Enhanced bio-oil upgrading by sub-microscale dispersed silanol-free ZSM-5 nanosheets and evidence for revealing an unconventional mechanism

Abstract

Silanol-free ZSM-5 nanosheet with merely 35 nm thickness in the b-axis was synthesized by seeded growth from defect-free 10 nm silicalite-1 in a fluoride medium (denoted as F35). Submicron-scaled stöber sol silica beads were introduced into the gap between nanosheets to serve as a spacer for the prevention of neighboring crystals' close contact with each other, which can improve the heat and mass transportation during the catalytic reactions when compared to the aggregated zeolite crystals. Methanol-to-hydrocarbons (MTH) and model bio-oil upgrading were conducted by using dispersed F35, respectively, and the results were compared to the aggregated ZSM-5. The effluent from bio-oil upgrading through dispersed F35 contains no heavier compound, which was considered as the coke precursor, and significantly reduced amount of unreacted feeding molecule. GC–MS revealed that the coke solution from dispersed F35 contains a considerably reduced (61 %) amount of heavier carbon species. Among them, some species have molecular configurations highly consistent with the zeolite channel structure. The dispersed F35 shows a 33 % longer life in catalytic reactions and a 60 % decreased amount of external thermal cock. An unconventional ‘temperature-determined flexible channel’ mechanism that explains the ‘host–guest’ interactive behavior under catalytic reaction was proposed.