On the Performance of Confined Deep Eutectic Solvents and Ionic Liquids for Separations of Carbon Dioxide from Methane: Molecular Dynamics Simulations.

Classical molecular dynamics simulations were used to investigate the performance of slit graphite and titania (rutile) pores of 5.2 nm in width, partially and completely filled with deep eutectic solvents (DESs) or ionic liquids (ILs), for gas separations of a carbon dioxide-methane mixture of 5:95 molar ratio and temperatures and pressures on the order of 318 K and 100 bar, respectively. The DESs studied were ethaline and levuline (1:2 molar mixtures of choline chloride with ethylene glycol or levulinic acid), and the IL considered was 1- n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][NTf]. The performance of these systems in terms of solubility selectivity, diffusion selectivity, and permselectivity was compared against the performance of the bulk solvents (which could also be viewed as a model system for the micrometer-sized pores of a supported IL or DES membrane) and against carbon and rutile pores without preadsorbed solvent. The best performance in terms of permselectivity is obtained for bulk levuline and by rutile pores fully filled by ethaline, followed by graphite pores filled by ethaline and the IL. Empty rutile pores have the largest value of solubility selectivity, followed by bulk ethaline and rutile pores completely filled by the IL. The largest values of diffusivity selectivity were observed for bulk levuline, followed by ethaline completely filling a rutile nanopore and a graphite nanopore completely filled with the IL. These observations are rationalized by examining local density profiles and interaction energies among the different entities in our systems. In general, systems of nanopores fully filled by solvents, as well as the bulk solvents, have larger permselectivities than pores partially filled by the IL or the DESs. Drops of 2-3 orders of magnitude are observed in the gas diffusivity in pores filled with solvents with respect to systems of empty pores, which may be problematic if gas permeation is mainly controlled by diffusion. However, if adsorption dominates the gas permeation within the membrane, our results suggest that systems of levuline in the micrometer-sized pores of a supported DES membrane or ethaline confined in the rutile nanopores of a supported DES phase material might represent promising systems for gas separation.