<p>The presence of a minimum-boiling azeotrope (MIBA) between methanol (Me) and dimethyl sulfide (DMS) presents a challenge in developing distillation sequences for methyl mercaptan (MT) purification. This study introduces a virtual-component strategy to address this challenge in three stages. First, the optimal scheme for breaking the binary azeotrope is determined by rigorous simulations using Aspen Plus. Second, overall separation sequences are generated using both the Ordered Heuristics method and the Relative Cost Function (RCF) method. Third, the best separation configuration is selected based on rigorous simulation results. This strategy is applied to selecting the final distillation sequence for crude MT products, which contain five main components: dimethyl ether (DME), MT, DMS, methanol (Me), and water (H₂O). MIBA is introduced as a virtual component to replace the minor component DMS, constructing a sequence list [DME, MT, MIBA, Me, H₂O]. The resulting sequence developed with virtual-component strategy achieves the lowest total annual cost and CO₂ emissions. Compared to the traditional approach, the virtual component strategy is an effective methodology for synthesizing separation processes for azeotrope-containing mixture.</p>