Kinetics and mass transfer effects were studied for the complex catalytic liquid-phase hydrogenation in a semi-batch reactor, where finely dispersed and larger catalyst particles were used. Citral was used as a model molecule. The intrinsic kinetics was determined with crushed catalyst particles at 60 degrees C and at pressures ranging from 10 to 40 bar. A kinetic model was proposed and successfully fitted to the experimental data. In order to elucidate the influence of internal diffusion on the selectivity and activity in complex reactions, citral hydrogenation was performed with larger catalyst pellets, in a pressurized autoclave equipped with a catalyst basket. As expected, the activity decreased with increasing catalyst particle size. The product distribution was shifted from the primary hydrogenation product (citronellal) to the fully hydrogenated end product (3,7-dimethyloctanol) as the catalyst particle size was increased. The concentrations of the secondary hydrogenation products were minor throughout the experiment. A complete reaction-diffusion model was developed for large pellets and complex reactions systems. (c) 2005 Elsevier Ltd. All rights reserved.