Supported liquid membranes (SLMs) are promising in separating miscible liquid–liquid mixtures, which has been a key challenge in wastewater treatment and other applications. However, SLMs suffer from poor durability due to the loss of the liquid phase. In current work, ionic liquids (ILs) with high stability have been impregnated into polyvinylidene fluoride membranes to separate miscible benzene–heptane mixtures. The two imidazolium-based ILs, that is, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]­[PF6]) and 1-butyl-3-methylimidazolium tris­(pentafluoroethyl) trifluorophosphate ([BMIM]­[FAP]), were tested in supported ionic liquid membranes (SILMs) for the benzene–heptane separation. Both ILs show successful separation within 48 h as indicated by nuclear magnetic resonance results. Compared to the SILM with [BMIM]­[FAP], the SILM with [BMIM]­[PF6] has lower throughput and higher selectivity. The higher selectivity can be attributed to the higher hydrophilicity of [BMIM]­[PF6], which results in strong repulsion against heptane. The lower throughput can be attributed to the higher hydrophilicity as well since it lowers the solubility of benzene in [BMIM]­[PF6]. The stability of IL in SILMs has also been investigated via multiple separation cycles. The scanning electron microscopy, weight change of SILMs, and separation results indicate that the separation efficiency of the [BMIM]­[PF6] SILM does not degrade for up to 144 h. The SILM has been further optimized with curvature design (i.e., curved SILM) to increase the interfacial area and thus increase the separation throughput, where the curved SILM separation device was 3D-printed. The findings here have important implications on design and application of SILMs in separating miscible liquid–liquid mixtures.

3D printed membrane device, supported ionic liquid membrane, hydrogel-coated hydrophilic/oleophobic membrane, multi-component multi-phase separation.