Citation: 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]. Journal of Fuel Chemistry and Technology, ;2019, 47(9): 1137-1145. shu

Effect of sulfuric acid modification of Al₂O₃ support on the SCR performance of MnCe/Al₂O₃ catalysts

ZHANG Qiang ^1,, ,
LIU Lu ² ,
YU Meng-yun ¹ ,
Zhou ZHOU ¹

1.
State Key Laboratory of Heavy Oil Processing in China University of Petroleum(East China), Qingdao 266580, China
2.
Heilongjiang New Harmony Union Biotechnology Co. Ltd, Suihua 152000, China

Corresponding author: ZHANG Qiang, xyz@upc.edu.cn
Received Date: 4 April 2019
Revised Date: 15 July 2019

Fund Project: the National Natural Science Foundation of China 21406270The project was supported by the National Natural Science Foundation of China (21406270)

Figures(8)

With unmodified and modified Al₂O₃ as the support, a series of Mn-Ce catalysts were prepared by impregnation method and characterized by XRD, BET, NH₃-TPD, H₂-TPR and FT-IR. The catalytic performance in the NH₃-SCR of NO_x was investigated. The results show that the sulfuric acid modification to the support decreased the metal dispersion and weakened the oxidization property of the catalyst, increased the concentration of acid sites, especially, B acid sites. Besides, the optimum temperature window ranges for SCR of the modified catalyst moved to higher temperature and broadened, and increased with the increase of modified liquid concentration. The unmodified catalyst and the catalyst modified by 0.2 mol/L solution had same SCR reactivity within the temperature range of 200-250 ℃. However, the modified catalyst showed the best resistance to SO₂ and H₂O and presented 70% NO conversion at 250 ℃.
- NH₃-SCR,
- Mn-CeO_x,
- Al₂O₃,
- sulfuric acid-modified
1. [1]
  JI Sheng-xiao, ZHANG Wei-jian, ZHENG Yu-ying, ZHU Jian-feng. Low-temperature combustion synthesis of the Mn-CeO_x catalyst and its performance in the selective catalytic reduction of NO_x by NH₃[J]. J Fuel Chem Technol, 2019,47(2):224-235. doi: 10.3969/j.issn.0253-2409.2019.02.012
2. [2]
  KANG M, PARK J H, CHOI J S, PARK E D, YIE J E. Low-temperature catalytic reduction of nitrogen oxides with ammonia over supported manganese oxide catalysts[J]. Korean J Chem Eng, 2007,24(1):191-195.
3. [3]
  MOUSAVIA S M, PANAHI P N. Modeling and optimization of NH₃-SCR performance of MnO_x/γ-alumina nanocatalysts by response surface methodology[J]. J Taiwan Inst Chem E, 2016,69:68-77. doi: 10.1016/j.jtice.2016.09.033
4. [4]
  GUO Jing, LI Cai-ting, LU Pei, CUI Hua-fei, PENG Dun-liang, WEN Qing-bo. Research on SCR denitrification of MnO_x/Al₂O₃ modified by CeO₂ and its mechanism at low temperature[J]. Environ sci, 2011(8):2240-2246.
5. [5]
  JIN R B, LIU Y, WU Z B, WANG H Q, GU T T. Low-temperature selective catalytic reduction of NO with NH₃ over Mn-Ce oxides supported on TiO₂ and Al₂O₃:A comparative study[J]. Chemosphere, 2010,78(9):1160-1166. doi: 10.1016/j.chemosphere.2009.11.049
6. [6]
  KANG M, PARK E D, KIM J M, YIE J E. Cu-Mn mixed oxides for low temperature NO reduction with NH₃[J]. Catal Today, 2006,111(3/4):236-241.
7. [7]
  QI G, YANG R T. Low-temperature selective catalytic reduction of NO with NH₃ over iron and manganese oxides supported on titania[J]. App Catal B:Environ, 2003,44(3):217-225. doi: 10.1016/S0926-3373(03)00100-0
8. [8]
  NOTOYA F, SU C, SASAOKA E, NOJIMA S. Effect of SO₂ on the low-temperature selective catalytic reduction of nitric oxide with ammonia over TiO₂, ZrO₂, and Al₂O₃[J]. Ind Eng Chem Res, 2001,40(17):3732-3739. doi: 10.1021/ie000972f
9. [9]
  XIE G, LIU Z, ZHU Z, LIU Q, GE J, HUANG Z. Simultaneous removal of SO₂ and NO_x from flue gas using a CuO/Al₂O₃ catalyst sorbent Ⅱ. Promotion of SCR activity by SO₂ at high temperatures[J]. J Catal, 2004,224(1):42-49.
10. [10]
  YAO X J, WANG Z, YU S H, YANG F, DONG L. Acid pretreatment effect on the physicochemical property and catalytic performance of CeO₂ for NH₃-SCR[J]. Appl Catal A:Gen, 2017,542:282-288. doi: 10.1016/j.apcata.2017.06.003
11. [11]
  ZHANG L, ZOU W X, MA K L, CAO Y, XIONG Y, WU S G, TANG C J, GAO F, DONG L. Sulfated temperature effects on the catalytic activity of CeO₂ in NH₃-selective catalytic reduction conditions[J]. J Phys Chem C, 2015,119(2):1155-1163. doi: 10.1021/jp511282c
12. [12]
  LI Jing. Research on low-temperature Mn-based deNO_x catalyst[D]. Beijing: Institute of Petrochemical Technology, 2015.
13. [13]
  ZHAO W W, LI C T, LU P, WEN Q B, ZHAO Y P, ZHANG X, FAN C Z, TAO S S. Iron, lanthanumand manganese oxides loaded onγ-Al₂O₃ for selective catalytic reduction of NO with NH₃ at low temperature[J]. Environ Technol, 2012,34(1/4):81-90.
14. [14]
  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):1388-1394. doi: 10.3969/j.issn.0253-2409.2016.11.016
15. [15]
  ETTIREDDY P R, ETTIREDDY N, MAMEDOV S, BOOLCHAND P, SMIRNIOTIS P G. Surface characterization studies of TiO₂ supported manganese oxide catalysts for low temperature SCR of NO with NH₃[J]. Appl Catal B:Environ, 2007,76(1):123-134.
16. [16]
  AN Zhong-yi, ZHUO Yu-qun, CHEN Chang-he. Influence of calcination temperature on the catalytic activity of Mn/TiO₂ for NO oxidation[J]. J Fuel Chem Technol, 2014,42(3):370-377.
17. [17]
  ZHANG Zhi-an, YANG Bang-chao, DENG Mei-gen, HU Yong-da, WANG Bin-hua. Synthesis and characterization of nanostructured MnO₂ for supercapacitor[J]. Acta Chim Sin(Chin Ed), 2004,62(17):1617-1620. doi: 10.3321/j.issn:0567-7351.2004.17.008
18. [18]
  DU C H, QIN Y N, HE Y F, SHI X M, MA Z. Preparation and characterization of novel solid acid of sulfated anodized aluminium[J]. J Mol Catal, 2003,17(3):183-187.
19. [19]
  HOSSEINPOUR N, MORTAZAVI Y, BAZYARI A, KHODADADI A A. Synergetic effects of Y-zeolite and amorphous silica-alumina as main FCC catalyst components on triisopropylbenzene cracking and coke formation[J]. Fuel Process Technol, 2009,90(2):171-179. doi: 10.1016/j.fuproc.2008.08.013
20. [20]
  WANG Bin, ZHANG Qiang, HAN Dong-min, LI Chun-yi, YANG Chao-he, SHAN Hong-hong. Effects of acid strength of matrix in catalyst on the yield of small olefins during the catalytic cracking process[J]. Acta Pet Sin(Pet Process Sect), 2016,32(4):666-673. doi: 10.3969/j.issn.1001-8719.2016.04.002
21. [21]
  MORALES A, AGUDELO M M R D, HERNÁNDEZ F. Adsorption mechanism of phosphorus on alumina[J]. Appl Catal, 1988,41(41):261-271.
22. [22]
  ZHANG H, ZOU Y, PENG Y. Influence of sulfation on CeO₂-ZrO₂ catalysts for NO reduction with NH₃[J]. Chin J Catal, 2017,38(1):160-167. doi: 10.1016/S1872-2067(16)62581-0
23. [23]
  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.
24. [24]
  FAN Yin-ming. Experimental and molecular simulation study on cerium presence in the framework and the surface of Mn/SAPO-34 resistance to SO₂ and H₂O in NH₃-SCR at low temperature[D]. Guangzhou: South China University of Technology, 2017.
25. [25]
  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
26. [26]
  SUN Lu-shi, ZHAO Qing-sen, XIANG Jun, SHI Jin-ming, WANG Le-le, HU Song, SU Sheng. Adsorption of NO and NH₃ over CuO/γ-Al₂O₃ catalyst by DRIFTS[J]. CIESC J, 2009,60(2):444-450. doi: 10.3321/j.issn:0438-1157.2009.02.027
27. [27]
  XIE Tian. A thesis submitted in partial fulfillment of the requirements for the degree of master in engineering[D]. Wuhan: Huazhong University of Science and Technology, 2011.
28. [28]
  QI G, YANG R T. Characterization and FT-IR studies of MnO_x-CeO₂ catalyst for low-temperature selective catalytic reduction of NO with NH₃[J]. J Phys Chem B, 2004,108(40):15738-15747. doi: 10.1021/jp048431h
29. [29]
  KIJLSTRA W S, BRANDS D S, SMIT H I, POELS E K, BLIEK A. Mechanism of the selective catalytic reduction of NO with NH₃ over MnO_x/Al₂O₃ Ⅱ. Reactivity of adsorbed NH₃ and NO complexes[J]. J Catal, 1997,171(1):219-230.
30. [30]
  TOPSOE N Y, TOPSOE H, DUMESIC J A. Vanadia/titania catalysts for selective catalytic reduction (SCR) of nitric-oxide by ammonia:Ⅰ. Combined temperature-programmed in-situ FT-IR and on-line Mass-Spectroscopy studies[J]. J Catal, 1995,151(1):226-240. doi: 10.1006/jcat.1995.1024
31. [31]
  TOPSØE 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
1. [1]
  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
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]
  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
4. [4]
  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
5. [5]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
6. [6]
  Qiuping Liu , Yongxian Fan , Wenxian Chen , Mengdi Wang , Mei Mei , Genrong Qiang . Design of Ideological and Political Education for the Preparation Experiment of Ferrous Sulfate. University Chemistry, 2024, 39(2): 116-120. doi: 10.3866/PKU.DXHX202309083
7. [7]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
8. [8]
  Le Ye , Wei-Xiong Zhang . Structural phase transition in a new organic-inorganic hybrid post-perovskite: (N,N-dimethylpyrrolidinium)[Mn(N(CN)2)3]. Chinese Journal of Structural Chemistry, 2024, 43(6): 100257-100257. doi: 10.1016/j.cjsc.2024.100257
9. [9]
  Jijoe Samuel Prabagar , Kumbam Lingeshwar Reddy , Dong-Kwon Lim . Visible-light responsive gold nanoparticle and nano-sized Bi2O3-x sheet heterozygote structure for efficient photocatalytic conversion of N2 to NH3. Chinese Journal of Structural Chemistry, 2025, 44(4): 100564-100564. doi: 10.1016/j.cjsc.2025.100564
10. [10]
  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
11. [11]
  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
12. [12]
  Mingjiao Lu , Zhixing Wang , Gui Luo , Huajun Guo , Xinhai Li , Guochun Yan , Qihou Li , Xianglin Li , Ding Wang , Jiexi Wang . Boosting the performance of LiNi_0.90Co_0.06Mn_0.04O₂ electrode by uniform Li₃PO₄ coating via atomic layer deposition. Chinese Chemical Letters, 2024, 35(5): 108638-. doi: 10.1016/j.cclet.2023.108638
13. [13]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
14. [14]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
15. [15]
  Siyu HOU , Weiyao LI , Jiadong LIU , Fei WANG , Wensi LIU , Jing YANG , Ying ZHANG . Preparation and catalytic performance of magnetic nano iron oxide by oxidation co-precipitation method. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1577-1582. doi: 10.11862/CJIC.20230469
16. [16]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
17. [17]
  Lijun Dong , Pengcheng Du , Guangnong Lu , Wei Wang . Exploration and Practice of Independent Design Experiments in Inorganic and Analytical Chemistry: A Case Study of “Preparation and Composition Analysis of Tetraammine Copper(II) Sulfate”. University Chemistry, 2024, 39(4): 361-366. doi: 10.3866/PKU.DXHX202310041
18. [18]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267
19. [19]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
20. [20]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1160)
HTML views(117)

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

Effect of sulfuric acid modification of Al2O3 support on the SCR performance of MnCe/Al2O3 catalysts

Metrics

通讯作者: 陈斌, bchen63@163.com

Effect of sulfuric acid modification of Al₂O₃ support on the SCR performance of MnCe/Al₂O₃ catalysts