This paper presents the results of numerical computations for a large-scale OFz-425 CFB (circulating fluidized bed) boiler utilizing coal and syngas. Four different operating scenarios are considered, including the reference variant, corresponding to the conventional, mono-combustion of bituminous coal, and three tests involving replacement of secondary air and part of the coal stream with syngas fed by start-up burners. Pressure, gas velocity, temperature, and carbon dioxide distribution in the combustion chamber are discussed in the paper. The results indicate that the syngas supply leads to an increase in local temperature and carbon dioxide concentrations. The proposed concept is not advisable as it may lead to frequent emergency stops of the CFB boiler.