Based on the continuous two columns distillation technology, it is difficult to separate the ternary mixture of n-hexane/ethanol/butanone, which contains three binary minimum boiling point homoazeotropes. Through analyzing characteristics of batch distillation and the phase behavior, it is feasible to achieve high purity separation of this kind of complex mixture by two-column batch distillation. Three sequential two-column batch distillation processes including Process A (Double columns with series operation), Process B (Double columns with parallel-then series operation) and Process C (Single column-then double columns process) were designed and analyzed in this work. The processes were evaluated and optimized from the aspects of economy and environment. In terms of economy, environment impacts and operating time, Process B is prior to Process A and Process C. Based on the thermodynamic analysis of the column, the heat integration problem of Process B is considered, which includes a self-preheating scheme at first step, and a heat exchange scheme in which high-pressure column top vapor provide part of the heat to low-pressure column bottom at second step. Compared with the unimproved Process B, the operating cost of the improved Process B can be reduced by 28% and TAC can be reduced by 3% at step 1. The operating cost of the improved Process B can be reduced by 30% at step 2.