Diphenyl carbonate, a precursor in the production of polycarbonate, is traditionally synthesized by the transesterification reaction of dimethyl carbonate and phenol. In this study, phenyl acetate was used instead of phenol to react with dimethyl carbonate and yield diphenyl carbonate, due to its higher reaction conversion and the absence of side reactions and azeotropes. A plant-wide process with a reactive distillation (RD) column and a separation column was optimized by minimizing the total annual cost. The performance of the thermal coupling between these two columns was also investigated. RD with thermal coupling was demonstrated to provide better energy efficiency than conventional RD. The remixing phenomenon associated with thermodynamic inefficiency in conventional distillation sequences could be greatly reduced by implementing thermal coupling between columns. Reactant concentrations that were closer to stoichiometric balance in the reaction zone were given for the thermally coupled RD column. (C) 2013 Elsevier Ltd. All rights reserved.