The mixture of dimethyl carbonate (DMC) and ethanol is a common binary azeotrope system in industry that cannot be effectively separated by conventional separation methods. Two ionic liquids (ILs), namely, 1-butyl-3methylimidazolium dibutylphosphate ([BMIM][DBP]) and 1-butyl-3-methylimidazolium acetate ([BMIM][Ac]), were tried as novel entrainers for the separation of the DMC−ethanol azeotrope. The vapor−liquid equilibrium (VLE) data of the DMC−ethanol binary system and the DMC−ethanol−ILs ternary system at atmospheric pressure were determined. The results showed that both ILs could increase the relative volatility of DMC to ethanol, thus completely breaking the azeotrope at a certain concentration, and [BMIM][Ac] had more excellent separation capacity than [BMIM][DBP]. The NRTL model and the UNIFAC-Lei model were used to correlate the experimental VLE data, and the fitting results indicated that the NRTL model was in good agreement with the experimental data.
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