Empirical Kinetic Models for the CO2 Gasification of Biomass Chars. Part 1. Gasification of Wood Chars and Forest Residue Chars.

The gasification kinetics of charcoals and biomass chars is complicated by several factors, including chemical and physical inhomogeneities, the presence of mineral matter, and the irregular geometry of the pore structure. Even the theoretically deduced gasification models can only provide empirical or semiempirical descriptions. In this study, an empirical kinetic model from the earlier works of the authors was adapted for the CO2 gasification of biomass chars. It is based on a versatile polynomial approximation that helps to describe the dependence of the reaction rate on the progress of the conversion. The applicability of the model was tested by the reevaluation of 24 thermogravimetric analysis (TGA) experiments from earlier publications. The adjustable parameters of the model were determined by the method of least squares by evaluating groups of experiments together. Two evaluation strategies were tested. In the regular evaluations, the same kinetic parameters were employed for all the experiments with a given sample. The use of experiments with modulated and constant reaction rate (CRR) temperature programs made it possible to employ another approach too, when the preexponential factor was allowed to vary from experiment to experiment. The latter approach allows a formal kinetic description of the differences in the thermal deactivation of the samples caused by different thermal histories as well as of some inevitable systematic errors of the TGA experiments. The evaluations were carried out by both approaches, and the results were compared. The evaluations were based on 12 experiments. As a test, each evaluation of the study was repeated with only 8 experiments. The results of the latter test calculations indicated that the information content of the employed experiments is sufficient for the evaluation approaches of this work.