In one embodiment, the present invention is to a process for producing a anhydrous ethanol composition comprising hydrogenating acetic acid in the presence of a catalyst to form a crude ethanol product; separating in a first column at least a portion of the crude ethanol product into a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid; separating in a second column at least a portion of the first distillate into a second distillate comprising ethyl acetate and a second residue comprising ethanol and water; separating in a third column at least a portion of the second residue into a third distillate comprising ethanol and residual water and a third residue comprising separated water; and dehydrating at least a portion of the third distillate to form the anhydrous ethanol composition. The anhydrous ethanol composition, as formed, comprises less than 1 wt. % water, based on the total weight of the anhydrous ethanol composition.