KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Heverlee, Belgium.
Dalton Trans. 2014 Jan 28;43(4):1862-72. doi: 10.1039/c3dt52285g.
A new non-fluorinated malonamide-based ionic liquid extractant was synthesized and investigated for the extraction behavior of europium(III) and other trivalent rare-earth ions from nitric acid medium. The extractant was the functionalized ionic liquid trihexyl(tetradecyl)phosphonium N,N,N',N'-tetra(2-ethylhexyl)malonate, [P66614][MA], and it was used in combination with the non-fluorinated ionic liquid trihexyl(tetradecyl)phosphonium nitrate, [P66614][NO3], as diluents. The extraction behavior of europium in this ionic liquid solution was studied as a function of various parameters such as the pH, concentration of the extractant, the type of acidic medium, temperature, concentration of the salting-out agent and the metal concentration of the aqueous feed. The extraction behavior of [P66614][MA] in [P66614][NO3] was compared with that of [P66614][MA] in the chloride-containing ionic liquid diluent trihexyl(tetradecyl)phosphonium chloride, [P66614][Cl] (Cyphos IL 101). The nitrate system was found to be superior. Marked differences in extraction behavior were observed between [P66614][MA] and the molecular malonamide extractant N,N,N',N'-tetra(2-ethylhexyl)malonamide (TEHMA), i.e. the compound from which the anion of the ionic liquid extractant was prepared. The extraction behavior of other rare earths (La, Ce, Nd, Sm, Ho, Yb) and some transition metals (Ni, Co, Zn) was investigated using this functionalized ionic liquid. A good separation of the rare earths from the transition metals could be achieved. For the rare earths, the extraction efficiency increases over the lanthanide series. The effects of thermodynamic parameters, the stripping of europium(iii) from the ionic liquid and the reusability of the functionalized ionic liquid were studied in detail.
一种新型的非氟化丙二酰胺基离子液体萃取剂被合成,并研究了其从硝酸介质中萃取铕(III)和其他三价稀土离子的行为。萃取剂是功能化离子液体三己基(十四烷基)膦 N,N,N',N'-四(2-乙基己基)丙二酰胺,[P66614][MA],并与非氟化离子液体三己基(十四烷基)膦硝酸盐,[P66614][NO3],作为稀释剂一起使用。研究了在这种离子液体溶液中铕的萃取行为,作为各种参数的函数,如 pH 值、萃取剂的浓度、酸性介质的类型、温度、盐析剂的浓度和水相进料的金属浓度。比较了 [P66614][MA]在[P66614][NO3]中的萃取行为与在含氯离子液体稀释剂三己基(十四烷基)膦氯化物,[P66614][Cl](Cyphos IL 101)中的萃取行为。发现硝酸盐体系具有优越性。在 [P66614][MA]和分子丙二酰胺萃取剂 N,N,N',N'-四(2-乙基己基)丙二酰胺(TEHMA)之间观察到明显的萃取行为差异,即离子液体萃取剂的阴离子的前体化合物。使用这种功能化离子液体研究了其他稀土(La、Ce、Nd、Sm、Ho、Yb)和一些过渡金属(Ni、Co、Zn)的萃取行为。可以实现从过渡金属中很好地分离稀土。对于稀土,萃取效率在镧系元素系列中增加。详细研究了热力学参数、铕(III)从离子液体中的反萃以及功能化离子液体的可重复使用性的影响。