The separation of binary mixtures which form azeotropes is not possible through conventional distillation and they are usually separated by extractive or azeotropic distillation. The optimization of extractive distillation columns is usually performed using a process simulator; however, normally, the result is only obtained after several simulations and the simultaneous analysis of several graphs. This paper sets out to present a systematic procedure, using a process simulator (Aspen Plus (R)), in order to obtain the optimum condition for extractive distillation columns. The optimization achieved is characterized by the fact that it is not necessary to perform various simulations, and it also avoids the simultaneous analysis of dozens of curves. The dehydration of aqueous mixtures of ethanol using ethylene glycol as solvent was the system chosen as a case study. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.