Comprehensive evolution mechanism of SOx formation during pyrite oxidation

Pyrite (FeS₂) oxidation during coal combustion is one of the main sources of harmful SO₂ emission from coal-fired power plants. Density functional theory (DFT) study was performed to uncover the evolution mechanism of SO_x formation during pyrite oxidation. The results show that chemisorption mechanism is responsible for O₂, SO₂ and SO₃ adsorption on FeS₂ surface. The presence of formed oxidation layer (Fe₂O₃) weakens the interaction between O₂ molecule and FeS₂ surface. The adsorbed O₂ molecule easily dissociates into active surface O atom for SO_x formation. The dissociation reaction of O₂ is activated by 77.38?kJ/mol, and exothermic by 138.46?kJ/mol. Compared to the further oxidation of SO₂ into SO₃, SO₂ prefers to desorb from FeS₂ surface. The dominant reaction pathway of SO₂ formation from the oxidation of the outermost FeS₂ surface layer is a three-step process: surface lattice S oxidation, SO₂ desorption and replenishment of S vacancy by activated surface O atom. The elementary reaction of surface lattice S oxidation has an activation energy barrier of 197.96?kJ/mol, and is identified as the rate-limiting step. SO₂ formation from the further oxidation of bulk FeS₂ layer is controlled by a four-step process: bulk lattice S migration, lattice S oxidation, SO₂ desorption and surface O atom deposition. Migration of lattice S from bulk position to the outermost surface shows a high activation energy barrier of 175.83?kJ/mol. The deposition process of surface O atom is a relatively easy step, and is activated by 21.05?kJ/mol.