Catalytic fast pyrolysis with metal-modified ZSM-5 catalysts in inert and hydrogen atmospheres

The objective of this work was to determine the impact of hydrogen-activating metals on catalytic fast pyrolysis over ZSM-5 with and without hydrogen addition. Ga-, Ni-, Cu-, Co-, and Pt-modified ZSM-5 catalysts with metal to -aluminum molar ratios of 2 were prepared by incipient wetness method. The catalysts were evaluated for hydrocarbon and oxygenate yields and for deactivation by analytical pyrolysis (Py-GC MS), and post-reaction catalysts for characterization were prepared in a larger fixed-bed reactor. In inert atmosphere, there was a linear correlation between both the hydrocarbon yield and coke formation and density of strong acid sites, and the main impact of the metals was occlusion of active sites in ZSM-5, leading to proportional reductions in hydrocarbon and coke yields. With the addition of hydrogen, several metals (Pt, Ni, Cu, Co) activated hydrogen and further reduced coke formation, leading to improvements in the ratio of hydrocarbons to coke. No metal modified catalyst out-performed fresh unmodified ZSM-5 in terms of hydrocarbon yield; however, Ni/ZSM-5 and Cu/ZSM-5 in hydrogen produced comparable hydrocarbon yields to ZSM-5 while reducing coke formation.