Kinetic analysis of the interactions between calcium ferrite and coal char for chemical looping gasification applications: Identifying reduction routes and modes of oxygen transfer

Chemical Looping Gasification (CLG) is an emerging technology that shows promise for efficient coal gasification by eliminating the need for energy intensive gas separations to achieve a non-nitrogen diluted syngas stream. Oxygen from oxygen carriers, such as CaFe2O4, are used for coal gasification in place of conventionally produced gaseous oxygen from cryogenic separation of air. These oxygen carriers are unique for their ability to selectively oxidize coal to form syngas and show limited reactivity with syngas components (H2, CO). This study was carried out to determine the kinetic model representation and parameters associated with the selective oxidation of coal derived char (Wyodak and Illinois #6) with a metal ferrite (CaFe2O4) of which are needed for advancement of the process concept. Using thermogravimetric analysis (TGA) coupled with mass spectrometry, the selective oxygen release from metal ferrite in the presence of char by proximal contact was examined. The application of model fitting approaches was used to describe controlling resistances during oxygen release. A combination of the modified shrinking core model (SCM) with planar oxygen ion diffusion control and reaction order based models were applied for kinetic parameter determination. CaFe2O4 particle size plays a major role in the prevailing mode of oxygen release. Particle sizes on the range of 40–50µm tend to favor first order kinetically controlled regimes independent of geometric and diffusion controls. The probability for oxygen ion diffusion controlling regimes increased when the particle size range of the oxygen carrier was increased up to 350µm. Char type also impacted the prevalence of the controlling regime. Higher ranked chars react in a slower manner, limiting the gradient for oxygen ion release from the oxygen carrier. Activation energies determined for this process range from 120 to 200kJ/mol and oxygen ion diffusion coefficients are on the order of 10⁻⁸cm²/s. It is suggested that oxygen ion movement is regulated by lattice diffusion out of partially reduced phases (Ca2Fe2O5) and through reduced outer layers composed of CaO and Fe. The controlled movement of oxygen ions influences the rate of carbon oxidation in the char and therefore the selectivity towards partial oxidation products, which are desirable in CLG applications.