Unraveling the capture mechanism of gaseous As2O3 over H-ZSM-5 zeolite from coal-fired flue gas: Experimental and theoretical insights

Abstract

Gaseous As₂O₃ discharged from coal-fired power plants results in severe detriments to the ecological environment. It is of great urgency to develop highly efficient As₂O₃ capture technology for reducing atmospheric arsenic contamination. Utilizing solid sorbents for gaseous As₂O₃ capture is a promising treatment for As₂O₃ capture. The zeolite of H-ZSM-5 was applied for As₂O₃ capture at high temperatures of 500-900 °C. Special attention was paid to clarifying its capture mechanism and identifying the influence of flue gas components via density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. Results revealed that due to high thermal stability with large specific areas, H-ZSM-5 demonstrated excellent arsenic capture at 500-900 °C. The captured arsenic consisted of As³⁺ and As⁵⁺ speciations, ascribed to As₂O₃ adsorption and oxidation. Moreover, As³⁺ and As⁵⁺ compounds were both through physisorption or chemisorption at 500-600 °C while dominant chemisorption at 700-900 °C. In particular, As³⁺ compounds were much more steadily fixed in products at all operating temperatures. Combining the characterization analysis and DFT calculations, it further verified that both Si-OH-Al groups and external Al species of H-ZSM-5 could chemisorb As₂O₃, and the latter exhibited much stronger affinities via orbital hybridization and electron transfer. The introduced O₂ could facilitate As₂O₃ oxidation and fixation in H-ZSM-5, especially at a lower concentration of 2%. Additionally, H-ZSM-5 possessed great acid gas resistance for As₂O₃ capture under the concentration of NO or SO₂ less than 500 ppm. AIMD simulations further identified that compared to NO and SO₂, As₂O₃ was far more competitive and occupied the active sites of the Si-OH-Al groups and external Al species of H-ZSM-5. Overall, it demonstrated that H-ZSM-5 is a promising sorbent for As₂O₃ capture from coal-fired flue gas.

Keywords: As(2)O(3) capture; DFT calculations and AIMD simulations; Flue gas components; Functional groups; H-ZSM-5; Thermal stability.