A Comparison of Hydrothermal Aging, SO<sub>2</sub> and Propene Poisoning Effects on NH<sub>3</sub>-SCR over Cu-ZSM-5 and Cu-SAPO-34 Catalysts — Oak Academic Publishing
Research ArticleOpen AccessGoogle Scholar indexed
A Comparison of Hydrothermal Aging, SO<sub>2</sub> and Propene Poisoning Effects on NH<sub>3</sub>-SCR over Cu-ZSM-5 and Cu-SAPO-34 Catalysts
Unité de Formation et de Recherche des Sciences et de Technologies (UFR ST), Université Alassane Ouattara, Bouaké, Côte d’Ivoire
,
Unité de Formation et de Recherche Environnement (UFR E), Université Jean Lorougnon Guédé, Daloa, Côte d’Ivoire
,
Unité de Formation et de Recherche des Sciences des Structures, de la Matière et de Technologie (UFR SSMT), Abidjan, Côte d’Ivoire
,
Unité de Formation et de Recherche des Sciences et de Technologies (UFR ST), Université Alassane Ouattara, Bouaké, Côte d’Ivoire
1 Unité de Formation et de Recherche des Sciences et de Technologies (UFR ST), Université Alassane Ouattara, Bouaké, Côte d’Ivoire
2 Unité de Formation et de Recherche Environnement (UFR E), Université Jean Lorougnon Guédé, Daloa, Côte d’Ivoire
3 Unité de Formation et de Recherche des Sciences des Structures, de la Matière et de Technologie (UFR SSMT), Abidjan, Côte d’Ivoire
4 Unité de Formation et de Recherche des Sciences et de Technologies (UFR ST), Université Alassane Ouattara, Bouaké, Côte d’Ivoire
This study was aimed to investigate the effects of hydrothermal aging, propene and SO<sub>2</sub> poisoning on the ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) performance of both Cu-SAPO-34 and Cu-ZSM-5. The catalytic activities of fresh, aged and poisoned samples were tested in ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) of NO<sub>x</sub> conditions. The XRD, TG and N<sub>2</sub>-desorption results showed that the structures of the Cu-SAPO-34 and Cu-ZSM-5 remained intact after 750˚C hydrothermally aged, SO<sub>2</sub> and propene poisoned. After hydrothermal aging at 750˚C for 12 h, the NO reduction performance of Cu-ZSM-5 was significantly reduced at lower temperatures, while that of Cu-SAPO-34 was less affected. Moreover, Cu-SAPO-34 catalyst showed high NO conversion with SO<sub>2</sub> or propene compared to Cu-ZSM-5. However, Cu-ZSM-5 showed a larger drop in catalytic activity with SO<sub>2</sub> or propene compared to Cu-SAPO-34 catalyst. The H<sub>2</sub>-TPR results showed that Cu<sup>2 </sup> ions could be reduced to Cu<sup> </sup> and Cu<sup>0</sup> for Cu-ZSM-5, while no significant transformation of copper species was observed for Cu-SAPO-34. Meanwhile, the UV-vis DRS results showed that CuO species were formed in Cu-ZSM-5, while little changes were observed for the Cu-SAPO-34. Cu-SAPO-34 showed high sulfur and hydrocarbon poison resistance compared to Cu-ZSM-5. In summary, Cu-SAPO-34 with small-pore zeolite showed higher hydrothermal stability and better hydrocarbon and sulfur poison resistant than Cu-ZSM-5 with medium-pore.
KeywordsHydrothermal AgingPropene and SO<sub>2</sub>PoisoningAmmonia-Selective Catalytic Reduction (NH<sub>3</sub>-SCR)
Kwak, J.H., Tran, D., Burton, S.D., Szanyi, J., Lee, J.H. and Peden, C.H.F. (2012) Effects of Hydrothermal Aging on NH 3 -SCR Reaction over Cu/Zeolites. Journal of Catalysis , 287, 203-209. https://doi.org/10.1016/j.jcat.2011.12.025
Doi, Y., Haneda, M. and Ozawa, M. (2014) Direct Decomposition of NO on Ba Catalysts Supported on Rare Earth Oxides. Journal of Molecular Catalysis A : Chemical , 383-384, 70-76. https://doi.org/10.1016/j.molcata.2013.11.033
Ma, L., Cheng, Y., Cavataio, G., Mcabe, R.W., Fu, L. and Li, J. (2013) Characterization of Commercial Cu-SSZ-13 and Cu-SAPO-34 Catalysts with Hydrothermal Treatment for NH 3 -SCR of NO x in Diesel Exhaust. Chemical Engineering Journal , 225, 323-330. https://doi.org/10.1016/j.cej.2013.03.078
Franco, R.M., Moliner, M., Franch, C., Kustov, A. and Corma, A. (2012) Rational Direct Synthesis Methodology of Very Active and Hydrothermally Stable Cu-SAPO-34 Molecular Sieves for the SCR of NO x . Applied Catalysis B : Enviro n mental , 127, 273-280. https://doi.org/10.1016/j.apcatb.2012.08.034
Gabrielsson, L.T. (2004) Urea-SCR in Automotive Applications. Topics in Catalysis , 28, 177-184. https://doi.org/10.1023/B:TOCA.0000024348.34477.4c
Wang, D., Jangjou, Y., Liu, Y., Sharma, M.K., Luo, J., Li, J., Kamasamudram, K. and Epling, W.S. (2015) A Comparison of Hydrothermal Aging Effects on NH 3 -SCR of NO x over Cu-SSZ-13 and Cu-SAPO-34 Catalysts. Applied Catalysis B : Enviro n mental , 165, 438-445. https://doi.org/10.1016/j.apcatb.2014.10.020
Kwak, J.H., Zhu, H., Lee, J.H., Peden, C.H.F. and Szanyi, J. (2012) Two Different Cationic Positions in Cu-SSZ-13? Chemical Communications , 48, 4758-4760. https://doi.org/10.1039/c2cc31184d
Iwamoto, M., Furukawa, H., Mine, Y., Uemura, F., Mikuriya, S.-I. and Kagawa, S. (1986) Copper (II) Ion-Exchanged ZSM-5 Zeolite as Highly Active Catalysts for Direct and Continuous Decomposition of Nitrogen Oxide. Journal of the Chemical Society , Chemical Communications , No. 16, 1272-1273. https://doi.org/10.1039/c39860001272
Ye, Q., Wang, L. and Yang, R.T. (2012) Activity, Propene Poisoning Resistance and Hydrothermal Stability of Copper Exchanged Chabazite-Like Zeolite Catalysts for SCR of NO with Ammonia in Comparison to Cu/ZSM-5. Applied Catalysis A : General , 427-428, 24-34. https://doi.org/10.1016/j.apcata.2012.03.026
Gomez, S.A., Campero, A., Martinez-Hermandez, A. and Fuentes, G.A. (2000) Changes in Cu 2 Environment upon Wet Deactivation of Cu-ZSM-5 DeNO x Catalyst. Applied Catalysis A : General , 197, 157-164. https://doi.org/10.1016/S0926-860X(99)00546-3
Cu-SAPO-34
Cu-ZSM-5
Kucherov, A.V., Hubbard, C.P. and Shelef, M. (1995) Rearrangement of Cationic Sites in CuH-ZSM-5 and Reactivity Loss upon High Temperature Calcination and Steam Aging. Journal of Catalysis , 157, 603-610. https://doi.org/10.1006/jcat.1995.1325
Tanabe, T., Iijima, T., Koiwai, A., Mizuno, J., Yokota, K. and Isogai, A. (1995) ESR Study of the Deactivation of Cu-ZSM-5 in a Net Oxidizing Atmosphere. Applied Catalysis B : Environmental , 6, 145-153. https://doi.org/10.1016/0926-3373(95)00012-7
Rokosz, M.J., Kucherov, A.V., Jen, H.W. and Shelef, M. (1997) Spectroscopic Studies of the Stability of the Zeolitc deNO x Catalysts. Catalysis Today , 35, 65-73. https://doi.org/10.1016/S0920-5861(96)00144-7
Kucherov, A.V., Gerlock, J.L., Jen, H.W. and Shelef, M. (1995) In situ ESR Monitoring of CuH-ZSM-5 up 500˚C in Flowing Dry Mixtures of NO (NO 2 ), C 3 H 6 (C 2 H 5 OH), and an Excess O 2 . Journal of Catalysis , 152, 63-69. https://doi.org/10.1006/jcat.1995.1060
Zhang, Y. and Stephanopoulos, M.F. (1996) Hydrothermal Stability of Cerium Modified Cu-ZSM-5 Catalyst for Nitric Oxide Decomposition. Journal of Catalysis , 164, 131-145. https://doi.org/10.1006/jcat.1996.0369
Breggrund, M., Ingelsten, H.H., Skoglundh, M. and Palmqvist, A.E.C. (2009) Influence of Synthesis for ZSM-5 on the Hydrothermal Stability of Cu-ZSM-5. Catalysis Letters , 130, 79-85. https://doi.org/10.1007/s10562-009-9890-5
Gabova, V., Dedeeek, J. and Cejka, J. (2003) Control of Al Distribution in ZSM-5 by Condition of Zeolite Synthesis. Chemical Communications , No. 10, 1196-1197. https://doi.org/10.1039/b301634j
Wang, J., Fan, D., Yu, T., Wang, J., Hao, T., Hu, X. and Shen, M. (2015) Improvement of Low-Temperature Hydrothermal Stability of Cu/SAPO-34 Catalysts by Cu 2 Species. Journal of Catalysis , 322, 84-90. https://doi.org/10.1016/j.jcat.2014.11.010
Luo, J., Wang, D., Kumar, A., Li, J., Kamasamudram, K., Currier, N. and Yezerets, A. (2016) Identification of Two Types of Cu Sites in Cu-SSZ-13 and Their Unique Responses to Hydrothermal Aging and Sulfur Poisoning. Catalysis Today , 267, 3-9. https://doi.org/10.1016/j.cattod.2015.12.002
Briend, M., Vomscheid, R., Peltre, M.J., Man, P.P. and Barthomeuf, D. (1995) Influence of the Choice of the Template on the Short-and Long-Term Stability of SAPO-34 Zeolite. Journal of Physical Chemistry , 99, 8270-8276.
Sultana, A., Nanba, T., Sasaki, M., Haneda, M., Suzuki, K. and Hamada, H. (2011) Selective Catalytic Reduction of NO x with NH 3 over Different Copper Exchanged Z eolites in the Presence of Decane. Catalysis Today , 164, 495-499. https://doi.org/10.1016/j.cattod.2010.11.036
Tukur, N.M. and Al-Khattaf, S. (2005) Catalytic Cracking of n -Dodecane and Alkyl Benzenes over FCC Zeolite Catalysts. Time and Stream and Reactant Converter Models. Chemical Engineering and Processing , 44, 1257-1268. https://doi.org/10.1016/j.cep.2005.02.009
He, C., Wang, Y., Cheng, Y., Lambert, C.K. and Yang, R.T. (2009) Activity, Stability and Hydrocarbon Deactivation of Fe/Beta Catalyst for SCR of NO with Ammonia. Applied Catalysis B : General , 368, 121-126. https://doi.org/10.1016/j.apcata.2009.08.020
Luo, J.Y., Oh, H., Henry, C. and Epling, W. (2012) Effect of C3H6 on Selective Catalytic Reduction of NO x by NH 3 over a Cu/Zeolite Catalyst: A Mechanistic Study. Applied Catalysis B : Environmental , 123-124, 296-305. https://doi.org/10.1016/j.apcatb.2012.04.038
Ma, L., Su, W., Li, Z., Li, J., Fu, L. and Hao, J. (2015) Mechanism of Propene Poisoning on Cu-SSZ-13 Catalysts for SCR of NO x with NH 3 . Catalysis Today , 245, 16-21. https://doi.org/10.1016/j.cattod.2014.05.027
Selleri, T., Nova, I., Tronconi, E., Weibel, M. and Schmmeiβer, V. (2017) Modelling Inhibition Effect of Short-Chain Hydrocarbons on a Small-Pore Cu-Zeolite NH 3 -SCR Catalysts. Topics in Catalysis , 60, 214-219. https://doi.org/10.1007/s11244-016-0600-4
Wang, D., Li, Z. and Song, C. (2021) The Enhanced Catalytic Activity of Cu/ SAPO-34 by Ion Exchange Method for Selective Catalytic Reduction of Nitric Oxide. Materials Research Express , 8, Article 025507. https://doi.org/10.1088/2053-1591/abe6d3
Zhang, Q., Li, Z., Cui, J., Ma, Y., et al . (2023) Efficiency of Temperature on Ce and La Doping Cu Modified IM-5 Catalyst in DeNO x Performance and SO 2 /H 2 O Resistance. Research on Chemical Intermediates , 49, 4997-5013. https://doi.org/10.1007/s11164-023-05127-y
Ma, J., Si, Z., Weng, D., Wu, X. and Ma, Y. (2015) Potassium Poisoning on Cu-SAPO-34 Catalyst for Selective Catalytic Reduction of NO x with Ammonia. Chemical Engineering Journal , 267, 191-200. https://doi.org/10.1016/j.cej.2014.11.020
Wang, J., Huang, Y., Yu, T., Zhu, S., Shen, M., Li, W. and Wang, J. (2014) The Migration of Cu Species over Cu-SAPO-34 and It Effect on NH 3 Oxidation at High Temperature. Catalysis Science & Technology , 4, 3004-3012. https://doi.org/10.1039/C4CY00451E
Cao, Y., Zou, S., Yang, Z., Xu, H., Lin, T., Gong, M. and Chen, Y. (2015) Promotional Effect of Ce on Cu-SAPO-34 Monolith Catalyst for Selective Catalytic Reduction of NO x Ammonia. Journal of Molecular Catalysis A : Chemical , 398, 304-311. https://doi.org/10.1016/j.molcata.2014.12.020
Pang, L., Fan, C., Shao, L., Song, K., Yi, J., Cai, X., Wang, J., Kang, M. and Li, T. (2014) The Ce Doping Cu/ZSM-5 as a New Superior Catalyst to Remove NO from Diesel Engine Exhaust. Chemical Engineering Journal , 253, 394-401. https://doi.org/10.1016/j.cej.2014.05.090
Zhang, T., Liu, J., Wang, D.X., Zhao, Z., Wei, Y.C., Cheng, K., Jiang, G.Y. and Duan, A.J. (2014) Selective Catalytic Reduction of NO with NH 3 over HZSM-5-Supported Fe-Cu Nanocomposite Catalysts: The Fe-Cu Bimetallic Effect. Applied Catalysis B : Environmental , 148-149, 520-531. https://doi.org/10.1016/j.apcatb.2013.11.006
Zhang, L., Wang, D., Liu, Y., Kamassamudram, K., Li, J. and Epling, W. (2014) SO 2 Poisoning Impact on the NH 3 -SCR Reaction over a Commercial Cu-SAPO-34 SCR Catalyst. Applied Catalysis B : Environmental , 156-157, 371-377. https://doi.org/10.1016/j.apcatb.2014.03.030
Heo, I., Lee, Y., Nam, I.-S., Choung, J.W., Lee, J.-H. and Kim, H.-J. (2011) Effect of Hydrocarbon Slip on NO Removal Activity of Cu-ZSM-5, Fe-ZSM-5 and V 2 O 5 /TiO 2 Catalysts by NH 3 . Microporous and Mesoporous Materials , 141, 8-15. https://doi.org/10.1016/j.micromeso.2010.02.005
Ma, L., Li, J., Cheng, Y., Lambert, C.K. and Fu, L. (2012) Propene Poisoning on Three Typical Fe-Zeolites for SCR of NO x with NH 3 : From Mechanism Study to Coating Modified Architecture. Environmental Science & Technology , 46, 1747-1754. https://doi.org/10.1021/es203070g
Yan, J.Y., Sachtler, W.M.H. and Kung, H.H. (1997) Effect of Cu Loading Addition of Modifiers on the Stability of Cu/ZSM-5 in Lean NO x Reduction Catalysis. Catal y sis Today , 33, 279-290. https://doi.org/10.1016/S0920-5861(96)00100-9
Zhang, T., Shi, J., Liu, J., Wang, D., Zhao, Z., Cheng, K. and Li, J. (2016) Enhanced Hydrothermal Stability of Cu-ZSM-5 Catalyst via Surface Modification in the Selective Catalytic Reduction of NO with NH 3 . Applied Surface Science , 375, 186-195. https://doi.org/10.1016/j.apsusc.2016.03.049
Yan, J.Y., Lei, G.-D., Sachtler, W.M.H. and Kung, H.H. (1996) Deactivation of Cu-ZSM-5 Catalyst for Lean NO x Reduction: Characterization of Changes of Cu State and Zeolite Support. Journal of Catalysis , 161, 43-54. https://doi.org/10.1006/jcat.1996.0160
Dang, T.T.H., Zubowa, H.L., Bentrup, U., Richter, M. and Martin, A. (2009) Microwave-Assisted Synthesis and Characterization of Cu-Containing ALPO 4 -5 and SAPO-5. Microporous and Mesoporous Materials , 123, 209-220. https://doi.org/10.1016/j.micromeso.2009.04.003
Wang, L., Gaudet, J.R., Li, W. and Weng, D. (2013) Migration of Cu Species in Cu/SAPO-34 during Hydrothermal Aging. Journal of Catalysis , 306, 68-77. https://doi.org/10.1016/j.jcat.2013.06.010
Su, W., Li, Z., Zhang, Y., Meng, C. and Li, J. (2017) Identification of Sulfate Species and Their Influence on SCR Performance of Cu/CHA Catalyst. Catalysis Science & Technology , 7, 1523-1528. https://doi.org/10.1039/C7CY00302A
Zhang, D. and Yang, R.T. (2017) NH 3 -SCR of NO over One-Pot Cu-SAPO-34 Catalyst: Performance Enhancement by Doping Fe and MnCe and Insight into N 2 O Formation. Applied Catalysis A : General , 543, 247-256. https://doi.org/10.1016/j.apcata.2017.06.021