The effects of different Ca-based additives on the sulfur removal of coals during pyrolysis up to 900 degreesC have been studied in a fixed-bed reactor. It was found that Ca(OH)(2) and CaO were quite effective to capture the sulfur-containing gases, 95% of the sulfur evolved from untreated coal was retained in the char by the use of additives. Both the tar yield and the sulfur content of the tar decreased with addition of Ca-based additives. The effect of Ca(OH)(2) was better than that of CaO due to its higher activity, but CaCO3 had little effect because of its higher decomposition temperature (-900 degreesC) than the peak temperature range (400-500 degreesC) of sulfur-containing gases emission. There is remarkable sulfur retention effect with Ca(OH)(2) prepared by impregnation and ultrasonic treatment due to the higher dispersion in coal particles than by simple mechanical mixing. The ultrasonic treatment is the best method with regard to the lowest SO2 release during the char combustion. XRD results showed that the sulfur captured by Ca-based additives during pyrolysis turned into CaS. FeS detected in pyrolysis char without additives disappeared in chars with additives, which indicated that CaO could react with FeS through solid-solid reaction. When the chars with calcium-additives were burned in fixed bed reactor, they gave out less SO2 than the raw coal added with same additives. The best total desulfurization efficiency could reach to about 85%. (C) 2003 Elsevier Ltd. All rights reserved.