The synthesis of two different esters, ethyl acetate and hexyl acetate, by heterogeneously catalysed reactive distillation has been studied. The investigated column set-ups were equipped with liquid-liquid separators for the distillate to separate water from the organic components. Experimental and theoretical investigations of operating conditions and different catalytic column internals, as well as different scales were performed. For the modelling and simulation of the reactive distillation columns, the rate-based approach was applied. The simulation results are in satisfactory agreement with the experimental data. Performed simulation studies demonstrate the influence of both operating conditions and catalytic internals on the overall process performance.