In this work, we have explored the potential of two ionic liquids,
[BMPYR][DCA] and [EMIM][SCN], to be used as entrainers
for the separation of the methyl acetate + methanol azeotropic
mixture by extractive distillation. To examine the effect of the ILs
on the separation factor, isothermal vapor–liquid equilibria of
two corresponding ternary systems and all five constituting binary
subsystems have been determined at 327.31 K. Two HSGC techniques
employed for the purpose do not need any external calibration
of GC response and are both rapid and accurate. The HSGC
methodology developed here has proved to be very efficient to
study VLE of IL-containing mixtures. It presents distinct advantages
compared to conventional dynamic measurements using recirculation
stills, in particular because of a considerably lower
consumption of ILs and an uncompromised accuracy for higher
IL-contents mixtures for which the dynamic techniques fail to give
accurate results due to unsmooth boiling. The observed complex
thermodynamic behavior of the examined systems provided a
challenge for modeling: among various models tested the NRTL appears
to perform the best. The NRTL predictions of separation factor
based only on binary data are fairly accurate; their
improvement can hardly be obtained even when additional ternary
parameters based on numerous ternary data covering well the ternary
composition space are employed. As entrainers [BMPYR]
[DCA] and [EMIM][SCN] perform very well, breaking the methyl