Advertisement

The influence of the pore structure on the SO2 tolerance for selective catalytic reduction of NOx with NH3 over MnOx-TiO2/MWCNTs catalysts

  • Chong Xie
  • Jian-Wen ShiEmail author
  • Shenghui YangEmail author
  • Xifei LiEmail author
Research Paper
  • 47 Downloads

Abstract

The MnOx-TiO2/MWCNTs nanocomposites were used as De-NOx catalysts to study the deep-rooted reason for the deactivation. Based on a series of characterization on as-prepared catalyst and poisoned catalyst, the results showed that the chief culprit for the deactivation is the micropores in the De-NOx catalyst. The formed ammonium (bi)sulfate in the micropores during the SCR reaction process could not be took away by the gas flow soon and then deposited on the catalyst surface gradually, and further covered the active sites. And the poisoned catalysts could be recovered partly rather than fully by heat treatment at 500 °C because of the decomposition of the ammonium (bi)sulfate and the phase transition of the TiO2.

Keywords

De-NOx catalysts Carbon nanotubes Deactivation Pore structure Nanostructures 

Notes

Funding information

Financial support was provided by the National Key Research and Development Program of China (Project No. 2018YFB0105900).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. Cai SX, Hu H, Li HR, Shi LY, Zhang DS (2016) Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic and SO2 tolerence. Nanoscale 8:3588–3598.  https://doi.org/10.1039/C5NR08701E CrossRefGoogle Scholar
  2. Gan LN, Li KZ, Xiong SC, Zhang Y, Chen J, Peng Y, Li J (2018) MnOx-CeO2 catalysts for effective NOx reduction in the presence of chlorobenzene. Catal Commun 117:1–4.  https://doi.org/10.1016/j.catcom.2018.08.008 CrossRefGoogle Scholar
  3. Gao C, Shi JW, Fan ZY, Gao G, Niu CM (2018) Sulfur and water resistance of Mn-based catalysts for low-temperature selective catalytic reduction of NOx: a review. Catalysts 8:11.  https://doi.org/10.3390/catal8010011 CrossRefGoogle Scholar
  4. Izumi F (1978) The polymorphic crystallization of titanium (IV) oxide under hydrothermal conditions. II. The roles of inorganic anions in the nucleation of rutile and anatase from acid solutions. Bull Chem Soc Jpn 51:1771–1776.  https://doi.org/10.1246/bcsj.51.1771 CrossRefGoogle Scholar
  5. Jangjou Y, Wang D, Kumar A, Li JH, Epling WS (2016) SO2 poisoning of the NH3-SCR reaction over Cu-SAPO-34:effect of ammonium sulfate versus other S-containing species. ACS Catal 6:6612–6622.  https://doi.org/10.1021/acscatal.6b01656 CrossRefGoogle Scholar
  6. Jiang BQ, Liu Y, Wu ZB (2009) Low-temperature selective catalytic reduction of NO on MnOx/TiO2 prepared by different methods. J Hazard Mater 162:1249–1254.  https://doi.org/10.1016/j.jhazmat.2008.06.013 CrossRefGoogle Scholar
  7. Krishnan AT, Boehman AL (1998) Selective catalytic reduction of nitric oxide with ammonia at low temperatures. Appl Catal B Environ 18:189–198.  https://doi.org/10.1016/S0926-3373(98)00036-8 CrossRefGoogle Scholar
  8. Kusakabe K, Kashima M, Morooka S, Kato Y (1988) Rate of reduction of nitric oxide with ammonia on coke catalysts activated with sulphuric acid. Fuel 67:714–718.  https://doi.org/10.1016/0016-2361(88)90304-3 CrossRefGoogle Scholar
  9. Kusakabe K, Kawamura H, Kim HJ, Morooka S (1990) Effect of SO2 on coke catalyzed reduction of NO by ammonia. Fuel 69:917–919.  https://doi.org/10.1016/0016-2361(90)90242-I CrossRefGoogle Scholar
  10. Li CL, Tang XL, Yi HH, Wang LF, Cui XX, Chu C, Li JY, Zhang RC, Yu QJ (2018) Rational design of template-free MnOx-CeO2 hollow nanotube as de-NOx catalyst at low temperature. Appl Surf Sci 428:924–932.  https://doi.org/10.1016/j.apsusc.2017.09.131 CrossRefGoogle Scholar
  11. Liu C, Shi JW, Gao C, Niu CM (2016) Manganese oxide-based catalysts for low temperature selective catalytic reduction of NOx with NH3: a review. Appl Catal Gen 522:54–69.  https://doi.org/10.1016/j.apcata.2016.04.023 CrossRefGoogle Scholar
  12. Matsuda S, Kamo T, Kato A, Nakajima F (1981) Deposition of ammonium bisulfate in the selective catalytic reduction of nitrogen oxides with ammonia. Ind Eng Chem Prod Res Dev 21:48–52.  https://doi.org/10.1021/i300005a009 CrossRefGoogle Scholar
  13. Meng DM, Zhan WC, Guo Y, Guo YL, Wang L, Lu GZ (2015) A highly effective catalyst of Sm-MnOx for the NH3-SCR of NOx at low temperature: promotional role of Sm and its catalytic performance. ACS Catal 5:5973–5983.  https://doi.org/10.1021/acscatal.5b00747 CrossRefGoogle Scholar
  14. Smirniotis PG, Peña DA, Uphade BS (2001) Low-temperature selective catalytic reduction (SCR) of NO with NH3 by using Mn, Cr, and Cu oxides supported on Hombikat TiO2. Angew Chem Int Ed Eng 40:2479–2482.  https://doi.org/10.1002/1521-3773(20010702)40:13<2479::AID-ANIE2479>3.0.CO;2-7 CrossRefGoogle Scholar
  15. Xie C, Yang SH, Li BB, Wang HK, Shi JW, Li GD, Niu CM (2016) C-doped mesoporous anatase TiO2 comprising 10 nm crystallites. J Colloid Interface Sci 476:1–8.  https://doi.org/10.1016/j.jcis.2016.01.080 CrossRefGoogle Scholar
  16. Xie C, Yang SH, Shi JW, Li BB, Gao C, Niu CM (2017) MnOx-TiO2 and Sn doped MnOx-TiO2 selective reduction catalysts prepared using MWCNTs as the pore template. Chem Eng J 327:1–8.  https://doi.org/10.1016/j.cej.2017.06.079 CrossRefGoogle Scholar
  17. Yan LJ, Liu YY, Zha KW, Li HR, Shi LY, Zhang DS (2017) Scale–activity relationship of MnOx-FeOy nanocage catalysts derived from Prussian blue analogues for low-temperature NO Reduction: Experimental and DFT Studies. ACS Appl Mater Interfaces 9:2581−2593.  https://doi.org/10.1021/acsami.6b15527 CrossRefGoogle Scholar
  18. Zha KW, Cai SX, Hu H, Li HR, Yan TT, Shi LY, Zhang DS (2017) In situ DRIFTs investigation of promotional effects of tungsten on MnOx-CeO2/meso-TiO2 catalysts for NOx reduction. J Phys Chem C 121:25243–25254.  https://doi.org/10.1021/acs.jpcc.7b08600 CrossRefGoogle Scholar
  19. Zha KW, Kang L, Feng C, Han LP, Li HR, Yan TT, Maitarad P, Shi LY, Zhang DS (2018) Improved NOx reduction in the presence of alkali metals by using hollandite Mn–Ti oxide promoted Cu-SAPO-34 catalysts. Environ Sci: Nano 5:1408–1419.  https://doi.org/10.1039/C8EN00226F CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Institute of Advanced Electrochemical Energy & School of Materials Science and EngineeringXi’an University of TechnologyXi’anChina
  2. 2.Center of Nanomaterials for Renewable Energy, State Key Laboratory of Electrical Insulation and Power Equipment, School of Electrical EngineeringXi’an Jiaotong UniversityXi’anChina
  3. 3.School of Materials Science and EngineeringXi’an University of TechnologyXi’anChina

Personalised recommendations