Among biofuels, bioethanol has increased in importance in many countries because it can be used directly or mixed with gasoline in combustion engines. The production of bioethanol in a fermentative process usually gives a dilute solution from which the bioethanol must be obtained in high concentration in order to be used as biofuel. The separation of an azeotropic mixture of ethanol and water using batch and semibatch distillation was studied considering ethylene glycol and ionic liquids as entrainers. The simulation and experimental results indicate that the separation is favored using ethylene glycol in comparison to the use of ionic liquid; however, the ionic liquid is considered a green solvent and the use of ethylene glycol could be forbidden in the near future. (c) 2012 Elsevier B.V. All rights reserved.