Mechanistic Investigation of the Pyrolysis of Brown Grease

The conversion of brown grease using pyrolysis reactions represents a very promising option for the production of renewable fuels and chemicals. Brown grease forms a mixture of alkanes, alkenes, and ketones at a temperature above 300°C at atmospheric pressure. This work is a computational study of the detailed reaction mechanisms of brown grease pyrolysis using DFT methodology. Prior experimental investigations confirmed product formation consistent with a set of radical reactions with CO2 elimination, as well as ketone by product formation, CO forming reactions, and formation of alcohols and aldehydes as minor byproducts. In this work, computational quantum chemistry was used to explore these reactions in greater detail. Particularly, a nonradical pathway formed ketone byproducts via the ketene, which we refer to as Pathways A1 and A2. Radical formation by thermal decomposition of unsaturated fatty acids initiates a set of reactions which eliminate CO2, regenerating alkyl radicals leading to hydrocarbon products (Pathway B). A third pathway (Pathway C) is an alternative set of radical reactions, resulting in decarbonylation and formation of minor byproducts. The results of the calculations are in good agreement with recent experimental studies.