The hydrogenation of gas-phase methyl crotonate (MC) over Pt/Al2O3 was investigated with the aim to understand CC hydrogenation in unsaturated methyl esters. Three Pt/Al2O3 catalysts with different Pt dispersions were prepared by varying calcination temperature and evaluated for MC hydrogenation. The main products were found to be methyl butyrate (MB) and methyl 3-butenoate (M3B), resulting from hydrogenation and shift of the CC bond in MC, respectively. The measured activity for both hydrogenation and shift of the CC in MC was found to depend on the Pt dispersion where higher Pt dispersion favors the CC hydrogenation reaction. The effect of reactant concentrations on the activity and selectivity for MC hydrogenation over the Pt/Al2O3 catalyst was examined in detail. Under the investigated conditions, the CC hydrogenation was found to have a negative reaction order with respect to MC concentration but a positive H2 order. Further understanding of the MC hydrogenation was provided from H2 chemisorption experiments over the catalyst with and without pre-adsorbed MC and from transient experiments using alternating MC and H2 feeds. Based on the present experimental results, a reaction pathway was proposed to describe gas-phase MC hydrogenation over Pt/Al2O3. In order to gain more insight into the reaction, a kinetic analysis of MC hydrogenation was performed by fitting a power-law model to the kinetic data, moreover, dissociative H2 adsorption on the catalyst was found to be the rate-determining step by comparing the power-law model with the overall rate expressions derived from mechanistic considerations.
Hu, C., Creaser, D., Grönbeck, H., Ojagh, H., & Skoglundh, M. (2015). Selectivity and kinetics of methyl crotonate hydrogenation over Pt/Al2O3. Catalysis Science and Technology, 5(3), 1716–1730. https://doi.org/10.1039/c4cy01470g