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In this paper, the effect of Ba(NO3)2 on the efficiency of sulfur fixation of calcium oxide during coal combustion was studied. The results showed that addition of barium nitrate to the CaO can enhance the sulfur removal rate of CaO significantly. The X-ray diffraction spectrum of residual ash of coal added some sulfur fixative expressed that Ba2+ can form a compound of Ba-Al-Si-O which encloses the CaSO4 to prevent it’s decomposition, so Ba2+ can improve the action of sulfur fixation of CaO. The combustion character os the original coal and original coal added sulfur fixative was researched with thermal-gravity analyzer and the results expressed that adding some sulfur fixative to the coal will make the combustion character of coal change little.