This paper presents a systematic procedure for generating a catalog of the most promising separation sequences for homogeneous azeotropic mixtures without boundary crossing. First, the azeotropic mixtures are classified into classes, of azeotropic systems. This is followed by the generation of feasible distillation sequences for each class of azeotropic system. The sequences generated are screened using new heuristics developed here by means of geometric reasoning, as well as some well-established sequencing heuristics, to give the most promising distillation sequence for each class of azeotropic system. The procedure results in a new catalog of classes of azeotropic systems with their corresponding most promising separation sequences.