Pervaporation (PV), a membrane process in which the feed is a liquid mixture and the permeate is removed as a vapour, offers an energy-efficient alternative to conventional separation processes such as distillation, and can be applied to mixtures that are difficult to separate, such as azeotropes. Here the principles of pervaporation and its industrial applications are outlined. Two classes of material that show promise for use in PV membranes are described: Polymers of intrinsic microporosity (PIMs) and 2D materials such as graphene. The literature regarding PV utilizing the prototypical PIM (PIM-1) and it hydrophilic hydrolysed form (cPIM-1) is reviewed. Self-standing PIM-1 membranes give competitive results compared to other membranes reported in the literature for the separation of alcohols and other volatile organic compounds from aqueous solution, and for organic/organic separations such as methanol/ethylene glycol and dimethyl carbonate/methanol mixtures. Blends of cPIM-1 with conventional polymers improve the flux for dehydration of alcohols. The incorporation of fillers, such as functionalised graphene-like fillers, into PIM-1 to form mixed matrix membranes can enhance the separation performance. Thin film composite (TFC) membranes enable very high fluxes to be achieved when a suitable support with high surface porosity is utilised. When functionalised graphene-like fillers are introduced into the selective layer of a TFC membrane, the lateral size of the flakes needs to be carefully controlled. There is a wide range of PIMs and 2D materials yet to be explored for PV applications, which offer potential to create bespoke membranes for a wide variety of organic/aqueous and organic/organic separations.

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Ethyl tert-butyl ether (ETBE) is one of the most promising oxygenates used as high-octane components of fuels. A method to purify ETBE from an ethanol/ETBE azeotropic mixture formed during industrial synthesis is pervaporation. In this study, hybrid membranes containing nanodiamond particles incorporated into the P84 copolyimide matrix have been synthesized for the pervaporation purification of ETBE. The membrane structure has been studied by scanning electron microscopy and via determining the experimental and theoretical density and free volume. The transport properties of the membranes have been determined in sorption and pervaporation experiments. It has been shown that the introduction of up to 1 wt % of nanodiamonds in the P84 matrix leads to an increase in the main mass transfer parameters, namely, the flux and the separation factor of the azeotropic mixture.

Novel polymer composite materials, including unique nanoparticles, contribute to the progress of modern technologies. In this work, the endohedral fullerene C60 with incapsulated iron atom (endometallofullerene Fe@C60) is used for modification of P84 copolyimide. The impact of 0.1, 0.5, and 1 wt % endometallofullerene on the structure and physicochemical properties of polymer films is studied through scanning electron microscopy, thermogravimetric analysis, and thermomechanical tests. Transport properties are estimated through sorption and pervaporation techniques toward methanol and methyl acetate mixture. The inclusion of endometallofullerene into the copolyimide matrix improves membrane permeability and selectivity in the separation of methanol—methyl acetate mixtures. The maximal effect is achieved with a composite containing 0.5 wt % Fe@C60. The developed composites are effective for energy and resource saving purification of methyl acetate by pervaporation.