Characteristics of Flue Gas Dechlorination by Ethanol-Digested Calcium Oxide and Its Effect on Mercury Speciation and...

This study aims to investigate the feasibility of ethanol-digested calcium oxide (CaO-E) as a novel dechlorination sorbent for the efficient removal of hydrogen chloride (HCl) from coal-fired flue gas and further evaluate its influence on mercury speciation and transformation in flue gas, thereby addressing the low efficiency and limited multi-pollutant control capability of conventional dry dechlorination technologies. Based on a laboratory-scale injection reaction system, ethanol-digested calcium-based sorbents were injected into simulated coal-fired flue gas to systematically examine the effects of key factors, including Ca/Cl molar ratio, SO₂, and fly ash, on dechlorination efficiency. Density functional theory (DFT) calculations were further employed to elucidate the reaction mechanisms. Meanwhile, mercury-laden flue gas was introduced to investigate the removal characteristics of elemental mercury (Hg⁰) and oxidized mercury (Hg²⁺) by CaO-E. The experimental results demonstrated that ethanol-digested CaO exhibited significantly superior performance compared with untreated samples, and the formation of a porous calcium hydroxide structure was identified as the key factor responsible for its high dechlorination efficiency. When the Ca/Cl molar ratio reached 4.0, the dechlorination efficiency could be stably maintained above 80%. SO₂ showed a pronounced inhibitory effect on the dechlorination process, whereas fly ash exhibited a slight promoting effect. Mercury removal experiments revealed that CaO-E had limited removal capability toward Hg⁰ but effectively reduced the concentration of Hg²⁺. Specifically, when the Ca/Cl molar ratios were 3 and 5, the Hg²⁺ concentrations decreased to 1.4 and 0.6 μg/m³, respectively. This behavior can be attributed to the fact that Hg²⁺ mainly exists in chlorinated forms such as HgCl₂, which possess strong polarity and can be readily adsorbed by the alkaline active sites on the CaO-E surface. In addition, as the dechlorination process proceeded, chlorine-containing species in the flue gas were gradually consumed, suppressing the oxidation conversion of Hg⁰ to Hg²⁺ and thereby further reducing the Hg²⁺ concentration. Theoretical calculations indicated that both HCl and SO₂ could undergo chemisorption on calcium active sites, while HCl possessed a lower reaction energy barrier and therefore dominated the competitive adsorption process, exhibiting preferential reactivity. Overall, ethanol-digested calcium oxide not only demonstrates excellent HCl removal performance, but also shows the capability to regulate mercury speciation in flue gas to a certain extent, providing both theoretical insights and technical support for the synergistic control of multiple pollutants in coal-fired flue gas.