Skip to main content
SpringerLink
Log in

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

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7

Similar content being viewed by others

References

  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 40:5312–5318

    Article  Google Scholar 

  2. Romanov A, Sloss L, Jozewicz W (2012) Mercury emissions from the coal-fired energy generation sector of the Russian Federation. Energy Fuel 26:4647–4654

    Article  Google Scholar 

  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. https://doi.org/10.1007/s10853-013-7697-7

    Article  Google Scholar 

  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 29:369–376

    Article  Google Scholar 

  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 169:186–193

    Article  Google Scholar 

  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 220:53–60

    Article  Google Scholar 

  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 135:168–173

    Article  Google Scholar 

  8. Park KS, Seo YC, Lee SJ, Lee JH (2008) Emission and speciation of mercury from various combustion sources. Powder Technol 180:151–156

    Article  Google Scholar 

  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 24:711–715

    Article  Google Scholar 

  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 36:76–83

    Article  Google Scholar 

  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 85:215–237

    Article  Google Scholar 

  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 304:121–128

    Article  Google Scholar 

  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 27:3875–3882

    Article  Google Scholar 

  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 153:361–369

    Article  Google Scholar 

  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 27:1117–1122

    Article  Google Scholar 

  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 59:78–82

    Article  Google Scholar 

  17. Li H, Wu C, Li Y, Zhang J (2012) Superior activity of MnO x –CeO2/TiO2 catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures. Appl Catal B Environ 111:381–388

    Article  Google Scholar 

  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 263:356–363

    Article  Google Scholar 

  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 241:131–137

    Article  Google Scholar 

  20. Smith CA, Krishnakumar B, Helble JJ (2011) Homo- and heterogeneous mercury oxidation in a bench-scale flame-based flow reactor. Energy Fuel 25:4367–4376

    Article  Google Scholar 

  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 21:145–156

    Article  Google Scholar 

  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 NO x on mercury speciation. Office of Scientific and Technical Information Technical Reports. https://www.osti.gov/scitech/servlets/purl/824958/

  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 55:1866–1875

    Article  Google Scholar 

  24. Senior CL (2006) Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants. J Air Waste Manag 56:23–31

    Article  Google Scholar 

  25. Eswaran S, Stenger HG (2005) Understanding mercury conversion in selective catalytic reduction (SCR) catalysts. Energy Fuel 19:2328–2334

    Article  Google Scholar 

  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 23:253–259

    Article  Google Scholar 

  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 47:10056–10062

    Article  Google Scholar 

  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 49:7373–7379

    Article  Google Scholar 

  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 October

  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 99:272–278

    Article  Google Scholar 

  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 132:401–407

    Article  Google Scholar 

  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 254:82–87

    Article  Google Scholar 

  33. Putluru SSR, Gardini D, Mossin S, Wagner JB, Jensen AD, Fehrmann R (2014) Superior DeNO x activity of V2O5–WO3/TiO2 catalysts prepared by deposition–precipitation method. J Mater Sci 49:2705–2713. https://doi.org/10.1007/s10853-013-7926-0

    Article  Google Scholar 

  34. Lee W, Bae G (2009) Removal of elemental mercury (Hg0) by nanosized V2O5/TiO2 catalysts. Environ Sci Technol 43:1522–1527

    Article  Google Scholar 

  35. Presto AA, Granite EJ (2006) Survey of catalysts for oxidation of mercury in flue gas. Environ Sci Technol 40:5601–5609

    Article  Google Scholar 

  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 42:5304–5309

    Article  Google Scholar 

  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 347:392–400

    Article  Google Scholar 

  38. Xu W, Wang H, Zhou X, Zhu T (2014) CuO/TiO2 catalysts for gas-phase Hg0 catalytic oxidation. Chem Eng J 243:380–385

    Article  Google Scholar 

  39. Wang P, Su S, Xiang J, You H, Cao F, Sun L, Hu S, Zhang Y (2014) Catalytic oxidation of Hg0 by MnO x –CeO2/gamma-Al2O3 catalyst at low temperatures. Chemosphere 101:49–54

    Article  Google Scholar 

  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 35:2847–2853

    Article  Google Scholar 

  41. Lopez-Anton MA, Yuan Y, Perry R, Maroto-Valer MM (2010) Analysis of mercury species present during coal combustion by thermal desorption. Fuel 89:629–634

    Article  Google Scholar 

Download references

Acknowledgements

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).

Author information

Authors and Affiliations

  1. Department of Environmental Science and Engineering, North China Electric Power University, Baoding, 071003, Hebei, China

    Chuanmin Chen, Wenbo Jia, Songtao Liu & Yue Cao

Authors
  1. Chuanmin Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wenbo Jia
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Songtao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yue Cao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Chuanmin Chen.

Ethics declarations

Conflict of interest

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, C., Jia, W., Liu, S. et al. Mechanism of Hg0 oxidation in the presence of HCl over a CuCl2-modified SCR catalyst. J Mater Sci 53, 10001–10012 (2018). https://doi.org/10.1007/s10853-018-2287-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2287-3

Keywords

Search

Navigation