4.2 Article

Research on properties and catalytic behaviour in CO hydrogenation at atmospheric and high pressure of bimetallic systems (10%Co+0.5%Pd)/TiO2 (Al2O3)

Journal

REACTION KINETICS MECHANISMS AND CATALYSIS
Volume 135, Issue 2, Pages 589-618

Publisher

SPRINGER
DOI: 10.1007/s11144-022-02194-x

Keywords

CO hydrogenation; Atmospheric and high pressure; Co-Pd catalysts; In situ DRIFTS; Stability tests; Selectivity

Funding

  1. Bulgarian National Science Fund [KP-06-H29-9/2018]

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The properties of prereduced (10%Co + 0.5%Pd)/Al2O3 (TiO2) systems in the CO hydrogenation reaction were studied, and it was found that catalysts using alumina or titania as supports exhibited different selectivity towards methane and activity. The reaction led to metal surface reconstruction and increased formation of CH2 groups, especially with titania-supported catalysts. Stability tests and high-pressure catalytic tests revealed the different behaviors and product distributions of both systems.
The properties of prereduced (10%Co + 0.5%Pd)/Al2O3 (TiO2) systems in the CO hydrogenation reaction at atmospheric and high pressure were studied. At atmospheric pressure, alumina-supported catalysts were more selective toward methane but those using titania were more active. Alumina containing samples demonstrated high temperature H-2 desorption, firmly held surface carbonate species, high tendency to agglomeration. During the reaction metal surface reconstruction and increased formation of CH2 groups occurred being more pronounced with titania-supported catalysts. Stability tests at 250 degrees C showed opposite behaviour of both systems. Monodentate carbonate intermediates adsorbed on sites of moderate strength prevailed on titania samples, while formate species predominated on high strength sites of alumina-supported catalysts. High pressure catalytic tests revealed dependence of activity on T-red, synthesis of C2+ hydrocarbons, decreased CO2 production, a higher CH4/CO2 ratio for alumina containing system. Due to SMSI, increased CO2 production on titania samples was preserved. Titania-supported catalysts revealed a stronger decrease of CO conversion rising T-red while alumina catalysts had almost unchanged activity. CO conversion decreased with time due to difficulties in surface diffusion of reagents/intermediates/products and metal particle agglomeration. Concerning T-red comparison of product distribution showed a steady trend. Because of stable CO and CHx surface species, titania containing catalysts produced lower content of C5+ compounds. Alumina-supported samples showed a higher selectivity to C5+ compounds at the expense of methane. A higher selectivity ratio for CH4 and CO2 determined in catalytic CO hydrogenation over a certain catalyst at atmospheric pressure could indicate that a given sample is predisposed to form C2+ hydrocarbons at a higher pressure.

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