Catalytic co-cracking of distilled bio-oil and ethanol over Ni-ZSM-5/ MCM-41 in a fixed-bed

摘要

The bio-oil from rice hull fast pyrolysis was distillated under reduced pressure at 0.005 Mpa, then mixed with ethanol (2:3 by weight). The mixture was subjected to catalytic co-cracking over Ni-ZSM-5/MCM-41 molecular sieves in a fixed-bed at 500 ℃ and 3.75 h~(-1) of the WHSV. The distillation results showed the distilled bio-oil, compared with raw bio-oil, contained lower oxygen content (decreased from 45.91 wt.% in raw bio-oil to 33.74 wt.%), higher (H/C)_(eff) ratio (0.35) and HHV value (22.81 MJ/kg). The ethanol was involved in the ketonization, esterification, aromatization and dehydration during the catalytic co-cracking of distilled bio-oil and ethanol. The Ni loaded on ZSM-5/MCM-41 molecular sieves reduced char formation compared with ZSM-5/MCM-41. The ZSM-5/MCM-41 catalyst exhibited higher activity in the esterification and aromatization, which converted acids in upgraded bio-oil to esters, aromatics or phenols. The Ni-ZSM-5/MCM-41 catalysts showed excellent activity that transformed acids to ketones by ketonization process. The 6% Ni-ZSM-5/MCM-41 catalyst performed the good activity with the minimum char formation (7.3 wt.%) and higher upgraded bio-oil (40.8 wt.%). Moreover, the acid content in the upgraded bio-oil dropped to 0.1 wt.% and the total concentration of CO_2 and CO in the gas products was 36.8 vol.%.