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Moutiers, G.; Mekki, S.; Billard, I.
CEA Saclay, Dept. de Physico-Chimie, Service de Chimie Physique, 91 - Gif sur Yvette (France)2007
CEA Saclay, Dept. de Physico-Chimie, Service de Chimie Physique, 91 - Gif sur Yvette (France)2007
AbstractAbstract
[en] One of the solutions proposed for the optimization of the long term storage and conditioning of spent nuclear fuel is to separate actinide and lanthanide both from each other and from other less radioactive metallic species. The industrial proposed processes, based on liquid liquid extraction steps, involve solvents with non negligible vapour pressure and may generate contaminated liquid wastes that will have to be reprocessed. During the last decade, some room-temperature ionic liquids have been studied and integrated into industrial processes. The interest on this class of solvent came out from their 'green' properties (non volatile, non flammable, recyclable, etc...), but also from the variability of their physico-chemical properties (stability, hydrophobicity, viscosity) as a function of the RTIL chemical composition. Indeed, it has been shown that classical chemical industrial processes could be transferred into those media, even more improved, while a certain number of difficulties arising from using traditional solvent can be avoided. In this respect, it could be promising to investigate the ability to use room temperature ionic liquid into the spent nuclear fuel reprocessing field. The aim of this this study is to test the ability of the specific ionic liquid bumimTf2N to allow trivalent europium extraction. The choice of this metal is based on the chemical analogy with trivalent minor actinides Curium and Americium which are contributing the greatest part of the long-lived high level radioactive wastes. Handling these elements needs to be very cautious for the safety and radioprotection aspect. Moreover, europium is a very sensitive luminescent probe to its environment even at the microscopic scale. The report is structured with four parts. In a first chapter, we present the main physico-chemical properties of an imidazolium-based ionic liquid family, and then we choose the ionic liquid bumimTf2N for the whole thesis and start with the electrochemical study. In the second chapter, we present the study of europium solvation in the ionic liquid media. In the third part, we expose the results concerning TTA solvation and its complexation with europium in bumimTf2N under different conditions. Finally in the last chapter, we present the results obtained for the europium extraction in a three-stage extraction system: water/bumimTf2N/supercritical CO2. This work highlights the potential use of ionic liquids and particularly bumimTf2N in the spent nuclear fuel reprocessing. The ability to extract quantitatively a trivalent lanthanide has been demonstrated. This fundamental study can be regarded as a feasibility demonstration to build an ionic liquid-containing extraction system, in the aim of possible large-scale application. (authors)
Original Title
Application d'un liquide ionique basse temperature pour les procedes de separation: speciation de l'europium trivalent et effets solvatation
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Secondary Subject
Source
2007; 227 p; [210 refs.]
Record Type
Report
Report Number
Country of publication
AMPEROMETRY, CARBON DIOXIDE, CHELATING AGENTS, CHEMICAL REACTION KINETICS, CHEMICAL STATE, EUROPIUM COMPLEXES, EUROPIUM IONS, FEASIBILITY STUDIES, IMIDAZOLES, INFRARED SPECTRA, KETONES, LASER SPECTROSCOPY, NEUTRON ACTIVATION ANALYSIS, SOLVATION, SOLVENT EXTRACTION, SPECTROPHOTOMETRY, SUPERCRITICAL GAS EXTRACTION, TTA
ACTIVATION ANALYSIS, AZOLES, CARBON COMPOUNDS, CARBON OXIDES, CHALCOGENIDES, CHARGED PARTICLES, CHEMICAL ANALYSIS, COMPLEXES, EXTRACTION, HETEROCYCLIC COMPOUNDS, IONS, KETONES, KINETICS, NONDESTRUCTIVE ANALYSIS, ORGANIC COMPOUNDS, ORGANIC FLUORINE COMPOUNDS, ORGANIC HALOGEN COMPOUNDS, ORGANIC NITROGEN COMPOUNDS, ORGANIC SULFUR COMPOUNDS, OXIDES, OXYGEN COMPOUNDS, QUANTITATIVE CHEMICAL ANALYSIS, RARE EARTH COMPLEXES, REACTION KINETICS, SEPARATION PROCESSES, SOLVENT EXTRACTION, SPECTRA, SPECTROSCOPY, TITRATION, VOLUMETRIC ANALYSIS
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