Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling

Dhruba J. Deka; Rohil Daya; Austin Ladshaw; Dylan Trandal; Saurabh Y. Joshi; William P. Partridge

doi:10.1016/j.apcatb.2022.121233

Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling

Dhruba J. Deka, Rohil Daya, Austin Ladshaw, Dylan Trandal, Saurabh Y. Joshi, William P. Partridge

Applied Catalysis&Emissions Res. Group

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

Abstract

The SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H₂-TPR, NH₃-TPD, SO₂-TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.

Original language	English
Article number	121233
Journal	Applied Catalysis B: Environmental
Volume	309
DOIs	https://doi.org/10.1016/j.apcatb.2022.121233
State	Published - Jul 15 2022

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). We thank Neal Currier, Unmesh Menon, Karthik Venkata Rama Krishna Dadi, Aleksey Yezerets and Krishna Kamasamudram from Cummins Inc. for their valuable support and promotion of the CRADA (cooperative research and development agreement) partnership within which this work was performed, and their SCR-catalyst insights. We thank Josh Pihl, group leader of the ORNL Applied Catalysis and Emissions Research Group, for his critical review and suggestions regarding catalysis methods and experiments, and help with experimental system automation. We thank DOE VTO Program & Technology Managers: Gurpreet Singh, Siddiq Khan, and Ken Howden for supporting the CRADA project.

Funders	Funder number
DOE Public Access Plan
DOE VTO
United States Government
U.S. Department of Energy

Keywords

Cu-SSZ-13 catalyst field aging
SCR Cu-redox cycle
SCR kinetic modeling
Selective catalytic reduction
Transient response methodology

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.apcatb.2022.121233

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title = "Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling",

abstract = "The SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H2-TPR, NH3-TPD, SO2-TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.",

keywords = "Cu-SSZ-13 catalyst field aging, SCR Cu-redox cycle, SCR kinetic modeling, Selective catalytic reduction, Transient response methodology",

author = "Deka, {Dhruba J.} and Rohil Daya and Austin Ladshaw and Dylan Trandal and Joshi, {Saurabh Y.} and Partridge, {William P.}",

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AU - Deka, Dhruba J.

AU - Daya, Rohil

AU - Ladshaw, Austin

AU - Trandal, Dylan

AU - Joshi, Saurabh Y.

AU - Partridge, William P.

PY - 2022/7/15

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N2 - The SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H2-TPR, NH3-TPD, SO2-TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.

AB - The SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H2-TPR, NH3-TPD, SO2-TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.

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Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling

Abstract

Funding

Keywords

UN SDGs

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