Two batch extractive distillation (BED) separation of two minimum boiling azeotropic mixtures (acetone − methanol + water as entrainer, isopropyl alcohol − water + DMSO) are simulated and optimized with GA. Production series consist of three consecutive batches. Both off-cuts are recycled to the next charge. The entrainer regenerated is also reused in the next batch. The objective function to be maximized is the profit of the whole production series. The optimization variables are the reflux ratios of all steps (main cuts, intermediate and after-cut), duration of the heating-up and the intermediate cut withdrawal and location and flow rate of entrainer feeding.