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AbstractAbstract
[en] The molten salt fast reactor (MSFR) is one of the six nuclear reactor concepts retained during the Forum GEN IV in 2001. The particularity of this concept is to use a liquid fuel consisting of a molten salt, LiF-ThF4-UF4 /UF3 (77-19-4 mol%) and to have an integrated spent fuel treatment process. This treatment consists of successive chemical separation steps based on redox and acid-base properties of the elements produced in the reactor by nuclear reactions: soluble and gaseous fission products, metals elements and soluble minor actinides. One of the major steps of the treatment method is a reducing extraction which consists to contact the molten salt and a liquid metal, bismuth, containing the reducing element, lithium. This step allows separating the minor actinides and lanthanides. Minor actinides are reintroduced in the nuclear reactor to be burned while the lanthanides are confined in deep storage. The work in this thesis had two objectives: (i) assess the feasibility of reducing extraction of actinides and lanthanides, a step that had previously only been validated on the basis of thermodynamic calculations and (ii) study the chemistry of molten fluoride salts (and especially the fuel salt) by developing a methodology for the determination of fundamental data such as the activity coefficients in fluorides media, coefficients activities which quantify the solvation properties. To experimentally realize a reducing extraction, the first step is to prepare a metal layer of liquid Bi-Li with predefined composition. An electrolysis technique in molten salt LiCl-LiF at 550 deg. C was chosen to achieve these metal solutions. We have shown that only this molten medium could be used for the manufacture of such metal alloys. Extraction tests were then carried out by contact between LiF-ThF4 (with UF4 and NdF3 are introduced to simulate respectively the actinides and lanthanides) and Bi-Li at 650 deg. C. The main results show that the extraction of neodymium and uranium was obtained with yields of around 1% and 15% respectively in the best conditions. These values are low compared to previous thermodynamic calculations. Low efficiency of the extraction is due to a simultaneous extraction of thorium in the liquid metal phase which forms intermetallic compounds at the metal/salt interphase and blocks the transfer. Methods have been developed to achieve fundamental data that are lacking in molten fluoride medium, in particularly the solvation properties. Speciation of some metallic cations by fluoride ions with high temperature was particularly studied and calculation of complexation constants by simulated experimental results was done. Carried out for two lanthanides, neodymium and lanthanum, two actinides, thorium and uranium, and also for a transition metal, nickel, this study achieves to calculate the activity coefficients of these elements in different fluoride molten salt. The study of the speciation of thorium was an important step to understand the chemistry of the fuel salt LiF-ThF4. We were able to calculate the activity coefficient of the fluoride ion in this environment at 650 deg. C. Finally, all of this work allows giving a first estimate of the reactivity of each element of the periodic table (present in the nuclear reactor after operation) at each stage of the treatment of the spent fuel salt. (author)
[fr]
Le reacteur a sels fondus rapides (MSFR) est un des six concepts de reacteur nucleaire retenu lors du Forum Generation IV en 2001. La particularite de ce concept est d'utiliser un combustible liquide constitue d'un sel fondu, LiF-ThF4-UF4/UF3 (77-19-4 mol%) et d'integrer un procede de traitement du sel use. Ce traitement est constitue d'etapes successives de separation chimiques basees sur les proprietes redox et acido-basiques des elements produits dans le reacteur par des reactions nucleaires: produits de fission solubles et gazeux, elements metalliques et actinides mineurs solubles. L'une des etapes majeures du procede de traitement est une extraction reductrice qui consiste a mettre en contact le sel fondu et un metal liquide, le bismuth, contenant un element reducteur, le lithium. Cette etape permet notamment de separer les actinides mineurs des lanthanides. Les actinides mineurs sont reintroduits dans le reacteur nucleaire afin d'y etre brûle alors que les lanthanides seront confines en stockage profond. Le travail realise au cours de cette these avait deux objectifs: (i) verifier la faisabilite de l'extraction reductrice des actinides et des lanthanides, etape qui avait ete validee au prealable uniquement sur la base de calculs thermodynamiques et (ii) etudier la chimie des sels fluorures fondus (et notamment le sel combustible LiF-ThF4-UF4) en developpant une methodologie pour la determination de donnees fondamentales telles que les coefficients d'activite dans les milieux fluorures, coefficients qui quantifient les proprietes de solvatation. La speciation de plusieurs cations metalliques par les ions fluorures a haute temperature a notamment ete etudiee et les constantes de complexation calculees experimentaux. En particulier, l'etude de la speciation du thorium a ete une etape importante dans la connaissance de la chimie du sel combustible LiF-ThF4 puisque nous avons pu en deduire le coefficient d'activite de l'ion fluorure dans ce milieu a 650 deg. C. Les etudes experimentales sur l'etape d'extraction reductrice ont ensuite ete realisees par contact entre LiF-ThF4-UF4-NdF3 et Bi-Li a 650 deg. C. Les principaux resultats montrent que l'extraction du neodyme et de l'uranium a ete obtenue avec des rendements respectivement de l'ordre de 1% et 15% dans les meilleures conditions. Ces valeurs sont faibles comparees aux calculs thermodynamiques previsionnels. On explique la faible efficacite de l'extraction par une extraction simultanee du thorium dans la nappe metallique liquide qui forme des composes intermetalliques a l'interface metal/sel et bloque le transfert interphasique. Enfin, l'ensemble de ce travail a conduit a donner une premiere estimation de la reactivite de chaque element de la classification periodique (present dans le reacteur nucleaire apres operation) a chaque etape du traitement du sel combustible use. (auteur)Original Title
Solvatation du thorium par les fluorures en milieu sel fondu a haute temperature: application au procede d'extraction reductrice pour le concept MSFR
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Secondary Subject
Source
4 Dec 2015; 159 p; 155 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; These de doctorat de l'Universite Paris-Saclay, Specialite: Chimie
Record Type
Miscellaneous
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Thesis/Dissertation
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CHEMICAL REACTION YIELD, CHEMICAL STATE, DIFFUSION, ELECTROLYSIS, FEASIBILITY STUDIES, INTERMETALLIC COMPOUNDS, LANTHANUM, LITHIUM FLUORIDES, MOLTEN SALT FUELED REACTORS, NEODYMIUM, NICKEL, REDOX POTENTIAL, REDUCTIVE EXTRACTION, REPROCESSING, SOLVATION, THERMODYNAMIC ACTIVITY, THORIUM FLUORIDES, URANIUM, URANIUM TETRAFLUORIDE
ACTINIDE COMPOUNDS, ACTINIDES, ALKALI METAL COMPOUNDS, ALLOYS, ELEMENTS, EXTRACTION, FLUID FUELED REACTORS, FLUORIDES, FLUORINE COMPOUNDS, HALIDES, HALOGEN COMPOUNDS, LITHIUM COMPOUNDS, LITHIUM HALIDES, LYSIS, METALS, MOLTEN SALT REACTORS, RARE EARTHS, REACTORS, SEPARATION PROCESSES, THORIUM COMPOUNDS, THORIUM HALIDES, TRANSITION ELEMENTS, URANIUM COMPOUNDS, URANIUM FLUORIDES, URANIUM HALIDES, YIELDS
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