Char oxidation at elevated pressures

Approximately 100 char oxidation experiments were performed at atmospheric and elevated pressures, with two sizes (70 and 40 μm) of Utah and Pittsburgh bituminous coal chars at 1, 5, 10, and 15 atm total pressure. Reactor temperatures were varied between 1000 and 1500 K with 5% to 21% oxygen in the bulk gas, resulting in average particle temperatures ranging from 1400 to 2100 K and burnoff from 15% to 96% (daf). Independently determined particle temperature and overall reaction rate allowed an internal check on the data consistency and provided insight into the products of combustion. The chars burned in a reducing density and reducing diameter mode in an intermediate regime between the kinetic and pore diffusion zones, irrespective of total pressure. Significant surface CO₂ formation occurred at particle temperatures below about 1800 K over the entire pressure range. Particle temperatures were strongly dependent on the oxygen and total pressures; increasing oxygen pressure at constant total pressure resulted in substantial increases in particle temperature, while increasing the total pressure at constant oxygen pressure led to substantial decreases in particle temperature. Increasing total pressure from 1 to 5 atm in an environment of constant gas composition led to modest increases in the reaction rate; the rate decreased with further increases in pressure. Results indicate that ambient pressure global model kinetic parameters cannot be accurately extrapolated to elevated pressures. The apparent reaction rate coefficients (based on the partial pressure form of the nth-order rate equation) showed significant pressure dependence, since both the activation energy and frequency factor decreased with increasing pressure. This suggests that the empirical nth-order rate equation is not valid over the range of pressures encountered in the experiments. However, simulations indicate that the global model can be used to model elevated pressure char oxidation provided pressure-dependent kinetic parameters are used.