Skip to main content
SpringerLink
Log in

Promotion of Nonthermal Plasma on the SO2 and H2O Tolerance of Co–In/Zeolites for the Catalytic Reduction of NO x by C3H8 at Low Temperature

  • Original Paper
  • Published:
Plasma Chemistry and Plasma Processing Aims and scope Submit manuscript

Abstract

Effects of nonthermal plasma (NTP) on the selective catalytic reduction of NO x by C3H8 (C3H8-SCR) over Co–In/zeolites were investigated in the presence of SO2 and H2O at low temperatures (<below 648 K). Co–In/H-(Beta/USY) displayed the highest low-temperature activity in the NTP-facilitated C3H8-SCR (PF-C3H8-SCR) hybrid system because of the enhancement of chemisorbed oxygen, acid sites, and weak adsorption species (NO2 − and NO x ) on Co–In/H-(Beta/USY). The assistance of NTP significantly promoted the tolerance of SO2 and H2O on both Co–In/H-Beta and Co–In/H-(Beta/USY) in C3H8-SCR reaction. Co–In/H-(Beta/USY) even exhibited excellent SO2 tolerance in the PF-C3H8-SCR hybrid system when a relatively high concentration of SO2 (1000–2000 ppm) and 7 % H2O were introduced into the feed gas. Sulfate species formed on the active sites of Co–In/H-(Beta/USY) were unstable because of the relatively low-temperature (below 600 K) desorption of sulfate species. The unstable sulfate species contributed slight inhibition to C3H8 activation and nitrogen-containing formation on the active sites of Co–In/H-(Beta/USY) in the PF-C3H8-SCR hybrid system. The PF-C3H8-SCR hybrid system with Co–In/H-(Beta/USY) may be a potential candidate for DeNO x industrial applications.

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.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Held W, Köning A, Richter T, Ruppe L (1990) Catalytic NOx reduction in net oxidizing exhaust gas. SAE Paper 900496, pp 13–20

  2. Iwamoto M (1990) In: Proceedings of the meeting on catalyst technology and removal of NO. Tokyo, pp 17–22

  3. Tabata T, Ohtsuka H, Sabatino LMF, Bellussi G (1998) Selective catalytic reduction of NOx by propane on Co-loaded zeolites. Microporous Mesoporous Mater 21:517–524

    Article  CAS  Google Scholar 

  4. Tabata T, Kokitsu M, Ohtsuka H, Okada O, Sabatino LMF, Bellussi G (1996) Study on catalysts of selective reduction of NOx using hydrocarbons for natural gas engines. Catal Today 27:91–98

    Article  CAS  Google Scholar 

  5. Ohtsuka H, Tabata T, Okada O, Sabatino LMF, Bellussi G (1997) A study on selective reduction of NOx by propane on Co-Beta. Catal Lett 44:265–270

    Article  CAS  Google Scholar 

  6. Chen HH, Shen SC, Chen XY, Kawi S (2004) Selective catalytic reduction of NO over Co/beta-zeolite: effects of synthesis condition of beta-zeolites, Co precursor, Co loading method and reductant. Appl Catal B 50:37–47

    Article  CAS  Google Scholar 

  7. Čapek L, Dědeček J, Sazama P, Wichterlová B (2010) The decisive role of the distribution of Al in the framework of beta zeolites on the structure and activity of Co ion species in propane-SCR-NOx in the presence of water vapour. J Catal 272:44–54

    Article  Google Scholar 

  8. Pietrzyk P, Dujardin C, Gora-Marek K, Granger P, Sojka Z (2012) Spectroscopic IR, EPR, and operando DRIFT insights into surface reaction pathways of selective reduction of NO by propene over the Co-BEA zeolite. Phys Chem Chem Phys 14:2203–2215

    Article  CAS  Google Scholar 

  9. Shi Y, Su QF, Chen J, Wei JW, Yang JT, Pan H (2009) Combination of nonthermal plasma and low temperature-C3H8-selective catalytic reduction over Co–In/H-Beta catalyst for nitric oxide abatement. Environ Eng Sci 26:1107–1113

    Article  CAS  Google Scholar 

  10. Lonyi F, Solt HE, Valyon J, Boix A, Gutierrez LB (2012) The SCR of NO with methane over In, H- and Co, In, H-ZSM-5 catalysts: the promotional effect of cobalt. Appl Catal B 117:212–223

    Article  Google Scholar 

  11. Li F, Xiao DH, Li J, Yang X (2010) Effect of the addition of In to Co/HMCM-49 catalyst for the selective catalytic reduction of NO under lean-burn conditions. Z Phys Chem 224:907–920

    Article  CAS  Google Scholar 

  12. Kubacka A, Janas J, Sulikowski B (2006) In/Co-ferrierite: a highly active catalyst for the CH4-SCR NO process under presence of steam. Appl Catal B 69:43–48

    Article  CAS  Google Scholar 

  13. Zhang J, Fan W, Liu Y, Li R (2007) Synthesis and catalytic property of a Co2+-exchanged Beta/Y composite for the selective catalytic reduction of NO by CH4 in the presence of excess oxygen. Appl Catal B 76:174–184

    Article  CAS  Google Scholar 

  14. Zhang JQ, Liu YY, Fan WB, He Y, Li RF (2007) Effect of SO2 on catalytic performance of Co-HFBZ for selective catalytic reduction of NO by CH4 in the presence of O2. Environ Eng Sci 24:292–300

    Article  CAS  Google Scholar 

  15. Chen SW, Yan XL, Wang Y, Chen JQ, Pan DH, Ma JH, Li RF (2011) Effect of SO2 on Co sites for NO-SCR by CH4 over Co-Beta. Catal Today 175:12–17

    Article  CAS  Google Scholar 

  16. Bamwenda GR, Obuchi A, Ogata A, Oi J, Kushiyama S, Yagita H, Mizuno K (1999) Kinetic and in situ DRIFT spectroscopy studies of NO oxidation, and reduction by C3H6 in excess O2 over gamma-Al2O3 and Au/gamma-Al2O3. Stud Surf Sci Catal 121:263–268

    Article  CAS  Google Scholar 

  17. Penetrante BM, Brusasco RM, Merrit BT, Pitz WJ, Vogtlin GE, Kung MC, Kung HH, Wan CZ, Voss KE (1998) Plasma-assisted catalytic reduction of NOx. SAE Technical Paper Series #982508, SAE, Warrendale, PA

  18. Dorai R, Kushner MJ (1999) Effect of propene on the remediation of NOx from engine exhausts. SAE Technical Paper Series #1999-01-3683, SAE, Warrendale, PA

  19. Niu JH, Zhang ZH, Liu DP, Wang Q (2008) Low-temperture plasma-catalytic reduction of NOx by C2H2 in the presence of excess oxygen. Plasma Sour Sci Technol 10:466–470

    Article  CAS  Google Scholar 

  20. Li JH, Ke R, Li W, Hao JM (2007) A comparion study on non-thermal plasma-assisted catalytic reduction of NO by C3H6 at low temperatures between Ag/USY and Ag/Al2O3 catalysts. Catal Today 126:272–278

    Article  CAS  Google Scholar 

  21. Miessner H, Francke KP, Rudolph R (2002) Plasma-enhanced HC-SCR of NOx in the presence of excess oxygen. Appl Catal B 36:53–62

    Article  CAS  Google Scholar 

  22. Tran DN, Aardahl CL, Rappe KG, Park PW, Boyer CL (2004) Reduction of NOx by plasma-facilitated catalysis over In-doped gamma-alumina. Appl Catal B 48:155–164

    Article  CAS  Google Scholar 

  23. Yu QQ, Liu T, Wang H, Xiao LP, Chen M, Jiang XY, Zheng XM (2012) Cold plasma-assisted selective catalytic reduction of NO over B2O3/gamma-Al2O3. Chin J Catal 33:783–789

    Article  CAS  Google Scholar 

  24. Hammer T (2002) Non-thermal plasma application to the abatement of noxious emissions in automotive exhaust gases. Plasma Sour Sci Technol 11:196–201

    Article  Google Scholar 

  25. Li Y, Armor JN (1994) Selective reduction of NOx by methane on Co-Ferrierites: I. Reaction and kinetic studies. J Catal 150:376–387

    Article  CAS  Google Scholar 

  26. Lukyanov DB, Still G, d’Itri JL, Hall WK (1995) Comparison of catalyzed and homogeneous reactions of hydrocarbons for selective catalytic reduction (SCR) of NOx. J Catal 153:265–274

    Article  CAS  Google Scholar 

  27. Meunier FC, Breen JP, Zuzaniuk V, Olsson M, Ross JRH (1999) Mechanistic aspects of the selective reduction of NO by propene over alumina and silver–alumina catalysts. J Catal 187:493–505

    Article  CAS  Google Scholar 

  28. Hamada H, Kintaichi Y, Inaba M, Tabata M, Yoshinari T, Tsuchida H (1996) Role of supported metals in the selective reduction of nitrogen monoxide with hydrocarbons over metal/alumina catalysts. Catal Today 29:53–57

    Article  CAS  Google Scholar 

  29. Eranen K, Klingstedt F, Arve K, Lindfors LE, Murzin DY (2004) On the mechanism of the selective catalytic reduction of NO with higher hydrocarbons over a silver/alumina catalyst. J Catal 227:328–343

    Article  Google Scholar 

  30. Martens JA, Cauvel A, Francis A, Hermans C, Jayat F, Remy M, Keung M, Lievens J, Jacobs PA (1998) NOx abatement in exhaust from lean-burn combustion engines by reduction of NO2 over silver-containing zeolite catalysts. Angew Chem Int Ed 37:1901–1903

    Article  CAS  Google Scholar 

  31. Tennison P, Lambert C (2004) NOx control development with urea SCR on a diesel passenger car. SAE Trans 113:573–579

    Google Scholar 

  32. Chi JN, Dacosta HFM (2005) Modeling and control of a urea-SCR after treatment system. SAE Technical Paper Series 2005-01-0966, Warrendale, PA

  33. Bin G, He L, Qi C, Zhen H (2011) Removal of NOx with selective catalytic reduction based on nonthermal plasma preoxidation. Ind Eng Chem Res 50:5401–5413

    Article  Google Scholar 

  34. Nie Y, Wang JY, Zhong K, Wang LM, Guan ZC (2007) Synergy study for plasma-facilitated C2H4 selective catalytic reduction of NOx over Ag/gamma-Al2O3 catalyst. IEEE T Plasma Sci 35:663–669

    Article  CAS  Google Scholar 

  35. Wagner CD, Riggs WM, Davis LE, Moulder JF, Muilenberg GE (1979) Handbook of X-ray photoelectron spectroscopy. Perkin–Elmer Corporation, Eden Prairie

    Google Scholar 

  36. Chupin C, van Veen AC, Konduru M, Despres J, Mirodatos C (2006) Identity and location of active species for NO reduction by CH4 over Co-ZSM-5. J Catal 241:103–114

    Article  CAS  Google Scholar 

  37. Maunula T, Ahola J, Hamada H (2006) Reaction mechanism and kinetics of NOx reduction by methane on In/ZSM-5 under lean conditions. Appl Catal B 64:13–24

    Article  CAS  Google Scholar 

  38. Zamaro JM, Miró EE, Boix AV, Martínez-Hernández A, Fuentes GA (2010) In-zeolites prepared by oxidative solid state ion exchange (OSSIE): surface species and structural characterization. Microporous Mesoporous Mater 129:74–81

    Article  CAS  Google Scholar 

  39. Beltramone AR, Pierella LB, Requejo FG, Anunziata OA (2003) Fourier transform IR study of NO + CH4 + O2 coadsorption on In-ZSM-5 DeNOx catalyst. Catal Lett 91:19–24

    Article  CAS  Google Scholar 

  40. Schmidt C, Sowade T, Löffler E, Birkner A, Grünert W (2002) Preparation and structure of In-ZSM-5 catalysts for the selective reduction of NO by hydrocarbons. J Phys Chem B 106:4085–4097

    Article  CAS  Google Scholar 

  41. Lónyi F, Solt HE, Valyon J, Boix A, Gutierrez LB (2011) The activation of NO and CH4 for NO-SCR reaction over In- and Co-containing H-ZSM-5 catalysts. J Mol Catal A 345:75–80

    Article  Google Scholar 

  42. Kang M, Park ED, Kim JM, Yie JE (2007) Manganese oxide catalysts for NOx reduction with NH3 at low temperatures. Appl Catal A 327:261–269

    Article  CAS  Google Scholar 

  43. Tang XF, Li YG, Huang XM, Xu YD, Zhu HQ, Wang JG, Shen WJ (2006) MnOx–CeO2 mixed oxide catalysts for complete oxidation of formaldehyde: Effect of preparation method and calcination temperature. Appl Catal B 62:265–273

    Article  CAS  Google Scholar 

  44. Parry EP (1963) An infrared study of pyridine adsorbed on acidic solids: characterization of surface acidity. J Catal 2:371–379

    Article  CAS  Google Scholar 

  45. Ramallo-López JM, Requejo FG, Gutierrez LB, Miró EE (2001) EXAFS, TDPAC and TPR characterization of PtInFerrierite: the role of surface species in the SCR of NOx with CH4. Appl Catal B 29:35–46

    Article  Google Scholar 

  46. Ren LL (2014) The cooperative effect of In2O3 and In/HZSM-5 for reduction of nitric oxide with methane. J Chem 2014:1–7

    Article  Google Scholar 

  47. Ferreira AP, Henriques C, Ribeiro MF, Ribeiro FR (2005) SCR of NO with methane over Co-HBEA and PdCo-HBEA catalysts—the promoting effect of steaming over bimetallic catalyst. Catal Today 107–108:181–191

    Article  Google Scholar 

  48. Li JH, Zhu YQ, Ke R, Hao JM (2008) Improvement of catalytic activity and sulfur-resistance of Ag/TiO2–Al2O3 for NO reduction with propene under lean burn conditions. Appl Catal B 80:202–213

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21006093) and Natural Science Basic Research Plan in Shaanxi Province of China (No. 2014JQ2-2009). This project was also supported by the Guangxi Education Department Project (2013YB111) and the Fundamental Research Funds for the Central Universities.

Author information

Authors and Affiliations

  1. Department of Environmental Science and Engineering, Xi’an Jiaotong University, Xi’an, 710049, People’s Republic of China

    Hua Pan & Yanfei Jian

  2. Longjing Environment Technology Co. Ltd, Xiamen, 361009, People’s Republic of China

    Qingfa Su

  3. College of Environmental Science and Technology, Guilin University of Technology, Guilin, 541004, People’s Republic of China

    Jianwen Wei

Authors
  1. Hua Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qingfa Su
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jianwen Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yanfei Jian
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qingfa Su or Jianwen Wei.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pan, H., Su, Q., Wei, J. et al. Promotion of Nonthermal Plasma on the SO2 and H2O Tolerance of Co–In/Zeolites for the Catalytic Reduction of NO x by C3H8 at Low Temperature. Plasma Chem Plasma Process 35, 831–844 (2015). https://doi.org/10.1007/s11090-015-9633-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11090-015-9633-x

Keywords

Search

Navigation