Exploring bioenergy prospects from malt bagasse: Insights through pyrolysis with multi-component kinetic analysis and thermodynamic parameter estimation

Abstract

Malt bagasse is a by-product of little commercial value in the brewing industry. Under this scenario, the current study represents the first investigation aiming to determine the kinetic triplet and thermodynamic parameters for malt bagasse pyrolysis using a multi-component kinetic approach to elucidate its bioenergy prospects. The pyrolysis progress profiles of malt bagasse were obtained through slow pyrolysis experiments on a thermogravimetric scale in an inert atmosphere, employing four distinct heating rates (10, 15, 25, and 40 °C min−1). This investigation also used the Frazer-Suzuki deconvolution function to elucidate the relative contributions of hemicellulose, cellulose, and lignin to malt bagasse pyrolysis. Activation energies for devolatilization reactions were determined by the isoconversional methods of Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, and Starink, and revealed the lowest and highest mean values for pseudo-hemicelluloses (158.3−215.3 kJ mol−1) and pseudo-lignin (279.5−294.8 kJ mol−1), respectively. Frequency factors in malt bagasse pyrolysis ranging from 8.9 × 1016 and 2.2 × 1023 min−1 offer evidence of a simplified reaction chemistry pathway in the conversion towards bioenergy production. The integral master plot indicates the involvement of order-based and geometrical contraction-based mechanisms in malt bagasse pyrolysis. After defining multiple kinetic triplets, a differential equation encompassing contributions from all pseudo-components was formulated, and the simulated results aligned closely with experimental data, accurately describing pyrolysis progress profiles with at least 92.8% precision. The thermodynamic analysis reveals positive ΔH and ΔG values, indicating the non-spontaneous nature of malt bagasse pyrolysis. Higher disorder in the resultant products is attributed to volatile release and molecular rearrangement and is signified by positive ΔS values compared to the initial reactants. This study provided valuable insights into the valorization of malt bagasse, offering crucial information for optimizing pyrolysis reactors, scaling, and designing malt bagasse conversion into valuable biofuels, constituting an effort towards bio-circular economy principles based on the zero-waste concept.