Microcosmic insights into Hg0-SO2 interaction on CuFe2O4 catalyst

Abstract

CuFe2O4 is considered as a very promising kind of catalysts for Hg0 oxidation in the industrial flue gas. The flue gas produced by solid-fuel combustion usually contains acid gas component SO2, which can exhibit the versatile effects on Hg0 oxidation. However, the effects of SO2 on Hg0 oxidation catalyzed by CuFe2O4 catalyst and its reaction mechanism remain elusive. Herein, the reaction mechanism governing the effects of SO2 on Hg0 oxidation was investigated via the Hg0 oxidation experiments and density functional theory (DFT) calculations. The experimental results show that the temperature change and SO2 presence can affect the Hg0 removal efficiency of CuFe2O4 catalyst. SO2 has a certain degree of inhibition effect on the Hg0 oxidation of CuFe2O4 catalyst. The inhibition effect of SO2 is relatively weak in the low temperature range of 50–150 °C, which is closely associated with the competitive adsorption between SO2 and Hg0. SO2 exhibits a relatively strong inhibition effect on Hg0 oxidation in the high temperature range of 200–350 °C, which is related to the high-temperature sulfation of CuFe2O4 catalyst surface. Mercury species on the CuFe2O4 catalyst surface mainly exists in the forms of HgSO4 and HgO in the presence of SO2. The DFT-calculation results indicate that the conversion process of SO2 to SO3 includes two steps: SO2 adsorption and SO2 oxidation. The activation energy barrier of SO2 oxidation reaction is 216.42 kJ/mol. The oxidation of Hg0 on the surface of CuFe2O4 catalyst includes four steps: Hg0 adsorption, Hg* oxidation into HgO*, HgO*-to-HgSO4* conversion and HgSO4 desorption. HgSO4 is formed by the bimolecular reaction of HgO* and SO3* on CuFe2O4 catalyst. Hg* oxidation into HgO* is found to be the rate-determining step of HgSO4 formation.