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Fluidized Bed Catalytic Pyrolysis of Eucalyptus over HZSM-5: Effect of Acid Density and Gallium Modification on Catalyst Deactivation

Mullen, Charles A., Tarves, Paul C., Raymundo, Lucas M., Schultz, Emerson L., Boatend, Akwasi A., Trierweiler, Jorge O.
Energy & Fuels 2018 v.32 no.2 pp. 1771-1778
Eucalyptus, aluminum oxide, aromatic compounds, aromatization, biofuels, biomass, carbon dioxide, carbon monoxide, catalysts, catalytic activity, decarboxylation, dehydrogenation, ethylene production, fluidized beds, gallium, hydrogen, ion exchange, olefin, oligomerization, oxidation, pellets, pyrolysis, silica, wood
Catalytic fast pyrolysis of eucalyptus wood was performed on a continuous laboratory-scale fluidized bed fast pyrolysis system. Catalytic activity was monitored from use of fresh catalyst up to a cumulative biomass/catalyst ratio (B/C) of 4:1 over extruded pellets of three different ZSM-5 catalysts by tracking CO, CO(2), H2, and C(2)H(4) production and bio-oil quality. The catalysts employed were extruded HZSM-5 with two different silica/alumina ratios (30 and 80) as well as one modified with Ga (SiO(2)/Al(2)O(3) = 30) by ion exchange, which was reduced under H2 prior to pyrolysis. The deactivation of the catalysts over the course of the experiment was reflected in the decline in deoxygenation activity, following the order HZSM-5 (30) > HZSM-5 (80) > GaZSM-5 (30). HZSM-5 (30) lost most of its activity before a cumulative B/C of 2:1 was reached, while HZSM-5 (80) still showed significant deoxygenated activity at this exposure level. GaZSM-5 (30) still showed deoxygenation activity at B/C of >4:1. The improvement exhibited by HZSM-5 with an increasing SiO2/Al2O3 ratio was attributed to reduced acid site density that decreased the propensity for coke formation as a result of reactions occurring between substrates at adjacent active acid sites. For reduced GaZSM-5, initial dehydrogenation activity aided in the production of aromatics by the olefin oligomerization and aromatization route up to B/C of ∼1.5:1, after which Ga became completely oxidized; however, the oxidized GaZSM-5 catalyst continued to exhibit improved decarbonylation and decarboxylation activities.