Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng–Robinson–Stryjek–Vera equation of state and the Wong–Sandler mixing rules

Due to the economics of the ethylene market and the subsidized production of fermentation-based ethanol in some countries, use of the ethylene hydration process to make ethanol has been steadily declining. The economics of this process might improve by combining the reaction and separation in a reactive distillation column, whose conceptual design requires a study of the combined chemical and phase equilibrium (CPE) of the reacting system. In this work, the Peng–Robinson–Stryjek–Vera equation of state was combined with the UNIQUAC activity coefficient model through the Wong–Sandler (WS) mixing rules in order to correlate the available experimental data for the vapor–liquid equilibria (VLE) of the ethylene–water, ethylene–ethanol, and ethanol–water binary systems at 200 °C. The interaction energies of the UNIQUAC model and the binary interaction coefficient of the WS mixing rules were used as the fitting parameters. From the optimum values of these parameters, both the VLE and the combined CPE of the ethylene–water–ethanol ternary system were predicted at 200 °C and various pressures. At this temperature, the catalytic activity of a H-pentasil zeolite has already been reported to exhibit a maximum for ethylene hydration, and also the experimentally measured two-phase region of the ternary system is sufficiently wide. By means of the reactive flash method, the chemical equilibrium compositions of the liquid and vapor phases were determined for several pressures, and the equilibrium conversion and the vapor fraction were calculated as functions of the ethylene to water feed mole ratio. It turns out that the vapor–liquid mixed-phase hydration of ethylene achieves equilibrium conversions much higher than those computed for a vapor-phase reaction that would hypothetically occur at the same conditions of pressure and feed mole ratio. It was found that the reactive phase diagram of the ternary system exhibits a critical point at 200 °C and 155 atm.

► We calculated chemical and phase equilibrium for hydration of ethylene to ethanol.
► We used PRSV2 equation of state, UNIQUAC model, and Wong–Sandler mixing rules.
► Vapor–liquid hydration achieves higher conversions than vapor-phase hydration.
► No reactive azeotrope exists for ethylene–water–ethanol at 200 °C.
► The reactive phase diagram exhibits a critical point at 200 °C and 155 atm.