Abstract: Based on the bench-scale opposed multi-burner (OMB) coal-water slurry gasification experimental platform, the transformation and release characteristics of sodium during the reaction of coal in the gasifier were studied. Particles sampled at different axial distances from burner plane to top and bottom along the gasifier chamber were analyzed. After the microwave digestion and chemical fractionation analysis, the content of sodium was tested by flame atomic absorption spectrometer (FASS). The morphololgy and elements of particles were analyzed by scanning electron microscopy and energy spectrum application system (SEM-EDS). The FASS results showed that the release rate of sodium increased first then decreased with increasing distance to the burner plane. The area near the burner plane was the major release area of sodium. With the reaction in progress in the gasifier the occurrence form of sodium was transformed from water-soluble sodium and ion-exchangeable sodium into the acid-soluble sodium and residual sodium. Combining the SEM-EDS and FASS results, the spherical particles which were formed through melt minerals reacted with sodium in the gas phase to form silicate and sialic acid salt in gasifier. The increasing number of spherical particles led to an increase in the sodium content in the particles.