Industrial practice has confirmed that decreasing the bed material size substantially diminishes nitrogen oxide (NOx) emissions in coal-fired circulating fluidized bed (CFB) boilers. This reduction allows for compliance with the stringent ultra-low emissions standard (NOx < 50 mg/Nm3@6%O₂, dry) proposed by the Chinese government, all without the need for supplementary denitrification devices. Consequently, it becomes essential to delve into the mechanisms through which particle size, as a gas–solid flow characteristic, directly affects the chemical reaction dynamics within the coal combustion process. Due to the difficulty of field tests, this paper employs the Eulerian-Eulerian numerical method suitable for wide particle size distributions to investigate the impact of bed material particle size on gas–solid flow and NOx concentration. Furthermore, the generalized QC-EMMS drag model is utilized to predict the heterogeneous flow across varying particle size conditions. Industrial test data validated the simulation accuracy, with prediction errors of bed pressure drop, temperature, and NOx emission concentration ranging from 5 % to 8.1 %. The analysis revealed that the particle concentration distribution heterogeneity decreases as the particle size diminishes. The variation trends of NOx with particle size exhibit distinct differences between the lower dense phase region and the upper dilute phase region within the bed. For finer bed material particles, the high NOx concentration generated in the dense phase region experiences a more thorough reduction in the dilute phase region. Through the analysis of material concentration and reaction rate, it is believed that this phenomenon is related to the increased catalytic effect of fine ash particles in the dilute phase region, that is, the reduction in particle size leads to an increase in catalytic specific surface area, enhancing NOx reduction, thus achieving ultra-low emissions at the outlet. These research results provide theoretical support for further development of ultra-low emission coal-fired CFB boilers.