Thermodynamic Analysis for the Synthesis of Dimethyl Carbonate from Dimethyl Ether

The standard enthalpy of formation, free energy and thermal capacity of the synthesis of dimethyl carbonate (DMC) from dimethy ether were calculated using the method of Benson group contributions. The thermodynamic analysis of the synthesis processes was carried out with the emphasis on the calculations of free energy for DMC synthesis from dimethyl ether (DME) with CO and O_2 or DME with CO_2 at different temperature and pressure. Results showed that DMC synthesis by oxidation carbonylation of DME is thermodynamically feasible, but the direct synthesis of DMC from DME and CO_2 is unfeasible. Thus, it is necessary to design other reaction routes for the synthesis of DMC from DME and CO. Optimum reaction conditions for DMC synthesis were investigated, which provides the thermodynamic basis for designing DMC synthesis process and developing catalysts for such process.