Biofuels are present in the global scenario as an energy source derived from organic biomass, representing an economic and environmental alternative. They are a renewable source of energy with low rates of pollutants emissions and, consequently, less carbon dioxide is released into the atmosphere. The obtaining of bioethanol is originated from a fermentation process, in which a multi-component mix is generated and the anhydrous bioethanol is separated. To obtain such compounds, some operations are required, such as extractive distillation, where solvents are added in order to "break" the ethanol-water azeotrope. In the present work two solvents were used: Glycerol and the ionic liquid [BMIM][BF4]. Starting from a multi-component mixture composed by ethanol, water, acetic acid and isoamyl alcohol, the bioethanol purification process was simulated using the computational tool Aspen Plus® simulator. Through a comparative analysis, it was possible to determine which solvent presented the best performance, where operational parameters such as the reflux ratio, distillate rate and the solvent flow were analyzed. The purity degree of 99.7% in mass and an approximate production of 2764 kg/h of anhydrous bioethanol were fixed and the results showed that glycerol was the solvent that presented greater economic and environmental viability for the process, considering the operational parameters mentioned above.