Onghena Bieke, Jacobs Jeroen, Van Meervelt Luc, Binnemans Koen
KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, 3001 Leuven, Belgium.
Dalton Trans. 2014 Aug 14;43(30):11566-78. doi: 10.1039/c4dt01340a. Epub 2014 Jun 18.
The ionic liquid choline bis(trifluoromethylsulfonyl)imide, [Chol][Tf2N], was used for the extraction of neodymium(III), in combination with choline hexafluoroacetylacetonate, [Chol][hfac], as the extractant. The binary mixture of [Chol][Tf2N] and water shows temperature-dependent phase behavior, with an upper critical solution temperature of 72 °C. A novel extraction technique, homogeneous liquid-liquid extraction (HLLE), was applied to this solvent system. HLLE is based on the use of thermomorphic solvent mixtures and has the advantage of forming a homogeneous phase during mixing. Extraction is not kinetically hindered by an interface and the extraction equilibrium is reached faster than in the case of heterogeneous mixing in conventional solvent extraction. Several extraction parameters were studied for the extraction of neodymium(III) with [Chol][hfac]: temperature, pH, extractant concentration and loading of the ionic liquid phase. A speciation study was performed to determine the stoichiometry of the extracted neodymium(III) complex and a plausible extraction mechanism is proposed. Neodymium is extracted as a tetrakis hexafluoroacetylacetonate complex with one choline cation as counter ion. The crystal structure of the extracted complex showed the presence of a coordination bond between the choline counter ion and the neodymium(III) center, resulting in a coordination number of nine. The stripping of the loaded neodymium and the influence of acid and extractant concentrations on the phase behavior of the [Chol][Tf2N]-H2O system were investigated.
离子液体胆碱双(三氟甲基磺酰)亚胺([Chol][Tf2N])与胆碱六氟乙酰丙酮([Chol][hfac])作为萃取剂联合用于钕(III)的萃取。[Chol][Tf2N]与水的二元混合物呈现出温度依赖性相行为,其临界溶解温度上限为72℃。一种新型萃取技术——均相液 - 液萃取(HLLE)被应用于该溶剂体系。HLLE基于热致变溶剂混合物的使用,具有在混合过程中形成均相的优点。萃取不受界面的动力学阻碍,并且比传统溶剂萃取中的非均相混合更快达到萃取平衡。研究了用[Chol][hfac]萃取钕(III)的几个萃取参数:温度、pH值、萃取剂浓度和离子液相的负载量。进行了形态研究以确定萃取的钕(III)配合物的化学计量,并提出了一种合理的萃取机理。钕以四(六氟乙酰丙酮)钕配合物形式被萃取,其中一个胆碱阳离子作为抗衡离子。萃取配合物的晶体结构表明胆碱抗衡离子与钕(III)中心之间存在配位键,导致配位数为9。研究了负载钕的反萃以及酸和萃取剂浓度对[Chol][Tf2N] - H2O体系相行为的影响。