Abstract
This work integrates experimental characterization, kinetic analysis, and molecular modeling to clarify lignocellulosic biomass conversion under oxidative and non-oxidative conditions. It examines cellulose, hemicellulose (xylan), lignin, andtwo softwood feedstocks (Douglas fir and red cedar) using thermogravimetric and evolved gas analyses. Binary and ternary mixtures demonstrate that the thermal decomposition behavior of lignocellulose is not a simple superposition of individual components. Interactions generate overlapping and synergistic effects: cellulose–hemicellulose blends devolatilize more rapidly, while incorporation of lignin widens the decomposition interval. A reactive molecular dynamics simulation of xylan oxidation at elevated temperatures offers a complementary mechanistic view at the molecular level. This
simulation captures the main experimental kinetic features, such as stepwise decomposition and the progression of product formation. The consistency of these findings with the experimental results supports the application of reactive force-
field approaches as a link between microscopic reaction mechanisms and macroscopic conversion behavior.
This study shows that lignocellulosic biomass conversion is controlled by the interplay of its composition, structural features, reaction conditions, and prior thermal exposure. These insights underpin the formulation of composition-resolved
kinetic models that are crucial for enhancing combustion performance, optimizing pyrolysis and gasification, lowering pollutant emissions, and expanding the efficient use of lignocellulosic feedstocks.