A coalescence-fragmentation model has been developed to predict the behaviors of coal mineral particles during the combustion of pulverized bituminous coals or coal blends. Based on the computer-controlled scanning electron microscope (CCSEM) characterization of coal minerals, the particle size distributions (PSDs) and mineral species of ash particles can be simulated. In particular, the interactions among excluded minerals (mainly referring to the excluded Ca-bearing-species and Fe-bearing-species) and included minerals are accounted for in this model. The PSDs and the mineral species of ash particles are derived from the coalescence and fragmentation of coal mineral particles. Based on this proposed model, both of the predicted PSDs and the mineral species of ash particles are in good agreement with their corresponding experimentally measured values. And the comparisons further demonstrate that the combined effects of coalescence of included minerals and fragmentation of excluded minerals have direct impacts on the ash-forming process. In addition, for the coals rich in excluded Ca- and/or Fe-bearing-species, the interactions among included minerals and excluded minerals are another important mechanism governing ash formation for high-rank coals.