Biofuels and bioethanol are catalyzing the attention of researchers due to the big potential in reducing the dependence on crude oil together with the possible reduction in the pollution associated with the combustion processes. The bioethanol separation process is significant in terms of its production cost. In this paper, the availability of new distillation sequences for the separation of pure ethanol from the fermentation broth is considered. The new sequences are generated following a step-by-step procedure. Extending the concept of thermally coupled structures and column sections recombination, already successfully applied to ideal mixtures, it was possible to generate new distillation sequences for azeotropic mixtures. The new arrangements are proved to have a lower energy consumption together with a reduced capital cost compared to the classical sequence proposed in the literature. (C) 2012 Elsevier B.V. All rights reserved.