Citation: WANG Hui-min, MA Yan-ping, CHEN Xi-ying, XU Si-yuan, CHEN Jin-ding, ZHANG Qiu-lin, ZHAO Bin, NING Ping. Promoting effect of SO₄^2- functionalization on the performance of Fe₂O₃ catalyst in the selective catalytic reduction of NO_x with NH₃[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(5): 584-593. shu

Promoting effect of SO₄^2- functionalization on the performance of Fe₂O₃ catalyst in the selective catalytic reduction of NO_x with NH₃

Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China

Corresponding author: ZHANG Qiu-lin, qiulinzhang.kmust@163.com ZHAO Bin, 2859981152@qq.com
Received Date: 13 January 2020
Revised Date: 22 April 2020

Fund Project: Analysis and Testing Center of Kunming University of Science and Technology 2019M20182207001The project was supported by the National Natural Science Foundation of China (21666014) and Analysis and Testing Center of Kunming University of Science and Technology (2019M20182207001)the National Natural Science Foundation of China 21666014

Figures(10)

Fe(OH)₃ and Fe₂O₃ were first prepared by a precipitation method and then sulfated to obtain the SO₄^2--functionalized SO₄^2-/Fe(OH)₃ and SO₄^2-/Fe₂O₃ catalysts for the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR); the promoting effect of SO₄^2- functionalization on the performance of Fe₂O₃ catalyst in NH₃-SCR was then investigated. The results indicate that the SCR activity of the SO₄^2--functionalized Fe₂O₃ catalysts is significantly improved in comparison with that of unmodified Fe₂O₃. In particular, the SO₄^2-/Fe(OH)₃ catalyst exhibits excellent performance in NH₃-SCR, with the NO_x conversion of over 80% at 250-450 ℃; besides, it also display high catalytic stability and resistance towards H₂O + SO₂. A series of characterization results including XRD, Raman spectroscopy, TG analysis, FT-IR spectroscopy, H₂-TPR, NH₃-TPD and in situ DRIFTS reveal that the functionalization with sulfuric acid can inhibit the growth of Fe₂O₃ grains; moreover, SO₄^2- combines with Fe³⁺ to form the sulfate complex, leading to an increase in the number of surface acid sites and the acid strength, which can inhibit the ammonia over-oxidation on Fe₂O₃ and enhance the deNO_x performance of Fe₂O₃.
- sulfation treatment,
- Fe₂O₃,
- selective catalytic reduction with NH₃,
- denitration,
- surface acidity,
- ammonia oxidation
1. [1]
  SUN C Z, LIU H, CHEN W, CHEN D Z, YU S H, LIU A N, DONG L, FENG S. Insights into the Sm/Zr co-doping effects on N₂ selectivity and SO₂ resistance of a MnO_x-TiO₂ catalyst for the NH₃-SCR reaction[J]. Chem Eng J, 2018,347:27-40.
2. [2]
  LIU Z M, SU H, LI J H, LI Y. Novel MoO₃/CeO₂-ZrO₂ catalyst for the selective catalytic reduction of NO_x by NH₃[J]. Catal Commun, 2015,65:51-54.
3. [3]
  MARBERGERA A, FERRI D, ELSENER M, SAGAR A, ARTNER C, SCHERMANZ K, KROCHER O. Relationship between structures and activities of supported metal vanadates for the selective catalytic reduction of NO by NH₃[J]. Appl Catal B:Environ, 2017,218:731-742.
4. [4]
  YAN Chun-di, CHENG Hao, WANG Shu-dong. Effects of copper content in Cu-SAPO-34 on its catalytic performance in NH₃-SCR of NO_x[J]. J Fuel Chem Technol, 2014,42(6):743-750.
5. [5]
  PUTLURU S S R, SCHILL L, GODIKSEN A, POREDDY R, MOSSIN S, JENSEN A D, FEHRMANN R. Promoted V₂O₅/TiO₂ catalysts for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B:Environ, 2016,183:282-290.
6. [6]
  YANG Y J, LIU J, LIU F, WANG Z, DING J Y, HUANG H. Reaction mechanism for NH₃-SCR of NO_x over CuMn₂O₄ catalyst[J]. Chem Eng J, 2019,361:578-587.
7. [7]
  YAO X J, KONG T T, CHEN L, DING S M, YANG F M, DONG L. Enhanced low-temperature NH₃-SCR performance of MnO_x/CeO₂ catalysts by optimal solvent effect[J]. Appl Surf Sci, 2017,420:407-415.
8. [8]
  ZHANG T, CHANG H Z, LI K Z, PENG Y, LI X, LI J H. Different exposed facets VO_x/CeO₂ catalysts for the selective catalytic reduction of NO with NH₃[J]. Chem Eng J, 2018,349:184-191.
9. [9]
  ANDREOLI S, DEORSOLA F A, PIRONE R. MnO_x-CeO₂ catalysts synthesized by solution combustion synthesis for the low-temperature NH₃-SCR[J]. Catal Today, 2015,253:199-206.
10. [10]
  LIU Xin, NING Ping, LI Hao, SONG Zhong-xian, WANG Yan-cai, ZHANG Jin-hui, TANG Xiao-su, WANG Ming-zhi, ZHANG Qiu-lin. Probing NH₃-SCR catalytic activity and SO₂ resistance over aqueous-phase synthesized Ce-W@TiO₂ catalyst[J]. J Fuel Chem Technol, 2016,44(2):225-231.
11. [11]
  KANG L, HAN L P, HE J B, LI H R, YAN T T, CHEN G R, ZHANG J P, SHI L Y, ZHANG D S. Improved NO_x reduction in the presence of SO₂ by using Fe₂O₃-promoted halloysite-supported CeO₂-WO₃ catalysts[J]. Environ Sci Technol, 2019,53:938-945.
12. [12]
  YE D, REN X Y, QU R Y, LIU S J, ZHENG C H, GAO X. Designing SO₂-resistant cerium-based catalyst by modifying with Fe₂O₃ for the selective catalytic reduction of NO with NH₃[J]. Mol Catal, 2019,462:10-18.
13. [13]
  LIU Z M, SU H, CHEN B C, LI J H, WOO S I. Activity enhancement of WO₃ modified Fe₂O₃ catalyst for the selective catalytic reduction of NO_x by NH₃[J]. Chem Eng J, 2016,299:255-262.
14. [14]
  XIONG Z B, NING X, ZHOU F, YANG B, TU Y W, JIN J, LU W, LIU Z H. Environment-friendly magnetic Fe-Ce-W catalyst for the selective catalytic reduction of NO_x with NH₃:Influence of citric acid content on its activity-structure relationship[J]. RSC Adv, 2018,8:21915-21925.
15. [15]
  WANG Ji-feng, WANG Hui-min, ZHANG Ya-qing, ZHANG Qiu-lin, NING Ping. Promotion effect of tungsten addition on N₂ selectivity of MnO_x-Fe₂O₃ for NH₃-SCR[J]. J Fuel Chem Technol, 2019,47(7):814-822.
16. [16]
  SHAN W P, LIU F D, HE H, SHI X Y, ZHANG C B. A superior Ce-W-Ti mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B:Environ, 2012,115/116:100-106.
17. [17]
  LIU Z M, ZHANG S X, LI J H, MA L L. Promoting effect of MoO₃ on the NO_x reduction by NH₃ over CeO₂/TiO₂ catalyst studied with in situ DRIFTS[J]. Appl Catal B:Environ, 2014,144:90-95.
18. [18]
  CHENG K, LIU B, SONG W Y, LIU J, CHEN Y S, ZHAO Z, WEI Y C. Effect of Nb promoter on the structure and performance of iron titanate catalysts for the selective catalytic reduction of NO with NH₃[J]. Ind Eng Chem Res, 2018,57(23):7802-7810.
19. [19]
  ZEB F, ISHAQUE M, NADEEM K, KAMRAN M, KRENN H, SZABO D V, BROSSMANN U, LETOFSKY-PAPST I. Reduced surface effects in weakly interacting ZrO₂ coated MnFe₂O₄ nanoparticles[J]. J Magn Magn Mater, 2019,469:580-586.
20. [20]
  NIU Ru-jie, WANG Cheng-zhang, LIU Xiao-yue, YI Chun-xiong, CHEN Liang, MI Tie, WU Zheng-shun. Preparation of Zr-based perovskite supported Fe₂O₃ catalyst and its performance in the reverse water gas shift reaction[J]. J Fuel Chem Technol, 2019,47(3):92-97.
21. [21]
  MANSOUR H, BARGOUGUI R, AUTRET-LAMBERT C, GADRI A, AMMAR S. Co-precipitation synthesis and characterization of tin-doped α-Fe₂O₃ nanoparticles with enhanced photocatalytic activities[J]. J Phys Chem Solids, 2018,114:1-7.
22. [22]
  GUO S, WANG H J, YANG W, FIDA H, YOU L M, ZHOU K. Scalable synthesis of Ca-doped α-Fe₂O₃ with abundant oxygen vacancies for enhanced degradation of organic pollutants through peroxymonosulfate activation[J]. Appl Catal B:Environ, 2020,262:118250-118261.
23. [23]
  SONG L Y, CHAO J D, FANG Y J, HE H, LI J, QIU W G, ZHANG G Z. Promotion of ceria for decomposition of ammonia bisulfate over V₂O₅-MoO₃/TiO₂ catalyst for selective catalytic reduction[J]. Chem Eng J, 2016,303:275-281.
24. [24]
  GAO S, CHEN X B, WANG H Q, MO J S, WU Z B, LIU Y, WENG X L. Ceria supported on sulfated zirconia as a superacid catalyst for selective catalytic reduction of NO with NH₃[J]. J Colloid Interface Sci, 2013,394:515-521.
25. [25]
  CHANG H Z, MA L L, YANG S J, LI J H, CHEN L, WANG W, HAO J M. Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH₃-SCR[J]. J Hazard Mater, 2013,262:782-788.
26. [26]
  QU R Y, GAO X, CEN K F, LI J H. Relationship between structure and performance of a novelcerium-niobium binary oxide catalyst for selective catalytic reduction of NO with NH₃[J]. Appl Catal B:Environ, 2013,142-143:290-297.
27. [27]
  ZIC M, RISTIC M, MUSIC S. ⁵⁷Fe Mössbauer, FT-IR and FE SEM investigation of the formation of hematite and goethite at high pH values[J]. J Mol Struct, 2007,834/836:141-149.
28. [28]
  YAN Z X, XU Z H, YANG Z H, YUE L, HUANG L Y. Graphene oxide/Fe₂O₃ nanoplates supported Pt for enhanced room-temperature oxidation of formaldehyde[J]. Appl Surf Sci, 2019,467/468:277-285.
29. [29]
  YAMAGUCHI T, JIN T, ISHIDA I, TANABE K. Structural identification of acid sites of sulfur-promoted solid super acid and construction of its structure on silica support[J]. Mater Chem Phys, 1986,17(1/2):3-19.
30. [30]
  KAYO A, YAMAGUCHI T, TANABE K. The effect of preparation method on the acidic and catalytic properties of iron oxide[J]. J Catal, 1983,83(1):99-106.
31. [31]
  ZIELINSKI J, ZGLINICKA I, ZNAK L, KASZKUR Z. Reduction of Fe₂O₃ with hydrogen[J]. Appl Catal A:Gen, 2010,381(1/2):191-196.
32. [32]
  LI H J, SONG H L, CHEN L W, XIA C G. Designed SO₄^2-/Fe₂O₃-SiO₂ solid acids for polyoxymethylene dimethyl ethers synthesis:the acid sites control and reaction pathways[J]. Appl Catal B:Environ, 2015,165:466-476.
33. [33]
  MENG D M, XU Y, GUO Y L, GUO Y, WANG L L, LU G Z, ZHAN W C. Spinel structured Co_aMn_bO_x mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B:Environ, 2018,221:652-663.
34. [34]
  WANG X X, SHI Y, LI S J, LI W. Promotional synergistic effect of Cu and Nb doping on a novel Cu/Ti-Nb ternary oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B:Environ, 2018,220:234-250.
35. [35]
  MU J C, LI X Y, SUN W B, FAN S Y, WANG X Y, WANG L, QIN M C, GAN G Q, YIN Z F, ZHANG D K. Inductive effect boosting catalytic performance of advanced Fe_1-_xV_xO_δ catalysts in low-temperature NH₃ selective catalytic reduction:Insight into the Structure, Interaction, and Mechanisms[J]. ACS Catal, 2018,8:6760-6774.
36. [36]
  GAO C, SHI J W, FAN Z Y, WANG B R, WANG Y, HE C, WANG X B, LI J, NIU C M. "Fast SCR" reaction over Sm-modified MnO_x-TiO₂ for promoting reduction of NO_x with NH₃[J]. Appl Catal A:Gen, 2018,564:102-112.
37. [37]
  MA S B, ZHAO X Y, LI Y S, ZHANG T R, YUAN F L, NIU X Y, ZHU Y J. Effect of W on the acidity and redox performance of the Cu_0.02Fe_0.2W_aTiO_x (a=0.01, 0.02, 0.03) catalysts for NH₃-SCR of NO[J]. Appl Catal B:Environ, 2019,248:226-238.
38. [38]
  GUO M Y, LIU Q L, ZHAO P P, HAN J F, LI X, HA Y, FU Z C, SONG C F, JI N, LIU C X, MA D G, LI Z G. Promotional effect of SO₂ on Cr₂O₃ catalysts for the marine NH₃-SCR reaction[J]. Chem Eng J, 2019,361:830-838.
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Promoting effect of SO42- functionalization on the performance of Fe2O3 catalyst in the selective catalytic reduction of NOx with NH3

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Promoting effect of SO₄^2- functionalization on the performance of Fe₂O₃ catalyst in the selective catalytic reduction of NO_x with NH₃