Starting from a reference and comprehensive chemical mechanism for alkali metal emissions (Glarborg and Marshall, 2005), combined with an hydrocarbon oxidation described with a skeleton mechanism (Kazakov and Frenklach, 1994), reduced and optimized chemical kinetics are derived. The objective is to provide a set of chemical schemes useful for three-dimensional (3D) numerical simulations of alkali metal emissions by pulverized solidfuel combustion systems. An automated procedure relying on one-dimensional (1D) premixed flames is applied to obtain a combined reduced mechanism, whose performance is then evaluated in one-dimensional strained diffusion flames, micro-mixing based canonical problems and three-dimensional carrier-phase direct numerical simulation (DNS) of coal combustion. Predictions of the reduced mechanism on major sodium species, i.e., Na, NaOH, NaCl and Na 2 SO 4 agree well with that of the detail reference scheme under all the considered conditions. A parametric study with 14 two-dimensional (2D) DNS cases is then performed to better understand the reactive flow properties and estimate the prediction capabilities of the reduced mechanism for various Na/Cl/S ratio in the volatiles. After pursuing the chemistry reduction, a global sodium mechanism with only 9 species and 8 reaction-steps is also discussed. The systematic comparison between the 3D DNS results obtained with the reference chemical scheme against those with the reduced ones confirm the validity of the reduction strategy. A reduction of up to 84% in computational cost is reached with the optimized global scheme, thus allowing for addressing real pulverized-coal combustion systems.