Catalyst performance for noble metal catalysed alcohol oxidation: reaction-engineering modelling and experiments

Abstract

A reaction-engineering model is presented, which describes catalyst performance as a function of the catalyst activity profile, the reaction kinetics, and the degree of catalyst deactivation. With this model, the catalyst activity profile can be optimised for Pt catalysed methyl α- d-glucopyranoside (slowly-reactive) and glucose (highly-reactive) oxidations. This is done by comparing modelling results with experimentally obtained data for catalysts of different activity distributions. Experiments in a semi-batch stirred reactor showed that for methyl α- d-glucopyranoside (MGP) oxidation at oxygen partial pressures below 40 kPa, egg shell catalytic activity distribution gives a higher rate of oxidation than a uniform distribution. It was also observed that with increase in oxygen concentration from 10 to 40 kPa, the rate of deactivation due to catalyst over-oxidation increased dramatically. For glucose oxidation, both catalyst activity distributions give the same oxidation rate for all investigated oxygen partial pressures (5–100 kPa). The developed model adequately describes the observed experimental results of both reactions. It was found that the active metal particle size has a significant influence on the catalyst deactivation for MGP oxidation; the uniform catalyst with higher dispersion shows a higher deactivation rate than the egg shell catalyst. For modelling glucose oxidation, the effect of catalyst particle-to-bubble adhesion and higher diffusivity or partition coefficient for oxygen have to be taken into account.