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Novel Approaches to Catalytic Upgrading of Bio-Oil

Published by the American Society of Agricultural and Biological Engineers, St. Joseph, Michigan

Citation:  Paper number  066035,  2006 ASAE Annual Meeting . (doi: 10.13031/2013.21981) @2006
Authors:   Courtney Fisk and Czarena Crofcheck, Mark Crocker and Rodney Andrews, John Storey and Sam Lewis Sr.
Keywords:   Bio-Oil, Base Catalyst, Mild Cracking, Biomass, Pyrolysis

To date the upgrading of bio-oils has primarily been achieved by means of acid catalyzed cracking or hydrotreating. Given that hydrotreating requires large volumes of hydrogen, which has a significant impact on process economics, cracking represents a more economically attractive option. However, there are difficulties encountered in the use of acid cracking catalysts such as H-ZSM-5. These include high yields of gaseous hydrocarbons of low value, and the occurrence of coke formation. Coke formation results in rapid catalyst deactivation (as a consequence of the high polymerization activity of pyrolysis oils). An alternative concept aimed at catalytic deoxygenation of bio-oil to a stabilized product is mild cracking over base catalysts. To maximize liquid product yields, mild cracking has been studied for the decomposition of polysaccharides and polysaccharide-derived products in the crude bio-oil, without cracking the lignin-derived oil. Commercial ZnO and freshly calcined Zn/Al and Mg/Al layered double hydroxides were used to upgrade a synthetic bio-oil composed of methanol (5%), acetaldehyde (12%), acetic acid (14%), glyoxal (4%), acetol (8%), furfural (4%), glucose (8%), guaiacol (17%), vanillin (8%), and water (20%). These compounds correspond to some of the main components found in pyrolysis oils, and represent the most reactive functional groups present (aldehyde, carboxylic acid, ketone, and phenol). The composition of the upgraded bio-oil was assessed based on GC, GC/MS, and elemental analysis (for C, H, and O).

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