Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH<sub>4</sub> in excess oxygen

doi:10.1007/s11783-009-0016-5

Front Envir Sci Eng Chin

2009, Vol. 3

Issue (2) : 186-193 https://doi.org/10.1007/s11783-009-0016-5

RESEARCH ARTICLE

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH₄ in excess oxygen

Shicheng XU, Junhua LI(

), Dong YANG, Jiming HAO

Department of Environmental Science and Engineering, Tsinghua University, Beijing 100084, China

Download: PDF(194 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Br?nsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Br?nsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.

Keywords selective catalytic reduction (SCR) nitric oxide (NO) methane support acidity Br?nsted acid sites NO_y species

Corresponding Author(s): LI Junhua,Email:lijunhua@tsinghua.edu.cn

Issue Date: 05 June 2009

Cite this article:

Shicheng XU,Junhua LI,Dong YANG, et al. Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH₄ in excess oxygen[J]. Front Envir Sci Eng Chin, 2009, 3(2): 186-193.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-009-0016-5
https://academic.hep.com.cn/fese/EN/Y2009/V3/I2/186

Fig.1 NO conversion rate over (a) InWZr and (b) InSTi at 450°C
Gas mixture: 1000 ppm of NO or NO, 3000 ppm of CH, 0 or 10% of O, N as balance; GHSV= 12000 h

Fig.2 DRIFTS spectra of NO-CH-O reactions over (a) InWZr and (b) InSTi under various temperatures
Gas mixture: 1000 ppm of NO, 3000 ppm of CH, 10% of O, N as balance

Fig.3 FTIR spectra of pyridine adsorbed on (a) InWZr and (b) InSTi at 200°C and 350°C

Fig.4 Calculated value of 1/ under various oxygen concentrations at 450°C
Gas mixture: 1000 ppm of NO, 3000 ppm of CH, 0.1% to 20% of O, N as balance; GHSV= 12000 h

Fig.5 DRIFTS spectra of reactions on NO groups on RhSZr
(NO+ O co-adsorption was first performed under a flow containing 1000 ppm of NO and 10% of O in N at 450°C for 15 min)

Fig.6 Linear regression results of kinetic parameters: (a) logarithmic plot of vs. rhodium content and (b) linear plot of (the obtained slope from panel a) vs.

1	Li Y, Armor J N. Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen. Applied Catalysis B: Environmental , 1992, 1(4): 31-40 doi: 10.1016/0926-3373(92)80050-A
2	Kantcheva M, Cayirtepe I. FT-IR spectroscopic investigation of the surface reaction of CH₄ with NOx species adsorbed on Pd/WO₃-ZrO₂ catalyst. Catalysis Letters , 2007, 115(3–4): 148-162 doi: 10.1007/s10562-007-9081-1
3	Fokema M D, Ying J Y. The selective catalytic reduction of nitric oxide with methane over nonzeolitic catalysts. Catalysis Reviews—Science and Engineering , 2001, 43(1-2): 1-29 doi: 10.1081/CR-100104385
4	Li Y, Armor J N. Selective catalytic reduction of NOx with methane over metal exchange zeolites. Applied Catalysis B: Environmental , 1993, 2(2-3): 239-256 doi: 10.1016/0926-3373(93)80051-E
5	Zhang X K, Walters A B, Vannice M A. Catalytic reduction of NO by CH₄ over Li-promoted MgO. Journal of Catalysis , 1994, 146(2): 568-578 doi: 10.1006/jcat.1994.1095
6	Feeley J S, Deeba M, Farrauto R J, Beri G, Haynes A. Lean NOx reduction with hydrocarbons over Ga/S-ZrOx and S-GaZr/zeolite catalysts. Applied Catalysis B: Environmental , 1995, 6(1): 79-96 doi: 10.1016/0926-3373(95)00004-6
7	Li N, Wang A Q, Tang J W, Wang X D, Liang D B, Zhang T. NO reduction by CH₄ in the presence of excess O₂ over Co/sulfated zirconia catalysts. Applied Catalysis B: Environmental , 2003, 43(2): 195-201 doi: 10.1016/S0926-3373(02)00301-6
8	Li N, Wang A Q, Wang X D, Zheng M Y, Cheng R H, Zhang T. NO reduction by CH₄ in the presence of excess O₂ over Mn/sulfated zirconia catalysts. Applied Catalysis B: Environmental , 2004, 48(4): 259-265 doi: 10.1016/j.apcatb.2003.11.002
9	Chin Y H, Pisanu A, Serventi L, Alvarez W E, Resasco D E. NO reduction by CH₄ in the presence of excess O₂ over Pd/sulfated zirconia catalysts. Catalysis Today , 1999, 54(4): 419-429 doi: 10.1016/S0920-5861(99)00205-9
10	Cordoba L F, Sachtler W M H, de Correa C M. NO reduction by CH₄ over Pd/Co-sulfated zirconia catalysts. Applied Catalysis B: Environmental , 2005, 56(4): 269-277 doi: 10.1016/j.apcatb.2004.09.012
11	Quincoces C E, Guerrero S, Araya P, Gonzalez M G. Effect of water vapor over Pd-Co/SZ catalyst for the NO selective reduction by methane. Catalysis Communications , 2005, 6(1): 75-80 doi: 10.1016/j.catcom.2004.11.002
12	Li N, Wang A Q, Lin L, Wang X D, Ren L L, Zhang T. NO reduction by CH₄ in the presence of excess O₂ over Pd/sulfated alumina catalysts. Applied Catalysis B: Environmental , 2004, 50(1): 1-7 doi: 10.1016/j.apcatb.2003.10.009
13	Li N, Wang A Q, Ren W L, Zheng M Y, Wang X D, Zhang T. Pd/sulfated alumina: A new effective catalyst for the selective catalytic reduction of NO with CH₄. Topics in Catalysis , 2004, 30-31(1-4): 103-105 doi: 10.1023/B:TOCA.0000029736.23302.20
14	Chin Y H, Alvarez W E, Resasco D E. Sulfated zirconia and tungstated zirconia as effective supports for Pd-based SCR catalysts. Catalysis Today , 2000, 62(2-3): 159-165 doi: 10.1016/S0920-5861(00)00417-X
15	Chin Y H, Alvarez W E, Resasco D E. Comparison between methane and propylene as reducing agents in the SCR of NO over Pd supported on tungstated zirconia. Catalysis Today , 2000, 62(4): 291-302 doi: 10.1016/S0920-5861(00)00431-4
16	Okumura K, Kusakabe T, Niwa M. Durable and selective activity of Pd loaded on WO₃/ZrO₂ for NO-CH₄-O₂ in the presence of water vapor. Applied Catalysis B: Environmental , 2003, 41(1-2): 137-142 doi: 10.1016/S0926-3373(02)00206-0
17	Kantcheva M, Vakkasoglu A S. Cobalt supported on zirconia and sulfated zirconia II. Reactivity of adsorbed NOx compounds toward methane. Journal of Catalysis , 2004, 223(2): 364-371 doi: 10.1016/j.jcat.2004.02.006
18	Djega-Mariadassou G. From three-way to deNOx catalysis: A general model. Catalysis Today , 2004, 90(1-2): 27-34 doi: 10.1016/j.cattod.2004.04.004
19	Yang D, Li J H, Wen M F, Song C L. Selective catalytic reduction of NOx with methane over indium supported on tungstated zirconia. Catalysis Communications , 2007, 8(12): 2243-2247 doi: 10.1016/j.catcom.2007.04.035
20	Yang D, Li J H, Wen M F, Song C L. Selective catalytic reduction of NOx with CH₄ over the In/sulfated TiO₂ catalyst. Catalysis Letters , 2008, 122(1-2): 138-143 doi: 10.1007/s10562-007-9360-x
21	Miller J T, Glusker E, Peddi R, Zheng T, Regalbuto J R. The role of acid sites in cobalt zeolite catalysts for selective catalytic reduction of NOx. Catalysis Letters , 1998, 51(1-2): 15-22 doi: 10.1023/A:1019072631175
22	Busca G. Spectroscopic characterization of the acid properties of metal oxide catalysts. Catalysis Today , 1998, 41(1-3): 191-206 doi: 10.1016/S0920-5861(98)00049-2
23	Reshetenko T V, Avdeeva L B, Khassin A A, Kustova G N, Ushakov V A, Moroz E M, Shmakov A N, Kriventsov V V, Kochubey D I, Pavlyukhin Y T, Chuvilin A L, Ismagilov Z R. Coprecipitated iron-containing catalysts (Fe-Al₂O₃, Fe-Co-Al₂O₃, Fe-Ni-Al₂O₃) for methane decomposition at moderate temperatures: I. Genesis of calcined and reduced catalysts. Applied Catalysis A: General , 2004, 268(1-2): 127-138 doi: 10.1016/j.apcata.2004.03.045
24	Kantcheva M, Kucukkal M U, Suzer S. Spectroscopic investigation of species arising from CO chemisorption on titania-supported manganese. Journal of Catalysis , 2000, 190(1): 144-156 doi: 10.1006/jcat.1999.2757
25	Adelman B J, Beutel T, Lei G D, Sachtler W M H. Mechanistic cause of hydrocarbon specificity over Cu/ZSM-5 and Co/ZSM-5 catalysts in the selective catalytic reduction of NOx. Journal of Catalysis , 1996, 158(1): 327-335 doi: 10.1006/jcat.1996.0031
26	Hadjiivanov K I. Identification of neutral and charged N_xO_y surface species by IR spectroscopy. Catalysis Reviews , 2000, 42(1): 71-144 doi: 10.1081/CR-100100260
27	Wong M S N. Supremolecular templating of mesoporous zirconia-based nanocomposite catalysts. Dissertation for the Doctoral Degree . Boston: Massachusett Institute of Technology, 2000
28	Arata K. Preparation of superacids by metal oxides for reactions of butanes and pentanes. Applied Catalysis A: General , 1996, 146(1): 3-32 doi: 10.1016/0926-860X(96)00046-4
29	Mantilla A, Tzompantzi F, Ferrat G, López-Ortegac A, Alfaroa S, Gómezb R, Torres M. Oligomerization of isobutene on sulfated titania: Effect of reaction conditions on selectivity. Catalysis Today , 2005, 107-108: 707-712 doi: 10.1016/j.cattod.2005.07.153
30	Halász J, Kónya Z, Fudala á, Béres A, Kiricsi I. Indium and gallium containing ZSM-5 zeolites: Acidity and catalytic activity in propane transformation. Catalysis Today , 1996, 31(3-4): 293-304 doi: 10.1016/S0920-5861(96)00019-3
31	Ansell G P, Diwell A F, Golunski S E, Hayes J W, Rajaram R R, Truex T J, Walker A P. Mechanism of the lean NOx reaction over Cu/ZSM-5. Applied Catalysis B: Environmental , 1993, 2(1): 81-100 doi: 10.1016/0926-3373(93)80028-C
32	Kikuchi E, Ogura M, Terasaki I, Goto Y. Selective reduction of nitric oxide with methane on gallium and indium containing H-ZSM-5 catalysts: Formation of active sites by solid-state ion exchange. Journal of Catalysis , 1996, 161(1): 465-470 doi: 10.1006/jcat.1996.0205
33	Li Y J, Armor J N. Selective catalytic reduction of NO with methane on gallium catalysts. Journal of Catalysis , 1994, 145(1): 1-9 doi: 10.1006/jcat.1994.1001
34	Shelef M, Montreuil C N, Jen H W. NO₂ formation over Cu-ZSM-5 and the selective catalytic reduction of NO. Catalysis Letters , 1994, 26(3-4): 277-284 doi: 10.1007/BF00810600
35	Beutel T, Adelman B J, Sachtler W M H. FTIR study of the nitrogen isotopic exchange between adsorbed ¹⁵NO₂ complexes and ¹⁴NO over Cu/ZSM-5 and Co/ZSM-5. Applied Catalysis B: Environmental , 1996, 9(1-4): 1-10

[1]	Ying Xu, Hui Gong, Xiaohu Dai. High-solid anaerobic digestion of sewage sludge: achievements and perspectives[J]. Front. Environ. Sci. Eng., 2021, 15(4): 71-.
[2]	Mona Akbar, Muhammad Farooq Saleem Khan, Ling Qian, Hui Wang. Degradation of polyacrylamide (PAM) and methane production by mesophilic and thermophilic anaerobic digestion: Effect of temperature and concentration[J]. Front. Environ. Sci. Eng., 2020, 14(6): 98-.
[3]	Chao Pang, Chunhua He, Zhenhu Hu, Shoujun Yuan, Wei Wang. Aggravation of membrane fouling and methane leakage by a three-phase separator in an external anaerobic ceramic membrane bioreactor[J]. Front. Environ. Sci. Eng., 2019, 13(4): 50-.
[4]	Yuzhou Deng, Shengpan Peng, Haidi Liu, Shuangde Li, Yunfa Chen. Mechanism of dichloromethane disproportionation over mesoporous TiO₂ under low temperature[J]. Front. Environ. Sci. Eng., 2019, 13(2): 21-.
[5]	Alvyn P. Berg, Ting-An Fang, Hao L. Tang. Unlocked disinfection by-product formation potential upon exposure of swimming pool water to additional stimulants[J]. Front. Environ. Sci. Eng., 2019, 13(1): 10-.
[6]	Yi Chen, Shilong He, Mengmeng Zhou, Tingting Pan, Yujia Xu, Yingxin Gao, Hengkang Wang. Feasibility assessment of up-flow anaerobic sludge blanket treatment of sulfamethoxazole pharmaceutical wastewater[J]. Front. Environ. Sci. Eng., 2018, 12(5): 13-.
[7]	Zechong Guo, Lei Gao, Ling Wang, Wenzong Liu, Aijie Wang. Enhanced methane recovery and exoelectrogen-methanogen evolution from low-strength wastewater in an up-flow biofilm reactor with conductive granular graphite fillers[J]. Front. Environ. Sci. Eng., 2018, 12(4): 13-.
[8]	Bai-Hang Zhao, Jie Chen, Han-Qing Yu, Zhen-Hu Hu, Zheng-Bo Yue, Jun Li. Optimization of microwave pretreatment of lignocellulosic waste for enhancing methane production: Hyacinth as an example[J]. Front. Environ. Sci. Eng., 2017, 11(6): 17-.
[9]	Yulun Nie, Xike Tian, Zhaoxin Zhou, Yu-You Li. Impact of food to microorganism ratio and alcohol ethoxylate dosage on methane production in treatment of low-strength wastewater by a submerged anaerobic membrane bioreactor[J]. Front. Environ. Sci. Eng., 2017, 11(6): 6-.
[10]	Takashi Osada, Makoto Shiraishi, Teruaki Hasegawa, Hirofumi Kawahara. Methane, Nitrous Oxide and Ammonia generation in full-scale swine wastewater purification facilities[J]. Front. Environ. Sci. Eng., 2017, 11(3): 10-.
[11]	Chong Liu, Jianzheng Li, Shuo Wang, Loring Nies. A syntrophic propionate-oxidizing microflora and its bioaugmentation on anaerobic wastewater treatment for enhancing methane production and COD removal[J]. Front. Environ. Sci. Eng., 2016, 10(4): 13-.
[12]	Min GOU,Jing ZENG,Huizhong WANG,Yueqin TANG,Toru SHIGEMATSU,Shigeru MORIMURA,Kenji KIDA. Microbial community structure and dynamics of starch-fed and glucose-fed chemostats during two years of continuous operation[J]. Front. Environ. Sci. Eng., 2016, 10(2): 368-380.
[13]	Yuyao ZHANG,Huan LI,Can LIU,Yingchao CHENG. Influencing mechanism of high solid concentration on anaerobic mono-digestion of sewage sludge without agitation[J]. Front. Environ. Sci. Eng., 2015, 9(6): 1108-1116.
[14]	Roberta DYCK,Geneviève COOL,Manuel RODRIGUEZ,Rehan SADIQ. Treatment, residual chlorine and season as factors affecting variability of trihalomethanes in small drinking water systems[J]. Front. Environ. Sci. Eng., 2015, 9(1): 171-179.
[15]	Xiaomao WANG,Garcia Leal M I,Xiaolu ZHANG,Hongwei YANG,Yuefeng XIE. Haloacetic acids in swimming pool and spa water in the United States and China[J]. Front. Environ. Sci. Eng., 2014, 8(6): 820-824.

Viewed

Full text

Abstract

Cited

Shared

Discussed