Ca-based additives have been widely used as a sulfur adsorbent during coal pyrolysis and gasification. The Ca speciation and evolution during the pyrolysis of coal with Ca additives have attracted great attention. In this paper, Ca species in the coal chars prepared from the pyrolysis of Ca(OH)2 or CaCO3-added coals are studied by using Ca K-edge X-ray absorption near-edge structural spectroscopy. The results demonstrate that Ca(OH)2 , CaSO4 , CaS and CaO coexist in the Ca(OH)2-added chars, while Ca(OH)2 and CaSO4 are the main species in the Ca(OH)2-added chars. Besides, a carboxyl-bound Ca is also formed during both the pyrolysis for the Ca(OH)2-added and the CaCO3-added coals. A detailed discussion about the Ca speciation is given.
