Kinetics of Dicyclopentadiene Hydroformylation over Rh–SiO2 Catalysts

The hydroformylation of dicyclopentadiene (DCPD) to monoformyltricyclodecenes (MFTD) represents a key intermediate step in the conversion of the C5 fraction derived from the petrochemical process to value-added fine chemicals, for example, diformyltricyclodecanes and tricyclodecanedimethylol. Although both heterogeneous and homogeneous catalysts can catalyse this reaction, the heterogeneously catalysed pathway has received significantly less attention due to its lower catalytic activities. We demonstrate in this work that a low Rh loaded heterogeneous 0.1% Rh–SiO2 catalyst can present a similar performance relative to the homogeneous Rh(PPh3)Cl, a reference catalyst for this reaction. Furthermore, an extensive kinetic study of DCPD hydroformylation to MFTD using heterogeneous 0.1% Rh–SiO2 catalysts has been performed. A series of kinetic experiments was carried out over a broad range of conditions (temperature: 100–120 °C; pressure: 1.5–5 MPa; catalyst-to-reactant mass ratio: 0.02–0.05; PPh3 concentration: 5–12.5 g L−1). A kinetic analysis was carried out, indicating the activation energy for the reaction to be 84.7 kJ mol−1. DCPD conversion and MFTD yield could be optimised to be as high as 99% at 0.1% Rh loading, a DCPD/catalyst mass ratio of 25, a PPh3 concentration of 10 g L−1, a reaction time of 4 h and a reaction pressure of 4 MPa.