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Highlights • The entrainers p -xylene, butyl propionate and isobutyl acetate were selected. • The VLE data for (DMC + entrainers) and (ethanol + isobutyl acetate) were measured. • The measured VLE data were correlated by the NRTL, UNIQUAC and Wilson models. • The extractive distillation process for separating DMC and ethanol was proposed. Abstract Dimethyl carbonate and ethanol can form an azeotrope with the minimum boiling point. To separate the azeotrope (dimethyl carbonate + ethanol) by extractive distillation, p -xylene, butyl propionate, and isobutyl acetate were chosen as entrainers, and the isobaric vapour-liquid equilibrium (VLE) data for the binary systems of (dimethyl carbonate + p -xylene), (dimethyl carbonate + butyl propionate), (dimethyl carbonate + isobutyl acetate) and (ethanol + isobutyl acetate) were measured at 101.3 kPa using a modified Rose type recirculating still. The thermodynamic consistency of the VLE experimental data for the four binary mixtures was tested by the Herington and van Ness methods. Furthermore, the measured VLE data were correlated by the NRTL, UNIQUAC and Wilson thermodynamic models and the binary interaction parameters of the three models were regressed. Based above, an extractive distillation process with the entrainer of p -xylene was proposed and simulated to separate the azeotrope (dimethyl carbonate + ethanol). [ABSTRACT FROM AUTHOR]