First principle-based rate equation theory for the carbonation kinetics of CaO with CO2 in calcium looping

Calcium oxide (CaO), a CO2 sorbent and key ingredient in the process of making cement, exhibits excellent potential for carbon capture, utilization, and storage (CCUS) applications through calcium looping and integrated carbon capture and utilization, owing to its outstanding kinetic properties and high recyclability. From a fundamental standpoint, it is important to establish a comprehensive and precise carbonation kinetic model for CaO. In the present study, a density functional theory (DFT)-based rate equation was developed to predict the gas-solid reaction kinetics of CaO carbonation with CO2 in calcium looping. The reaction pathway of CaO carbonation, including surface reactions and structural transformations, was obtained by a transition state search of DFT calculations, and the transition state theory was used to calculate the reaction rate constants. The nucleation model was implemented in the mean-field surface reaction model to describe the nucleation of the CaCO3 product at the gas-solid interface. A grain model was developed to couple the surface reaction and CO2 diffusion through the product layer. The developed theory was validated using a wide range of experimental data, and the negative activation energy of CaO carbonation close to equilibrium was accurately predicted. The developed first principle-based rate equation provides a detailed theoretical framework for predicting CaO performance and optimizing the microstructure of Ca-based sorbents.

Automated summary

A density functional theory-based rate equation was developed to predict the gas-solid reaction kinetics of CaO carbonation with CO2 in calcium looping. The negative activation energy of CaO carbonation close to equilibrium was accurately predicted through experimental validation.