Thomas Steiner, Kai Schulze, Norbert Kienzl, Magdalena Pauritsch, Viktor Hacker, Sebastian Bock, Alberto Abad, Robert Scharler and Andrés Anca-Couce
Reliable experimental data and models are required to better understand and design chemical looping processes with oxygen carrier materials like ilmenite. A dubious variability of suggested kinetics for similar oxygen carrier materials has been presented in the literature. Part I of this work focuses on thermogravimetric analysis (TGA) of gas–solid kinetics and addresses several of its challenges, which are possible reasons behind such deviations. The reduction of synthetic ilmenite (60 mass% Fe2O3 + 40 mass% TiO2 powder with H2 in a TGA system was investigated for this purpose.
Multiple steps were necessary to overcome mass transfer limitations during the measurements: (i) small sample masses down to 1.6 mg, (ii) high gas flow rates, (iii) a suitable sample carrier and (iv) proper sample dispersion on the sample carrier. Three types of sample carriers (crucible, basket and plate) were tested; the plate showed the best performance overall. It was alarming that an exemplary increase in sample mass from 1.6 to 3 mg, which was still significantly lower than all other studies reviewed, already introduced a noticeable influence of diffusion. Isothermal (650–950 °C, 17–50 vol% H2) and nonisothermal parameter studies were conducted and yielded vastly different isoconversional activation energies. A computational fluid dynamics (CFD) study of the TGA system suggested considerable axial dispersion of H2 influencing the initial conversion period.
These findings help to assess the reliability of kinetic studies and guide towards diffusion-free, kinetic measurements. The results will be used for model development in part II.
Fuel, 2024