Catalytic conversion of furanic compounds over Ga-modified ZSM-5 zeolites as a route to biomass-derived aromatics

Herein we report a mechanistic study of aromatization of furanics, as model compounds for cellulosic biomass, over (Ga)HZSM-5 catalysts. Applying combined gas chromatography and mass-spectrometry product analysis we were able to analyse conversion and selectivity reaction profiles with high temporal resolution. The thorough analysis of the product distribution allowed us to resolve the deoxygenation pathways of the furan molecules. We found that depending on the methyl substitution oxygen is removed either as water or COx, effecting the carbon efficiency of the process. While unsubstituted furan undergoes decarbonylation to form COx, methylated furans are deoxygenated by dehydration, resulting in a much higher carbon-efficiency. Furthermore, using in situ IR spectroscopy, we found that promotion of HZMS-5 with Ga in addition to enhanced aromatic selectivity influences the deactivation pathway leading to the preferential formation of proton-deficient polycyclic aromatic compounds.