Modelling and simulation of the reactive distillation column have bean carried out for the carbonylation process of ethanol with dimethyl carbonate (DMC) producing diethyl carbonate (DEC). As it includes three azeotropes and two cascade reversible reactions with an undesired intermediate, methyl-and-ethyl carbonate (MEC), the reactive distillation is ideally appropriate. Calculations via a robust transient method reveal that a complete DMC conversion, a sound DEC selectivity over 99.5%, a perfect overcoming of azeotropic limitation, as well as a thorough separation of the alcohols from carbonates can be accomplished in the studied column. The model reliability is analyzed by assuming several values of Murphree tray efficiency, showing no considerable difference between the equilibrium and non-equilibrium models for this system. Moreover, effects of the feed locations of the two reactants and the reflux ratio on the performance of the column are discussed, too.