Resource utilization and sustainable wastewater treatment have received widespread attention because of their efficient use of energy. In this study, an ethanol (EtOH)/ethyl tert-butyl ether/water ternary azeotropic system was used to explore the separation efficiency of various extractants. The relative volatility, toxicity, and process modeling of extractants were analyzed to provide a theoretical basis and practical guidance for screening the optimal extractant among nine commonly used extractants. Extractive distillation (ED) was optimized for six processes with a focus on total energy consumption (TEC) and total annual cost (TAC). The ED-EtOH process was the most economical, whereas the extractive ED-DMSO process had the lowest TEC. After heat integration (HI) treatment, the TAC and TEC of each process were reduced, among which HI-ED-EtOH and HI-ED-glycerol (GLY) had the best and lowest economy, respectively. Although high-boiling point and high latent heat extractants (such as GLY and EtOH) increase the heat demand and operating costs, their high latent heat characteristics can effectively recycle heat energy during the HI process. The optimal balance between economy and energy consumption was determined through multi objective optimization considering the physical and chemical properties, environmental impact, and adaptability of extractants.