Comparative Kinetic Analysis of CaCO3/CaO Reaction System for Energy Storage and Carbon Capture

The calcium carbonate looping cycle is an important reaction system for processes such as thermochemical energy storage and carbon capture technologies, which can be used to lower greenhouse gas emissions associated with the energy industry. Kinetic analysis of the reactions involved (calcination and carbonation) can be used to determine kinetic parameters (activation energy, pre-exponential factor, and the reaction model), which is useful to translate laboratory-scale studies to large-scale reactor conditions. A variety of methods are available and there is a lack of consensus on the kinetic parameters in published literature. In this paper, the calcination of synthesized CaCO3 is modeled using model-fitting methods under two different experimental atmospheres, including 100% CO2, which realistically reflects reactor conditions and is relatively unstudied kinetically. Results are compared with similar studies and model-free methods using a detailed, comparative methodology that has not been carried out previously. Under N2, an activation energy of 204 kJ mol−1 is obtained with the R2 (contracting area) geometric model, which is consistent with various model-fitting and isoconversional analyses. For experiments under CO2, much higher activation energies (up to 1220 kJ mol−1 with a first-order reaction model) are obtained, which has also been observed previously. The carbonation of synthesized CaO is modeled using an intrinsic chemical reaction rate model and an apparent model. Activation energies of 17.45 kJ mol−1 and 59.95 kJ mol−1 are obtained for the kinetic and diffusion control regions, respectively, which are on the lower bounds of literature results. The experimental conditions, material properties, and the kinetic method are found to strongly influence the kinetic parameters, and recommendations are provided for the analysis of both reactions.