Gas-liquid hydrogenation in continuous flow - The effect of mass transfer and residence time in powder packed-bed and catalyst-coated reactors

Catalyst-coated tube reactors have been compared with the reactors packed with catalyst powder in alkyne semi-hydrogenation over a 5 wt% Pd/ZnO catalyst and cinnamic ester full hydrogenation over a 2.4 wt% Pd/C catalyst. The powder packed-bed reactors (packing with catalyst powder below 30 mu m) showed irreproducible performance in time due to mobility of the catalyst layer in the bed which altered the fluidic path and therefore affected the mean liquid residence time and the dispersion. The catalyst-coated tube reactors demonstrated an ideal plug-flow behaviour (Peclet number > 120), while the powder packed-bed showed a considerable back-mixing (Peclet similar to 25). Under all conditions studied, the reaction rate in the powder packed-bed was limited by external mass transfer, while in the coated tube - by the intrinsic kinetics. The coated tubes demonstrated a much lower pressure drop, an improved alkene selectivity, and a 5 times higher throughput compared to the powder packed-bed. The dilution of the catalyst bed with glass beads improved the throughput 4-fold at the expense of 4-fold increase in the pressure drop. In full hydrogenation reaction, the catalyst-coated tube showed a 14 times higher throughput than in the powder packed-bed at the full alkyne conversion. A reactor model for the catalyst-coated tube has been proposed that takes into account the change in the fluid velocity during the reaction. The model described the reaction kinetics demonstrating that the catalyst-coated tubes can be used as a tool to obtain kinetic data in gas-liquid reactions in flow.