Citation: ZHUANG Ke, ZHANG Ya-ping, HUANG Tian-jiao, LU Bin, SHEN Kai. Sulfur-poisoning and thermal reduction regeneration of holmium-modified Fe-Mn/TiO₂ catalyst for low-temperature SCR[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(11): 1356-1364. shu

Sulfur-poisoning and thermal reduction regeneration of holmium-modified Fe-Mn/TiO₂ catalyst for low-temperature SCR

1.
State Power Environmental Protection Research Institute, Nanjing 210031, China
2.
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China

Corresponding author: ZHANG Ya-ping, amflora@seu.edu.cn
Received Date: 17 May 2017
Revised Date: 10 August 2017

Fund Project: The project was supported by the Key Research Program of Jiangsu Province(BE2015677)and Environmental Nonprofit Industry Research Subject(2016YFC0208102)Environmental Nonprofit Industry Research Subject 2016YFC0208102the Key Research Program of Jiangsu Province BE2015677

Figures(9)

The effect of SO₂ on the low-temperature SCR activity and the thermal reduction regeneration for holmium-modified Fe-Mn/TiO₂ catalyst were investigated by activity assessment and various characterization methods. The deposition of ammonium sulfate ((NH₄)₂SO₄) on catalyst surface and the sulfuration of active component (MnSO₄) were proved to be the main causes for the deactivation in the presence of SO₂. The catalyst Fe_0.3Ho_0.1Mn_0.4/TiO₂ exhibited superior SO₂ durability when the concentration of SO₂ was lower than 0.04%, and the catalytic activity could markedly recover with the termination of sulfur-poisoning source. The deactivation behavior was irreversible when the concentration of SO₂ was increased to 0.1% but the poisoned catalyst could be regenerated after thermal reduction (350 ℃) for 60 min by 5% NH₃. The microstructure and physicochemical properties could be significantly restored after the thermal reduction regeneration. Moreover, the NO_x conversion could return to about 80%.
- SCR,
- denitration,
- low-temperature,
- thermal reduction regeneration,
- (NH₄)₂SO₄
1. [1]
  SHEN B, LIU T, ZHAO N, YANG X, DENG L. Iron-doped Mn-Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. J Environ Sci-China, 2010,22(9):1447-1454. doi: 10.1016/S1001-0742(09)60274-6
2. [2]
  JIANG B, DENG B, ZHANG Z, WU Z, TANG X, YAO S, LU H. Effect of Zr addition on the low-temperature SCR activity and SO₂ tolerance of Fe-Mn/Ti catalysts[J]. J Phys Chem C, 2014,118(27):14866-14875. doi: 10.1021/jp412828p
3. [3]
  KIJLSTRA W S, BIERVLIET M, POELS E K, 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(4):327-337. doi: 10.1016/S0926-3373(97)00089-1
4. [4]
  FAN Yun-zhu, CAO Fa-hai. Thermal decomposition kinetics of ammonium sulfate[J]. J Chem Eng Chin Univ, 2011(02):341-346.
5. [5]
  QI G S, YANG R T. Low-temperature selective catalytic reduction of NO with NH₃ over iron and manganese oxides supported on titania[J]. Appl Catal B:Environ, 2003,44(3):217-225. doi: 10.1016/S0926-3373(03)00100-0
6. [6]
  HUANG Hai-feng, YU He, ZHANG Feng, ZHOU Xiao-yan, LU Han-feng. Study on the sulfur tolerance and regeneration of Mn₁Fe_xCe_1-x/TiO₂ catalyst for low temperature NH₃-selective catalytic reduction[J]. Proc CSEE, 2011,31(35):29-34.
7. [7]
  HUANG J, TONG Z, HUANG Y, ZHANG J. Selective catalytic reduction of NO with NH₃ at low temperatures over iron and manganese oxides supported on mesoporous silica[J]. Appl Catal B:Environ, 2008,78(3/4):309-314.
8. [8]
  LIU F, HE H. Selective catalytic reduction of NO with NH₃ over manganese substituted iron titanate catalyst:Reaction mechanism and H₂O/SO₂ inhibition mechanism study[J]. Catal Today, 2010,153(3/4):70-76.
9. [9]
  JIANG B Q, WU Z B, LIU Y, LEE S C, HO W K. DRIFT study of the SO₂ effect on low-temperature SCR reaction over Fe-Mn/TiO₂[J]. J Phys Chem C, 2010,114(11):4961-4965. doi: 10.1021/jp907783g
10. [10]
  MA Jian-rong, HUANG Zhang-gen, LIU Zhen-yu, GUO Shi-jie. Effect of regeneration method on activity for simultaneous removal of SO₂ and NO over V₂O₅/AC catalyst-sorbent[J]. Chin J Catal, 2005,26(6):463-469.
11. [11]
  SHI Y, SHU H, ZHANG Y, FAN H, ZHANG Y, YANG L. Formation and decomposition of NH₄HSO₄ during selective catalytic reduction of NO with NH₃ over V₂O₅-WO₃/TiO₂ catalysts[J]. Fuel Process Technol, 2016,150:141-147. doi: 10.1016/j.fuproc.2016.05.016
12. [12]
  YANG Chao, CHENG Hua, HUANG Bi-chun. Review of de NO_x catalysts with SO₂ and H₂O poisoning resistance for low-temperature NH₃-SCR[J]. Chem Ind Eng Prog, 2014,33(4):907-913.
13. [13]
  ZHU Z P, NIU H X, LIU Z Y, LIU S J. Decomposition and reactivity of NH₄HSO₄ on V₂O₅/AC catalysts used for NO reduction with ammonia[J]. J Catal, 2000,195(2):268-278. doi: 10.1006/jcat.2000.2961
14. [14]
  XU W, HE H, YU Y. Deactivation of a Ce/TiO₂ catalyst by SO₂ in the selective catalytic reduction of NO by NH₃[J]. J Phys Chem C, 2009,113(11):4426-4432. doi: 10.1021/jp8088148
15. [15]
  ZHANG L, LI L, CAO Y, YAO X, GE C, GAO F, DENG Y, TANG C, DONG L. Getting insight into the influence of SO₂ on TiO₂/CeO₂ for the selective catalytic reduction of NO by NH₃[J]. Appl Catal B:Environ, 2015,165:589-598. doi: 10.1016/j.apcatb.2014.10.029
16. [16]
  HUANG J, TONG Z, HUANG Y, ZHANG J. Selective catalytic reduction of NO with NH₃ at low temperatures over iron and manganese oxides supported on mesoporous silica[J]. Appl Catal B:Environ, 2008,78(3/4):309-314.
17. [17]
  TOPSOE N Y. Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line fourier transform infrared spectroscopy[J]. Science, 1994,265(5176):1217-1219. doi: 10.1126/science.265.5176.1217
18. [18]
  RAMIS G, YI L, BUSCA G. Ammonia activation over catalysts for the selective catalytic reduction of NO_x and the selective catalytic oxidation of NH₃. An FT-IR study[J]. Catal Today, 1996,28(4):373-380. doi: 10.1016/S0920-5861(96)00050-8
19. [19]
  TSYGANENKO A A, POZDNYAKOV D V, FILIMONOV V N. Infrared study of surface species arising from ammonia adsorption on oxide surfaces[J]. J Mol Struct, 1975,291(2):299-318.
20. [20]
  LIETTI L, RAMIS G, BERTI F, TOLEDO G, ROBBA D, BUSCA G, FORZATTI P. Chemical, structural and mechanistic aspects on NO_x SCR over commercial and model oxide catalysts[J]. Catal Today, 1998,42(1/2):101-116.
21. [21]
  MATRALIS H K, CIARDELLI M, RUWET M, GRANGE P. Vanadia catalysts supported on mixed TiO₂-Al₂O₃ supports:Effect of composition on the structure and acidity[J]. J Catal, 1995,157(2):368-379. doi: 10.1006/jcat.1995.1302
22. [22]
  ZHANG Y, GUO W, WANG L, SONG M, YANG L, SHEN K, XU H, ZHOU C. Characterization and activity of V₂O₅-CeO₂/TiO₂-ZrO₂ catalysts for NH₃-selective catalytic reduction of NO_x[J]. Chin J Catal, 2015,37(10):1701-1710.
23. [23]
  LONG R Q, YANG R T. Selective catalytic reduction of nitrogen oxides by ammonia over Fe³⁺-exchanged TiO₂-pillared clay catalysts[J]. J Catal, 1999,186(2):254-268. doi: 10.1006/jcat.1999.2558
24. [24]
  LARRUBIA M A, RAMIS G, BUSCA G. An FT-IR study of the adsorption of urea and ammonia over V₂O₅-MoO₃-TiO₂ SCR catalysts[J]. Appl Catal B:Environ, 2000,27(3):L145-L151. doi: 10.1016/S0926-3373(00)00150-8
25. [25]
  GUTIERREZ-ALEJANDRE A, RAMIREZ J, BUSCA G. A vibrational and spectroscopic study of WO₃/TiO₂-Al₂O₃ catalyst precursors[J]. Langmuir, 1998,14(3):630-639. doi: 10.1021/la970993n
26. [26]
  LUO Hong-cheng, HUANG Bi-chun, FU Ming-li, WU Jun-liang, YE Dai-qi. SO₂ Deactivation mechanism of MnO_x/MWCNTs catalyst for low-temperature selective catalytic reduction of NO_x by ammonia[J]. Acta Phys-Chim Sin, 2012(09):2175-2182. doi: 10.3866/PKU.WHXB201207062
1. [1]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
2. [2]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
3. [3]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
4. [4]
  Lisha LEI , Wei YONG , Yiting CHENG , Yibo WANG , Wenchao HUANG , Junhuan ZHAO , Zhongjie ZHAI , Yangbin DING . Application of regenerated cellulose and reduced graphene oxide film in synergistic power generation from moisture electricity generation and Mg-air batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1151-1161. doi: 10.11862/CJIC.20240202
5. [5]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
6. [6]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
7. [7]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
8. [8]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
9. [9]
  Jihua Deng , Xinshi Wu , Dichang Zhong . Exploration of Green Teaching and Ideological and Political Education in Chemical Experiment of “Preparation of Ammonium Ferrous Sulfate”. University Chemistry, 2024, 39(10): 325-329. doi: 10.12461/PKU.DXHX202405046
10. [10]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ^-壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-. doi: 10.1016/j.actphy.2025.100081
11. [11]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
12. [12]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
13. [13]
  Yuping Wei , Yiting Wang , Jialiang Jiang , Jinxuan Deng , Hong Zhang , Xiaofei Ma , Junjie Li . Interdisciplinary Teaching Practice——Flexible Wearable Electronic Skin for Low-Temperature Environments. University Chemistry, 2024, 39(10): 261-270. doi: 10.12461/PKU.DXHX202404007
14. [14]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
15. [15]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
16. [16]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
17. [17]
  Xianghai Song , Xiaoying Liu , Zhixiang Ren , Xiang Liu , Mei Wang , Yuanfeng Wu , Weiqiang Zhou , Zhi Zhu , Pengwei Huo . Insights into the greatly improved catalytic performance of N-doped BiOBr for CO₂ photoreduction. Acta Physico-Chimica Sinica, 2025, 41(6): 100055-. doi: 10.1016/j.actphy.2025.100055
18. [18]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
19. [19]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
20. [20]
  Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO₂/BiOBr S-Scheme Heterostructure for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-. doi: 10.3866/PKU.WHXB202407021

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1771)
HTML views(101)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Sulfur-poisoning and thermal reduction regeneration of holmium-modified Fe-Mn/TiO2 catalyst for low-temperature SCR

Metrics

通讯作者: 陈斌, bchen63@163.com

Sulfur-poisoning and thermal reduction regeneration of holmium-modified Fe-Mn/TiO₂ catalyst for low-temperature SCR