Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 O-okayama, Tokyo 152-8550, Japan.
Dalton Trans. 2011 Oct 21;40(39):10125-30. doi: 10.1039/c1dt10755k. Epub 2011 Sep 2.
Novel ammonium based hydrophobic ionic liquids (ILs) have been synthesised and characterised, and their use in the liquid-liquid extraction of uranium(VI) from an aqueous nitric acid solution using tri-n-butyl phosphate (TBP), studied. On varying the nitric acid concentration, each IL was found to give markedly different results. Relatively hydrophilic ILs showed high uranium(VI) extractability at 0.01 M nitric acid solution which progressively decreased from 0.01 to 2 M HNO(3) and then increased again as the nitric acid concentration was increased to 6 M. An analysis of the mechanisms involved for one such IL, pointed to cationic-exchange being the predominant route at low nitric acid concentrations whilst at high nitric acid concentrations, anionic-exchange predominated. Strongly hydrophobic ILs showed low extractability for nitric acid concentrations below 0.1 M but increasing extractability from 0.1 M to 6 M nitric acid. The predominant mechanism in this case involved the partitioning of a neutral uranyl complex. The uranyl complexes were found to be UO(2)(2+)·(TBP)(3) for the cationic exchange mechanism, UO(2)(NO(3))(2)(TBP)(2) for the neutral mechanism and UO(2)(NO(3))(3)(-)·(TBP) for the anionic exchange mechanism.
已合成并表征了新型铵基疏水性离子液体 (ILs),并研究了它们在使用三丁基磷酸 (TBP) 从硝酸水溶液中液 - 液萃取铀 (VI) 中的应用。通过改变硝酸浓度,发现每种 IL 给出了明显不同的结果。相对亲水的 IL 在 0.01 M 硝酸溶液中具有高的铀 (VI) 萃取率,从 0.01 到 2 M HNO(3)逐渐降低,然后随着硝酸浓度增加到 6 M 再次增加。对一种此类 IL 的机制分析表明,在低硝酸浓度下阳离子交换是主要途径,而在高硝酸浓度下,阴离子交换占主导地位。强疏水性 IL 在低于 0.1 M 的硝酸浓度下表现出低的萃取率,但从 0.1 M 到 6 M 硝酸的萃取率增加。在这种情况下,主要机制涉及中性铀酰配合物的分配。发现铀酰配合物对于阳离子交换机制是 UO(2)(2+)·(TBP)(3),对于中性机制是 UO(2)(NO(3))(2)(TBP)(2),对于阴离子交换机制是 UO(2)(NO(3))(3)(-)·(TBP)。