In industrial processes, 2-methylpyridine/water mixtures can be separated via the conventional heterogeneous azeotropic distillation (HAD) using benzene as entrainer. 2-Methylpyridine and water can form a heterogeneous azeotrope by themselves, based on which an improved HAD process is proposed. This allows for reducing the total operating cost and total annual cost (TAC) by more than one-tenth compared with the conventional HAD process. Two different control structures were established for the enhanced HAD process. The results indicate that applying the feedforward ratio controllers to the control structure can handle the feed disturbances and maintain product purities with smaller transient deviations and shorter settling times.