Catalytic glycerol hydrogenolysis to 1,3-propanediol in a gas–solid fluidized bed

Abstract

Glycerol is a potential feedstock to produce 1,3-propanediol (1,3-PDO), which is a valuable commercial polyester monomer. Here, we report the gas-phase glycerol hydrogenolysis to 1,3-propanediol over Pt/WO₃/Al₂O₃ in a fluidized bed operating above 240 °C and at ambient pressure. Fluidized beds are ideal contactors for this reaction because the heat transfer rates are sufficiently high to vaporize glycerol thereby minimizing its combustion and thermal degradation. The yield of 1,3-PDO approached 14% after 2 h at 260 °C. The major co-products were 1,2-PDO (18%), 1-propanol (28%) and 2-propanol (15%). In the first step, glycerol may dehydrate to acrolein, followed by rehydration to 3-hydroxypropanal and then hydrogenation to 1,3-PDO. The concentrations of the by-products including acrolein, ethylene glycol, propane, and acetone increased with increasing temperature.