Recently, an understanding of new sources of liquid hydrocarbons such as bio-ethanol is economically very important. The present dissertation is also designed with purpose of developing the energy-saving process for the separation of bio-ethanol. In order to illustrate the predictability of proposed process for the separation of bio-ethanol, the experimental data from literatures and real plant data are used. Application of the thermodynamics of multicomponent mixtures and phase equilibria to the extractive distillation process with syntheses of heat exchanger network has enabled the development of energy-saving process for different separating agents. Developed process is capable of minimizing the energy usage and the environmental effect. This extractive process is also able to properly describe the effect of impurities, the choice of separating agent. Simulation results of extractive distillation using ethylene glycol show that impurities do not affect to extractive distillation operation and agent, ethylene glycol, was recycled without any loss. It is possible that extraction distillation has various heat network for anhydride ethanol and recovery of ethanol is maximized. Ethylene glycol as separating agent has a high boiling point to eliminate azeotropic point and on the contrary solubility of agent is low to be almost completed recovered. Proposed process is also the energy efficient process configuration in which 99.85mole% anhydride ethanol can be produced with low energy of 1.37198 (kg steam/kg anhydride ethanol).