In situ hydrodeoxygenation of heavy bio-oil using a Ce/Fe-based oxygen carrier in methanol-zero valent aluminum media

Resource recovery from solid organic wastes, such as degradable plastics, and upgrading raw bio-oil are important ways for reducing carbon and pollution emissions. Hydrodeoxygenation (HDO) is a common thermochemical treatment to upgrade crude bio-oil. In this study, in order to realize in situ HDO during the hydropyrolysis of heavy bio-oil and degradable plastics, a reduced Fe/Ce oxygen carrier (OC) was used to catalytically remove oxygen from organics under the methanol-zero valent aluminum (ZV Al) media, where the hydrogen was produced during pyrolysis instead of a direct hydrogen supply. The results showed that the reduced OC captured the oxygen from the pyrolysis products of heavy bio-oil and degradable plastic, representing the multi-selectivity of reduced OC to phenols, ketones, etc. The ZV Al system promoted the production and utilization of hydrogen, as evidenced by the increased hydrogen content in gas phase and hydrocarbon content in liquid phase. The hydrocarbon component distribution in the liquid phase increased clearly when hydropyrolysis with degradable plastics addtion, but the excess degradable plastics addition caused increasing of the liquid product viscosity, and decreasing of the liquid products yield for the higher ash content in degradable plastic, and a higher ZV Al amount was required to maintain the hydropyrolysis. Molecular dynamics simulations verified the synergistic effect of degradable plastics and bio-oil by the pyrolysis behavior in different systems and temperatures, and the pyrolysis pathways were proposed. This non-autocatalytic system realized the resource recovery and heavy bio-oil upgrading using an Fe/Ce OC.