Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

Heterogeneous rhodium catalysts supported on SiO2 were modified with PPh3 for the gas-phase hydroformylation of propene to produce nand isobutanal. High selectivity to aldehydes was achieved, with no propane or alcohols formed. Investigation of the effects of reaction temperature, reactant partial pressures, total pressure, and PPh3/Rh ratio suggested that the supported catalyst behaved similarly to the homogeneous catalyst. In particular, the supported catalyst showed similar activation energies and partial and total pressure dependences of the reaction rates to those observed in homogeneous, liquidphase reactions. The first order dependence of the hydroformylation rate on the partial pressures of propene, CO, and H2 individually led to a cubic dependence of butanal formation on total pressure for equimolar reactant mixtures. High regioselectivity with a typical n/i ratio of 14 was achieved.