Styrene and ethylbenzene absorption in ionic liquids : comparing DFT affinity calculations with experimental data

Styrene is a widely used bulk chemical produced by dehydrogenation of ethylbenzene (EB). Purification of styrene to contain <100 ppm EB is not cost-effective by conventional separation methods. One separation method is extractive distillation with an ionic liquid (IL) as a binding agent for one of the components, thereby lowering the vapour pressure of this component. In this study, using quantum density functional theory (DFT), we have simulated 22 IL anion–cation pairs, styrene and EB affinities to them, and ion-pair dimer affinities of the ILs. These are compared with experimental liquid–liquid equilibrium studies of M.T.G. Jongmans, B. Schuur, and A.B. de Haan, Ind. Eng. Chem. Res. 50 (2011), pp. 10800–10810. It is shown that experimental selectivity and distribution coefficients of styrene and EB in the ILs are related to computed gas phase anion–cation stabilisation energies and ion-pair–ion-pair dimer affinities. The inverse of molar volume is found to strongly correlate with the selectivity. The computational results also qualitatively correlate with molar volume, and consequently, it is possible to use DFT calculations as a qualitative prediction tool in screening of ILs for this separation process. This tool does not account for effects caused by long alkyl chains, as the length does not seem to affect dimer stabilisation energy beyond ethyl group