Impact of sulfation and desulfation on NOx reduction using Cu-chabazite SCR catalysts

Brookshear, Daniel William; Nam, Jeong -Gil; Nguyen, Ke; Toops, Todd J.; Binder, Andrew J.

doi:10.1016/j.cattod.2015.04.029

Title: Impact of sulfation and desulfation on NO_x reduction using Cu-chabazite SCR catalysts

Journal Article · Fri Jun 05 00:00:00 EDT 2015 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2015.04.029· OSTI ID:1201286

Brookshear, Daniel William ^[1]; Nam, Jeong -Gil ^[2]; Nguyen, Ke ^[3]; Toops, Todd J. ^[1]; Binder, Andrew J. ^[3]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Mokpo National Maritime Univ., Mokpo (Republic of Korea)
Univ. of Tennessee, Knoxville, TN (United States)

This bench reactor study investigates the impact of gaseous sulfur on the NO_x reduction activity of Cu-chabazite SCR (Cu-CHA) catalysts at SO₂ concentrations representative of marine diesel engine exhaust. After two hours of 500 ppm SO₂ exposure at 250 and 400 °C in the simulated diesel exhaust gases, the NO_x reduction activity of the sulfated Cu-CHA SCR catalysts is severely degraded at evaluation temperatures below 250 °C; however, above 250 °C the impact of sulfur exposure is minimal. EPMA shows that sulfur is located throughout the washcoat and along the entire length of the sulfated samples. Interestingly, BET measurements reveal that the sulfated samples have a 20% decrease in surface area. Moreover, the sulfated samples show a decrease in NO_x/nitrate absorption during NO exposure in a DRIFTS reactor which suggests that Cu sites in the catalyst are blocked by the presence of sulfur. SO₂ exposure also results in an increase in NH₃ storage capacity, possibly due to the formation of ammonium sulfate species in the sulfated samples. In all cases, lean thermal treatments as low as 500 °C reverse the effects of sulfur exposure and restore the NO_x reduction activity of the Cu-CHA catalyst to that of the fresh condition.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1201286

Alternate ID(s):: OSTI ID: 1257872

Journal Information:: Catalysis Today, Vol. 258, Issue P2; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 44 works

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References (24)

Simultaneous Removal of SO ₂ and NO _x by Calcium Hydroxide at Low Temperature: Effect of SO ₂ Absorption on NO ₂ Removal Chen, Guoqing; Gao, Jihui; Gao, Jianmin Industrial & Engineering Chemistry Research, Vol. 49, Issue 23 https://doi.org/10.1021/ie101594x	journal	December 2010
Characterization of Ceria’s Interaction with NO _x and NH ₃ Zhang, Li; Pierce, John; Leung, Victor L. The Journal of Physical Chemistry C, Vol. 117, Issue 16 https://doi.org/10.1021/jp401442e	journal	April 2013
A pilot plant study for selective catalytic reduction of NO by NH3 over mordenite-type zeolite catalysts Nam, In-Sik; Choo, Soo Tae; Koh, Dong Jun Catalysis Today, Vol. 38, Issue 2 https://doi.org/10.1016/S0920-5861(97)00064-3	journal	October 1997
The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites Fickel, Dustin W.; D’Addio, Elizabeth; Lauterbach, Jochen A. Applied Catalysis B: Environmental, Vol. 102, Issue 3-4 https://doi.org/10.1016/j.apcatb.2010.12.022	journal	February 2011
In situ DRIFTS and temperature-programmed technology study on NH3-SCR of NO over Cu-SSZ-13 and Cu-SAPO-34 catalysts Ma, Lei; Cheng, Yisun; Cavataio, Giovanni Applied Catalysis B: Environmental, Vol. 156-157 https://doi.org/10.1016/j.apcatb.2014.03.048	journal	September 2014
NH ₃ as a Probe Molecule for NMR and IR Study of Zeolite Catalyst Acidity Yin, F.; Blumenfeld, A. L.; Gruver, V. The Journal of Physical Chemistry B, Vol. 101, Issue 10 https://doi.org/10.1021/jp9618542	journal	March 1997
A new active zeolite structure for the selective catalytic reduction (SCR) of nitrogen oxides: ITQ7 zeolite Palomares, Antonio E.; Prato, J. G.; Corma, A. Catalysis Today, Vol. 75, Issue 1-4 https://doi.org/10.1016/S0920-5861(02)00066-4	journal	July 2002
Impact of different forms of feed sulfur on small-pore Cu-zeolite SCR catalyst Kumar, Ashok; Smith, Michael A.; Kamasamudram, Krishna Catalysis Today, Vol. 231 https://doi.org/10.1016/j.cattod.2013.12.038	journal	August 2014
Inhibitory effect of NO2 on the selective catalytic reduction of NOx with NH3 over one-pot-synthesized Cu–SSZ-13 catalyst Xie, Lijuan; Liu, Fudong; Liu, Kuo Catalysis Science & Technology, Vol. 4, Issue 4 https://doi.org/10.1039/c3cy00924f	journal	January 2014
Identification of Neutral and Charged N _x O _y Surface Species by IR Spectroscopy Hadjiivanov, Konstantin I. Catalysis Reviews, Vol. 42, Issue 1-2 https://doi.org/10.1081/CR-100100260	journal	May 2000
Impact of sulfur oxide on NH3-SCR over Cu-SAPO-34 Wijayanti, Kurnia; Andonova, Stanislava; Kumar, Ashok Applied Catalysis B: Environmental, Vol. 166-167 https://doi.org/10.1016/j.apcatb.2014.11.043	journal	May 2015
Isolated Cu ²⁺ ions: active sites for selective catalytic reduction of NO Korhonen, Satu T.; Fickel, Dustin W.; Lobo, Raul F. Chem. Commun., Vol. 47, Issue 2 https://doi.org/10.1039/C0CC04218H	journal	January 2011
In situ DRIFTS-MS studies on the oxidation of adsorbed NH3 by NOx over a Cu-SSZ-13 zeolite Zhu, Haiyang; Kwak, Ja Hun; Peden, Charles H. F. Catalysis Today, Vol. 205 https://doi.org/10.1016/j.cattod.2012.08.043	journal	April 2013
On the mechanism of the SCR reaction on Fe/HBEA zeolite Klukowski, D.; Balle, P.; Geiger, B. Applied Catalysis B: Environmental, Vol. 93, Issue 1-2 https://doi.org/10.1016/j.apcatb.2009.09.028	journal	November 2009
In Situ-DRIFTS Study of Selective Catalytic Reduction of NO _x by NH ₃ over Cu-Exchanged SAPO-34 Wang, Di; Zhang, Li; Kamasamudram, Krishna ACS Catalysis, Vol. 3, Issue 5 https://doi.org/10.1021/cs300843k	journal	April 2013
Reaction Mechanism of Selective Catalytic Reduction of NO with NH3 over Fe-ZSM-5 Catalyst Long, R. Q.; Yang, R. T. Journal of Catalysis, Vol. 207, Issue 2 https://doi.org/10.1006/jcat.2002.3528	journal	April 2002
SO2 poisoning impact on the NH3-SCR reaction over a commercial Cu-SAPO-34 SCR catalyst Zhang, Li; Wang, Di; Liu, Yong Applied Catalysis B: Environmental, Vol. 156-157 https://doi.org/10.1016/j.apcatb.2014.03.030	journal	September 2014
Thermal durability of Cu-CHA NH3-SCR catalysts for diesel NOx reduction Schmieg, Steven J.; Oh, Se H.; Kim, Chang H. Catalysis Today, Vol. 184, Issue 1 https://doi.org/10.1016/j.cattod.2011.10.034	journal	April 2012
The different impacts of SO2 and SO3 on Cu/zeolite SCR catalysts Cheng, Yisun; Lambert, Christine; Kim, Do Heui Catalysis Today, Vol. 151, Issue 3-4 https://doi.org/10.1016/j.cattod.2010.01.013	journal	June 2010
Testing zeolite SCR catalysts under protocol conditions for NOx abatement from stationary emission sources Ramachandran, Bala; Herman, Richard G.; Choi, Sukwon Catalysis Today, Vol. 55, Issue 3 https://doi.org/10.1016/S0920-5861(99)00252-7	journal	January 2000
Characterization of Cu-SSZ-13 NH3 SCR catalysts: an in situ FTIR study Szanyi, János; Kwak, Ja Hun; Zhu, Haiyang Physical Chemistry Chemical Physics, Vol. 15, Issue 7 https://doi.org/10.1039/c2cp43467a	journal	January 2013
Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3 Kwak, Ja Hun; Tonkyn, Russell G.; Kim, Do Heui Journal of Catalysis, Vol. 275, Issue 2 https://doi.org/10.1016/j.jcat.2010.07.031	journal	October 2010
Vibrational Spectroscopy of NH ₄ ⁺ Ions in Zeolitic Materials: An IR Study Zecchina, A.; Marchese, L.; Bordiga, S. The Journal of Physical Chemistry B, Vol. 101, Issue 48 https://doi.org/10.1021/jp9717554	journal	November 1997
F Guter, Eran Aesthetics A–Z https://doi.org/10.1515/9780748630066-009	book	October 2010

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Mechanism-based kinetic modeling of Cu-SSZ-13 sulfation and desulfation for NH ₃ -SCR applications Jangjou, Yasser; Sampara, Chaitanya S.; Gu, Yuntao Reaction Chemistry & Engineering, Vol. 4, Issue 6 https://doi.org/10.1039/c8re00210j	journal	January 2019
Enhanced Low Temperature NO Reduction Performance via MnOx-Fe2O3/Vermiculite Monolithic Honeycomb Catalysts Zhang, Ke; Yu, Feng; Zhu, Mingyuan Catalysts, Vol. 8, Issue 3 https://doi.org/10.3390/catal8030100	journal	February 2018
Lean and rich aging of a Cu/SSZ-13 catalyst for combined lean NO _x trap (LNT) and selective catalytic reduction (SCR) concept Auvray, Xavier; Grant, Ann; Lundberg, Björn Catalysis Science & Technology, Vol. 9, Issue 9 https://doi.org/10.1039/c8cy02572j	journal	January 2019
Effects of SO ₂ on Cu-SSZ-39 catalyst for the selective catalytic reduction of NO _x with NH ₃ Du, Jinpeng; Shi, Xiaoyan; Shan, Yulong Catalysis Science & Technology, Vol. 10, Issue 5 https://doi.org/10.1039/c9cy02186h	journal	January 2020

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Title: Impact of sulfation and desulfation on NO_x reduction using Cu-chabazite SCR catalysts