Production of anhydrous ethanol in large scale has been made by extractive distillation using conventional solvents like ethylene-glycol. In the present paper, extractive distillation process is studied to obtain pure ethanol using ethylene-glycol and tetra ethylene-glycol as solvents. Residue curve maps are used to analyse the proposed distillation processes in interpreting mixture behaviours and feasibility of distillation columns. The industrial process is simulated at steady state from residue curve map analysis. Simulation results for the ethanol/water mixture using ethylene-glycol, the conventional solvent, and tetra ethylene-glycol, an alternative solvent, are presented. These results showed that the process using tetraethylene-glycol is reliable, although it requires more energy than the process with ethylene-glycol. However, ethylene-glycol has a considerable toxicity level while tetra ethylene-glycol is non-toxic. (C) 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.