Gasification of coal or biomass with in-situ CO2 capture is an emerging technology aiming to address the problem of climate change. Development of a CO2 sorbent with desirable properties and understanding the behavior of such a material in carbonation/calcination reactions is an important part of developing the technology. In this paper, we report experimental results describing the carbonation behavior of three synthetic CaO-based sorbents. We also present a physically-based model of the reactive transport processes in sorbent particles, which have complicated pore structures. This modeling is based on the conditional approach (i.e., conditional moment closure (CMC)), which has proven to be successful in modeling reactive transport phenomena in porous media. The model predictions are in good agreement with the experimental data.