Citation: CAO Yue, CHEN Chuan-min, LIU Song-tao, JIA Wen-bo. Study on the Hg⁰ and NH₃ oxidation performance of copper modified attapulgite catalysts[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(10): 1171-1178. shu

Study on the Hg⁰ and NH₃ oxidation performance of copper modified attapulgite catalysts

CAO Yue ^1,2 ,
CHEN Chuan-min ^1,2,, ,
LIU Song-tao ^1,2,, ,
JIA Wen-bo ^1,2

1.
Hebei Key Lab of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China
2.
MOE Key Laboratory of Resources and Environmental Systems Optimization, North China Electric Power University, Beijing 102206, China

Corresponding author: CHEN Chuan-min, hdccm@126.com LIU Song-tao, taonyliu@163.com
Received Date: 10 September 2020
Revised Date: 28 September 2020

Fund Project: The Fundamental Research Funds for the Central Universities 2018MS118The project was supported by the National Natural Science Foundation of China (51976060) and the Fundamental Research Funds for the Central Universities (2018MS118).the National Natural Science Foundation of China 51976060

Figures(10)

A copper-modified attapulgite (Cu₃-ATP) catalyst with both mercury oxidation and ammonia oxidation activities was prepared by an improved wet impregnation method. Several characterization including SEM, H₂-TPR and NH₃-TPD were performed on it, and its mercury oxidation and ammonia oxidation performance were tested at 150-400 ℃. The results show that the copper species is successfully loaded on ATP surface, which significantly improves the redox ability of the catalyst, increases the strong acid sites and partial strong acid sites on the surface, and thus promotes the oxidation of Hg⁰ and NH₃. HCl plays an important role in Hg⁰ oxidation. High temperature is not conducive to the Hg⁰ oxidation reaction, but can promote the oxidation of NH₃. At 350 ℃, the oxidation efficiencies of Hg⁰ and NH₃ over Cu₃-ATP are both above 90%. Experiments on the influencing factors show that NH₃ has an obvious inhibitory effect on mercury oxidation at high space velocity, while low concentrations of Hg⁰ and HCl have no significant influence on ammonia oxidation. When the gas hourly space velocity (GHSV) is lower than 5×10⁴ h^-1, Cu₃-ATP can simultaneously oxidize NH₃ and Hg⁰. In addition, the mercury oxidation reaction shows good sulfur resistance and water resistance, but SO₂ has a certain inhibitory effect on ammonia oxidation.
- copper,
- attapulgite,
- mercury oxidation,
- ammonia oxidation,
- bifunctional catalyst
1. [1]
  GOLDING G R, KELLY C A, SPARLING R, LOEWEN P C, BARKAY T. Evaluation of mercury toxicity as a predictor of mercury bioavailability[J]. Environ Sci Technol, 2007,41(16):5685-5692. doi: 10.1021/es070138i
2. [2]
  PACYNA E G, PACYNA J M, SUNDSETH K, MUNTHE J, KINDBOM K, WILSON S, STEENHUISEN F, MAXSON P. Global emission of mercury to the atmosphere from anthropogenic sources in 2005 and projections to 2020[J]. Atmos Environ, 2010,44(20):2487-2499. doi: 10.1016/j.atmosenv.2009.06.009
3. [3]
  LIU Y, ADEWUYI Y G. A review on removal of elemental mercury from flue gas using advanced oxidation process:Chemistry and process[J]. Chem Eng Res Des, 2016,112:199-250. doi: 10.1016/j.cherd.2016.06.024
4. [4]
  LI Jian-rong, HE Chi, SHANG Xue-song, CHEN Jin-sheng, YU Xiao-wei, YAO Yuan-jun. Oxidation efficiency of elemental mercury in flue gas by SCR De-NO_x catalysts[J]. J Fuel Chem Technol, 2012,40(2):241-246.
5. [5]
  EOM Y, JEON S H, NGO T A, KIM J, LEE T G. Heterogeneous mercury reaction on a selective catalytic reduction (SCR) catalyst[J]. Catal Lett, 2008,121(3):219-225.
6. [6]
  KAMATA H, UENO S, NAITO T, YUKIMURA A. Mercury oxidation over the V₂O₅(WO₃)/TiO₂ commercial SCR catalyst[J]. Ind Eng Chem Res, 2015,47(21):8136-8141.
7. [7]
  DRANGA B, LAZAR L, KOESER H. Oxidation catalysts for elemental mercury in flue gases-A review[J]. Catalysts, 2012,2(4):139-170.
8. [8]
  WANG Y, CHANG H, SHI C, DUAN L, LI J, ZHANG G, GUO L, YOU Y. Novel Fe-Ce-O mixed metal oxides catalyst prepared by hydrothermal method for Hg⁰ oxidation in the presence of NH₃[J]. Catal Commun, 2017,100:210-213.
9. [9]
  LI H, ZHANG W, WANG J, YANG Z, LI L, SHIH K. Coexistence of enhanced Hg⁰ oxidation and induced Hg²⁺ reduction on CuO/TiO₂ catalyst in the presence of NO and NH₃[J]. Chem Eng J, 2017,330:1248-1254. doi: 10.1016/j.cej.2017.08.043
10. [10]
  WU W, ZENG Z, LU P, XING Y, YUE H, LI R. Simultaneous oxidation of Hg⁰ and NH₃-SCR of NO by nanophase Ce_xZr_yMn_zO₂ at low temperature:the interaction and mechanism[J]. Environ Sci Pollut R, 2018,25:14471-14485. doi: 10.1007/s11356-018-1657-3
11. [11]
  ZHAO B, YI H, TANG X, LI Q, LIU D, GAO F. Using CuO-MnO_x/AC-H as catalyst for simultaneous removal of Hg⁰ and NO from coal-fired flue gas[J]. J Hazard Mater, 2019,364:700-709. doi: 10.1016/j.jhazmat.2018.04.001
12. [12]
  LI H, WU C, LI Y, ZHANG J. Superior activity of MnO_x-CeO₂/TiO₂ catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures[J]. Appl Catal B:Environ, 2012:111-388.
13. [13]
  ZHANG S, ZHANG Q, ZHAO Y, YANG J, XU Y, ZHANG J. Enhancement of CeO₂ modified commercial SCR catalyst for synergistic mercury removal from coal combustion flue gas[J]. RSC Adv, 2020,10:25325-25338. doi: 10.1039/D0RA04350H
14. [14]
  ZHANG S, ZHAO Y, YANG J, ZHANG Y, SUN P, YU X, ZHANG J, ZHENG C. Simultaneous NO and mercury removal over MnO_x/TiO₂ catalyst in different atmospheres[J]. Fuel Process Technol, 2017,166:282-290.
15. [15]
  XU H, QU Z, ZONG C, QUAN F, MEI J, YAN N. Catalytic oxidation and adsorption of Hg⁰ over low-temperature NH₃-SCR LaMnO₃ perovskite oxide from flue gas[J]. Appl Catal B:Environ, 2016,186:30-40.
16. [16]
  CHEN W, MA Y, YAN N, QU Z, YANG S, XIE J, GUO Y, HU L, JIA J. The co-benefit of elemental mercury oxidation and slip ammonia abatement with SCR-Plus catalysts[J]. Fuel, 2014,133:263-269. doi: 10.1016/j.fuel.2014.04.086
17. [17]
  SHI Bo-wen. Preparation and characterization of palygorskite supported transition metal oxides catalyst for low-temperature selected catalytic reduction(SCR) of NO by NH₃[D]. Hefei: Hefei University of Technology, 2012.
18. [18]
  CHEN Hao, HUANG Ya-ji, DONG Lu, CAO Jian-hua, XIA Zhi-peng, QIN Wen-hui. Study on the preparation of magnetic attapulgite and its mercury removal performance[J]. J Fuel Chem Technol, 2018,46(11):1392-1400.
19. [19]
  CHEN T, LIU H, LI J, CHEN D, CHANG D, KONG D, FROST R. Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite:Change of surface acid-alkali properties[J]. Chem Eng J, 2011,166(3):1017-1021.
20. [20]
  HAN Fen-nv. Preparation of SCR catalyst supported on attapulgite and its performance of denitrification and mercury removal[D]. Nanjing: Nanjing University of Science Technology 2019.
21. [21]
  LU Yu, WU Fei, ZHANG Qiu-xiang, MA Hai-bo, LU Hong-bin, XU Qi. Molten salt synthesis of Fe₂O₃-ATP for catalytic oxidation of elemental mercury[J]. Appl Chem Ind, 2017,46(3):405-408.
22. [22]
  SHI D, LU Y, TANG Z, HAN F, CHEN R, XU Q. Removal of elemental mercury from simulated flue gas by cerium oxide modified attapulgite[J]. Korean J Chem Eng, 2014,31(8):1405-1412.
23. [23]
  CHEN C, CAO Y, LIU S, JIA W. The catalytic properties of Cu modified attapulgite in NH₃-SCO and NH₃-SCR reactions[J]. Appl Surf Sci, 2019,480:537-547.
24. [24]
  RUTKOWSKA M, PIWOWARSKA Z, MICEK E, CHMIELARZ L. Hierarchical Fe-, Cu- and Co-Beta zeolites obtained by mesotemplate-free method. Part Ⅰ:Synthesis and catalytic activity in N₂O decomposition[J]. Microporous Mesoporous Mater, 2015,209:54-65. doi: 10.1016/j.micromeso.2014.10.011
25. [25]
  LI Y, DENG J, SONG W, LIU J, ZHAO Z, GAO M, WEI Y, ZHAO L. Nature of Cu species in Cu-SAPO-18 catalyst for NH₃-SCR:Combination of experiments and DFT calculations[J]. J Phys Chem C, 2016,120(27):14669-14680. doi: 10.1021/acs.jpcc.6b03464
26. [26]
  WANG J, YU T, WANG X, QI G, XUE J, SHEN M, LI W. The influence of silicon on the catalytic properties of Cu/SAPO-34 for NO_x reduction by ammonia-SCR[J]. Appl Catal B:Environ, 2012,127:137-147. doi: 10.1016/j.apcatb.2012.08.016
27. [27]
  VALYON J, HALL W K. Effects of reduction and reoxidation on the infrared spectra from Cu-Y and Cu-ZSM-5 zeolites[J]. J Phys Chem, 1993,97(27):7054-7060.
28. [28]
  SULTANA A, NANBA T, HANEDA M, SASAKI M, HAMADA H. Influence of co-cations on the formation of Cu⁺ species in Cu/ZSM-5 and its effect on selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B:Environ, 2010,101(1):61-67.
29. [29]
  RICHTER M, FAIT M J G, ECKELT R, SCHREIER E, SCHNEIDER M, POHL M M, FRICKE R. Oxidative gas phase carbonylation of methanol to dimethyl carbonate over chloride-free Cu-impregnated zeolite Y catalysts at elevated pressure[J]. Appl Catal B:Environ, 2007,73(3):269-281.
30. [30]
  YAMAGUCHI A, AKIHO H, ITO S. Mercury oxidation by copper oxides in combustion flue gases[J]. Powder Technology, 2008,180(1/2):222-226.
31. [31]
  LI H, WU S, WU C, WANG J, LI L, SHIH K. SCR atmosphere induced reduction of oxidized mercury over CuO-CeO₂/TiO₂ catalyst[J]. Environ Sci Technol, 2015,49(12):7373-7379. doi: 10.1021/acs.est.5b01104
32. [32]
  CHEN C, CAO Y, LIU S, JIA W. The effect of SO₂ on NH₃-SCO and SCR properties over Cu/SCR catalyst[J]. Appl Surf Sci, 2020,507145153.
33. [33]
  JABŁOHSKA M, PALKOVITS R. Copper based catalysts for the selective ammonia oxidation into nitrogen and water vapour-Recent trends and open challenges[J]. Appl Cataly B:Environ, 2016,181:332-351.
34. [34]
  HE S, ZHANG C, YANG M, ZHANG Y, XU W, CAO N, HE H. Selective catalytic oxidation of ammonia from MAP decomposition[J]. Sep Purif Technol, 2007,58(1):173-178.
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Study on the Hg⁰ and NH₃ oxidation performance of copper modified attapulgite catalysts