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As there is an azeotropic point between methanol and ethyl formate, they cannot be completely separated by ordinary distillation. In this paper, extractive distillation was applied and dimethyl sulfoxide (DMSO) and ethylene glycol (EG) were used as entrainers. Vapor−liquid equilibrium (VLE) data for methanol−ethyl formate, methanol−ethyl formate−DMSO, and methanol− ethyl formate−EG were measured at 101.3 kPa, and the NRTL model was applied for data fitting. It was found that the experimental value and the calculated value were accordant well through the deviation value. Then, the NRTL model was used for simulation by Aspen Plus to achieve the separation goal, and it verified the feasibility of the experimental scheme.

There are challenges in the separation process of methanol and ethyl formate because of the azeotropic phenomenon. Here, extractive distillation was chosen as the separation method, and 1,3-dimethylimidazoledimethyl phosphate ([MMIM][DMP]) and 1-ethyl-3-methylimidazole acetate ([EMIM][OAC]) were used as entrainers. The isobaric vapor−liquid equilibrium (VLE) data were determined at atmospheric pressure employing a vapor−liquid equilibrium kettle. These values were used for the thermodynamic consistency test and correlated based on the NRTL model, and they were in good accordance with the original data; the binary interactive parameters were also obtained. It was found that both [MMIM][DMP] and [EMIM][OAC] could effectively eliminate the azeotropic phenomenon for methanol + ethyl formate, but the influence on the separation ability produced by [EMIM][OAC] was better than that by [MMIM][DMP].