This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO(2) removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 degrees C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 degrees C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 degrees C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe(2)O(3) and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO(2) absorption capacity in terms of mol of SO(2) per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents. (C) 2010 Elsevier Ltd. All rights reserved.