TG-FTIR pyrolysis of coal and secondary biomass fuels: Determination of pyrolysis kinetic parameters for main species and NOx precursors

Co-firing of secondary biomass fuels with coal in coal-fired pulverized fuel boilers is facing increased application in large-scale power production. Fundamental knowledge on the thermochemical behavior of biomass and waste fuels is still lacking, especially regarding the release of the fuel bound nitrogen. Characterization of chicken litter (CL), biomass mix (BM) and meat and bone meal (MBM) and an HV coal blend was performed using TG-FTIR analysis. Three heating rate profiles were applied (10, 30 and 100 °C/min), with a final temperature of 900 °C. NH₃ was found to be the major gaseous N-product, while HCN and HNCO were also released in substantial amounts. Kinetic parameters for the pyrolysis of biomass fuels were obtained using a model based on parallel first-order reactions with a Gaussian distribution of activation energies. Input files for the coal FG-DVC (functional group-devolatilization, vaporization, cross-linking) and FG-BioMass pyrolysis models were prepared. The fit of model parameters to TG-FTIR product-evolution data was found to be generally good, but the model-predicted yields for some species did not fit experimental data at all heating rates equally well. This problem can be overcome by improvements in the FG-BioMass model. The results of this study can be used to have an improved input of initial pyrolysis in CFD modeling of co-fired boilers.