Citation: Rao XIAO, Jun-feng ZHANG, Ling-kui ZHAO. An ammonia-free denitration method: Direct reduction of NO_x over activated carbon promoted by Cu-K bimetals[J]. Journal of Fuel Chemistry and Technology, ;2022, 50(5): 628-640. doi: 10.1016/S1872-5813(21)60183-4 shu

An ammonia-free denitration method: Direct reduction of NO_x over activated carbon promoted by Cu-K bimetals

Rao XIAO ^{1, 2,} ,
Jun-feng ZHANG ^{1, 2,,} ,
Ling-kui ZHAO ^{1, 2}

1.
Department of Environmental Science and Engineering, College of Environment and Resources, Xiangtan University, Xiangtan 411105, China
2.
Hunan Provincial Environmental Protection of Engineering Technology Center of Air Complex Pollution control (XTU), Xiangtan 411105, China

Corresponding author: Jun-feng ZHANG, xtuzhjf@163.com
Received Date: 10 September 2021
Revised Date: 22 November 2021
Available Online: 9 June 2022

Figures(17)

As ammonia slip becomes more serious with the traditional deNO_x application, ammonia-free technologies have received more and more attention recently. Cu-K bimetal loaded activated carbon catalysts were prepared by equivalent-volume impregnation method for the direct reduction of NO and showed good NO reduction performance in a wide temperature range under temperature-programmed surface reactions (TPSRs) conditions in aerobic and anaerobic environments. The catalysts were characterized by BET, SEM, XRD, XPS, H₂-TPR, Raman and FT-IR techniques and the NO reduction mechanism was analyzed. Experimental results show that the active functional groups formed on the surface of activated carbon are the important intermediate products and play a key role in the reduction reaction. The presence of O₂ greatly promotes the formation of the intermediate, C(O) (Oxygen-containing functional groups on the carbon surface), leading to the increase reduction rate of NO. The bimetallic oxides catalysts are obviously effective to directly reduce NO. When the ratio of copper: potassium is 2∶1, the NO reduction efficiency is about 90% at 300 °C. The catalytic activity mainly depends on the redox cycle of CuO/Cu₂O, and the potassium inhibits the agglomeration of copper on the surface of carbon materials and enhances the catalytic reactivity of Cu.
- activated carbon,
- ammonia-free denitration,
- bimetal catalysis,
- Cu,
- K
1. [1]
  QIANG L, XIAO Y L, HONG W, QIAN Q H. Current situation and trend analysis of clean heating in north China[J]. Energy China,2021,1:17−22.
2. [2]
  CHANG Z. Research on development and engineering application of key technology of denitration of central heating boiler flue gas[D]. Nanjing: Southeast University, 2018.
3. [3]
  ZHANG X, FUNG J, LAU A, HOSSAIN, M. S. HUANG, W. Air quality and synergistic health effects of ozone and nitrogen oxides in response to China's integrated air quality control policies during 2015–2019[J]. Chemosphere,2020,268(2021):129385.
4. [4]
  HENDRYX M, ZULLIG K J, LUO J H. Impacts of coal use on health[J]. Annu Rev Publ Health,2020,41(1):397−415. doi: 10.1146/annurev-publhealth-040119-094104
5. [5]
  TAO Z, ZHEN H Z. Effects of nitrogen oxides and meteorological factors on ozone pollution in the ambient air of Rizhao city[J]. Energy Conserv Environ Prot,2019,2:80−81.
6. [6]
  YUE J S, NIAN X Z. Ammonia emission without participating in the reduction reaction of denitrification[J]. Sci Manag,2019,39(6):68−75.
7. [7]
  JIAN T, JIAN H Y, OU C, GUANG X Y. Excessive ammonia escape is another cause of aggravating atmospheric haze[J]. Energy China,2020,42(10):45−47.
8. [8]
  YAN W, XUE J D. Ammonia pollution: the neglected culprit of smog[J]. Ecolog Econ,2017,33(6):6−9.
9. [9]
  ZHANG Y, FENG Q, LI S, XU K, PEI Y, ZHU Y. Study on operation status of SCR denitration system in Chinese coal-fired power plants[J]. IOP Confer Ser: EES,2020,467(1):012119. doi: 10.1088/1755-1315/467/1/012119
10. [10]
  GAO Y W, PAN W G, GUO R T, ZHEN W L, ZHANG Q, SHI C L, ZHAO X. Review of denitration by SNCR in cement kilns[J]. Adv Mater Res,2013,864–867:1474−1477.
11. [11]
  CHEN H, LUO M, WANG Y, ZHANG Q, LIU Y. Influence of coal-fired boiler fly ash on SCR denitration catalysts and preventive measures[J]. J Combust Sci Technol,2017,23(3):200−211.
12. [12]
  YAO Y, GUI S, YANG J, WEI J, ZHANG W, LI P, XUE F, SU J, LIU X. Cause analysis and countermeasure of blockage in urea pyrolysis denitration system of coal-fired power plant[J]. IOP Confer Ser: EES,2021,651(2):022058. doi: 10.1088/1755-1315/651/2/022058
13. [13]
  ZHANG J. Research and application of dry flue gas denitration method for small coal-fired boiler[J]. Coal Chem Ind,2019,42(7):139−141.
14. [14]
  KE Y. Experimental study on the purification of NO_x by hot carbon reduction method[J]. Environ Prot Chem Ind,1984,3:4−47.
15. [15]
  MJ I G, LINARES S A, RADOVIC L R, SALINAS-MARTINEZ de LECEA C. NO reduction by activated carbons. 7. Some mechanistic aspects of uncatalyzed and catalyzed reaction[J]. Energy Fuels,1996,10(1):158−168. doi: 10.1021/ef950066t
16. [16]
  YANG J, MESTL G, HEREIN D, SCHLGL R, FIND J. Reaction of NO with carbonaceous materials: 1. Reaction and adsorption of NO on ashless carbon black[J]. Carbon,2000,38(5):715−727. doi: 10.1016/S0008-6223(99)00150-5
17. [17]
  SMITH R N, SWINEHART J, LESNINI D. The oxidation of cardon by nitric oxide[J]. J Phys Chem,1959,63(4):544−547.
18. [18]
  GRZYBEK T, KLINIK J, SAMOJEDEN B, SUPRUN V, PAPP H. Nitrogen-promoted active carbons as DeNO_x catalysts[J]. Catal Today,2008,137(2/4):228−234. doi: 10.1016/j.cattod.2007.11.009
19. [19]
  WANG Y, QIN N, CUI S, MA X, PENG S. Influence of biochar composition and micro-structure on the denitration of flue gases at high temperature[J]. Appl Sci-basel,2020,10(6):1920. doi: 10.3390/app10061920
20. [20]
  WU H X, CAI J, REN Q Q, XU J, CHU F H, LYU Q G. An efficient and economic denitration technology based on fuel pretreatment for cement cleaner production[J]. J Clean Prod,2020,272:122669. doi: 10.1016/j.jclepro.2020.122669
21. [21]
  LIN Y T, LI Y R, XU Z C, XIONG J, ZHU T Y. Transformation of functional groups in the reduction of NO with NH₃ over nitrogen-enriched activated carbons[J]. Fuel,2018,223(1):312−323.
22. [22]
  LI M X, YI Z J, LI N L, LI G W, ZHI Y L KAI W Z. Preparation and characterization of activated carbon modified by ferric oxide[J]. Carbon,2017,1:16−19.
23. [23]
  LI M X, KAI W Z. Preparation and characterization of copper oxide modified activated carbon[J]. Carbon,2017,3:24−32.
24. [24]
  ILLAN G M J, LINARES-SOLANO A, RADOVIC L R, SALINAS-MARTINEZ de LECEA C L. NO reduction by activated carbons. 4. Catalysis by calcium[J]. Energy Fuels,1995,9(1):112−118. doi: 10.1021/ef00049a017
25. [25]
  ILLAN G M J, LINARES-SOLANO A, SALINAS-MARTINEZ de LECEA C. NO reduction by activated carbon. 6. Catalysis by transition metals[J]. Energy Fuels,1995,9(6):976−983. doi: 10.1021/ef00054a007
26. [26]
  ILLANGOMEZ M J, LINARESSOLANO A, RADOVIC L R. NO reduction by activated carbons. 2. Catalytic effect of potassium[J]. Fuel Energy Abstracts,1995,36(3):97−103.
27. [27]
  SHU Y, ZHANG F, WANG F, WANG H M. Catalytic reduction of NO_x by biomass-derived activated carbon supported metals[J]. Chin J Chem Eng,2018,26(10):2077−2083. doi: 10.1016/j.cjche.2018.04.019
28. [28]
  TSCHAMBER V, BRILHAC] J F. Oxidation of carbon by NO_x, with particular reference to NO₂ and N₂O[J]. Fuel,2008,87:131−146. doi: 10.1016/j.fuel.2007.04.012
29. [29]
  BUENO-LÓPEZ A, SORIANO-MORA J M, GARCÍA-GARCÍA A. Study of the temperature window for the selective reduction of NO_x in O₂-rich gas mixtures by metal-loaded carbon[J]. Catal Commun,2006,7(9):678−684. doi: 10.1016/j.catcom.2006.02.010
30. [30]
  LEI Z, YAN J, FANG J, SHUI H, KANG S. Catalytic combustion of coke and NO reduction in-situ under the action of Fe, Fe-CaO and Fe-CeO₂[J]. Energy,2021,216:119246. doi: 10.1016/j.energy.2020.119246
31. [31]
  TIGHE C J, DENNIS J S, HAYHURST A N, TEIGG M. V. The reactions of NO with diesel soot, fullerene, carbon nanotubes and activated carbons doped with transition metals[J]. Proc Combust Inst,2009,32(2):1989−1996. doi: 10.1016/j.proci.2008.06.165
32. [32]
  YAMASHITA H, YAMADA H, TOMITA A. Reaction of nitric oxide with metal-loaded carbon in the presence of oxygen[J]. Appl Catal,1991,78(2):1−6. doi: 10.1016/0166-9834(91)80101-2
33. [33]
  BAILÓN-GARCÍA E, ELMOUWAHIDI A, RIBEIRO F, HENRIQUES C, PEREZ-CADENAS A F, MARÍN F C, MALDONADO-HÓDAR H J. Reduction of NO with new vanadium-carbon xerogel composites. Effect of the oxidation state of vanadium species[J]. Carbon,2020,156:194−204. doi: 10.1016/j.carbon.2019.09.047
34. [34]
  KIENER J, LIMOUSY L, JEGUIRIM M, LE MEINS J M, HAJJAR-GARREAU S, BIGOIN G, GHIMBEU C M. Activated carbon/transition metal (Ni, In, Cu) hexacyanoferrate nanocomposites for cesium adsorption[J]. Materials (Basel),2019,12(8):1253. doi: 10.3390/ma12081253
35. [35]
  YAN Y L, XIAN C L. Direct catalytic reduction of NO by zero-valent Iron nanocrystalline cluster supported on biomass activated carbon[J]. CIESC J,2019,70(3):1111−1119.
36. [36]
  LI X C, DONG Z, DOU J, YU J, TAHMASEBI A. Catalytic reduction of NO using iron oxide impregnated biomass and lignite char for flue gas treatment[J]. Fuel Process Technol,2016,148:91−98. doi: 10.1016/j.fuproc.2016.02.030
37. [37]
  YANG N, YU J L, DOU J X, TAHMASEBI A, SONG H, MOGHTADERI B, LUCAS J, WALL T. The effects of oxygen and metal oxide catalysts on the reduction reaction of NO with lignite char during combustion flue gas cleaning[J]. Fuel Process Technol,2016,152:102−107. doi: 10.1016/j.fuproc.2016.06.010
38. [38]
  ILLÁN-GÓMEZ M J, RAYMUNDO-PIÑERO E, GARĆIA-GARĆIA A, LINARES-SOLANO A, SALINAS-MARTÍNEZ de LECEA C. Catalytic NO_x reduction by carbon supporting metals[J]. Appl Catal B: Environ,1999,20:267−275. doi: 10.1016/S0926-3373(98)00119-2
39. [39]
  CATALAO R A, MALDONADO-HÓDAR F J, FERNANDES A, HENRIQUES C, RIBEIRO M F. Reduction of NO with metal-doped carbon aerogels[J]. Appl Catal B: Environ,2009,88(1/2):135−141. doi: 10.1016/j.apcatb.2008.09.019
40. [40]
  FENG B, LU G, WANG Y Q, GUO Y, GUO Y. Cocatalytic effect of potassium on NO reduction by activated carbon catalyzed by copper oxide[J]. Chin J Catal,2011,32(5):853−861.
41. [41]
  VENEZUELA P, LAZZERI M, MAURI F. Theory of double-resonant Raman spectra in graphene: Intensity and line shape of defect-induced and two-phonon bands[J]. Phys Rev,2011,84(3):1−25.
42. [42]
  ZHANG G Q, ZHONG L, ZHENG H Y, FU T J, JU Y B, WANG Y C. Influence of the surface oxygenated groups of activated carbon on preparation of a nano Cu/AC catalyst and heterogeneous catalysis in the oxidative carbonylation of methanol[J]. Appl Catal B: Environ,2015,179:95−105. doi: 10.1016/j.apcatb.2015.05.001
43. [43]
  TENG H, SUUBERG E M. Chemisorption of nitric oxide on char. 1. Reversible nitric oxide sorption[J]. J Chem Inform,1993,97(2):478−483.
44. [44]
  TENG H, SUUBERG E M. Chemisorption of nitric oxide on char. 2. Irreversible carbon oxide formation[J]. Ind Eng Chem Res,1993,32(3):416−423. doi: 10.1021/ie00015a004
45. [45]
  ULÁN-GÓMEZ M J, LINARES SOLANO A, RADOVIC A L R, SALINAS-MARTÍNEZ de LECEA C. No reduction by activated carbons. some mechanistic aspects of uncatalyzed and catalyzed reaction[J]. Coal Sci Technol,1995,24(1):1799−1802.
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

An ammonia-free denitration method: Direct reduction of NOx over activated carbon promoted by Cu-K bimetals

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通讯作者: 陈斌, bchen63@163.com

An ammonia-free denitration method: Direct reduction of NO_x over activated carbon promoted by Cu-K bimetals