The potential oxidation characteristics of CaCr2O4 during coal combustion with solid waste in a fluidized bed boiler: A thermogravimetric analysis.

CaCr2O4 (Cr (III)), mainly generated through the decomposition of CaCrO4 (Cr (VI)), is a significant intermediate for toxic Cr (VI) formation during solid fuel combustion. In this study, the formation, oxidation and sulfation kinetics of CaCr2O4 were analyzed to forecast the potential of CaCr2O4 oxidation during co-firing of coal and solid waste in a circulating fluidized bed boiler. The results indicated that the formation and oxidation of CaCr2O4 were fitted to a single step nucleation and growth model while CaCr2O4 sulfation was fitted to a shrinking core model. CaCr2O4 formation through CaCrO4 decomposition was favored in oxygen-lean atmosphere and considerably suppressed in the presence of oxygen. In contrast, CaCr2O4 oxidation was mainly determined by the contacts between CaCr2O4 and CaSO4/CaO, which influenced not only oxidation rates but also the product species. Moreover, the oxidation reactivity of CaCr2O4 was higher in the presence of CaO than that of CaSO4. On the other hand, CaCr2O4 sulfation can occur more easily than CaCr2O4 oxidation, the reaction rate of which was deeply affected by sulfate product layer. Findings in this study suggested that spraying calcium in furnace for desulphurization may increase the risk of CaCr2O4 oxidation. Measures including the adjustment of Ca/S ratio in blended fuel (with added limestone) and operating conditions (such as temperature and local atmosphere) in co-firing system could be taken to control CaCr2O4 formation and oxidation.