Abstract: Xinjiang high-alkali coal demonstrates distinctive attributes characterized by substantial geological reserves, low ash yield, enhanced ignition and burnout characteristics. Nevertheless, the elevated concentrations of alkali metals inherent in this fuel lead to safety issues such as ash deposition and slagging in boilers. Given the current energy consumption landscape in China, the participation of coal-fired power units in deep peak regulation has become an inevitable trend. During deep peak shaving conditions, significant changes occur in the combustion process of high-alkali coal and the migration and transformation characteristics of alkali metals. However, limited attention has been given to chemical kinetic simulations focusing on the migration and transformation characteristics of alkali metals under deep peak regulation scenarios while the microscopic reaction mechanisms of gaseous alkali metals require further in-depth research. This investigation conducts a chemical kinetic simulation study on the migration and transformation characteristics of gaseous alkali metals during the combustion of high-alkali coal under deep peak regulation scenarios. Analytical results reveal that the occurrence forms of sodium and sulfur content in the coal samples have a significant impact on the migration and transformation characteristics of gaseous sodium. In the oxidative combustion zone, as the reaction time increases, the elementary reactions NaHSO4+NaCl=Na2SO4+HCl and NaHSO4+NaOH=Na2SO4+H2O continuously occur, leading to an increase in the proportion of Na2SO4. The increase in unburned carbon contents inhibits the migration and transformation of Na into NaOH and NaCl. This study provides theoretical support for the development of key technologies for the safe combustion of high-alkali coal under deep peak shaving conditions.