High-temperature decomposition of amorphous and crystalline cellulose : reactive molecular simulations

Funding Information: We are grateful for the support by the FinnCERES Materials Bioeconomy Ecosystem. We want to especially thank Dr. Taina Ohra-Aho, Dr. Kristian Melin, Dr. Jukka Ketoja and Dr. Tuula Hakkarainen for their valuable comments. Publisher Copyright: © 2021, The Author(s).We study the thermal decomposition of cellulose using molecular simulations based on the ReaxFF reactive force field. Our analysis focuses on the mechanism and kinetics of chain scission, and their sensitivity on the condensed phase environment. For this purpose, we simulate the thermal decomposition of amorphous and partially crystalline cellulose at various heating rates. We find that thermal degradation begins with depolymerization via glycosidic bond cleavage, and that the order of events corresponds to a randomly initiated chain reaction. Depolymerization is followed by ring fragmentation reactions that lead to the formation of a number of light oxygenates. Water is formed mainly in intermolecular dehydration reactions at a later stage. The reaction rate of glycosidic bond cleavage follows a sigmoidal reaction model, with an apparent activation energy of 166 ± 4 kJ/mol. Neither the condensed phase environment nor the heating programme have appreciable effects on the reactions. We make several observations that are compatible with mechanisms proposed for cellulose fast pyrolysis. However, due to the absence of anhydrosugar forming reactions, the simulations offer limited insight for conditions of industrial interest. It remains unclear whether this is a natural consequence of the reaction conditions, or a shortcoming of the force field or its parameter set. Graphic abstract: [Figure not available: see fulltext.]Peer reviewe