Silica supported tungsta-zirconia catalysts for hydroisomerization–cracking of long alkanes

New acidic materials with uniform mesoporous texture were synthesized by dispersion of tungsten promoted zirconia over a wide pore silica carrier. The catalysts showed both an activation temperature and a coke deactivation pattern in acid catalyzed isomerization similar to bulk tungsten-zirconia cat...

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Veröffentlicht in:Applied catalysis. A, General General, 2009-02, Vol.355 (1), p.123-131
Hauptverfasser: Busto, Mariana, Lovato, María E., Vera, Carlos R., Shimizu, Kiyoyuki, Grau, Javier M.
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Sprache:eng
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Zusammenfassung:New acidic materials with uniform mesoporous texture were synthesized by dispersion of tungsten promoted zirconia over a wide pore silica carrier. The catalysts showed both an activation temperature and a coke deactivation pattern in acid catalyzed isomerization similar to bulk tungsten-zirconia catalysts. On a mass basis of active tungsten-zirconia phase some supported catalysts had a higher activity than bulk tungsten-zirconia. Their open pore structure made them more suitable for the reaction of bulky molecules. New acidic materials with fairly uniform mesoporous texture were synthesized by deposition of tungsten promoted zirconia (WZ) over a wide pore silica carrier (SiO 2). High dispersion of the tungsten-zirconia crystallites was achieved by a two-step controlled impregnation procedure. A first deposition of zirconia was performed by controlled hydrolysis of alkoxide. Impregnation of tungstate was performed by incipient wetness impregnation of ammonium metatungstate. The catalysts show an activation pattern for the reaction of 1-butene similar to bulk tungsten-zirconia catalyst, with an optimum at a calcination temperature of 750 °C. Supported zirconia crystallizes almost exclusively as tetragonal crystallites. The catalysts were tested in the reaction of hydroisomerization–cracking of n-octane (300 °C, 1 atm, WHSV = 1 h −1 and H 2/ n-C 8 = 6 mol/mol) for the production of light isoalkanes (isobutane, isopentane, isohexane) of high octane number. The tried catalysts had a high catalytic activity and this result was related to the high surface area of the supported catalyst. Both bulk and supported catalysts deactivated rapidly if they did not contain Pt. Impregnation with Pt and the use of H 2 in the reaction medium enable the hydrogenation of coke precursors and the stabilization of the catalyst. A stable performance was obtained at a moderate activity level. This was attributed to the presence of Pt/SiO 2 particles with a stronger metal function than Pt/WZ due to a lower metal–support interaction. Silica supported catalysts would have a higher hydrogenating activity and this would be crucial for enhancing their stability in comparison to bulk Pt/WZ catalysts. Tungsten addition to supported zirconia in amounts greater than 7.5% produced segregation of a WO 3 phase in the form of crystallites that plugged pores and produced a reduction of the available area and hence of the overall catalytic activity. For the WZ supported catalysts activity as a func
ISSN:0926-860X
1873-3875
DOI:10.1016/j.apcata.2008.12.009