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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2017, Vol. 11 Issue (2) : 4     https://doi.org/10.1007/s11783-017-0906-x
RESEARCH ARTICLE |
NO oxidation over Co-La catalysts and NOx reduction in compact SCR
Tiejun Zhang1,Jian Li1,2(),Hong He1,2,Qianqian Song1,Quanming Liang1
1. Key Laboratory of Beijing on Regional Air Pollution Control, Beijing University of Technology, Beijing 100124, China
2. Beijing Key Laboratory for Green Catalysis and Separation, Beijing University of Technology, Beijing 100124, China
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Abstract

The Co-La catalyst (pH= 1) exhibited maximum NO conversion of 43% at 180°C.

Acid modified catalyst enhanced the resistance to SO2.

The formed sulfates may block the pore structure of the catalyst.

The NO conversion of compact SCR was 91% at 180°C at the highest space velocity.

A series of Co-La catalysts were prepared using the wet impregnation method and the synthesis of catalysts were modified by controlling pH with the addition of ammonium hydroxide or oxalic solution. All the catalysts were systematically investigated for NO oxidation and SO2 resistance in a fixed bed reactor and were characterized by Brunanuer–Emmett–Teller (BET) method, Fourier Transform infrared spectroscopy (FTIR), X–ray diffraction (XRD), Thermogravimetric (TG) and Ion Chromatography (IC). Among the catalysts, the one synthesized at pH= 1 exhibited the maximum NO conversion of 43% at 180°C. The activity of the catalyst was significantly suppressed by the existence of SO2 (300 ppm) at 220°C. Deactivation may have been associated with the generation of cobalt sulfate, and the SO2 adsorption quantity of the catalyst might also have effected sulfur resistance. In the case of the compact selective catalytic reduction (SCR), the activity increased from 74% to 91% at the highest gas hourly space velocity (GHSV) of 300000 h1 when the NO catalyst maintained the highest activity, in excess of 50% more than that of the standard SCR.

Keywords NO catalytic oxidation      pH effect      Low temperature      Sulfur dioxide      High space velocity      SCR     
Corresponding Authors: Jian Li   
Issue Date: 10 April 2017
 Cite this article:   
Tiejun Zhang,Jian Li,Hong He, et al. NO oxidation over Co-La catalysts and NOx reduction in compact SCR[J]. Front. Environ. Sci. Eng., 2017, 11(2): 4.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-017-0906-x
http://journal.hep.com.cn/fese/EN/Y2017/V11/I2/4
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Tiejun Zhang
Jian Li
Hong He
Qianqian Song
Quanming Liang
Fig.1  Experimental apparatus for the catalytic testing: (a) 1 N2, 2 O2, 3 NO, 4 SO2, 5 mass flow meter (D08 – 4B/ZM, qixinghuachuang Co., Ltd. Beijing, China) , 6 mixing drum, 7 quartz tube reactor, 8 tubular reactor, 9 thermocouple, 10 flue gas analyzer (Testo 350, Testo Co., Germany), 11 temperature controller (CKW – 1100, Chaoyang Automatic Factory, Beijing, China); (b) 1 N2, 2 O2, 3 NO, 4 mass flow meter (D08 – 4B/ZM, qixinghuachuang Co., Ltd. Beijing, China), 5 mixing drum, 6 thermocouple, 7 quartz tube reactor, 8 tubular reactor, 9 temperature controller, 10 flue gas analyzer (Testo 350, Testo Co., Germany), 11 NH3
Fig.2  NO oxidation performance of different catalysts from pH= 1 to pH= 14: (a) pH=1–7, (b) pH=8–14

Reaction condition: [NO] = 700 ppm, [O2] = 5 vol%, N2 balance, GHSV= 27000 h-1

Fig.3  Effect of SO2 on the activity of catalysts with different pH: (a) effect of SO2 on NO conversion, (b) breakthrough curves of SO2

Reaction conditions: [NO] = 700 ppm; [O2] = 5 vol%, [SO2] = 300 ppm, N2 balance, GHSV= 27000 h-1

pH before sulfurresistance test after sulfurresistance test
surface area/(m2·g-1) pore volume/(cm3·g-1) pore diameter/nm surface area/(m2·g-1)
pH=1 74 0.28 16 69
pH=3–4 70 0.27 16 68
pH=6 67 0.27 16 66
pH=8 81 0.25 11 67
pH=10 81 0.26 12 77
pH=13–14 84 0.29 10 81
Tab.1  Micro-structure of catalysts
Fig.4  FT-IR and ion chromatography spectra of the catalyst: (a) FTIR spectra of the catalyst, (b) IC spectra of the fresh catalyst, (c) IC spectra of the spent catalyst
Fig.5  XRD patterns of fresh Co-La and the catalyst after reacting under SO2: (a) catalyst (pH= 1), (b) catalyst (pH= 1) after sulfur test, (c) catalyst (pH= 10), (d) catalyst (pH= 10) after sulfur test
Fig.6  Thermal gravimetric analysis of fresh catalysts and poisoned catalysts
Fig.7  NO conversion of the compact SCR
1 Jin Y Y, Li Y Y, Liu F Q. Combustion effects and emission characteristics of SO2, CO, NOx and heavy metals during co-combustion of coal and dewatered sludge. Frontiers of Environmental Science & Engineering, 2016, 10(1): 201–210
https://doi.org/10.1007/s11783-014-0739-9
2 Li J H, Peng Y, Chang H Z, Li X, Crittenden J C, Hao J M. Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources. Frontiers of Environmental Science & Engineering, 2016, 10(3): 413–427
https://doi.org/10.1007/s11783-016-0832-3
3 Koebel M, Madia G, Elsener M. Selective catalytic reduction of NO and NO2 at low temperatures. Catalysis Today, 2002, 73(3–4): 239–247
https://doi.org/10.1016/S0920-5861(02)00006-8
4 Irfan M F, Goo J H, Kim S D. Co3O4 based catalysts for NO oxidation and NOx reduction in fast SCR process. Applied Catalysis B: Environmental, 2008, 78(3–4): 267–274
https://doi.org/10.1016/j.apcatb.2007.09.029
5 Grossale A, Nova I, Tronconi E, Chatterjee D, Weibel M. The chemistry of the NO/NO2–NH3 “fast” SCR reaction over Fe-ZSM5 investigated by transient reaction analysis. Journal of Catalysis, 2008, 256(2): 312–322
https://doi.org/10.1016/j.jcat.2008.03.027
6 Li K, Tang X, Yi H, Ning P, Song J, Wang J. Mechanism of catalytic oxidation of NO over Mn-Co-Ce-Ox catalysts with the aid of nonthermal plasma at low temperature. Industrial & Engineering Chemistry Research, 2011, 50(19): 11023–11028
https://doi.org/10.1021/ie200957w
7 Yung M M, Holmgreen E M, Ozkan U S. Cobalt-based catalysts supported on titania and zirconia for the oxidation of nitric oxide to nitrogen dioxide. Journal of Catalysis, 2007, 247(2): 356–367
https://doi.org/10.1016/j.jcat.2007.02.020
8 Dawody J, Skoglundh M, Fridell E. The effect of metal oxide additives (WO3, MoO3, V2O5, Ga2O3) on the oxidation of NO and SO2 over Pt/Al2O3 and Pt/BaO/Al2O3 catalysts. Journal of Molecular Catalysis A Chemical, 2004, 209(1–2): 215–225
https://doi.org/10.1016/j.molcata.2003.08.025
9 Li L D, Shen Q, Cheng J, Hao Z P. Catalytic oxidation of NO over TiO2 supported platinum clusters I. Preparation, characterization and catalytic properties. Applied Catalysis B: Environmental, 2010, 93(3–4): 259–266
https://doi.org/10.1016/j.apcatb.2009.09.037
10 Li L D, Shen Q, Cheng J, Hao Z P. Catalytic oxidation of NO over TiO2 supported platinum clusters. II: Mechanism study by in situ FTIR spectra. Catalysis Today, 2010, 158(3–4): 361–369
https://doi.org/10.1016/j.cattod.2010.04.038
11 Zhao B H, Ran R, Wu X D, Weng D, Wu X Y, Huang C Y. Comparative study of Mn/TiO2 and Mn/ZrO2 catalysts for NO oxidation. Catalysis Communications, 2014, 56(1): 36–40
https://doi.org/10.1016/j.catcom.2014.07.003
12 Ren Z, Guo Y B, Zhang Z H, Liu C H, Gao P X. Nonprecious catalytic honeycombs structured with three dimensional hierarchical Co3O4 nano-arrays for high performance nitric oxide oxidation. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(34): 9897–9906
https://doi.org/10.1039/c3ta11156c
13 Lu W Z, Zhao X G, Wang H, Xiao W D. Catalytic oxidation of NO. Chinese Journal of Catalysis, 2000, 21(5): 423–427 (in Chinese)
14 Zhang J X, Zhang S L, Cai W, Zhong Q. The characterization of CrCe-doped on TiO2-pillared clay nanocomposites for NO oxidation and the promotion effect of CeOx. Applied Surface Science, 2013, 268: 535–540
https://doi.org/10.1016/j.apsusc.2012.12.169
15 Guo R T, Zhen W L, Pan W G, Zhou Y, Hong J N, Xu H J, Jin Q, Ding C G, Guo S Y. Effect of Cu doping on the SCR activity of CeO2 catalyst prepared by citric acid method. Journal of Industrial and Engineering Chemistry, 2014, 20(4): 1577–1580
https://doi.org/10.1016/j.jiec.2013.07.051
16 Peng L L, Huang Y, Li J G, Zhang J F. Catalytic performance of CoOx -CeOx /ZrO2 in NO oxidation and its resistance against SO2. Journal of Fuel Chemistry and Technology–China, 2012, 40(11): 1377–1383 (in Chinese)
17 Jang B W L, Spivey J J, Kung M C, Kung H H. Low-temperature NOx removal for flue gas cleanup. Energy & Fuels, 1997, 11(2): 299–306
https://doi.org/10.1021/ef960138w
18 Shang D H, Zhong Q, Cai W.High performance of NO oxidation over Ce–Co–Ti catalyst: the interaction between Ce and Co. Applied Surface Science, 2015, 325: 211–216
19 Guillén-Hurtado N, Atribak I, Bueno-López A, García-García A. Influence of the cerium precursor on the physico-chemical features and NO to NO2 oxidation activity of ceria and ceria–zirconia catalysts. Journal of Molecular Catalysis A Chemical, 2010, 323(1–2): 52–58
https://doi.org/10.1016/j.molcata.2010.03.010
20 Sun Y, Huang Y, Zhao W, Su Q, Zhang J, Yang L. Research on catalytic performance of supported perovskite catalyst for NO oxidation and resistance to SO2 poisoning. Journal of Fuel Chemistry and Technology–China, 2014, 42(10): 1246–1252 (in Chinese)
21 Waqif M, Bachelier J, Saur O, Lavalley J C. Acidic properties and stability of sulfate-promoted metal oxides. Journal of Molecular Catalysis, 1992, 72(1): 127–138
https://doi.org/10.1016/0304-5102(92)80036-G
22 Lee Y W, Kim H J, Park J W, Choi B U, Choi D K, Park J W. Adsorption and reaction behavior for the simultaneous adsorption of NO–NO2 and SO2 on activated carbon impregnated with KOH. Carbon, 2003, 41(10): 1881–1888
23 Yamamoto A, Teramura K, Hosokawa S, Tanaka T. Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst. Science and Technology of Advanced Materials, 2015, 16(2): 024901
https://doi.org/10.1088/1468-6996/16/2/024901 pmid: 27877768
24 Chilukoti S, Gao F, Anderson B G, Niemantsverdriet J W H, Garland M. Pure component spectral analysis of surface adsorbed species measured under real conditions. BTEM-DRIFTS study of CO and NO reaction over a Pd/gamma-Al2O3 catalyst. Physical Chemistry Chemical Physics, 2008, 10(36): 5510–5520
https://doi.org/10.1039/b806890a pmid: 18956085
25 Ruggeri M P, Grossale A, Nova I, Tronconi E, Jirglova H, Sobalik Z. FTIR in situ mechanistic study of the NH3 NO/NO2 “Fast SCR” reaction over a commercial Fe-ZSM-5 catalyst. Catalysis Today, 2012, 184(1): 107–114
https://doi.org/10.1016/j.cattod.2011.10.036
26 Li L, Qu L, Cheng J, Li J, Hao Z. Oxidation of nitric oxide to nitrogen dioxide over Ru catalysts. Applied Catalysis B: Environmental, 2009, 88(1–2): 224–231
https://doi.org/10.1016/j.apcatb.2008.09.032
27 Zhao Y, Hao R, Wang T, Yang C. Follow-up research for integrative process of pre-oxidation and post-absorption cleaning flue gas: Absorption of NO2, NO and SO2. Chemical Engineering Journal, 2015, 273: 55–65
https://doi.org/10.1016/j.cej.2015.03.053
28 Waqif M, Pieplu A, Saur O, Lavaleey J C, Blanchard G. Use of CeO2-Al2O3 as a SO2 sorbent. Solid State Ionics, 1997, 95(1–2): 163–167
https://doi.org/10.1016/S0167-2738(96)00577-2
29 Speight J G. Lange’s Handbook of Chemistry (6th edition). New York: McGraw-Hill Education, 2004
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