K2CO3-catalyzed char gasification with steam was carried out on a laboratory fix-bed reactor and it featured in the preparation of char from a high-sulfur coal by the prior addition of Ca(OH)(2) to the coal. This work was focused on the clarification of sulfur transformations during the coal pyrolysis and the char gasification. Sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy was employed to determine quantitatively the forms of sulfur in coal and their changes in process. Results showed that the addition of Ca(OH)(2) to coal promoted the decomposition of both pyrite and organic sulfur during the charring. In the K2CO3-catalyzed char gasification, the calcium additive enabled more sulfur to be retained eventually as K2SO4 rather than CaSO4. The formation of K2SO4 would be conducive to the recycled use of potassium catalyst. (C) 2012 Elsevier Ltd. All rights reserved.