Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff{\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (2) dehydrogenation of ethanol to acetaldehyde ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{CHO+H}}_{\mathrm{2}}), (3) esterification of acetic acid with ethanol ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+CH}}_{\mathrm{3}}\mathrm{COOH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (4) dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+O}}_{\mathrm{2}}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}\mathrm{O}). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.