Skip to main content
SpringerLink
Log in

The influence of molar ratios of Ce/Zr on the selective catalytic reduction of NO x with NH3 over Fe2O3-WO3/Ce x Zr1−x O2 (0 ≤ x ≤ 1) monolith catalyst

  • Article
  • Environmental Chemistry
  • Published:
Chinese Science Bulletin

Abstract

A series of Ce x Zr1−x O2 (0 ≤ x ≤ 1) with different molar ratios of Ce/Zr were syhthesized via coprecipitation method, and Fe2O3-WO3/Ce x Zr1−x O2 monolithic catalysts were prepared for selective catalytic reduction of nitrogen oxides by ammonia (NH3-SCR). The structural properties and redox behavior of the catalysts were comprehensively characterized by N2 physisorption, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), H2-temperature programmed reduction (H2-TPR) and activity measurement for NH3-SCR. The results showed that the NH3-SCR activities of the catalysts were gradually enhanced by increasing the molar ratios of Ce/Zr, especially the low-temperature catalytic activity and the reaction temperature window. Fe2O3-WO3/Ce0.68Zr0.32O2 monolithic catalyst presented the best NH3-SCR activity among the investigated catalysts, more than 90 % NO x could be removed in the temperature range of 247–454 °C on the catalyst under the gas hourly space velocities of 30,000 h−1. And it always held more than 99 % N2 selectivity and less than 20 ppm (1 ppm = 10−6 L/L ) N2O generation concentration between 200 and 500 °C, the catalyst also displayed its strong resistance of H2O and SO2. Good textural and structural properties, more surface Fe, Ce and active oxygen were together contributed to the excellent NH3-SCR performance of Fe2O3-WO3/Ce0.68Zr0.32O2 catalyst.

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.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Busca G, Larrubia MA, Arrighi L et al (2005) Catalytic abatement of NO x : chemical and mechanistic aspects. Catal Today 107–108:139–148

    Article  Google Scholar 

  2. Balle P, Geiger B, Kureti S (2009) Selective catalytic reduction of NO x by NH3 on Fe/HBEA zeolite catalysts in oxygen-rich exhaust. Appl Catal B 85:109–119

    Article  Google Scholar 

  3. Zhang Q, Qiu C, Xu H et al (2010) Activity of monolith Cu-ZSM-5 for selective catalytic reduction of NO with NH3. Chin J Catal 31:1411–1416 (in Chinese)

    Google Scholar 

  4. Kwak JH, Tonkyn RG, Kim DH et al (2010) Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NO x with NH3. J Catal 275:187–190

    Article  Google Scholar 

  5. Picone AL, Warrender SJ, Slawin AMZ et al (2011) A co-templating route to the synthesis of Cu SAPO STA-7, giving an active catalyst for the selective catalytic reduction of NO. Microp Mesop Mater 146:36–47

    Article  Google Scholar 

  6. Deka U, Lezcano-Gonzalez I, Warrender SJ et al (2013) Changing active sites in Cu-CHA catalysts: deNO x selectivity as a function of the preparation method. Micropor Mesopor Mat 166:144–152

    Article  Google Scholar 

  7. Collier JE, Laroze SC, Rajaram RR et al (2011) Non-zeolite base metal SCR catalyst. US Patent 7,985,391 B2, 26 July 2011

  8. Qi G, Yang RT (2003) A superior catalyst for low-temperature no reduction with NH3. Chem Commun 848–849

  9. Gao X, Jiang Y, Fu Y et al (2010) Preparation and characterization of CeO2/TiO2 catalysts for selective catalytic reduction of NO with NH3. Catal Commun 11:465–469

    Article  Google Scholar 

  10. Pietrogiacomi D, Magliano A, Sannino D et al (2005) In situ sulphated CuO x /ZrO2 and CuO x /sulphated-ZrO2 as catalysts for the reduction of NO x with NH3 in the presence of excess O2. Appl Catal B 60:83–92

    Article  Google Scholar 

  11. Xu H, Zhang Q, Qiu C et al (2012) Tungsten modified MnO x -CeO2/ZrO2 monolith catalysts for selective catalytic reduction of NO x with ammonia. Chem Eng Sci 76:120–128

    Article  Google Scholar 

  12. Murota T, Hasegawa T, Aozasa S et al (1993) Production method of cerium oxide with high storage capacity of oxygen and its mechanism. J Alloys Compd 193:298–299

    Article  Google Scholar 

  13. Li Y, Cheng H, Li D et al (2008) WO3/CeO2-ZrO2, a promising catalyst for selective catalytic reduction (SCR) of NO x with NH3 in diesel exhaust. Chem Commun 12:1470–1472

    Article  Google Scholar 

  14. Si Z, Weng D, Wu X et al (2010) Modifications of CeO2-ZrO2 solid solutions by nickel and sulfate as catalysts for NO reduction with ammonia in excess O2. Catal Commun 11:1045–1048

    Article  Google Scholar 

  15. Xu H, Wang Y, Cao Y et al (2014) Catalytic performance of acidic zirconium-based composite oxides monolithic catalyst on selective catalytic reduction of NO x with NH3. Chem Eng J 240:62–73

    Article  Google Scholar 

  16. Shen B, Wang Y, Wang F et al (2014) The effect of Ce-Zr on NH3-SCR activity over MnO x (0.6)/Ce0.5Zr0.5O2 at low temperature. Chem Eng J 236:171–180

    Article  Google Scholar 

  17. Ramis G, Yi L, Busca G et al (1995) Adsorption, activation, and oxidation of ammonia over SCR catalysts. J Catal 157:523–535

    Article  Google Scholar 

  18. Cheng LS, Yang RT, Chen N (1996) Iron oxide and chromia supported on titania-pillared clay for selective catalytic reduction of nitric oxide with ammonia. J Catal 164:70–81

    Article  Google Scholar 

  19. Long RQ, Yang RT (1999) Catalytic performance of Fe-ZSM-5 catalysts for selective catalytic reduction of nitric oxide by ammonia. J Catal 188:332–339

    Article  Google Scholar 

  20. Chen JP, Yang RT (1992) Role of WO3 in mixed V2O5-WO3/TiO2 catalysts for selective catalytic reduction of nitric oxide with ammonia. Appl Catal A 80:135–148

    Article  Google Scholar 

  21. Busca G, Lietti L, Ramis G et al (1998) Chemical and mechanistic aspects of the selective catalytic reduction of NO x by ammonia over oxide catalysts: a review. Appl Catal B 18:1–36

    Article  Google Scholar 

  22. Apostolescu N, Geiger B, Hizbullah K et al (2006) Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts. Appl Catal B 62:104–114

    Article  Google Scholar 

  23. Chen L, Li J, Ge M et al (2010) Enhanced activity of tungsten modified CeO2/TiO2 for selective catalytic reduction of NO x with ammonia. Catal Today 153:77–83

    Article  Google Scholar 

  24. Khodayari R, Odenbrand CUI (2001) Regeneration of commercial TiO2-V2O5-WO3 SCR catalysts used in bio fuel plants. Appl Catal B 30:87–99

    Article  Google Scholar 

  25. Wang J, Wen J, Shen M (2008) Effect of interaction between Ce0.7Zr0.3O2 and Al2O3 on structural characteristics, thermal stability, and oxygen storage capacity. J Phys Chem C 112:5113–5122

    Article  Google Scholar 

  26. Theocharis C, Kyriacou G, Christophidou M (2005) Preparation and characterization of nanoporous ceria containing heteroatoms, with and without a matrix. Adsorpt 11:763–767

    Article  Google Scholar 

  27. Alifanti M, Baps B, Blangenois N et al (2003) Characterization of CeO2-ZrO2 mixed oxides. Comparison of the citrate and sol-gel preparation methods. Chem Mater 15:395–403

    Article  Google Scholar 

  28. He H, Dai HX, Au CT (2004) Defective structure, oxygen mobility, oxygen storage capacity, and redox properties of RE-based (RE = Ce, Pr) solid solutions. Catal Today 90:245–254

    Article  Google Scholar 

  29. Noronha FB, Fendley EC, Soares RR et al (2001) Correlation between catalytic activity and support reducibility in the CO2 reforming of methane over Pt/Ce x Zr1−x O2 catalysts. Chem Eng J 82:21–31

    Article  Google Scholar 

  30. Gu T, Jin R, Liu Y et al (2013) Promoting effect of calcium doping on the performances of MnO x /TiO2 catalysts for NO reduction with NH3 at low temperature. Appl Catal B 129:30–38

    Article  Google Scholar 

  31. Xu H, Fang Z, Cao Y et al (2012) Influence of Mn/(Mn + Ce) ratio of MnO x -CeO2/WO3-ZrO2 monolith catalyst on selective catalytic reduction of NO x with ammonia. Chin J Catal 33:1927–1937

    Article  Google Scholar 

  32. Martínez A, Prieto G, Arribas MA et al (2007) Influence of the preparative route on the properties of WO x -ZrO2 catalysts: a detailed structural, spectroscopic, and catalytic study. J Catal 248:288–302

    Article  Google Scholar 

  33. Liu F, He H, Ding Y et al (2009) Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH3. Appl Catal B 93:194–204

    Article  Google Scholar 

  34. Ardizzone S, Bianchi CL, Signoretto M (1998) Zr(IV) surface chemical state and acid features of sulphated-zirconia samples. Appl Surf Sci 136:213–220

    Article  Google Scholar 

  35. Ardizzone S, Bianchi CL (2000) XPS characterization of sulphated zirconia catalysts: the role of iron. Surf Interface Anal 30:77–80

    Article  Google Scholar 

  36. Gao S, Chen X, Wang H et al (2013) Ceria supported on sulfated zirconia as a superacid catalyst for selective catalytic reduction of NO with NH3. J Colloid Interface Sci 394:515–521

    Article  Google Scholar 

  37. Fang J, Bi X, Si D et al (2007) Spectroscopic studies of interfacial structures of CeO2–TiO2 mixed oxides. Appl Surf Sci 253:8952–8961

    Article  Google Scholar 

  38. Shan W, Liu F, He H et al (2012) A superior Ce-W-Ti mixed oxide catalyst for the selective catalytic reduction of NO x with NH3. Appl Catal B 115–116:100–106

    Article  Google Scholar 

  39. Wu Z, Jin R, Wang H (2008) Ceria modified MnO x /TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature. Catal Commun 9:2217–2220

    Article  Google Scholar 

  40. Kang M, Park ED, Kim JM et al (2007) Manganese oxide catalysts for NO x reduction with NH3 at low temperatures. Appl Catal A 327:261–269

    Article  Google Scholar 

  41. Si Z, Weng D, Wu X et al (2012) NH3-SCR activity, hydrothermal stability, sulfur resistance and regeneration of Ce0.75Zr0.25O2-PO4 3− catalyst. Catal Commun 17:146–149

    Article  Google Scholar 

  42. Ma Z, Weng D, Wu X et al (2012) Effects of WO x modification on the activity, adsorption and redox properties of CeO2 catalyst for NO x reduction with ammonia. J Environ Sci 24:1305–1316

    Article  Google Scholar 

  43. Barton DG, Soled SL, Meitzner GD et al (1999) Structural and catalytic characterization of solid acids based on zirconia modified by tungsten oxide. J Catal 181:57–72

    Article  Google Scholar 

  44. Liu F, He H (2010) Structure-activity relationship of iron titanate catalysts in the selective catalytic reduction of NO x with NH3. J Phys Chem C 114:16929–16936

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21173153), the Project from Sichuan Provincial Environment Office of China (2011HB002) and the National High Technology Research and Development Program of China (2013AA065304).

Author information

Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    Haidi Xu, Yi Cao, Zhitao Fang, Tao Lin, Maochu Gong & Yaoqiang Chen

  2. College of Chemical Engineering, Sichuan University, Chengdu, 610064, China

    Yun Wang & Yaoqiang Chen

  3. Sichuan Provincial Environmental Protection Environmental Catalytic Materials Engineering Technology Center, Chengdu, 610064, China

    Yaoqiang Chen

Authors
  1. Haidi Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yi Cao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhitao Fang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tao Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Maochu Gong
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yaoqiang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yaoqiang Chen.

Additional information

SPECIAL TOPIC: Advanced Catalytic Materials for Environmental Application

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xu, H., Cao, Y., Wang, Y. et al. The influence of molar ratios of Ce/Zr on the selective catalytic reduction of NO x with NH3 over Fe2O3-WO3/Ce x Zr1−x O2 (0 ≤ x ≤ 1) monolith catalyst. Chin. Sci. Bull. 59, 3956–3965 (2014). https://doi.org/10.1007/s11434-014-0393-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-014-0393-4

Keywords

Search

Navigation