Fluidized Bed Catalytic Glycerol Hydrodeoxygenation to 1,3-Propanediol

1,3 propandiol (1,3-PDO) is a monomer for commercial polyesters like Corterra® (Shell) and Sorona® (DuPont). Glycerol is an attractive feedstock for this monomer because of its low cost. Here we propose a gas-phase hydrodeoxygenation process in which we atomize a dilute solution of glycerol to a fluidized bed of of Pt/WO3/Al2O3 operating above 240 °C and atmospheric pressure. Gas-solids fluidized beds have excellent heat transfer properties that vaporize the droplets within milliseconds thereby minimizing thermal degradation of the glycerol. After 2 h at 260 °C, 1,3-PDO yield reached 14%. The other products included 1,2-PDO (18%), 1-propanol (28%), and 2-propanol (15%). We postulate that glycerol first dehydrates to acrolein, then rehydrates to 3-hydroxypropanal followed by the hydrogenation to 1,3-PDO. The yield of other compounds (acrolein, ethylene glycol, propane, and acetone) increased at higher operating temperatures.