Citation: QIAO Nan-li, YANG Yi-xin, LIU Qing-long, SONG Huan-qiao, YU Geng-zhi, LUO Ming-sheng. Influence of different supports on the physicochemical properties and denitration performance of the supported MnCe-based catalysts for NH₃-SCR[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(6): 733-742. shu

Influence of different supports on the physicochemical properties and denitration performance of the supported MnCe-based catalysts for NH₃-SCR

1.
School of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
2.
School of Materials Science and Engineering, Beihang University, Beijing 100191, China

Corresponding author: LUO Ming-sheng, luomingsheng@bipt.edu.cn
Received Date: 18 January 2018
Revised Date: 18 April 2018

Fund Project: The project was supported by the National Natural Science Foundation of China (21676027), Beijing Key Laboratory of Clean Fuels and Efficient Catalytic Emission Reduction Technology(BZ041420180006)the National Natural Science Foundation of China 21676027Beijing Key Laboratory of Clean Fuels and Efficient Catalytic Emission Reduction Technology BZ041420180006

Figures(8)

A series of supported Mn-Ce-based catalysts were prepared using TiO₂, SAPO-34, and Al₂O₃ as supports. The physicochemical properties of the obtained catalysts, such as structure, specific surface area, reduction properties, surface elements and acidity were characterized with XRD, BET, H₂-TPR, XPS and Py-FTIR. The results showed that MnCeO_x/SAPO-34 catalyst exhibited a larger specific surface area (439.87 m²/g), medium amount of Lewis acid sites and the weakest reduction property. In the MnCeO_x/Al₂O₃ catalyst, the concentration of Mn⁴⁺ and Ce³⁺ was relatively high, and the amount of acid sites is the lowest. However, TiO₂ as the catalyst support could enhance the reduction property, and increase the amount of Lewis acid sites and the concentration of Mn and Ce. NH₃-SCR performances of the catalysts were evaluated using a flow type fixed bed reactor. The results showed that MnCeO_x/TiO₂ catalyst presented the best catalytic performance, over which near 100% NO conversion was reached at 280 ℃ under a gas hourly space velocity of 42000 h^-1. The combination of characterization and reaction results indicated that the good reduction behavior and large amount of Lewis acid sites were beneficial to the enhancement of the catalytic performance for low-temperature NH₃-SCR reaction.
- supports,
- Mn-Ce oxides,
- reducibility,
- surface acidity,
- low-temperature NH₃-SCR
1. [1]
  BUSCA G, LIETT L, RAMIS G, BERTI F. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts[J]. Appl Catal B:Environ, 1998,18(1):1-36.
2. [2]
  QI G S, YANG R T, CHANG R. MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B:Environ, 2004,51(2):93-106. doi: 10.1016/j.apcatb.2004.01.023
3. [3]
  DJERAD S, TIFOUTI L, CROCOLL M, WEISWEILER W. Effect of vanadia and tungsten loadings on the physical and chemical characteristics of V₂O₅-WO₃/TiO₂ catalysts[J]. J Mol Catal A:Chem, 2004,208(1):257-265.
4. [4]
  XUE J J, WANG X Q, QI G S, WANG J, SHENG M Q, LI W. Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NO_x with ammonia:Relationships between active Cu sites and de-NO_x performance at low temperature[J]. J Catal, 2013,297(1):56-64.
5. [5]
  FANG D, XIE J L, MEI D, ZHANG Y M, HE F, LIU X Q, LI Y M. Effect of CuMn₂O₄ spinel in Cu-Mn oxide catalysts on selective catalytic reduction of NO_x with NH₃ at low temperature[J]. RSC Adv, 2014,4(49):25540-25551. doi: 10.1039/c4ra02824d
6. [6]
  CAO F, SU S, XIANG J, WANG P Y, HU S, SUN L S, ZHANG A C. The activity and mechanism study of Fe-Mn-Ce/gamma-Al₂O₃ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Fuel, 2015,139(1):232-239.
7. [7]
  TIAN W, YANG H S, FAN X Y, ZHANG X B. Catalytic reduction of NO_x with NH₃ over different-shaped MnO₂ at low temperature[J]. J Hazard Mater, 2011,188(1/3):105-109.
8. [8]
  SJOERD KIJLSTRA W, BIERVLIET M, POELS E D, BLIEK A. Deactivation by SO₂ of MnO_x/Al₂O₃ catalysts used for the selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B:Environ, 1998,16(1):327-337.
9. [9]
  WANG L S, HUANG B C, SU Y X, ZHOU G Y, WANG K L, LUO H C. Manganese oxides supported on multi-walled carbon nanotubes for selective catalytic reduction of NO with NH₃:Catalytic activity and characterization[J]. Chem Eng J, 2012,192(1):232-241.
10. [10]
  JIANG B Q, LIU Y, WU Z B. Low-temperature selective catalytic reduction of NO on MnO_x/TiO₂ prepared by different methods[J]. J Hazard Mater, 2009,162(2/3):1249-1254.
11. [11]
  FANG D, HE F, MEI D, ZHANG Z, XIE J L, HU H. Thermodynamic calculation for the activity and mechanism of Mn/TiO₂ catalyst doped transition metals for SCR at low temperature[J]. Catal Commun, 2014,52(5):45-48.
12. [12]
  THIRUPATHI B, SMIRNIOTIS P G. Co-doping a metal (Cr, Fe, Ni, Cu, Zn, Ce and Zr) on Mn/TiO₂ catalyst and its effect on the selective reduction of NO with NH₃ at low-temperature[J]. Appl Catal B:Environ, 2011,110(2):195-206.
13. [13]
  WU Z B, JIN R B, WANG H Q, LIU Y. Effect of ceria doping on SO₂ resistance of Mn/TiO₂ for selective catalytic reduction of NO with NH₃ at low temperature[J]. Catal Commun, 2007,10(6):935-939.
14. [14]
  LIU C, SHI J W, GAO C, NIU C M. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NO_x with NH₃:A review[J]. Appl Catal A:Gen, 2016,522(25):54-69.
15. [15]
  CAO F, XIANG J, SU S, WANG P Y, HU S, SUN S L. Ag modified Mn-Ce/gamma-Al₂O₃ catalyst for selective catalytic reduction of NO with NH₃ at low-temperature[J]. Fuel Process Technol, 2015,135(1):66-72.
16. [16]
  ZHANG L, ZHANG D S, ZHANG J P, CAI S X, FANG C, HUANG L, LI H R, GAO R H, SHI L Y. Design of meso-TiO₂@MnO_x-CeO_x/CNTs with a core-shell structure as DeNO_x catalysts:promotion of activity, stability and SO₂-tolerance[J]. Nanoscale, 2013,5(20):9821-9829. doi: 10.1039/c3nr03150k
17. [17]
  YANG Dong-jie, YU Ya, XU Ying, HUANG Xue-ming. Effect of loading sequence of Mn and Ce on the activity of Mn-Ce/TiO₂catalysts at low-temperature[J]. Chem Ind Eng Prog (China), 2015,34(6):1652-1655.
18. [18]
  YAO X J, MA K L, ZOU W X, HE S G, AN J B, YANG F M, DONG L. Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO₂ catalysts for NH₃-SCR at low temperature[J]. Chin J Catal, 2017,38(1):146-159. doi: 10.1016/S1872-2067(16)62572-X
19. [19]
  YOU X C, SHENG Z Y, YU D Q, YANG L, XIAO X, WNAG S. Influence of Mn/Ce ratio on the physicochemical properties and catalytic performance of graphene supported MnO_x-CeO₂ oxides for NH₃-SCR at low temperature[J]. Appl Surf Sci, 2017,423(30):845-854.
20. [20]
  LI L L, SUN B W, SUN J F, YU S H, GE C Y, TANG C J, DONG L. Novel MnO_x-CeO₂ nanosphere catalyst for low-temperature NH₃-SCR[J]. Catal Commun, 2017,100(1):98-102.
21. [21]
  LI S H, HUANG B C, YU C L. A CeO₂-MnO_x core-shell catalyst for low-temperature NH₃-SCR of NO[J]. Catal Commun, 2017,98(10):47-51.
22. [22]
  SHEN Q, ZHANG L Y, SUN N N, WANG H, ZHONG L S, HE C, WEI W, SUN Y H. Hollow MnO_x-CeO₂ mixed oxides as highly efficient catalysts in NO oxidation[J]. Chem Eng J, 2017,322(15):46-55.
23. [23]
  GAO F Y, TANG X L, YI H H, LI J Y, ZHAO S Z, WANG J G, CHU C, LI C L. Promotional mechanisms of activity and SO₂ tolerance of Co- or Ni-doped MnO_x-CeO₂ catalysts for SCR of NO_x with NH₃ at low temperature[J]. Chem Eng J, 2017,98(1):47-51.
24. [24]
  QIU L, PANG D D, ZHANG C L, MENG J J, ZHU R S, OUYANG F. In situ IR studies of Co and Ce doped Mn/TiO₂ catalyst for low-temperature selective catalytic reduction of NO with NH₃[J]. Appl Surf Sci, 2015,357(1):189-196.
25. [25]
  CAO F, XIANG J, SU S, WNAG P Y, SUN L S, HU S, LEI S. The activity and characterization of MnO_x-CeO₂-ZrO₂/γ-Al₂O₃ catalysts for low temperature selective catalytic reduction of NO with NH₃[J]. Chem Eng J, 2014,243(1):347-354.
26. [26]
  KWON D W, NAM K B, HONG S C. Influence of tungsten on the activity of a Mn/Ce/W/Ti catalyst for the selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal A:Gen, 2015,497(1):160-166.
27. [27]
  XIONG Y, TANG C J, YAO X J, ZHANG L, LI L L, WANG X B, DENG Y, GAO F, DONG L. Effect of metal ions doping (M=Ti⁴⁺, Sn⁴⁺) on the catalytic performance of MnO_x/CeO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Appl Catal A:Gen, 2015,492(1):206-216.
28. [28]
  ZHNAG L J, CUI S P, GUO H X, MA X Y, LUO X G. The influence of K⁺ cation on the MnO_x-CeO₂/TiO₂ catalysts for selective catalytic reduction of NO_x with NH₃ at low temperature[J]. J Mol Catal A:Chem, 2014,390(1):14-21.
29. [29]
  YAO X, ZHAO R D, CHEN L, DU J, TAO C Y, YANG F M, DONG L. Selective catalytic reduction of NO_x by NH₃ over CeO₂ supported on TiO₂:Comparison of anatase, brookite, and rutile[J]. Appl Catal B:Environ, 2017,208(5):82-93.
30. [30]
  YU C L, HUANG B C, DONG L F, CHEN F, YANG Y, FAN Y M, YANG Y X, LIU X Q, WANG X N. Effect of Pr/Ce addition on the catalytic performance and SO₂ resistance of highly dispersed MnO_x/SAPO-34 catalyst for NH₃-SCR at low temperature[J]. Chem Eng J, 2017,98(15):47-51.
31. [31]
  YAO X J, KONG T T, YU S H, LI L I, YANG F M, DO NG. Influence of different supports on the physicochemical properties and denitration performance of the supported Mn-based catalysts for NH₃-SCR at low temperature[J]. Appl Surf Sci, 2017,402(30):208-217.
32. [32]
  LI J H, CHEN J, KE R, LUO C K, HAO J M. Effects of precursors on the surface Mn species and the activities for NO reduction over MnO_x/TiO₂ catalysts[J]. Catal Commun, 2007,8(12):1896-1900. doi: 10.1016/j.catcom.2007.03.007
33. [33]
  HE C, LI P, CHENG J, WANG H L, LI J J, LI Q, HAO Z P. Synthesis and characterization of Pd/ZSM-5/MCM-48 biporous catalysts with superior activity for benzene oxidation[J]. Appl Catal A:Gen, 2010,382(2):167-175. doi: 10.1016/j.apcata.2010.04.033
34. [34]
  ZHEN Kai-ji. Catalyst Basis[M]. Beijing:The Science Publishing Company, 2005.
35. [35]
  KAPTEIJN F, SINGOREDJO L, ANDREINI A, NOULIJN J A. Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J]. Appl Catal B:Environ, 1994,3(2):173-189.
36. [36]
  CARNO J, FERRANDON M, BJORNBOM E, JARAS S. Mixed manganese oxide/platinum catalysts for total oxidation of model gas from wood boilers[J]. Appl Catal A:Gen, 1997,155(2):265-281. doi: 10.1016/S0926-860X(97)80129-9
37. [37]
  GAO G, SHI J W, LIU C, GAO C, FAN Z Y, NIU C M. Mn/CeO₂ catalysts for SCR of NO_x with NH₃:comparative study on the effect of supports on low-temperature catalytic activity[J]. Appl Surf Sci, 2017,411(31):338-346.
38. [38]
  PARRY E P. An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity[J]. J Catal, 1963,2(5):371-379. doi: 10.1016/0021-9517(63)90102-7
39. [39]
  WU Z B, JIANG B Q, LIU Y, WNAG H Q, JIN R B. DRIFT study of manganese/titania-Based catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Environ Sci Technol, 2007,41(16):5812-5817. doi: 10.1021/es0700350
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Influence of different supports on the physicochemical properties and denitration performance of the supported MnCe-based catalysts for NH3-SCR

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通讯作者: 陈斌, bchen63@163.com

Influence of different supports on the physicochemical properties and denitration performance of the supported MnCe-based catalysts for NH₃-SCR