The aim of this work is to simulate and to optimize a saline extractive distillation process for purification of ethanol from the ethanol-water binary system. All the work was developed using ASPEN PLUS simulator, version 10.1-0, and the NRTL thermodynamic model developed for calculating activity coefficients of electrolytic systems, having as goal to get the anhydride ethanol (99.7 wt.%). In the development of this study, four saline agents were tested (NaCl, KCl, KI, CaCl2). The complete process and a methodology to optimize it were established in the simulator in such a way all variables were optimized. It was verified that using only the saline extractive distillation process, it is possible to purify the ethanol from the fermentation broth composition obtaining a product with high purity. Finally, a comparative study using electrolyte distillation process and the integrated distillation process (simple and extractive distillation) was carried out.