Determination of Binary Vapor Liquid Equilibria (vle) of Reactive Systems

The simulation of reactive distillation processes requires binary phase equilibrium data and information about the reaction kinetics and equilibrium. The phase equilibrium data for the binary reacting sub-systems are difficult to measure experimentally since the products of reaction affect the binary equilibrium as soon as they are formed. A novel apparatus has been constructed to measure these data for reaction rates with half-life time of 30 minutes and below. Experimental data are presented for compounds of ethanol and isopropanol with formic acid at 40 – 60°C as a model reaction for reactive distillation. The synthesis of ethyl formate is realized at these temperatures in technical columns. The proposed method can be applied to obtain binary interaction parameters of reactive compounds for commonly used gmodels, if the half-life time of the non-catalyzed reaction at the desired temperature is above 10 minutes.