Improvement of activity and SO₂ tolerance of Sn-modified MnOx-CeO₂ catalysts for NH₃-SCR at low temperatures

Environ Sci Technol. 2013 May 21;47(10):5294-301. doi: 10.1021/es304732h. Epub 2013 Apr 30.

Abstract

The performances of fresh and sulfated MnOx-CeO₂ catalysts for selective catalytic reduction of NOx by NH₃ (NH₃-SCR) in a low-temperature range (T < 300 °C) were investigated. Characterization of these catalysts aimed at elucidating the role of additive and the effect of sulfation. The catalyst having a Sn:Mn:Ce = 1:4:5 molar ratio showed the widest SCR activity improvement with near 100% NOx conversion at 110-230 °C. Raman and X-ray photoelectron spectroscopy (XPS) indicated that Sn modification significantly increases the concentration of oxygen vacancies that may facilitate NO oxidation to NO₂. NH₃-TPD characterization showed that the low-temperature NH₃-SCR activity is well correlated with surface acidity for NH3 adsorption, which is also enhanced by Sn modification. Furthermore, as compared to MnOx-CeO₂, Sn-modified MnOx-CeO₂ showed remarkably improved tolerance to SO₂ sulfation and to the combined effect of SO₂ and H₂O. In the presence of SO₂ and H₂O, the Sn-modified MnOx-CeO₂ catalyst gave 62% and 94% NOx conversions as compared to 18% and 56% over MnOx-CeO₂ at temperatures of 110 and 220 °C, respectively. Sulfation of SnO₂-modified MnOx-CeO₂ may form Ce(III) sulfate that could enhance the Lewis acidity and improve NO oxidation to NO₂ during NH₃-SCR at T > 200 °C.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Absorptiometry, Photon
  • Ammonia / chemistry*
  • Catalysis
  • Cerium / chemistry*
  • Cold Temperature*
  • Magnesium Oxide / chemistry*
  • Sulfur Dioxide / chemistry*
  • Thermogravimetry
  • Tin / chemistry*

Substances

  • Sulfur Dioxide
  • Cerium
  • Magnesium Oxide
  • ceric oxide
  • Tin
  • Ammonia