Glycerol valorization to glycolic acid through glyceraldehyde

L’objectif de cette thèse vise à la mise au point d’un procédé catalytique hautement sélectif pour la transformation du glycérol en aldéhyde et acide glycolique en l’absence de base. Pour cela, nous avons développé une approche de type catalyse hybride (i.e., couplage de catalyse enzymatique et de catalyse chimique). Cette étude résulte de la collaboration entre 3 laboratoires universitaires (i.e., l’UCCS, l’institut Viollette, le LGPC). Le travail de thèse présenté ici, est relative à la partie catalyse hétérogène. Afin d’atteindre nos objectifs, nous avons travaillé sur phase active à base de platine supporté sur différents supports (i.e., ZSM-5, TiO2, SiO2, Al2O3). Les catalyseurs ont été caractérisés (DRX, BET, XPS, ICP et MET) et testés en phase liquide en l’absence de base. Les conditions réactionnelles (température, concentration du glycérol, pression d’O2) ainsi que la formulation du catalyseur ont été optimisées. Cette optimisation a été couplée à une étude cinétique pour acquérir une meilleure compréhension des mécanismes de réaction et les facteurs les plus importants sur l’activité catalytique. Le glycéraldéhyde ainsi formé est ensuite transformé en un autre aldéhyde (i.e. le glycolaldéhyde) par catalyse enzymatique. Lors de la dernière partie de la thèse, nous avons optimisé différents paramètres (température et pression d’O2) afin d’augmenter l’oxydation du glycolaldéhyde en acide glycolique et glyoxal.The objective of this thesis is to develop a highly selective catalytic process for the conversion of glycerol to aldehydes and glycolic acid in the absence of base. For this, we have developed a hybrid catalysis approach (i.e., enzymatic catalysis and chemical catalysis coupling). This study results from the collaboration between 3 academic laboratories (i.e., UCCS, Viollette institute and LGPC). The thesis work presented here is relative to the heterogeneous catalysis part. In order to achieve our goals, we worked on a platinum-based active phase supported on different oxides (i.e., ZSM-5, TiO2, SiO2, Al2O3). The catalysts have been characterized (DRX, BET, XPS, ICP and MET) and tested in liquid phase in the absence of a base. The reaction conditions (i.e., temperature, glycerol concentration, O2 pressure) as well as the catalyst formulation have been optimized. This optimization was coupled with a kinetic study to gain a better understanding of the reaction mechanisms and the most important factors on catalytic activity. The glyceraldehyde thus formed is then converted into another aldehyde (i.e., glycolaldehyde) by enzymatic catalysis.The last part of the thesis consists on the optimization of the reaction conditions (temperature, O2 pressure) to increase the oxidation of glycolaldehyde to glycolic acid and glyoxal

Glycerol to Glyceraldehyde Oxidation Reaction Over Pt-Based Catalysts Under Base-Free Conditions

International audienceGlycerol valorization through partial oxidation is a good way of obtaining many different molecules with high added value such as glyceric acid, tartronic acid, dihydroxyacetone, etc. Among the potential products, glyceraldehyde is an interesting chemical compound for its various applications in different domains such as organic chemistry, medical, and cosmetic industries. In the present paper, we studied the effect of different supports on the glycerol oxidation reaction in a batch reactor applying base-free conditions. The tested catalysts were Pt-based materials deposited on various supports (i.e., SiO2, TiO2, ZSM-5, γ-Al2O3), which were synthesized using a deposition method followed by a chemical reduction. The catalysts were extensively characterized (BET, ICP, XRD, TEM, XPS), highlighting differences in terms of specific surface areas, textural properties, and Pt nanoparticles sizes. We evidenced a direct relation between glycerol conversion and glyceraldehyde selectivity (i.e., an increase in glycerol conversion leads to a decrease in glyceraldehyde selectivity). The Pt/γ-Al2O3 catalysts exhibited the highest activity, but their selectivity to glyceraldehyde significantly decreased with time on stream. Pt/SiO2 presented the highest selectivity to glyceraldehyde owing to a slower reaction rate, which allows envisioning technical opportunities to continuously extract the formed glyceraldehyde from the mixture

Glycerol Partial Oxidation over Pt/Al2O3 Catalysts under Basic and Base-Free Conditions-Effect of the Particle Size

International audienceThe glycerol partial oxidation reaction over Pt/Al2O3 catalysts was studied under basic (NaOH/GLY molar ratio 4) and base‐free conditions (NaOH/GLY molar ratio 0). Catalysts with small (2.95 nm) and large particle sizes (260.83 nm) were synthesized according to the use of different reducing agents, formaldehyde or sodium borohydride, and hydrazine, respectively. These different Pt particle sizes lead to a dramatic change in terms of activity, irrespective of the applied conditions. The biggest particles (i.e., 260 nm) seem to generate overoxidation products leading to a decrease in the carbon balance (to ~80%) while the smallest particles exhibit the highest initial glycerol transformation rate (i.e., ~10,000 mol h−1 molPt−1 under basic conditions at 60°C and ~2000 mol h−1 molPt−1 in the absence of a base at 100°C). In terms of selectivities, the main products are different as a function of the initial reaction conditions. For base‐free conditions, the two main products are glyceraldehyde and glyceric acid with a sum of selectivities always larger than 80%. Under basic conditions, the major product is glyceric acid while no trace of glyceraldehyde is detected

Liquid phase glycerol oxidation: Choice of the catalysts and the ad-hoc reaction conditions for the right target molecule

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From Monometallic to Bimetallic Systems: Improving Glycerol Liquid Phase Catalytic Oxidation

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Comparative study of solvolysis of technical lignins in flow reactor

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