Skip to main content
SpringerLink
Log in

Preparation of High Catalytic Active Mn–La0.5/TiO2 Denitration Catalyst by In Situ Deposition Method

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

Mn–La0.5/TiO2 denitration catalysts were prepared by impregnation, combustion, coprecipitation, reverse coprecipitation, and in situ deposition method, and their catalytic activities were compared. The catalyst prepared by the in situ deposition method had the highest catalytic activity and N2 selectivity with a T80 of 104.8 °C, a NO conversion of up to 100%, and a temperature window of 104.8–365.6 °C. The water and sulfur resistance of the catalysts prepared by the in situ deposition method and the coprecipitation method were compared. The elemental valence state, composition, redox ability, and surface acidic sites of the catalysts were analyzed by XPS, XRF, H2-TPR and NH3-TPD. The adsorption behavior and NH3-SCR reaction of the catalysts were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy. Results showed the catalyst prepared by the in situ deposition method had better water and sulfur resistance, higher Mn4+ content, H2 consumption and medium acidic sites, and faster adsorption rate of NH3 and NO when compared with those prepared by other methods. The NH3-SCR reaction on two catalysts followed the Eley–Rideal mechanism, and “fast SCR” played a key role in the reaction.

Graphical Abstract

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
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Ministry of Ecology and Environment (2011) PRC. GB13223-2011. Emission standards of air pollutants from thermal power plants (in Chinese)

  2. Chang HZ, Chen XY, Li JH, Ma L, Wang CZ, Liu CX, Johannes WS, Hao JM (2013) Improvement of activity and SO2 tolerance of Sn-modified MnOx–CeO2 catalysts for NH3-SCR at low temperatures. J Environ Sci Technol 47(10):5294–5301

    Article  CAS  ADS  Google Scholar 

  3. Han LP, Cai SX, Gao M, Hasegawa J, Wang PL, Zhang JP, Shi LY, Zhang DS (2019) Selective catalytic reduction of NOx with NH3 by using novel catalysts: state of the art and future prospects. Chem Rev 119(19):10916–10976

    Article  CAS  PubMed  Google Scholar 

  4. Chen C, Xie HD, He PW, Liu X, Yang C, Wang N, Ge CM (2022) Comparison of low-temperature catalytic activity and H2O/SO2 resistance of the Ce-Mn/TiO2 NH3-SCR catalysts prepared by the reverse co-precipitation, co-precipitation and impregnation method. Appl Surf Sci 571:151285

    Article  CAS  Google Scholar 

  5. Wang N, Ye CF, Xie HD, Wang L, Zheng B, He YY, Yang C, Zhou JH, Ge CM (2021) High-temperature vanadium free catalyst for selective catalytic reduction of NO with NH3 and theoretical study of La2O3 over CeO2/TiO2. Catal Sci Technol 11:6112–6125

    Article  CAS  Google Scholar 

  6. Tang XL, Hao JM, Xu WG, Li JH (2007) Low temperature selective catalytic reduction of NOx with NH3 over amorphous MnOx catalysts prepared by three methods. Catal Commun 8(3):329–334

    Article  CAS  ADS  Google Scholar 

  7. Zhang XL, Zhang XC, Yang XJ, Chen YZ, Hu XR, Wu XP (2021) CeMn/TiO2 catalysts prepared by different methods for enhanced low-temperature NH3-SCR catalytic performance. Chem Eng Sci 238:116588

    Article  CAS  Google Scholar 

  8. Guo K, Ji J, Osuga R, Zhu YX, Sun JF, Tang CJ, Kondo JN, Dong L (2021) Construction of Fe2O3 loaded and mesopore confined thin-layer titania catalyst for efficient NH3-SCR of NOx with enhanced H2O/SO2 tolerance. Appl Catal B 287:1199822

    Article  Google Scholar 

  9. Xie SZ, Qin QJ, Liu H, Jin LJ, Wei XL, Liu JX, Liu X, Yao YC, Dong L, Li B (2020) MOF-74-M (M = Mn Co, Ni, Zn, MnCo, MnNi, and MnZn) for low-temperature NH3-SCR and in situ DRIFTS study reaction mechanism. ACS Appl Mater Interface 12(43):48476–48485

    Article  CAS  Google Scholar 

  10. Zhou X, Yu F, Sun RB, Tian JQ, Wang Q, Dai B, Dan JM, Pfeiffer H (2020) Two-dimensional MnFeCo layered double oxide as catalyst for enhanced selective catalytic reduction of NOx with NH3 at low temperature (25–150 ℃). Appl Catal A 592:117432

    Article  CAS  Google Scholar 

  11. Zhang XL, Hu XR, Liu SW, Chen YZ, Jin S, Wang XY, Wang JW, Xiao KS, Wu XP (2022) MnOx-pillared rectorite prepared by in situ deposition as efficient catalysts for low-temperature NH3-SCR: the influences of manganese(II) precursors. J Environ Chem Eng 10(2):107318

    Article  CAS  Google Scholar 

  12. Zhu YJ, Xiao XX, Wang JT, Ma C, Jia XF, Qiao WM, Ling LC (2021) Enhanced activity and water resistance of hierarchical flower-like Mn–Co binary oxides for ammonia-SCR reaction at low temperature. Appl Surf Sci 569:150989

    Article  CAS  Google Scholar 

  13. Chen L, Ren S, Jiang YH, Liu L, Wang MM, Yang J, Chen ZC, Liu WZ, Liu QC (2022) Effect of Mn and Ce oxides on low-temperature NH3-SCR performance over blast furnace slag-derived zeolite X supported catalysts. Fuel 320:123969

    Article  CAS  Google Scholar 

  14. Chen L, Ren S, Liu WZ, Yang J, Chen ZC, Wang MM, Liu QC (2021) Low-temperature NH3-SCR activity of M (M = Zr, Ni and Co) doped MnOx supported biochar catalysts. J Environ Chem Eng 9(6):106504

    Article  CAS  Google Scholar 

  15. Ye D, Qu RY, Zheng CH, Cen KF, Gao X (2018) Mechanistic investigation of enhanced reactivity of NH4HSO4 and NO on Nb- and Sb-doped VW/Ti SCR catalysts. Appl Catal A 549:310–319

    Article  CAS  Google Scholar 

  16. Suga S, Imada S, Muro T, Fukawa T, Shishidou T, Tokura Y, Moritomo Y, Miyahara T (1996) La4d and Mn core absorption magnetic circular dichroism, XPS and inverse photoemission spectroscopy of La1−xSrxMnO3. J Electron Spectrosc 78:283–286

    Article  CAS  Google Scholar 

  17. Yang J, Li ZF, Yang CL, Ma YY, Li YY, Zhang Q, Song K, Cui JX (2022) Significant promoting effect of La doping on the wide temperature NH3-SCR performance of Ce and Cu modified ZSM-5 catalysts. J Solid State Chem 305:122700

    Article  CAS  Google Scholar 

  18. Guo H, Zhang ZX, Jiang Z, Chen MX, Einaga H, Shangguan W (2020) Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis. J Environ Sci 98:196–204

    Article  CAS  Google Scholar 

  19. Yu CL, Huang BC, Dong LF, Chen F, Yang Y, Fan YM, Yang YX, Liu XQ, Wang XN (2017) Effect of Pr/Ce addition on the catalytic performance and SO2 resistance of highly dispersed MnOx/SAPO-34 catalyst for NH3-SCR at low temperature. Chem Eng J 316:1059–1068

    Article  CAS  Google Scholar 

  20. Cao L, Wu XB, Chen Z, Ma Y, Ran R, Si ZC, Weng D, Wang BD (2019) A comprehensive study on sulfur tolerance of niobia modified CeO2/WO3–TiO2 catalyst for low-temperature NH3-SCR. Appl Catal A Gen 580:121–130

    Article  CAS  Google Scholar 

  21. Xie HD, He PW, Chen C, Yang C, Chai SN, Wang N, Ge CM (2023) Enhanced water and sulfur resistance by Sm3+ modification of Ce-Mn/TiO2 for NH3-SCR. Catal Lett 153:850–862

    Article  CAS  Google Scholar 

  22. Fan AD, Jing Y, Guo JX, Shi XK, Yuan S, Li JJ (2022) Investigation of Mn doped perovskite La–Mn oxides for NH3-SCR activity and SO2/H2O resistance. Fuel 310:122237

    Article  CAS  Google Scholar 

  23. Gong PJ, Xie JL, Fang D, He F, Li FX, Qi K (2020) Enhancement of the NH3-SCR property of Ce–Zr–Ti by surface and structure modification with P. Appl Surf Sci 505:144641

    Article  CAS  Google Scholar 

  24. Li YF, Hou YQ, Zhang YZ, Yang YT, Huang ZG (2022) Confinement of MnOx@Fe2O3 core-shell catalyst with titania nanotubes: enhanced N2 selectivity and SO2 tolerance in NH3-SCR process. J Colloid Interface Sci 608:2224–2234

    Article  CAS  PubMed  ADS  Google Scholar 

  25. Jia Y, Jiang J, Zheng RZ, Guo LN, Yuan J, Zhang SL, Gu MY (2021) Insight into the reaction mechanism over PMoA for low temperature NH3-SCR: a combined in situ DRIFTs and DFT transition state calculations. J Hazard Mater 412:125258

    Article  CAS  PubMed  Google Scholar 

  26. Chen LQ, Yuan FL, Li ZB, Niu XY, Zhu YJ (2018) Synergistic effect between the redox property and acidity on enhancing the low temperature NH3-SCR activity for NOx removal over the Co0.2CexMn0.8−xTi10 (x = 0–0.40) oxides catalysts. Chem Eng J 354:393–406

    Article  CAS  Google Scholar 

  27. Zeng YQ, Song W, Wang YN, Zhang SL, Wang TX, Zhong Q (2020) Novel Fe-doped CePO4 catalyst for selective catalytic reduction of NO with NH3: the role of Fe3+ ions. J Hazard Mater 383:121212

    Article  CAS  PubMed  Google Scholar 

  28. Hadjiivanov KI (2000) Identification of neutral and charged NxOy surface species by IR spectroscopy. Catal Rev 42:71–144

    Article  CAS  Google Scholar 

  29. Chen Y, Wang JP, Yan Z, Liu LL, Zhang ZT, Wang XD (2015) Promoting effect of Nd on the reduction of NO with NH3 over CeO2 supported by activated semi-coke: an in situ DRIFTS study. Catal Sci Technol 5:2251–2259

    Article  CAS  Google Scholar 

  30. Wang MM, Ren S, Jiang YH, Su BX, Chen ZC, Liu WZ, Yang J, Chen L (2022) Insights into co-doping effect of Sm and Fe on anti-Pb poisoning of Mn–Ce/AC catalyst for low-temperature SCR of NO with NH3. Fuel 319:123763

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China under Grant No. 51978556 and Major Scientific and Technological Innovation Projects of Shandong Province under Grant No. 2019JZZY010343.

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an, 710055, Shaanxi, People’s Republic of China

    Xiao Liu, Huidong Xie, Ge Mu, Peiwen He & Kangkang Wang

  2. Comprehensive Engineering Training Centre, Xi’an University of Architecture and Technology, Xi’an, 710055, Shaanxi, People’s Republic of China

    Chang Yang

  3. Department of Environmental Science and Engineering, State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an, 710049, Shaanxi, People’s Republic of China

    Shouning Chai

Authors
  1. Xiao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Huidong Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ge Mu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Peiwen He
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kangkang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chang Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shouning Chai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Huidong Xie.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, X., Xie, H., Mu, G. et al. Preparation of High Catalytic Active Mn–La0.5/TiO2 Denitration Catalyst by In Situ Deposition Method. Catal Lett 154, 899–909 (2024). https://doi.org/10.1007/s10562-023-04353-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-023-04353-8

Keywords

Search

Navigation