Cellulose pyrolysis kinetic model: Detailed description of volatile species

Lignocellulosic biomass is typically composed by a major fraction of cellulose. Its decomposition influences on large extent the biomass rate of pyrolysis and product distribution, affecting process behaviour in thermochemical conversion processes. Containing approximately 90 % of volatile matter, volatile products from cellulose pyrolysis are very important in the characteristics of flames and ignition properties. Recent developments in analytical methods allowed a detailed identification of these volatile products, giving valuable information to process development and better understanding of kinetics. Predictions of a previous kinetic model are compared with these new findings, revealing large space for improvements. In this work, we propose a multi-step kinetic model of cellulose pyrolysis, incorporating the most recent experimental findings into the detailed product description. The model consists of four main reactions for the decomposition of cellulose, with formation of gases, volatiles, char and metaplastic species. The release of metaplastic species is described by a set of six reactions. The formation and release of 13 oxygenated hydrocarbons is predicted by the model, including anhydrosugars, furans, aldehydes, alcohols, ketones and carboxylic acids. The model also describes the formation of levoglucosan in metaplastic state before its release, explaining high heating rate mass loss behaviour. The model is compared with a large variety of experiments from literature, and validated for mass loss rates and product distribution, achieving overall good agreement despite experimental uncertainties and the large simplifications characteristic of the model formulation. Besides effectively quantifying the yields of gaseous, condensable and solid products, the model accurately captures the distribution of volatiles in terms of functional groups and C-chain length.