First principle based rate equation (1pRE) for reduction kinetics of Fe2O3 with syngas in chemical looping

Abstract

Chemical looping combustion (CLC) of solid fuel is a promising technology with inherent CO separation and low energy penalty for CO capture. Syngas is main intermediate species of solid fuel conversion in CLC, the reduction kinetics of oxygen carriers with syngas play a crucial role in CLC systems. However, the current research obtains the reaction rate constants by fitting the apparent models with the experimental data, and cannot explain the reduction kinetics behavior from a microscopic level. It remains a challenge to compute the reduction kinetics of oxygen carriers with syngas directly from first-principles density functional theory (DFT) without fitting experimental data. This study proposes a first-principle-based rate equation (1pRE) theory and integrates it into the random pore model (RPM) to predict the kinetics of FeO reduction by syngas in CLC. The developed 1pRE theory utilizes DFT calculations to search for reaction pathways and energy barriers of elementary reactions. Then the DFT data are introduced into the statistical mechanics partition function and transition state theory (TST) to calculate the reaction rate constants. Microkinetic rate equations of elementary reactions occurring at the surface scale are developed to describe the change of surface coverage of different surface species. The 1pRE theory is integrated into the RPM to account for the influence of particle-scale structural changes on the overall conversion rate during the reduction process. The theory can predict the reduction kinetics of oxygen carriers without fitting experimental data and establishes a connection between microscopic insights and macroscopic phenomena. The accuracy was validated by experimental data of FeO oxygen carriers obtained from the thermogravimetric analyzer (TGA) in the atmosphere of syngas. The developed 1pRE predicts the reduction kinetics of oxygen carriers accurately and can be used to optimize the design of oxygen carrier materials and the scale up of CLC reactors.