Thermal lag, fusion, and the compensation effect during biomass pyrolysis

Results from a numerical model for endothermic biomass pyrolysis, which includes both high activation energy kinetics and heat transfer across a boundary layer to the reacting solid particle, are presented. The model accounts for conventional thermocouple thermal lag and unconventional thermal lag due to heat demand by the chemical reaction (which is governed by Arrhenius kinetics). Biomass fusion, first identified quantitatively by Lede and Villermaux, is shown to be a manifestation of severe thermal lag that results from the chemical reaction heat demand. Over the wide range of conditions studied, the true substrate temperature remains almost constant during pyrolysis, as is the case with compounds undergoing fusion or sublimation at constant pressure. A simple algebraic model, whose derivation presupposes the idea that biomass pyrolysis mimics the melting of a block of ice, accurately predicts the maximum value of thermal lag during pyrolysis. Unidentified thermal lag in TGA experiments lowers the values of the apparent activation energy and frequency factor associated with the experimental data but approximately retains the true value of their ratio. Thus, the widely varying values of kinetic parameters for cellulose pyrolysis reported; in the literature may be a result of differing thermal lag characteristics of the experiments.