Citation: LIANG Yan-zheng, WANG Xue-tao, LUO Shao-feng, ZHOU Yu-feng. Performance of the modified Cu-Mn/SAPO-34 catalysts in the selective catalytic reduction of NO_x by NH₃[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(6): 728-734. shu

Performance of the modified Cu-Mn/SAPO-34 catalysts in the selective catalytic reduction of NO_x by NH₃

Department of Energy and Power Engineering, Henan University of Science and Technology, Luoyang 471003, China

Corresponding author: WANG Xue-tao, wxt7682@163.com
Received Date: 12 May 2020
Revised Date: 1 June 2020

Fund Project: National Natural Science Foundation of China 50806020Henan Science and Technology Innovation Talent Program (Outstanding Youth) 114100510010The project was supported by National Natural Science Foundation of China (50806020), Henan Science and Technology Innovation Talent Program (Outstanding Youth) (114100510010) and Project Supported by National Natural Science Foundation of Henan Province (182300410256)Project Supported by National Natural Science Foundation of Henan Province 182300410256

Figures(7)

A series of Cu-Mn/SAPO-34 catalysts with different mass ratios of Cu to Mn were prepared by impregnation method. The influence of Cu and Mn loading on the denitrification performance was investigated in a fixed-bed reactor. XRD, NH₃-TPD, H₂-TPR, XPS were used to characterize and analyze the catalysts. The results show that the bimetallic modified Cu-Mn/SAPO-34 have excellent catalytic activity and broad active temperature window. Especially, the Cu-Mn/SAPO-34/1:4 catalyst with a Cu/Mn mass ratio of 1:4 has the widest active temperature window, its denitrification rates could reach 85.39% at 250℃, 96% at 300-400℃, and up to 90% at 450℃. Cu and Mn species are highly dispersed on the surface of the catalyst and do not change the crystal structure of SAPO-34. Co-doping of Cu and Mn promotes the transformation of Cu²⁺ to Cu⁺, increases the ratio of Mn⁴⁺ to Mn³⁺, improves the activity at low temperature and promotes the catalytic reaction. Cu-Mn/SAPO-34/1:4 catalyst has rich acid sites, good redox performance and resistance to SO₂ and H₂O, which can improve the activity and stability of the catalysts.
- denitration,
- Cu-Mn/SAPO-34,
- NH₃-SCR,
- NO_x,
- catalyst
1. [1]
  GUO Feng, YU Jian, MU Yang, CHU Mo, XU Guang-wen. Preparation of catalyst with wide working-temperature and the reaction mechanism of flue gas denitration[J]. J Fuel Chem Technol, 2014,42(1):101-109.
2. [2]
  HU Hai-peng, WANG Xue-tao, ZHANG Xing-yu, SU Xiao-xin, YANG Xiao-dong, SHI Rui-hua. Performance of Fe-Cu/ZSM-5 catalyst in the DeNO_x process via NH₃-SCR[J]. J Fuel Chem Technol, 2018,46(2):225-232. doi: 10.3969/j.issn.0253-2409.2018.02.013
3. [3]
  XIONG Zhi-bo, LU Chun-mei. Study on the modification of iron-cerium mixed oxide catalyst for selective catalytic reduction of NO[J]. J Fuel Chem Technol, 2013,41(3):361-367. doi: 10.3969/j.issn.0253-2409.2013.03.016
4. [4]
  PANAHI P N, SALARI D, TSENG H H, NIAEI A, MOUSAVI S M. Effect of the preparation method on activity of Cu-ZSM-5 nanocatalyst for the selective reduction of NO by NH₃[J]. Environ Technol, 2017,38(15):1852-1861. doi: 10.1080/09593330.2016.1238964
5. [5]
  VENNESTRØM P N R, JANSSENS T V W, KUSTOV A, GRILL M, PUIG-MOLINA A, LUNDEGAARD L F, TIRUVALAM R R, CONCEPCIÓN P, CORMA A. Influence of lattice stability on hydrothermal deactivation of Cu-ZSM-5 and Cu-IM-5 zeolites for selective catalytic reduction of NO_x by NH₃[J]. J Catal, 2014,309:477-490. doi: 10.1016/j.jcat.2013.10.017
6. [6]
  PARK J H, PARK H J, BAIK J H, NAM I S, SHIN C H, LEE J H, CHO B K, OH S H. Hydrothermal stability of CuZSM5 catalyst in reducing NO by NH₃ for the urea selective catalytic reduction process[J]. J Catal, 2006,240(1):47-57.
7. [7]
  YAN C D, CHENG H, YUAN Z S, WANG S D. The role of isolated Cu²⁺ location in structural stability of Cu-modified SAPO-34 in NH₃-SCR of NO[J]. Environ Technol, 2015,36(2):169-177.
8. [8]
  HUANG L M, WANG X M, YAO S L, JIANG B Q, CHEN X Y, WANG X. Cu-Mn bimetal ion-exchanged SAPO-34 as an active SCR catalyst for removal of NO_x from diesel engine exhausts[J]. Catal Commun, 2016,81:54-57. doi: 10.1016/j.catcom.2016.03.010
9. [9]
  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]. J Fuel Chem Technol, 2018,46(6):733-742. doi: 10.3969/j.issn.0253-2409.2018.06.012
10. [10]
  TAN J, LIU Z M, BAO X H, LIU X C, HAN X W, HE C Q, ZHAI R S. Crystallization and Si incorporation mechanisms of SAPO-34[J]. Microporous Mesoporous Mater, 2002,53(1):97-108.
11. [11]
  LIU G Y, TIAN P, LI J Z, ZHANG D Z, FAN Z, LIU Z M. Synthesis, characterization and catalytic properties of SAPO-34 synthesized using diethylamine as a template[J]. Microporous Mesoporous Mater, 2008,111(1):143-149.
12. [12]
  ZHU Yan-tao, LÜ Gang, SONG Chong-lin, LI Bo, CHEN Ke. Catalytic oxidation of soot over monovalent copper modified ZSM-5[J]. J Fuel Chem Technol, 2017,45(1):106-112. doi: 10.3969/j.issn.0253-2409.2017.01.015
13. [13]
  CAO Y, LAN L, FENG X, YANG Z Z, ZOU S, XU H D, LI Z Q, GONG M C, CHEN Y Q. Cerium promotion on the hydrocarbon resistance of a Cu-SAPO-34 NH₃-SCR monolith catalyst[J]. Catal Sci Technol, 2015,5(9):4511-4521. doi: 10.1039/C5CY00704F
14. [14]
  ZHANG Qiang, LIU Lu, YU Meng-yun, ZHOU Zhou. Effect of sulfuric acid modification of Al₂O₃ support on the SCR performance of MnCe/Al₂O₃ catalysts[J]. J Fuel Chem Technol, 2019,47(9):1137-1145. doi: 10.3969/j.issn.0253-2409.2019.09.014
15. [15]
  FANG Qi-long, ZHU Bao-zhong, SUN Yun-lan, YIN Shou-lai, ZI Zhao-hui, SHI Jin-xing, LI Guo-bo. Study on the performance of low temperature De-NO_x based on Mn-Fe/Al₂O₃ catalysts[J]. J Mol Catal, 2018,32(4):18-27.
16. [16]
  HUANG Zeng-bin, LI Cui-qing, WANG Zhen, XU Sheng-mei, FENG Ling-bo, WANG Hong, SONG Yong-ji, ZHANG Wei. Performance of Mn-Ce catalysts supported on different zeolites in the NH₃-SCR of NO_x[J]. J Fuel Chem Technol, 2016,44(11):1388-1393. doi: 10.3969/j.issn.0253-2409.2016.11.016
17. [17]
  LONG R Q, YANG R T. Temperature-programmed desorption/surface reaction (TPD/TPSR) study of Fe-exchanged ZSM-5 for selective catalytic reduction of nitric oxide by ammonia[J]. J Catal, 2001,198(1):20-28.
18. [18]
  YANG Ying-xin, MA Jie-wen, YU Cheng-long, SUN Meng-ting, HUNAG Bi-chun, WU You-ming. Low temperature NH₃-SCR activity of manganese oxides supported on different SAPO molecular sieves catalysts[J]. Acta Sci Circumstantiae, 2016,36(9):3400-3408.
19. [19]
  WANG C, ZHAO Y, ZHANG C, YAN X, CAO P. Effect of iron doping on SO₂ and H₂O resistance of honeycomb cordierite-based Mn-Ce/Al₂O₃ catalyst for NO removal at low temperature[J]. Res Chem Intermed, 2018,44(5):3135-3150. doi: 10.1007/s11164-018-3297-0
20. [20]
  KAPTELJN F, SMGOREDJO L, ANDREML A, MOULIJN 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(3):173-189.
21. [21]
  LIU Q, FU Z, MA L, NIU H, LIU C, LI J, ZHANG Z. MnO_x-CeO₂ supported on Cu-SSZ-13:A novel SCR catalyst in a wide temperature range[J]. Appl Catal A:Gen, 2017,547:146-154. doi: 10.1016/j.apcata.2017.08.024
22. [22]
  ZAHNG Chuan, GUO Fang, XU Jun-qaing, QIN Ya-hua, XIE Jia-qing. Influence of Ce and Zr Modified Mn/ZSM-5 Catalyst on C₃H₆-SCR Reaction Performance[J]. J Chin Ceram Soc, 2019,47(4):486-493.
23. [23]
  PANAHI P N. MnO_x catalysts supported on γ-Al₂O₃, ZSM-5, and SAPO-34:Effect of support on the activity of Mn supported catalysts in NO abatement by NH₃[J]. Russ J Appl Chem, 2016,89(8):1365-1371. doi: 10.1134/S1070427216080243
24. [24]
  LUO Hang. Preparation of Mn/SAPO-34 molecular sieve catalyst and NH₃-SCR performance at low temperature[D]. Chongqing: Chongqing University, 2018.
25. [25]
  TANG Nan, HUANG Yan, LI Yuan-yuan, ZHAO Yong-qian, ZHOU Ting, ZHANG Jun-feng, YANG Liu-chun. Low temperature selective catalytic reduction of NO with NH₃ over Fe-Mn catalysts prepared by hydrothermal method[J]. J Mol Catal, 2018,32(3):240-248.
26. [26]
  JIN Q, SHEN Y, ZHU S, LI X, HU M. Promotional effects of erincorporation in CeO₂ (ZrO₂)/TiO₂ for selective catalytic reduction of NO by NH₃[J]. Chin J Catal, 2016,37(9):1521-1528. doi: 10.1016/S1872-2067(16)62450-6
27. [27]
  WAN Yi-ling, ZHANG Chuan-hui, GUO Yang-long, GUO Yun, LU Guan-zhong. Catalytic combustion of vinyl chloride emission over CeO₂-MnO_x catalyst[J]. Chin J Catal, 2012,33(3):557-562.
28. [28]
  HE Peng-fei, SHEN De-kui, LIU Guo-fu. NH₃-SCR performance of modified SAPO-34 molecular sieve[J]. J Southeast Univ:Nat Sci Ed, 2017,47(3):513-520.
29. [29]
  SHAN J H, LIU X Q, SUN L B, RONG C. Cu-Ce bimetal ion-exchanged Y zeolites for selective adsorption of thiophenic sulfur[J]. Energy Fuels, 2008,22(6):3955-3959. doi: 10.1021/ef800296n
30. [30]
  CHOI E Y, NAM I S, KIM Y G. TPD study of mordenite-type zeolites for selective catalytic reduction of NO by NH₃[J]. J Catal, 1996,161(2):597-604.
31. [31]
  WANG C, WANG J, WANG J Q, YU T, SHEN M Q, WANG W L, LI W. The effect of sulfate species on the activity of NH₃-SCR over Cu/SAPO-34[J]. Appl Catal B:Environ, 2017,204:239-249. doi: 10.1016/j.apcatb.2016.11.033
32. [32]
  CHEN Xiao-xue, SONG Min, MENG Fan-yue, WEI Yue-xing. Mechanism study on SO₂ poisoning of Fe_xMnCe₁-AC catalyst for low-temperature SCR[J]. CIESC J, 2019,70(8):3000-3010.
33. [33]
  WANG Xiao-bo, GUI Ke-ting. Low-temperature selective catalytic reduction of NO with NH₃ over Iron based catalysts[J]. J Eng Thermophys, 2013,34(9):1671-1674.
34. [34]
  QIAO J S, WANG N, WANG Z H, SUN W, SUN K N. Porous bimetallic Mn₂Co₁O_x catalysts prepared by a one-step combustion method for the low temperature selective catalytic reduction of NO_x with NH₃[J]. Catal Commun, 2015,72:111-115. doi: 10.1016/j.catcom.2015.09.023
35. [35]
  LIU G F, ZHANG W J, HE P F, GUAN S P, YUAN B, LI R, SUN Y, SHEN D K. H₂O and/or SO₂ tolerance of Cu-Mn/SAPO-34 catalyst for NO reduction with NH₃ at low temperature[J]. Catal, 2019,9(3)289. doi: 10.3390/catal9030289
36. [36]
  SHU Yun, ZHANG Fan, WANG Chang, SHI Ying-jie, ZHU Jin-wei. Sulfur resistance of rice husk based activated carbon catalyst for the low-temperature selective catalytic reduction of NO by NH₃[J]. Chin Environ Sci, 2019,39(11):4620-4627. doi: 10.3969/j.issn.1000-6923.2019.11.017
1. [1]
  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
2. [2]
  Jinpeng Du , Junlin Chen , Yulong Shan , Tongliang Zhang , Yu Sun , Zhongqi Liu , Xiaoyan Shi , Wenpo Shan , Yunbo Yu , Hong He . Insight into the effects of C₃H₆ on fresh and hydrothermally aged Cu-SSZ-39 catalysts. Chinese Chemical Letters, 2025, 36(3): 110019-. doi: 10.1016/j.cclet.2024.110019
3. [3]
  Jiayi Yang , Jianxiu Hao , Huacong Zhou , Quansheng Liu . “Gorgeous Transformation” of Carbon Dioxide into Cyclic Carbonates: Catalyst Types and Roles. University Chemistry, 2026, 41(2): 178-189. doi: 10.12461/PKU.DXHX202502105
4. [4]
  Feibin Wei , Yongfang Rao , Yu Huang , Wei Wang , Hui Mei . The new challenges for the development of NH₃-SCR catalysts under new situation of energy transition in power generation industry. Chinese Chemical Letters, 2024, 35(6): 108931-. doi: 10.1016/j.cclet.2023.108931
5. [5]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
6. [6]
  Wentao Xu , Xuyan Mo , Yang Zhou , Zuxian Weng , Kunling Mo , Yanhua Wu , Xinlin Jiang , Dan Li , Tangqi Lan , Huan Wen , Fuqin Zheng , Youjun Fan , Wei Chen . Bimetal Leaching Induced Reconstruction of Water Oxidation Electrocatalyst for Enhanced Activity and Stability. Acta Physico-Chimica Sinica, 2024, 40(8): 2308003-0. doi: 10.3866/PKU.WHXB202308003
7. [7]
  Chenyang WANG , Yiyan BAI , Wei ZHANG , Zhaorong LIU , Yuchun WANG . Performance of photo-assisted copper oxide catalyzed hydrolysis of ammonia borane to produce hydrogen. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 97-110. doi: 10.11862/CJIC.20250116
8. [8]
  Zhaoyu Wen , Na Han , Yanguang Li . Recent Progress towards the Production of H₂O₂ by Electrochemical Two-Electron Oxygen Reduction Reaction. Acta Physico-Chimica Sinica, 2024, 40(2): 2304001-0. doi: 10.3866/PKU.WHXB202304001
9. [9]
  Wenruo NI , Hongpeng LI , Yun ZHANG , Yiran TIAN , Jiehui RUI , Yingcheng TONG , Xiaolin PI , Zhenyan TANG . Research progress of ruthenium alloy catalysts in hydrogen evolution reaction. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 23-44. doi: 10.11862/CJIC.20250188
10. [10]
  Shuting KONG , Fengshi ZHANG , Zhiyi LU , Yanling LIU , Minglang YE , Zhengfang HU , Longsheng WANG , Bing HU , Haiying WANG . Research advance of the preparation of tributyl citrate catalyzed by supported heteropolyacid catalysts. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 441-452. doi: 10.11862/CJIC.20250303
11. [11]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
12. [12]
  Mei-Xia Yang , Zhen-Hong He , Long-Rui Wang , You-Xing Yang . Route for Turning Waste CH₄ and CO₂ into Valuable Products: Reforming for Syngas. University Chemistry, 2026, 41(2): 197-207. doi: 10.12461/PKU.DXHX202503012
13. [13]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
14. [14]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
15. [15]
  Yuying JIANG , Jia LUO , Zhan GAO . Development status and prospects of solid oxide cell high entropy electrode catalysts. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1719-1730. doi: 10.11862/CJIC.20250124
16. [16]
  Wang Wang , Yucheng Liu , Shengli Chen . Use of NiFe Layered Double Hydroxide as Electrocatalyst in Oxygen Evolution Reaction: Catalytic Mechanisms, Electrode Design, and Durability. Acta Physico-Chimica Sinica, 2024, 40(2): 2303059-0. doi: 10.3866/PKU.WHXB202303059
17. [17]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
18. [18]
  Shijie Ren , Mingze Gao , Rui-Ting Gao , Lei Wang . Bimetallic Oxyhydroxide Cocatalyst Derived from CoFe MOF for Stable Solar Water Splitting. Acta Physico-Chimica Sinica, 2024, 40(7): 2307040-0. doi: 10.3866/PKU.WHXB202307040
19. [19]
  Qi Wang , Yuqing Liu , Jiefei Wang , Yuan-Yuan Ma , Jing Du , Zhan-Gang Han . Catalysts for electrocatalytic dechlorination of chlorinated aromatic hydrocarbons: synthetic strategies, applications, and challenges. Acta Physico-Chimica Sinica, 2025, 41(10): 100120-0. doi: 10.1016/j.actphy.2025.100120
20. [20]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(699)
HTML views(71)

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

Performance of the modified Cu-Mn/SAPO-34 catalysts in the selective catalytic reduction of NOx by NH3

Metrics

通讯作者: 陈斌, bchen63@163.com

Performance of the modified Cu-Mn/SAPO-34 catalysts in the selective catalytic reduction of NO_x by NH₃