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Centre National de la Recherche Scientifique / LCC

Country: France

Centre National de la Recherche Scientifique / LCC

1 Projects, page 1 of 1
  • Funder: French National Research Agency (ANR) Project Code: ANR-15-CE07-0008
    Funder Contribution: 502,988 EUR

    PICPOSS seeks to develop a continuous flow process for the sustainable production of fine chemicals and pharmaceuticals through sensitized photo-oxygenations. Various LED-driven microreactors will be constructed: due to their dimensions, mass, heat and light transfer phenomena are enhanced, thus enabling yields and selectivity to be increased, and safe and photon-efficient conditions to be possible. Contrary to conventionally studies reported in the literature, the sensitizer will not be solubilized in the reaction medium, but supported on silica/polymer beads or inside colloid systems instead. The advantage is to reduce downstream separation processes and to develop a new photochemical synthesis concept. Gas-liquid-solid “slurry Taylor” flows will be generated in flow reactors which can be readily adopted for industrial application using meso-scale continuous equipment. PICPOSS will focus on two benchmark reactions of industrial relevance: the photo-oxygenation of alpha-terpinene, a common essential oil component, and of furfural obtained from hemicelluloses contacting waste from agriculture. PICPOSS combines chemical engineering & process intensification (LGC-Toulouse. K. Loubière), mechanistic photochemistry (ICMR-Reims, N. Hoffmann), solid-supported sensitizer development (IPREM-Pau, S. Lacombe), organic chemistry and trioxane preparation (LCC-Toulouse, O. Dechy-Cabaret), and applied flow photochemistry (JCU-Australia, M. Oelgemoeller). PICPOSS involves four scientific tasks, supported by task 0 (coordination). Task 1 aims at studying benchmark photo-oxygenations in batch reactors. Eco-friendly solvents will be studied and various sensitizers investigated (commercially available, advanced sensitizers synthesized in Task 3). Side reactions (including sensitizer decomposition) will be determined, and analytical conditions for an easy reaction monitoring in microreactors will be established. Task 2 is devoted to the transfer of the benchmark photo-oxygenations to microreactors using solubilized photosensitizers. It also includes the characterization of gas-liquid mass transfer in microreactors and the determination of the incident photon flux. Task 3 concerns the preparation and characterization of various sensitizing materials. Commercial and advanced lab-made sensitizers will be firstly surface-fixed on commercial silica/polymer beads. Then, sensitizing colloids systems (polymer particle, microgel) will be synthetized as they offer higher surface area and/or enable core-functionalization. These materials will be characterized and their stability, photobleaching, turnover frequency and quantum yields of singlet oxygen production will be evaluated. The most efficient and stable sensitizing materials will be tested in batch reactors in view of their implementation in microreactors. In Task 4, photo-oxygenations will be carried out in microreactors using sensitizing materials. For each reaction, a screening of operating conditions will be performed to define an operating domain and to maximize the reaction’s outputs. Experiments will be also implemented in meso-scale flow-equipment to demonstrate proof-of-concept for scale-up. Finally, the performances of the different batch and microreactors will be compared depending on the sensitizing materials. Likewise, the effectiveness of the advanced solid-supported sensitizers will be demonstrated by comparison with their solubilized counterparts. Combining experiments and modelling tools, guidelines will be established to assess the feasibility of flow photochemistry with sensitizing materials, and to address smart scale-up issues. The breakthroughs developed will overcome safety and cost concerns of currently available technologies (batch reactors, energy-demanding mercury lamps), and thus open new opportunities for industrial synthesis of valuable fine chemicals via sensitized photo-oxygenation.

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