Reactivity of Oxygen Carriers for Chemical-Looping Combustion in Packed Bed Reactors under Pressurized Conditions

For the design, scale-up, and optimization of pressurized packed bed reactors for chemical-looping combustion (CLC), understanding of the effect of the pressure on the reactivity of the oxygen carriers is very important. In this work, the redox reactivity of CuO/Al2O3 and NiO/CaAl2O4 particles at elevated pressures have been measured in a pressurized high-temperature magnetic suspension balance. The experiments have demonstrated that the pressure has a negative influence on the reactivity and that this effect is kinetically controlled. The negative effect of the pressure might be caused by the decrease in the number of oxygen vacancies at higher pressures. Moreover, the reactant gas fraction has been demonstrated as an important parameter, probably related to competition between different species for adsorption on the oxygen carrier surface. These effects have been included in the kinetic model leading to a good description of the experimental results. The impact of these findings on packed bed CLC applications with larger oxygen carrier particles has been investigated with a particle model that considers diffusion limitations and kinetics. It has been shown that the impact of diffusion limitations decreases with increasing pressure, due to the decrease in reaction rates and the increase in diffusion fluxes caused by Knudsen diffusion. The results have been validated by experiments with 1.7 mm NiO/CaAl2O4 particles. These results corroborate that the selection of larger particles because of pressure drop considerations does not lead to a large decrease in effective reaction rates, which is beneficial for packed bed CLC applications.