Journal of Materials Science

, Volume 53, Issue 14, pp 10001–10012 | Cite as

Mechanism of Hg0 oxidation in the presence of HCl over a CuCl2-modified SCR catalyst

  • Chuanmin Chen
  • Wenbo Jia
  • Songtao Liu
  • Yue Cao
Chemical routes to materials


CuCl2-SCR catalysts prepared by an improved impregnation method were examined to evaluate the catalytic activity for gaseous elemental mercury (Hg0) oxidation in the presence of HCl at the typical SCR reaction temperature of 350 °C. It was found that Hg0 oxidation activity of commercial SCR catalyst was significantly improved by the introduction of CuCl2. The X-ray fluorescence and Hg0 temperature-programmed desorption (Hg0-TPD) methods were employed to characterize the catalysts. The results indicated that CuCl2 on CuCl2-SCR catalyst could release active Cl species in the presence of O2 at 350 °C, and the released active Cl species could be replenished in the presence of gas-phase HCl. CuCl2-SCR catalyst possessed the appropriate active sites for the adsorption of NH3 and HCl, which could scavenge the inhibiting effect of NH3 on Hg0 oxidation. Hg0-TPD results suggested that the oxidized mercury compounds mainly exited as HgCl2 once HCl was present. The Hg0 oxidation mechanism over CuCl2-SCR catalyst in the presence of HCl could be explained as follows: The adsorbed Hg0 reacted with active Cl species released by CuCl2 to form HgCl2. The reduced CuCl was re-chlorinated to CuCl2 via the intermediate copper oxychloride (Cu2OCl2) formation by being exposed to the gas-phase HCl.



The authors acknowledge financial supports by the Science and Technology Plan Project of Hebei Province of China (16273703D) and the Fundamental Research Funds for the Central Universities (2018MS118, 2017XS128).

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest existed in this manuscript.


  1. 1.
    Wu Y, Wang S, Streets DG, Hao J, Chan M, Jiang J (2006) Trends in anthropogenic mercury emissions in China from 1995 to 2003. Environ Sci Technol 40:5312–5318CrossRefGoogle Scholar
  2. 2.
    Romanov A, Sloss L, Jozewicz W (2012) Mercury emissions from the coal-fired energy generation sector of the Russian Federation. Energy Fuel 26:4647–4654CrossRefGoogle Scholar
  3. 3.
    Javadian H, Ghaemy M, Taghavi M (2014) Adsorption kinetics, isotherm, and thermodynamics of Hg2+ to polyaniline/hexagonal mesoporous silica nanocomposite in water/wastewater. J Mater Sci 49:232–242. CrossRefGoogle Scholar
  4. 4.
    Negreira AS, Wilcox J (2015) Uncertainty analysis of the mercury oxidation over a standard SCR catalyst through a lab-scale kinetic study. Energy Fuel 29:369–376CrossRefGoogle Scholar
  5. 5.
    Li H, Li Y, Wu C, Zhang J (2011) Oxidation and capture of elemental mercury over SiO2–TiO2–V2O5 catalysts in simulated low-rank coal combustion flue gas. Chem Eng J 169:186–193CrossRefGoogle Scholar
  6. 6.
    Gao W, Liu Q, Wu C, Li H, Li Y, Yang J, Wu G (2013) Kinetics of mercury oxidation in the presence of hydrochloric acid and oxygen over a commercial SCR catalyst. Chem Eng J 220:53–60CrossRefGoogle Scholar
  7. 7.
    Xiang J, Wang P, Su S et al (2015) Control of NO and Hg0 emissions by SCR catalysts from coal-fired boiler. Fuel Process Technol 135:168–173CrossRefGoogle Scholar
  8. 8.
    Park KS, Seo YC, Lee SJ, Lee JH (2008) Emission and speciation of mercury from various combustion sources. Powder Technol 180:151–156CrossRefGoogle Scholar
  9. 9.
    Yang X, Zhuo Y, Duan Y, Chen L, Yang L, Zhang L, Jiang Y, Xu X (2007) Mercury speciation and its emissions from a 220 MW pulverized coal-fired boiler power plant in flue gas. Korean J Chem Eng 24:711–715CrossRefGoogle Scholar
  10. 10.
    Liu R, Xu W, Tong L, Zhu T (2015) Mechanism of Hg0 oxidation in the presence of HCl over a commercial V2O5–WO3/TiO2 SCR catalyst. J Environ Sci China 36:76–83CrossRefGoogle Scholar
  11. 11.
    Xu M, Yan R, Zheng C, Qiao Y, Han J, Sheng C (2004) Status of trace element emission in a coal combustion process: a review. Fuel Process Technol 85:215–237CrossRefGoogle Scholar
  12. 12.
    Zhou Z, Liu X, Liao Z, Shao H, Hu Y, Xu Y, Xu M (2016) A novel low temperature catalyst regenerated from deactivated SCR catalyst for Hg0 oxidation. Chem Eng J 304:121–128CrossRefGoogle Scholar
  13. 13.
    Sun C, Snape CE, Liu H (2013) Development of low-cost functional adsorbents for control of mercury (Hg) emissions from coal combustion. Energy Fuel 27:3875–3882CrossRefGoogle Scholar
  14. 14.
    Zhao L, Li C, Zhang J, Zhang X, Zhan F, Ma J, Xie Y, Zeng G (2015) Promotional effect of CeO2 modified support on V2O5–WO3/TiO2 catalyst for elemental mercury oxidation in simulated coal-fired flue gas. Fuel 153:361–369CrossRefGoogle Scholar
  15. 15.
    Hong H, Ham S, Kim MH, Lee S, Lee J (2010) Characteristics of commercial selective catalytic reduction catalyst for the oxidation of gaseous elemental mercury with respect to reaction conditions. Korean J Chem Eng 27:1117–1122CrossRefGoogle Scholar
  16. 16.
    Yang J, Yang Q, Sun J, Liu Q, Zhao D, Gao W, Liu L (2015) Effects of mercury oxidation on V2O5–WO3/TiO2 catalyst properties in NH3-SCR process. Catal Commun 59:78–82CrossRefGoogle Scholar
  17. 17.
    Li H, Wu C, Li Y, Zhang J (2012) Superior activity of MnOx–CeO2/TiO2 catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures. Appl Catal B Environ 111:381–388CrossRefGoogle Scholar
  18. 18.
    Wang F, Li G, Shen B, Wang Y, He C (2015) Mercury removal over the vanadia-titania catalyst in CO2-enriched conditions. Chem Eng J 263:356–363CrossRefGoogle Scholar
  19. 19.
    Hou W, Zhou J, Qi P, Gao X, Luo Z (2014) Effect of H2S/HCl on the removal of elemental mercury in syngas over CeO2–TiO2. Chem Eng J 241:131–137CrossRefGoogle Scholar
  20. 20.
    Smith CA, Krishnakumar B, Helble JJ (2011) Homo- and heterogeneous mercury oxidation in a bench-scale flame-based flow reactor. Energy Fuel 25:4367–4376CrossRefGoogle Scholar
  21. 21.
    Cao Y, Chen B, Wu J, Cui H, Smith J, Chen C, Chu P, Pan W (2007) Study of mercury oxidation by a selective catalytic reduction catalyst in a pilot-scale slipstream reactor at a utility boiler burning bituminous coal. Energy Fuel 21:145–156CrossRefGoogle Scholar
  22. 22.
    Laudal DL, Pavlish JH, Galbreath KC, Thompson JS, Weber GF, Sondreal E (2000) Pilot-scale evaluation of the impact of selective catalytic reduction for NOx on mercury speciation. Office of Scientific and Technical Information Technical Reports.
  23. 23.
    Niksa S, Fujiwara N (2005) A predictive mechanism for mercury oxidation on selective catalytic reduction catalysts under coal-derived flue gas. J Air Waste Manag 55:1866–1875CrossRefGoogle Scholar
  24. 24.
    Senior CL (2006) Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants. J Air Waste Manag 56:23–31CrossRefGoogle Scholar
  25. 25.
    Eswaran S, Stenger HG (2005) Understanding mercury conversion in selective catalytic reduction (SCR) catalysts. Energy Fuel 19:2328–2334CrossRefGoogle Scholar
  26. 26.
    He S, Zhou J, Zhu Y, Luo Z, Ni M, Cen K (2009) Mercury oxidation over a vanadia-based selective catalytic reduction catalyst. Energy Fuel 23:253–259CrossRefGoogle Scholar
  27. 27.
    Zhou J, Hou W, Qi P, Gao X, Luo Z, Cen K (2013) CeO2–TiO2 sorbents for the removal of elemental mercury from syngas. Environ Sci Technol 47:10056–10062CrossRefGoogle Scholar
  28. 28.
    Li H, Wu S, Wu C, Wang J, Li L, Shih K (2015) SCR atmosphere induced reduction of oxidized mercury over CuO–CeO2/TiO2 catalyst. Environ Sci Technol 49:7373–7379CrossRefGoogle Scholar
  29. 29.
    Madsen K, Jensen DA, Frandsen RJ (2011) A mechanistic study of the inhibition of the DeNOx reaction on the mercury oxidation over SCR catalysts. In: Proceedings of air quality VIII conference, worldwide pollution control association, Arlington, 24 OctoberGoogle Scholar
  30. 30.
    Kim MH, Ham S, Lee J (2010) Oxidation of gaseous elemental mercury by hydrochloric acid over CuCl2/TiO2-based catalysts in SCR process. Appl Catal B Environ 99:272–278CrossRefGoogle Scholar
  31. 31.
    Li X, Liu Z, Kim J, Lee J (2013) Heterogeneous catalytic reaction of elemental mercury vapor over cupric chloride for mercury emissions control. Appl Catal B Environ 132:401–407CrossRefGoogle Scholar
  32. 32.
    Zhou X, Xu W, Wang H, Tong L, Qi H, Zhu T (2014) The enhance effect of atomic Cl in CuCl2/TiO2 catalyst for Hg0 catalytic oxidation. Chem Eng J 254:82–87CrossRefGoogle Scholar
  33. 33.
    Putluru SSR, Gardini D, Mossin S, Wagner JB, Jensen AD, Fehrmann R (2014) Superior DeNOx activity of V2O5–WO3/TiO2 catalysts prepared by deposition–precipitation method. J Mater Sci 49:2705–2713. CrossRefGoogle Scholar
  34. 34.
    Lee W, Bae G (2009) Removal of elemental mercury (Hg0) by nanosized V2O5/TiO2 catalysts. Environ Sci Technol 43:1522–1527CrossRefGoogle Scholar
  35. 35.
    Presto AA, Granite EJ (2006) Survey of catalysts for oxidation of mercury in flue gas. Environ Sci Technol 40:5601–5609CrossRefGoogle Scholar
  36. 36.
    Li Y, Murphy PD, Wu C, Powers KW, Bonzongo JJ (2008) Development of silica/vanadia/titania catalysts for removal of elemental mercury from coal-combustion flue gas. Environ Sci Technol 42:5304–5309CrossRefGoogle Scholar
  37. 37.
    Zhang X, Li C, Zhao L, Zhang J, Zeng G, Xie Y, Yu M (2015) Simultaneous removal of elemental mercury and NO from flue gas by V2O5–CeO2/TiO2 catalysts. Appl Surf Sci 347:392–400CrossRefGoogle Scholar
  38. 38.
    Xu W, Wang H, Zhou X, Zhu T (2014) CuO/TiO2 catalysts for gas-phase Hg0 catalytic oxidation. Chem Eng J 243:380–385CrossRefGoogle Scholar
  39. 39.
    Wang P, Su S, Xiang J, You H, Cao F, Sun L, Hu S, Zhang Y (2014) Catalytic oxidation of Hg0 by MnOx–CeO2/gamma-Al2O3 catalyst at low temperatures. Chemosphere 101:49–54CrossRefGoogle Scholar
  40. 40.
    Wang P, Hu S, Xiang J, Su S, Sun L, Cao F, Xiao X, Zhang A (2015) Analysis of mercury species over CuO–MnO2–Fe2O3/gamma-Al2O3 catalysts by thermal desorption. Proc Combust Inst 35:2847–2853CrossRefGoogle Scholar
  41. 41.
    Lopez-Anton MA, Yuan Y, Perry R, Maroto-Valer MM (2010) Analysis of mercury species present during coal combustion by thermal desorption. Fuel 89:629–634CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Environmental Science and EngineeringNorth China Electric Power UniversityBaodingChina

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