Preparation of BTESE-derived organosilica membranes for catalytic membrane reactors of methylcyclohexane dehydrogenation

High-performance organic–inorganic hybrid silica membranes were developed for use in membrane reactors for methylcyclohexane (MCH) dehydrogenation to toluene (TOL). The membranes were prepared via sol–gel processing using bis(triethoxysilyl)ethane (BTESE). In particular, the effect of hydrolysis conditions (H2O/BTESE molar ratio) on membrane performance was extensively investigated. Characterization based on TG-MASS, FTIR, N2 adsorption and positron annihilation lifetime (PAL) measurements of BTESE-derived silica gels revealed that the ethoxides of BTESE were almost completely hydrolyzed and the silica networks became dense by increasing the H2O/BTESE molar ratio from 6 to 240. BTESE-derived silica membranes showed a hydrogen permeance that was higher than 1×10−6mol/(m2sPa). H2/TOL selectivity increased from 100 to 10,000 by increasing the H2O/BTESE molar ratio from 6 to 240, while keeping a hydrogen permeance of more than 1×10−6mol/(m2sPa). In MCH dehydrogenation, a BTESE-derived silica membrane reactor with a Pt/γ-Al2O3/α-Al2O3 bimodal catalytic layer achieved MCH conversion of 75% that was higher than the equilibrium conversion of 60%, and a hydrogen purity in the permeate stream of more than 99.9% at 230°C. Pore size of BTESE-derived silica membrane for a membrane reactor of methylcyclohexane dehydrogenation was tuned by H2O/BTESE molar ratio in BTESE hydrolysis and condensation. [Display omitted] •Hybrid silica membranes were prepared from bis(triethoxysilyl)ethane (BTESE).•H2 permeance higher than 1×10−6mol/ (m2sPa) with H2/toluene selectivity of 10,000.•BTESE membrane reactors were applied to methylcyclohexane (MCH) dehydrogenation.•The membrane reactors increased MCH conversion with hydrogen purity more than 99.9%.