Influence of Biomass Inorganics on the Functionality of H+ZSM-5 Catalyst during In-Situ Catalytic Fast Pyrolysis

In this study, the contamination of H+ZSM-5 catalyst by calcium, potassium and sodium was investigated by deactivating the catalyst with various concentrations of these inorganics, and the subsequent changes in the properties of the catalyst are reported. Specific surface area analysis of the catalysts revealed a progressive reduction with increasing concentrations of the inorganics, which could be attributed to pore blocking and diffusion resistance. Chemisorption studies (NH3-TPD) showed that the Bronsted acid sites on the catalyst had reacted with potassium and sodium, resulting in a clear loss of active sites, whereas the presence of calcium did not appear to cause extensive chemical deactivation. Pyrolysis experiments revealed the progressive loss in catalytic activity, evident due the shift in selectivity from producing only aromatic hydrocarbons (benzene, toluene, xylene, naphthalenes and others) with the fresh catalyst to oxygenated compounds such as phenols, guaiacols, furans and ketones with increasing contamination by the inorganics. The carbon yield of aromatic hydrocarbons decreased from 22.3% with the fresh catalyst to 1.4% and 2.1% when deactivated by potassium and sodium at 2 wt %, respectively. However, calcium appears to only cause physical deactivation.