Reduced-order model for CaO carbonation kinetics measured using micro-fluidized bed thermogravimetric analysis

Abstract A reduced-order model was developed to describe the CaO carbonation kinetics by simplifying the detailed one-dimensional rate-equation-based grain model. The reduced-order model was derived using the Thiele modulus method and is an analytical model, which can be easily used in the reactor scale model or computational fluid dynamics (CFD) simulation. In the reduced-order model, physical/chemical steps occurring during the carbonation process were considered, including external diffusion of gas around the particle, intraparticle diffusion, surface reaction, product islands growth and product layer diffusion. This model can be used to investigate the complex kinetic behaviors such as reaction controlled steps, kinetics transition from chemical reaction to product layer diffusion, and the effect of particle structure change on intraparticle diffusion, such as pore plugging phenomenon. The prediction accuracy of reduced-order model was verified by the detailed one-dimensional model. In order to demonstrate the application of the reduced-order model for reactor scale analysis, the CaO carbonation kinetics under different temperatures (600∼750 °C), CO2 concentrations (25∼75 vol%) and particle sizes (0.2∼3 mm) were measured using a novel micro-fluidized bed thermogravimetric analysis (MFB-TGA) method, which is based on real-time mass measurement of CaO sample in a fluidizing state. The reduced-order model was implemented into a K-L two-phase bubbling bed reactor model to analyze the experimental data of a micro-fluidized bed reactor. Results indicated that the two-stage behavior of carbonation kinetics can be described successfully using the model, and the effect of particle structure change on pore plugging and intraparticle diffusion can be well predicted and explained. The carbonation is first-order reaction when the CO2 partial pressure is within 75% (1 bar). The effect of particle size on carbonation kinetics shows three-zone characteristics of reaction/diffusion combined controlling mechanism, and was discussed in detail. The reduced-order model provides a promising application for describing multiscale mechanisms (surface, particle and reactor) of carbonation kinetics.