Reaction mechanism of elemental mercury oxidation to HgSO4 during SO2/SO3 conversion over V2O5/TiO2 catalyst

Experiments and density functional theory calculations were conducted to uncover the reaction chemistry of Hg⁰ oxidation during SO₂/SO₃ conversion over V₂O₅/TiO₂ catalyst. The results show that SO₂ promotes Hg⁰ oxidation over V₂O₅/TiO₂ catalyst with the assistance of oxygen. The promotional effect is dependent on the reaction temperature, and is associated with the bimolecular reaction between Hg⁰ and SO₃ over V₂O₅/TiO₂ catalyst. SO₂ can be oxidized to SO₃ which has high oxidation ability for Hg⁰ oxidation. SO₂/SO₃ conversion proceeds through a three-step reaction process in the sequence of SO₂ adsorption → SO₂ oxidation → SO₃ desorption. SO₂ oxidation presents an activation energy barrier of 223.84 kJ/mol. HgSO₄ species is formed from the bimolecular reaction between Hg⁰ and SO₃ over V₂O₅/TiO₂ catalyst. Hg⁰ oxidation by SO₃ over V₂O₅/TiO₂ catalyst occurs through three reaction pathways, which are energetically favorable for HgSO₄ formation. SO₂* → SO₃* is identified as the rate-determining step of HgSO₄ formation. During Hg⁰ oxidation by SO₃ over V₂O₅/TiO₂ catalyst, HgSO₄ desorption is a highly endothermic reaction process and requires a higher external energy. The proposed skeletal reaction network can be used to well understand the reaction mechanism of Hg⁰ oxidation during SO₂/SO₃ conversion over V₂O₅/TiO₂ catalyst.