Oxy-fuel combustion combined with carbon capture and storage is the most effective and direct technology to achieve carbon neutrality in cement industry. In this work, numerical simulation was employed to investigate the effects of air combustion and oxy-fuel combustion with different O2/CO2 fractions on the airflow field, temperature field, pulverized coal combustion mechanism, heat transfer characteristics and NOx distribution in rotary kiln. The results show that the airflow field under different conditions has no significant change. When transitioning from the air condition to the oxy-fuel condition, the ignition point of pulverized coal extends backward by approximately 0.2 m. The maximum temperature decreases from 2306 K to 2052 K, and the temperature becomes more uniform. As the oxygen concentration in the primary air increases, both the maximum and average temperatures gradually rise, and the flame length shortens from 25.4 m to 24.16 m. In the rotary kiln, the locations of char oxidation and gasification reactions differ, but these reaction locations remain consistent under different conditions. Under oxy-fuel conditions, the oxidation rate and oxidation proportion of char decrease, while the gasification rate and gasification proportion of char increase, resulting in a shortening of the burnout distance of coal from 34.5 m to 31.3 m. With increasing oxygen concentration in the primary air, the rates of char oxidation and gasification gradually rise, further shortening the burnout distance. The decrease in temperature at the front end of the rotary kiln under oxy-fuel conditions reduces the total heat transfer in the burning zone by 15 %. When the oxygen content of the primary air is 70 %, it ensures stable calcination of clinker. Additionally, under oxy-fuel conditions, the NOx generation is significantly reduced. With the increase of oxygen concentration in the primary air, the NOx concentration at the outlet decreases slightly from 451 ppm to 406 ppm, due to the increase in kiln temperature that favors the reduction of fuel NOx.