It is of great significance to separate hazardous methyl tert-butyl ether (MTBE) from water in terms of environmental protection and human health. In the present work, α-Al2
-suppotred silica membranes were prepared by the sol-gel and dip-coating technique. Two fluorinated alkylsilanes (1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) and trifluoropropyltriethoxysilane (TFPTES)) and two non-fluorinated alkylsilanes (octyltriethoxysilane (OTES) and propyltriethoxysilane (PTES)) were adopted to silylate the silica membrane by the post-grafting method which is used for the separation of MTBE from water by pervaporation. The results show that silylation enhances the hydrophobicity of silica membranes. The silylated silica membranes are selective towards MTBE, and the MTBE/water separation factor varies with grafting agents in the order: PFOTES > TFPTES > OTES > PTES. Membranes silylated with fluorinated carbon chains seem to be more selective towards MTBE than those with non-fluorinated carbon chains. The total flux is proportional to the pore volume of silica membranes, which depends on grafting agents in the order: PTES > PFOTES > OTES > TFPTES. Considering both total flux and selectivity, the PFOTES-SiO2
membrane is most effective in separation, with a MTBE/water separation factor of 24.6 and a total flux of 0.35 kg m−2
under a MTBE concentration of 3.0% and a feed temperature of 30 °C.
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