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Sol-gel synthesis of iron catalysers supported on silica and titanium for selectively oxidising methane to formaldehyde
Síntesis sol-gel de catalizadores de hierro soportados sobre sílice y titania para la oxidación selectiva de metano hasta formaldehído
DOI:
https://doi.org/10.15446/ing.investig.v28n1.14869Keywords:
Fe/SiO2 catalysts, Fe/TiO2 catalysts, formaldehyde, selective oxidation, sol-gel (en)catalizadores Fe/SiO2, catalizadores Fe/TiO2, formaldehído, oxidación selectiva, sol-gel (es)
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Iron materials supported on silica were prepared by the sol-gel method for evaluating catalytic activity in selective oxidation of methane to formaldehyde. Four catalysts were prepared, one corresponding to the silica support (catalyst 1S), another to the titanium support (catalyst 1T) and two more having 0.5% weight iron loads, one for the silica support (catalyst 2FS) and the last one the titanium support (catalyst 2FT). The higher BET areas were 659 and 850 m2/g for catalysts 1S and 2FS, respectively while catalysts 1T and 2FT displayed areas of 65 and 54 m2/g, respectively. Scanning and transmission electronic microscopy displayed an amorphous structure in the silica-supported materials while titanium-supported materials displayed dense materials having defined structure. X-ray diffraction confirmed the silica’s amorphous structure in 1S and 2FS catalysts and displayed the 1T and 2FT catalysts’ anatase structure. The programmed temperature reduction for the 1S and 2FS catalysts did not display reducible species, while displaying hydrogen consumption peaks related to Fe3O4 reduction to α-Fe via FexO route for 1T and 2FT catalysts. The electronic spectroscopy X-ray photo confirmed the Fe(III) specie as having 710.6 e.V binding energy for both 2FS and 2FT catalysts. Catalytic activity was carried out at atmospheric pressure in a quartz reactor, reaction mixture as CH4/O2/N2 =7.5/1/4 at 400-800°C temperature range. The reaction products were analysed by gas chromatography on Hayesep R and T columns using 5Å molecular screening. The best response for selective oxidation of methane to formaldehyde was displayed by the 2FS catalyst with 3.4% mol methane conversion at 650°C, 11.9% mol formaldehyde selectivity and 0.0211 g HCHO/Kg catalyst yield.
Materiales de hierro soportados sobre sílice y titania fueron obtenidos por el método sol-gel para evaluar su actividad catalítica en la reacción de oxidación selectiva de metano hasta formaldehído. Se prepararon cuatro (4) catalizadores, uno del soporte de sílice (catalizador 1S), otro para el soporte de titania (catalizador 1T) y los dos (2) restantes con carga de hierro de 0,5% en peso, para el soportado en sílice (catalizador 2FS) y para el soportado sobre titania (catalizador 2FT). Las mayores áreas superficiales BET se obtienen para los materiales de sílice, catalizadores 1S y 2FS con valores de 659 y 850 m2/g respectivamente, mientras que los catalizadores sobre titania 1T y 2FT presentaron áreas de 65 y 54 m2/g respectivamente. Los análisis de microscopía electrónica de barrido y transmisión muestran estructuras amorfas en el caso del soporte de sílice, mientras que para el soporte de titania los materiales son densos con estructura definida. El análisis de difracción de rayos X confirma la estructura amorfa de los materiales preparados con sílice y presenta la estructura de la anatasa para los materiales de titania. Los experimentos de reducción a temperatura programada muestran para los catalizadores 1S y 2FS ausencia de especies potencialmente reducibles, y para el caso de los catalizadores 1T y 2FT se presentan picos de consumo de hidrógeno que para el caso del 2FT están relacionados con la reducción de Fe3O4 hasta α-Fe vía intermedio de FexO. La espectroscopia Fotoelectrónica de rayos X confirma la presencia de Fe(III) con el valor de la energía de enlace en 710,6 e.V tanto para el catalizador 2FS como para el 2FT. La actividad catalítica se realiza a presión atmosférica en reactor de cuarzo, mezcla de reacción CH4/O2/N2 =7,5/1/4, intervalo de temperatura 400-800°C. Los productos de reacción se analizan por cromatografía de gases con columnas Hayesep R y T y tamiz molecular de 5Å. La mejor respuesta para la oxidación del metano hasta formaldehído la presenta el catalizador 2FS, con un porcentaje de conversión de metano de 3,4% mol a 650°C, selectividad al formaldehído de 11,9% mol y rendimiento de 0,021 g HCHO/Kg catalizador.
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Copyright (c) 2008 Carlos Alberto Guerrero Fajardo, Francisco José Sánchez Castellanos, Anne Cécile Roger, Claire Courson
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