In this article, the design and optimization procedures of a dividing-wall column for heterogeneous azeotropic distillation (DWC-A) using cyclohexane as an entrainer for ethanol dehydration are investigated. The proposed procedures can detect the optimal values of the design variables and thereby guarantee the minimum energy requirements, which is related to the minimum CO2 emissions and the lowest total annual cost (TAC). Since ethanol and water form an azeotrope under atmosphere pressure, a conventional heterogeneous azeotropic distillation sequence (CHADS), including an azeotropic column and a recovery column, is usually used to perform the ethanol dehydration process. However, due to high energy requirements and equipment investments of CHADS, the TAC is at a relatively high level. DWC-A can be used to eliminate the condenser of the second column and decrease the degree of back-mixing. Both CHADS and DWC-A are simulated with Aspen Plus (R), and the results show that DWC-A has an energy saving of 42.17% and the TAC reduction of 35.18% along with higher thermodynamic efficiency and reduction in greenhouse gas emissions.