In order to investigate the dimethyl carbonate synthesis from methanol and supercritical CO2, the thermodynamic
behaviour of the reacting mixture, i.e. the quaternary methanol/CO2/DMC/water mixture, has to be known. The
SRK equation of state with MHV2 mixing rules has been chosen to predict fluid phase equilibria in the reactor. The
first part of this work is dedicated to the determination of binary interaction parameters, needed in the use of this
model. These parameters are deduced from the fitting of experimental data concerning binary or ternary sub-systems
existing in the quaternary mixture. Literature data was used for most of the binary sub-systems, but for the DMC/CO2 and DMC/water mixtures, specific experiments were carried out. The agreement between experimental and predicted fluid phase equilibria was found to be satisfactory. With a view to studying of the operating conditions for the reaction, the thermodynamic model was used to predict fluid phase equilibria in the reactor, by considering several hypothetical
feed ratios and conversions. This work shows that CO2 has to be used in large excess in order to be sure of running the reaction in a homogeneous fluid medium
