This work presents an evaluation of the industrial residue from exhausted black wattle bark after the extraction of tannin for use as a new feedstock for biofuel production, without competing with food production. The physicochemical and thermodynamic properties, the influence of temperature on pyrolysis products and multicomponent kinetics were evaluated. Principal component analysis showed that sugars, carboxylic acids, ethers/esters, furans and aldehydes were formed as primary products of pyrolysis at 450 °C. At 550 °C, phenols and mainly ketones were favored, especially acetone and 2,3-butanedione. Pyrolysis at 650 °C favored the production of aldehydes, alcohols, and 1-alkene, polyene and alkane hydrocarbons. After an upgrade, the series of 1-alkenes produced, with carbons C7 to C16, could be suitable for a range of gasoline and jet fuels. Kinetic modeling was based on the deconvolution of the mass loss of three events of the pseudo-components: hemicellulose (DE-HC), cellulose (DE-CL) and lignin (DE-LG). The activation energy for kinetic models Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose and Starink presented average values of ∼141.4–149.4 for DE-HC, ∼190.5–200.9 for DE-CL and ∼237.2–252.3 kJ mol−1 for DE-LG. This study encourages using agro-industrial waste to produce second-generation drop-in biofuels and bio-based chemicals, aiming at industrial decarbonization.
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