Hydroformylation of Cyclohexene with Carbon Dioxide and Hydrogen Using Ruthenium Carbonyl Catalyst: Influence of Pressures of Gaseous Components

Hydroformylation of cyclohexene was studied with a catalyst system of Ru3(CO)12 and LiCl using H2 and CO2 instead of CO in NMP. The influence of H2 and CO2 pressures on the total conversion and the product distribution was examined. It was shown that increasing total pressure of H2 and CO2 promoted the reverse water gas shift reaction and increased the yield of cyclohexanecarboxaldehyde. Its hydrogenation to cyclohexanemethanol was promoted with increasing H2 pressure but suppressed with increasing CO2 pressure. Cyclohexane was also formed along with those products and this direct hydrogenation was suppressed with increasing CO2 pressure. The roles of CO2 as a promoter as well as a reactant were further examined by phase behavior observations and high pressure FTIR measurements.