Combustion Kinetics of Biomass Materials in the Kinetic Regime

Wheat straw, willow from an energy plantation, and municipal sewage sludge were studied by thermogravimetry at linear and nonlinear heating programs in gas flows containing 4 and 20% oxygen. A kinetic scheme of successive devolatilization and char burnoff reactions was assumed. A distributed activation energy model (DAEM) was assumed for the devolatilization with a Gaussian distribution and a constant pre-exponential factor. The burnoff of the forming char was approximated by first-order kinetics with respect to the amount of char. The dependence of the reactions upon the oxygen concentration was described by power functions. This model gave a suitable description for the wheat straw and sewage sludge. An additional partial reaction with accelerating kinetics was needed for describing the oxidative cellulose pyrolysis in the willow sample. The evaluations were carried out by the method of least squares. 9-17 model parameters were determined from ten experiments for each sample. Good fit quality and reasonable kinetic parameters were obtained. Test evaluations revealed that the first-order kinetics, with respect to the amount of char is an adequate model; the assumptions of more complex char burnoff submodels did not led to notable improvements. The replacement of the DAEM devolatilization by simpler n-order kinetics gave inadequate performance. Earlier works with simpler models and linear temperature programs showed that the successive mechanism can be well-approximated by parallel reactions. Such approximations proved to be viable in the present case, too.