Thése CIFRE- Récupération de catalyseurs par procédés membranaires
Sisteron, France Fixed Term Posted on Apr. 18, 2025 Closing on Apr. 21, 2025RÉSUMÉ
Les catalyseurs sont des outils indispensables dans de nombreuses synthèses chimiques. Ils permettent de mettre en place une chimie de pointe pour aller au plus vite à la molécule cible en limitant au maximum les sous-produits et donc les étapes de purification nécessaire en aval. Souvent très coûteux et rares (à base de métaux nobles comme le palladium ou le ruthénium), il est d’un intérêt économique et environnemental majeur de gérer au mieux leur récupération. Une amélioration de cet aspect est donc un axe de développement stratégique pour garantir la viabilité de certaines synthèses en cours ou à venir mais aussi pour ouvrir de nouvelles perspectives aux équipes de chimie. En effet une amélioration significative permettrait d’imaginer de nouvelles voies d’accès et d’aller sur des procédés qui ne sont pas industrialisables à la date.
L’objectif est d’apporter une technologie pour casser ce verrou scientifique actuel et les procédés membranaires semblent une piste particulièrement intéressante.
INTRODUCTION, OBJECTIFS ET PERSPECTIVES
Une de nos synthèses en cours de développement rentre particulièrement dans cette thématique avec quatre étapes mettant en jeu du Palladium avec différents types de réaction chimique : hydrogénation, carbonylation, borylation et réaction de couplage. Cela représente des quantités de palladium extrêmement importantes à récupérer et des procédés complexes à mettre en œuvre.
Des études sont en cours pour optimiser les quantités utilisées, mais pour fixer de grandes tendances il est nécessaire d’utiliser 1700 kg d'équivalent de palladium pur pour produire 10T de principe actif (1% des volumes d’extractions annuels). Cette quantité représente environ 15% du cout global de la synthèse et donc plusieurs millions d’euros par an. Il vient à s’ajouter à cela l’impact environnemental de ce type de réactif. Par exemple pour l’étape de couplage suzuki et de borylation miyaura, pour 1,7T de palladium nous générons 10 000T d’effluents aqueux.
Sur cette étape, les deux produits de départs ont des masses molaires de 284 et 390 g.mol-1et le produit de 603 g.mol-1. Celle du catalyseur est de 786 g.mol-1. La réaction est réalisée dans du MeTHF et de l’eau.
Le projet de recherche envisagé s’articule autour de la récupération, et si possible la valorisation, de catalyseurs solubles contenus dans des flux chimiques afin i) de réduire les quantités d’effluents à traiter, ii) de récupérer les catalyseurs dans un état fonctionnel pour une nouvelle utilisation, ce qui permettra de réduire les coûts globaux de la synthèse chimique.
L’étude réalisée lors de cette thèse viserait des catalyseurs solubles dans des effluents majoritairement organiques, qui représentent davantage de difficulté à être récupérés que les catalyseurs hétérogènes. Ce projet se centrerait principalement autour des catalyseurs palladiés. Les catalyseurs sont souvent sensibles à tout type de traitement chimique qui risque de les détériorer. La mise en place d’un traitement physique, notamment grâce à l’utilisation de procédés membranaires, pourrait ainsi permettre une récupération des catalyseurs sans diminution de leurs capacités en vue de leur réutilisation.
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