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Simonnet, M.; 宮崎 有史*; 鈴木 伸一; 矢板 毅
Solvent Extraction and Ion Exchange, 37(1), p.81 - 95, 2019/00
被引用回数：10 パーセンタイル：30.32(Chemistry, Multidisciplinary)Cesium extraction from acidic media by seven dialkoxy-calix[4]arene-crown-6 compounds in several diluents was studied. 2-Nonanone was found to be a suitable diluent for cesium extraction. Nitric acid concentration variation reveals a maximum distribution ratio, whose position depends on extractant and diluent. This maximum was explained quantitatively by a competitive extraction of H
. An analytical mass-action extraction model accounting for activity effects is proposed that fits correctly the different datasets. The analysis showed a nitrate hyper-stoichiometry in alkyl ketone diluents. This effect yields efficient back-extraction at low acidity. Benzo substitution on the crown ether lowers nitric acid extraction, improves sodium separation, but also degrades potassium and rubidium separation.
Simonnet, M.; 宮崎 有史*; 鈴木 伸一; 矢板 毅
no journal, ,
Cs is a troublesome fission product for both nuclear waste reprocessing and the cleaning of contaminated areas (Fukushima). Because Cs belongs to the alkali elements, it is hard to separate from Na and K, whose natural abundances are high. Calixarenes crown-ether were found to be efficient alkali extractants, with the alkali selectivity determined by the number of ether functions. It was found that ligands with 6 ether functions are optimum for cesium whilst 4 is optimum for Na, yielding great Na separation factors. However, the resulting high oxygen contents yields a low solubility in aliphatic diluents. Different diluents were thus used in literature, such as alcohols, ketones, chloroform, nitrophenylalkylether or dodecane with a modifier. Whilst the distribution ratios greatly varied along with the diluent, few studies focused on understanding this phenomenon. The aim of the present work is thus to study the diluent effect at both macroscopic (distribution ratio and separation factor comparison) and microscopic (EXAFS analysis) scales. For the latter study, two diluents, chloroform and 2-nonanone, were chosen. Their properties (density, viscosity, dielectric constant, water solubility) are all different, except from the calixarene crown-ether solubility which is high in both cases. Additional interactions between the diluent and the counterion were also investigated. The study focuses on acidic aqueous solutions only.
Simonnet, M.; 宮崎 有史*; 鈴木 伸一; 小林 徹; 矢板 毅
no journal, ,
Results on cesium extraction by calixarene crown-ether in several diluents are presented. An extraction mechanism was proposed, which correctly fits the different datasets. Found empirical equilibrium constants were correlated with diluent parameters for a better comparison. Afterwards, chloroform and 2-nonanone were compared on the obtained distribution ratios, separation factors and atomic scale differences. EXAFS studies proved that the modification of diluent yields a change in the local cesium environment.
Simonnet, M.; 宮崎 有史*; 鈴木 伸一; 小林 徹; 土井 玲祐; 塩飽 秀啓; 矢板 毅
no journal, ,
Cs is one of the highest heat generators in nuclear waste. Removing it prior to deep geological disposal can thus help reducing the necessary volumes and costs of the final repository. This isotope is also one of the main contaminants that was released during the Fukushima Nuclear Power Plant accident. Liquid-liquid extraction can be a suitable method for decontamination. In this study, seven different extractants from the calix-mono-crown-arene family have been compared as respect to distribution ratio, separation factors and closer atoms distances to cesium. Distribution ratios also strongly depend on diluent nature. EXAFS study was thus conducted on two extractants in chloroform and 2-nonanone to investigate whether diluent nature can impact the cesium-ligand complex itself. Spectra showed that whilst no difference was observed on the first coordination shell, diluent nature impacted the second shell. However, oxygen positions remained similar in both diluents, leading to a probable change in benzene 
-electron interaction with cesium.
