This work provides an insight into the separation of azeotropic mixtures by using two different techniques: pressure swing distillation and extractive distillation. Both methods are used to separate an azeotropic mixture of methanol and benzene. This mixture exhibits a minimum boiling azeotrope at temperature 57.97 °C and pressure 1 bar with mole fractions of 0.61 and 0.39 for methanol and benzene, respectively. However, the azeotropic point in methanol and benzene mixture is pressure sensitive, which can be shifted by changing pressure with a process called pressure swing distillation. Extractive distillation with suitable solvent is another method to separate such kind of mixture. Both methods are rigorously simulated and optimized for minimum heat duties. Internal heat integration is applied too for increasing energy efficiency. New optimization techniques are carried out with process simulator Aspen HYSYS V8.4 and results reveal the best method for separation of methanol and benzene azeotropic mixture.