Récupération de catalyseurs par procédés membranaires (Thèse soutenue au M2P2 en 2024)
Activités
Génie des procédés :
récupération de complexes de palladium
ré-activation de catalyseurs
industrie pharmaceutique
-> Optimisation énergétique du traitement de l'eau potable (2024-2025)
-> Récupération de catalyseurs par procédés membranaires (2021-2024)
-> Recyclage de solvants organiques par distillations / pervaporation (2020-2021)
Publications scientifiques au M2P2
2023
Adrien Magne, Emilie Carretier, Lilivet Ubiera Ruiz, Thomas Clair, Morgane Le Hir, et al.. Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes. Membranes, 2023, 13 (8), pp.738. ⟨10.3390/membranes13080738⟩. ⟨hal-04543741⟩ Plus de détails...
Catalyst recovery is a major challenge for reaching the objectives of green chemistry for industry. Indeed, catalysts enable quick and selective syntheses with high reaction yields. This is especially the case for homogeneous platinoid catalysts which are almost indispensable for cross-coupling reactions often used by the pharmaceutical industry. However, they are based on scarce, expensive, and toxic resources. In addition, they are quite sensitive and degrade over time at the end of the reaction. Once degraded, their regeneration is complex and hazardous to implement. Working on their recovery could lead to highly effective catalytic chemistries while limiting the environmental and economic impacts of their one-time uses. This review aims to describe and compare conventional processes for metal removal while discussing their advantages and drawbacks considering the objective of homogeneous catalyst recovery. Most of them lead to difficulty recycling active catalysts due to their ability to only treat metal ions or to chelate catalysts without the possibility to reverse the mechanism. However, membrane processes seem to offer some perspectives with limiting degradations. While membranes are not systematically the best option for recycling homogeneous catalysts, current development might help improve the separation between pharmaceutical active ingredients and catalysts and enable their recycling.
Adrien Magne, Emilie Carretier, Lilivet Ubiera Ruiz, Thomas Clair, Morgane Le Hir, et al.. Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes. Membranes, 2023, 13 (8), pp.738. ⟨10.3390/membranes13080738⟩. ⟨hal-04543741⟩
Adrien Magne, Emilie Carretier, Lilivet Ubiera Ruiz, Thomas Clair, Morgane Le Hir, et al.. Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes. Membranes, 2023, 13 (8), pp.738. ⟨10.3390/membranes13080738⟩. ⟨hal-04202121⟩ Plus de détails...
Catalyst recovery is a major challenge for reaching the objectives of green chemistry for industry. Indeed, catalysts enable quick and selective syntheses with high reaction yields. This is especially the case for homogeneous platinoid catalysts which are almost indispensable for cross-coupling reactions often used by the pharmaceutical industry. However, they are based on scarce, expensive, and toxic resources. In addition, they are quite sensitive and degrade over time at the end of the reaction. Once degraded, their regeneration is complex and hazardous to implement. Working on their recovery could lead to highly effective catalytic chemistries while limiting the environmental and economic impacts of their one-time uses. This review aims to describe and compare conventional processes for metal removal while discussing their advantages and drawbacks considering the objective of homogeneous catalyst recovery. Most of them lead to difficulty recycling active catalysts due to their ability to only treat metal ions or to chelate catalysts without the possibility to reverse the mechanism. However, membrane processes seem to offer some perspectives with limiting degradations. While membranes are not systematically the best option for recycling homogeneous catalysts, current development might help improve the separation between pharmaceutical active ingredients and catalysts and enable their recycling.
Adrien Magne, Emilie Carretier, Lilivet Ubiera Ruiz, Thomas Clair, Morgane Le Hir, et al.. Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes. Membranes, 2023, 13 (8), pp.738. ⟨10.3390/membranes13080738⟩. ⟨hal-04202121⟩
Morgane Le Hir, Adrien Magne, Thomas Clair, Emilie Carretier, Philippe Moulin. Solvent Regeneration in Complex Mixture Using Pervaporation. Organic Process Research and Development, 2021, 25 (3), pp.469-485. ⟨10.1021/acs.oprd.0c00442⟩. ⟨hal-03515300⟩ Plus de détails...
This study aims to demonstrate the efficiency of dichloromethane (DCM) regeneration from a methanolic effluent by a combination of distillation and membrane pervaporation process. The presence of an azeotrope (MeOH/DCM/water) makes the regeneration of DCM via distillation alone impossible. A process simulation using ProSim software was carried out in order to evaluate the behavior of the azeotropic mixture. Two secondary treatments aiming to purify the DCM contained in the azeotrope were investigated. The first is the washing of the azeotrope with water. ProSim software was used to target the optimal conditions for washing before the experimental test. Residual water was recovered in the organic phase, meaning that the quality specifications for DCM were not reached. The second process studied for DCM purification was a pervaporation step. The feasibility of this had been proven at laboratory scale. The recovered DCM had the quality of a new solvent, and the whole process (distillation + pervaporation) reached a global DCM regeneration yield of 71.8% before optimization. This yield was limited by the distillation of methylal (also called dimethoxymethane) present in the methanolic effluent at the end of the distillation of the azeotrope, a compound retained by the pervaporation membrane. The pervaporation was performed on a hydrophilic Hybsi membrane letting methanol and water pass through and retaining the DCM (membrane surface = 0.15 m(2)). Optimization and scaling up were then carried out with a semi-industrial pervaporation pilot (membrane surface = 1.05 m(2)) which enabled the industrial scale-up. In order to facilitate the steering of the process and to ensure continuous and efficient monitoring of the regeneration operation, online monitoring by near-infrared probe (NIR) had been implemented allowing the composition of the mixture to be determined with an accuracy of +/- 0.05% on each compound. Finally, an assessment had been conducted of the regeneration pathways for methanol recovery at the bottom of the distillation column, for maximizing the regeneration of methanolic effluents by separating heavy compounds and methylal from methanol.
Morgane Le Hir, Adrien Magne, Thomas Clair, Emilie Carretier, Philippe Moulin. Solvent Regeneration in Complex Mixture Using Pervaporation. Organic Process Research and Development, 2021, 25 (3), pp.469-485. ⟨10.1021/acs.oprd.0c00442⟩. ⟨hal-03515300⟩
Morgane Le Hir, Adrien Magne, Thomas Clair, Emilie Carretier, Philippe Moulin. Solvent Regeneration in Complex Mixture Using Pervaporation. Organic Process Research and Development, 2021, 25 (3), pp.469-485. ⟨10.1021/acs.oprd.0c00442⟩. ⟨hal-03597582⟩ Plus de détails...
This study aims to demonstrate the efficiency of dichloromethane (DCM) regeneration from a methanolic effluent by a combination of distillation and membrane pervaporation process. The presence of an azeotrope (MeOH/DCM/water) makes the regeneration of DCM via distillation alone impossible. A process simulation using ProSim software was carried out in order to evaluate the behavior of the azeotropic mixture. Two secondary treatments aiming to purify the DCM contained in the azeotrope were investigated. The first is the washing of the azeotrope with water. ProSim software was used to target the optimal conditions for washing before the experimental test. Residual water was recovered in the organic phase, meaning that the quality specifications for DCM were not reached. The second process studied for DCM purification was a pervaporation step. The feasibility of this had been proven at laboratory scale. The recovered DCM had the quality of a new solvent, and the whole process (distillation + pervaporation) reached a global DCM regeneration yield of 71.8% before optimization. This yield was limited by the distillation of methylal (also called dimethoxymethane) present in the methanolic effluent at the end of the distillation of the azeotrope, a compound retained by the pervaporation membrane. The pervaporation was performed on a hydrophilic Hybsi membrane letting methanol and water pass through and retaining the DCM (membrane surface = 0.15 m(2)). Optimization and scaling up were then carried out with a semi-industrial pervaporation pilot (membrane surface = 1.05 m(2)) which enabled the industrial scale-up. In order to facilitate the steering of the process and to ensure continuous and efficient monitoring of the regeneration operation, online monitoring by near-infrared probe (NIR) had been implemented allowing the composition of the mixture to be determined with an accuracy of +/- 0.05% on each compound. Finally, an assessment had been conducted of the regeneration pathways for methanol recovery at the bottom of the distillation column, for maximizing the regeneration of methanolic effluents by separating heavy compounds and methylal from methanol.
Morgane Le Hir, Adrien Magne, Thomas Clair, Emilie Carretier, Philippe Moulin. Solvent Regeneration in Complex Mixture Using Pervaporation. Organic Process Research and Development, 2021, 25 (3), pp.469-485. ⟨10.1021/acs.oprd.0c00442⟩. ⟨hal-03597582⟩
