The design and optimization procedures of a heterogeneous thermally coupled azeotropic distillation sequence with a side stripper (TCADS-SS) for the purification of isopropanol has been investigated. The proposed procedures can detect the optimal values of the design variables and thereby guarantee the minimum energy consumption, which is related to the minimum CO2 emissions and the lowest total annual cost (TAG). The procedures are applied to the study of the separation of azeotropic mixtures using the two distillation sequences. In the TCADS-SS, the top end of the side stripper has both liquid and vapor exchange with the main column, which eliminates a condenser in contrast with the conventional heterogeneous azeotropic distillation sequence (CHADS). The results show that not only reductions in energy consumption and CO2 emissions but also higher thermodynamic efficiency can be obtained for the TCADS-SS.