Study On Vapour-liquid Equilibria Of Binary Systems Containing Carbon Monoxide Under High Pressures

The high pressure vapor-liquid equilibrium data (including composition, density and molar volume) of four binary systems (CO + methyl propionate, CO + ethyl propionate, CO + isopropanol and CO + isobutanol) have been measured at different temperatures and pressures with isothermal static analytical method through a self-designed variable-volume autoclave with a quartz window. The study aims to provide necessary thermodynamic data for the process optimization in the synthesis of propionate ester and low-carbon alcohol from carbon monoxide and also for the phase equilibrium calculation of multiple systems containing carbon monoxide.The vapor-liquid equilibrium data show that the solubilities of carbon monoxide in the four liquids increase with increasing pressures at the given temperatures, and the contents of four liquids in carbon monoxide also increase with increasing pressures at the given temperatures. While the solubilities of carbon monoxide in the four liquids decrease significantly with increasing temperatures at the given pressures, but the contents of four liquids in carbon monoxide increase faintly.The high-pressure vapour-liquid equilibrium data are also calculated with six methods for the above four systems. The PR and PRSV equations of state and four different mixing rules (van der waals-1 mixing rule, van der waals-2 mixing rule, Margules mixing rule and the mixing rule expressed by activity coefficient) are used. The calculation was optimized by using search method for the high pressure vapour-liquid equilibrium of the above binary systems. The influence of state equation, mixing rules and regression method on the calculation precision are discussed systemically. The method combining PRSV equation of state with van der waals-2 mixing rule gave excellent results.