Abstract: The present invention relates to the recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid. Separation and purification processes of crude ethanol product are employed to allow recovery of an anhydrous ethanol composition. The process involves separating the crude ethanol product using one or more extractive distillation columns that employ one or more extractive agents. The anhydrous ethanol composition comprises less than 1 wt. % water, based on the total weight of the anhydrous ethanol composition.