1a—1c) for uranyl ion was investigated by liquid-liquid extraction method. In the absence of HNO₃ and in the presence of 6 mol/L HNO₃, the extractability of compound 1a for uranyl ion was 99% and 94%, respectively. At the same high acidity, selective separation of uranyl from lanthanides(La, Eu and Yb) was achieved using compound 1a as extractant [SF_{U(VI)/Ln(III)}>20]. In contrast, compounds 1b and 1c were able to separate uranyl ion from lighter lanthanides(La and Eu). Result of lg-lg plot experiments indicated the stoichiometric ratios of compounds 1a, 1b and 1c with uranyl were found to fall between 1 and 2, suggesting the presence of two kinds of extracted species in 2∶1 and 1∶1 ratios(extractant∶uranyl). ¹H NMR and FTIR spectra of the extracted complexes implicated the involvement of nitrogen atom in the pyridine ring and carbonyl group in coordinating uranyl ion. The results showed that compound 1a is the most promising extractant and probably can be used in the recycling of uranyl ion.

Key words: Dipicolinamide, Uranyl ion, Extraction, Selectivity

中图分类号:

O655
O615

TrendMD:

陈龙, 李艳, 王真文, 彭智勇, 杨泽明, 袁立华, 冯文. N,N'-二乙基-N,N'-二(丙氧基苯基)-2,6-吡啶二酰胺对铀酰离子的选择性络合萃取. 高等学校化学学报, 2015, 36(8): 1485.

CHEN Long, LI Yan, WANG Zhenwen, PENG Zhiyong, YANG Zeming, YUAN Lihua, FENG Wen. High Efficiency and Selective Extraction of Uranyl Ion by N,N'-Diethyl-N,N'-bis(propoxyphenyl)-2,6-dipicolinamide^†. Chem. J. Chinese Universities, 2015, 36(8): 1485.

图/表 8

Fig.1 Chemical structures of compounds 1a—1c and 2

Table 1 Extractabilities(%) of UO22+ for compounds 1a—1c and 2 at various concentrations of HNO3

Compd.	c(HNO₃)/(mol·L^-1))
Compd.	0	1	2	3	4	5	6
1a^a	99.0±0.2	7.2±0.9	46.5±0.7	79.1±0.2	91.4±0.3	93.5±0.5	94.3±0.0
1b^a	15.8±0.2	<1^b	7.8±0.6	26.4±1.2	59.7±0.3	78.4±0.6	84.4±0.3
1c^a	24.3±2.2	<1^b	15.8±0.8	45.7±0.8	73.5±0.8	85.1±0.2	88.8±0.2
2^a	26.9±0.2	<1^b	2.6±1.6	17.7±1.9	42.4±0.5	63.6±0.2	78.0±0.6

Fig.2 Plots of lgD vs. lg[NO3-] for the extraction of UO22+ with compounds 1a—1c(a—c)

Fig.3 Distribution ratio(D) of UO22+ for all extrac-tants at various concentrations of HNO3

Table 2 Distribution ratio of selective lanthanides and actinides(1×10-4 mol/L) for compounds 1a—1c and 2 from HNO3 aqueous solution(6 mol/L) into F-3

Compd.	D
Compd.	La³⁺	Eu³⁺	Yb³⁺	U
1a	<0.01^*	0.02	0.86	18.2
1b	<0.01^*	0.08	4.06	6.02
1c	<0.01^*	0.07	7.24	8.09
2	0.01	0.04	1.8	3.39

Fig.4 Separation factor of UO22+ to some lanthanides(La3+, Eu3+ and Yb3+) from HNO3 aqueous solution(6 mol/L) into F-3

Fig.5 Plots of lgD vs. lg[L] for the extraction of UO22+ with compounds 1a—1c(a—c)

Scheme 1 Selective extraction of UO22+ by compound 1a

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