Rout Alok, Ramanathan Nagarajan
Materials Chemistry & Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102, India.
Indira Gandhi Centre for Atomic Research, A CI of Homi Bhabha National Institute, Kalpakkam, 603102, Tamil Nadu, India.
Chempluschem. 2024 May;89(5):e202300406. doi: 10.1002/cplu.202300406. Epub 2023 Nov 28.
Solvent extraction of Zr(IV) in an undiluted phosphonium based ionic liquid (IL) and its selective separation from Ln(III) and An(III) has been investigated in the present study. Eu(III)/Am(III) were chosen as the representative Ln(III)/An(III). Tri(hexyl)tetradecylphosphonium nitrate ([P][NO]) was chosen as IL phase and the feed phase was nitric acid containing the target metal ions. The extraction process was accomplished at different experimental parameters such as the concentration of initial nitric acid, initial feed metal concentration and equilibration time to explore the extractability of the proposed IL towards Zr(IV). The efficient extraction of Zr(IV) without any external ligand in IL phase and negligible extraction of Eu(III)/Am(III) were distinctly discerned leading to noteworthy separation factors for Zr(IV). The loading experiment revealed a noticeable growth of equilibrium concentrations of Zr(IV) in IL phase while that of Eu(III) was very less irrespective of the initial feed concentration. The association of two IL moieties in the complex formation process has been inferred. Nitrate ion was found to be superior as IL anion in terms of metal loading in comparison to other anions. Thermodynamics of extraction and the stripping of the loaded Zr(IV) from IL phase using a suitable stripping solution have also been investigated.
本研究考察了在未稀释的基于鏻的离子液体(IL)中溶剂萃取Zr(IV)及其与Ln(III)和An(III)的选择性分离。选择Eu(III)/Am(III)作为代表性的Ln(III)/An(III)。选择硝酸三(己基)十四烷基鏻([P][NO])作为离子液体相,进料相为含有目标金属离子的硝酸。通过改变初始硝酸浓度、初始进料金属浓度和平衡时间等不同实验参数来完成萃取过程,以探究所提出的离子液体对Zr(IV)的萃取能力。明显观察到在离子液体相中无需任何外部配体即可高效萃取Zr(IV),而Eu(III)/Am(III)的萃取可忽略不计,这导致Zr(IV)具有显著的分离因子。负载实验表明,无论初始进料浓度如何,离子液体相中Zr(IV)的平衡浓度均显著增加,而Eu(III)的平衡浓度则非常低。已推断出在络合物形成过程中有两个离子液体部分缔合。与其他阴离子相比,发现硝酸根离子作为离子液体阴离子在金属负载方面更具优势。还研究了萃取热力学以及使用合适的反萃溶液从离子液体相中反萃负载的Zr(IV)。