Two possible extractive dividing-wall column (DWC) arrangements are explored to find the potential benefits derived from thermally coupled distillations in separation of a mixture including the CO 2 –ethane azeotrope with a low boiling point. It is shown that the process including pre-fractionator in the DWC design in its optimized state leads to 51.6% reduction in total duties in comparison with the conventional process. Furthermore, a comparison between conventional extractive distillation columns and the new DWC process is made in terms of cost estimation, CO 2 removal efficiency and CO 2 emission reduction. Remarkable, the results clearly show that DWC process is interesting/feasible and the novel proposed DWC alternative reduces the steam requirements by 41% and the equipment costs by 31%.