To address the downstream processing challenges of the IBE (isopropanol-butanol-ethanol) system and obtain biobutanol products with a mass fraction of 0.9999, as well as obtain a mass fraction of 0.99975 for the IE (isopropanol-Ethanol) mixture product as a gasoline additive, this study proposes a four-column distillation process termed "Dehydration-Butanol-Extractive Four Column Distillation" (DBE-4CD). With the heat load as the optimization target, the DBE-4CD process was optimized to determine the optimal operating parameters. Based on the optimized process and considering the energy-saving potential of the dividing wall column, an “Azeotropic Dividing Wall-Extractive Three Column Distillation” (ADE-3CD) process was subsequently proposed to further enhance energy efficiency and reduce consumption. Compared to both conventional literature process and the DBE-4CD process, the total load of the ADE-3CD process decreased to 7433.5 kW, representing reductions of 20.35% and 10.11%, respectively. Additionally, the mass recovery rates of butanol and the IE mixture reached 99.90% and 99.64%, respectively, exceeding those of the conventional literature process, which were 99.11% and 99.18%.