The mixture of n-heptane and isobutanol creates a minimum-boiling azeotrope under atmospheric conditions. Extractive distillation was used for separating n-heptane and isobutanol. A sequential iterative optimization procedure optimized the steady state extractive distillation process to obtain a minimal total annual cost (TAC). The dynamic control of the optimal extractive distillation process showed poor controllability. It was found that the dynamic control performance could be improved if the solvent flow rate was increased properly with a small increase in TAC. Hence, the choice of the optimal extractive distillation process for separating a binary azeotropic mixture should be considered from the perspectives of both TAC and the dynamic control performance.