Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al2O3 Catalyst

Wang, Min; Chen, Hai-Ying; Lugo-Jose, Yuliana; Fedeyko, Joseph M.; Toops, Todd J.; Fidler, Jacqueline

doi:10.3390/catal14120847

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al₂O₃ Catalyst

Journal Article · Sat Nov 23 00:00:00 EST 2024 · Catalysts

DOI:https://doi.org/10.3390/catal14120847· OSTI ID:2478726

Wang, Min ^[1]; ^[1]; Lugo-Jose, Yuliana ^[2]; Fedeyko, Joseph M. ^[2]; ^[1]; Fidler, Jacqueline ^[3]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Johnson Matthey Inc., Wayne, PA (United States)
CONSOL Energy Inc., Canonsburg, PA (United States)

A PtPd/Al₂O₃ catalyst developed for the complete oxidation of methane from the ventilation air of underground coal mines is compared against a model PdO/Al₂O₃ catalyst. Although the PtPd/Al₂O₃ catalyst is substantially more active and stable than the model catalyst, the nature of active sites between the two catalysts is deemed to be fundamentally the same based on their response to different feed gas compositions and the evolution of surface CO adsorption complexes during time-resolved CO adsorption DRIFTS experiment. For both catalysts, coordinatively unsaturated Pd sites are considered the active centers for methane activation and the subsequent oxidation reaction. H₂O competes with CH₄ for the same active sites, resulting in severe inhibition. Additionally, the CH₄ oxidation reaction also causes self-inhibition. Taking both inhibition effects into consideration, a relatively simple kinetic model is developed. The model provides a good fit of the 72 sets of kinetic data collected on the PtPd/Al₂O₃ catalyst under practically relevant reaction conditions with CH₄ concentration in the range of 0.05–0.4%, H₂O concentration of 1.0–5.0%, and reaction temperatures of 450–700 °C. Kinetic parameters based on the model suggest that the CH₄ activation energy on the PtPd/Al₂O₃ catalyst is 96.7 kJ/mol, and the H₂O adsorption energy is –31.0 kJ/mol. Both values are consistent with the parameters reported in the literature. The model can be used to develop catalyst sizing guidelines and be incorporated into the control algorithm of the catalytic system.

View Journal Article

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

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AC05-00OR22725; AR0001532

OSTI ID:: 2478726

Alternate ID(s):: OSTI ID: 2483408

Journal Information:: Catalysts, Vol. 14, Issue 12; ISSN 2073-4344

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Development of a kinetic model for the oxidation of methane over Pd/Al2O3 at dry and wet conditions Hurtado, P. Applied Catalysis B: Environmental, Vol. 51, Issue 4 https://doi.org/10.1016/j.apcatb.2004.03.006	journal	August 2004
COMETTM – A New Ventilation Air Methane (VAM) Abatement Technology Hinde, By Peter; Mitchell, Ian; Riddell, Martin Johnson Matthey Technology Review, Vol. 60, Issue 3 https://doi.org/10.1595/205651316X692059	journal	June 2016
Methane Emission Control Raj, By Agnes Johnson Matthey Technology Review, Vol. 60, Issue 4 https://doi.org/10.1595/205651316X692554	journal	October 2016
A review on catalytic methane combustion at low temperatures: Catalysts, mechanisms, reaction conditions and reactor designs He, Li; Fan, Yilin; Bellettre, Jérôme Renewable and Sustainable Energy Reviews, Vol. 119 https://doi.org/10.1016/j.rser.2019.109589	journal	March 2020
Complete oxidation of methane at low temperature over noble metal based catalysts: a review Gélin, Patrick; Primet, Michel Applied Catalysis B: Environmental, Vol. 39, Issue 1, p. 1-37 https://doi.org/10.1016/S0926-3373(02)00076-0	journal	November 2002
Reaction kinetics and mechanism of complete methane oxidation on Pd/Mn2O3 catalyst Todorova, S.; Naydenov, A.; Kolev, H. Reaction Kinetics, Mechanisms and Catalysis, Vol. 123, Issue 2 https://doi.org/10.1007/s11144-018-1343-y	journal	January 2018
Kinetics of Catalytic Reactions Vannice, M. Albert Springer New York, NY https://doi.org/10.1007/b136380	book	January 2005
Isotopic Studies of Methane Oxidation Pathways on PdO Catalysts Au-Yeung, Jacky; Chen, Kaidong; Bell, Alexis T. Journal of Catalysis, Vol. 188, Issue 1 https://doi.org/10.1006/jcat.1999.2643	journal	November 1999
Stoichiometric adsorbate species interconversion processes in the chemisorbed layer. An infrared study of the carbon monoxide/palladium system Gelin, Patrick; Siedle, Allen R.; Yates, John T. The Journal of Physical Chemistry, Vol. 88, Issue 14 https://doi.org/10.1021/j150658a012	journal	July 1984
Water Inhibition in Methane Oxidation over Alumina Supported Palladium Catalysts Velin, Peter; Ek, Martin; Skoglundh, Magnus The Journal of Physical Chemistry C, Vol. 123, Issue 42 https://doi.org/10.1021/acs.jpcc.9b07606	journal	October 2019
Operando and Kinetic Study of Low-Temperature, Lean-Burn Methane Combustion over a Pd/γ-Al ₂ O ₃ Catalyst Xu, Jing; Ouyang, Like; Mao, Wei ACS Catalysis, Vol. 2, Issue 2 https://doi.org/10.1021/cs200694k	journal	January 2012
Low-temperature methane oxidation over oxide-supported Pd catalysts: inhibitory effect of water vapor Kikuchi, Ryuji; Maeda, Shingo; Sasaki, Kazunari Applied Catalysis A: General, Vol. 232, Issue 1-2 https://doi.org/10.1016/S0926-860X(02)00096-0	journal	June 2002
Kinetic Analysis of the Inhibition of CH ₄ Oxidation by H ₂ O on PdO/Al ₂ O ₃ and CeO ₂ /PdO/Al ₂ O ₃ Catalysts Alyani, Mina; Smith, Kevin J. Industrial & Engineering Chemistry Research, Vol. 55, Issue 30 https://doi.org/10.1021/acs.iecr.6b01881	journal	July 2016
Methane Oxidation over PdO: Towards a Better Understanding of the Influence of the Support Material Keller, Kevin; Lott, Patrick; Tischer, Steffen ChemCatChem, Vol. 15, Issue 11 https://doi.org/10.1002/cctc.202300366	journal	May 2023
The application of infrared spectroscopy to probe the surface morphology of alumina-supported palladium catalysts Lear, Timothy; Marshall, Robert; Antonio Lopez-Sanchez, J. The Journal of Chemical Physics, Vol. 123, Issue 17 https://doi.org/10.1063/1.2101487	journal	November 2005
CO Oxidation on PdO(101) during Temperature-Programmed Reaction Spectroscopy: Role of Oxygen Vacancies Zhang, Feng; Pan, Li; Li, Tao The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp509383v	journal	November 2014
Microkinetic Modeling of the Oxidation of Methane Over PdO Catalysts—Towards a Better Understanding of the Water Inhibition Effect Keller, Kevin; Lott, Patrick; Stotz, Henning Catalysts, Vol. 10, Issue 8 https://doi.org/10.3390/catal10080922	journal	August 2020
Compilation and evaluation of gas phase diffusion coefficients of reactive trace gases in the atmosphere: Volume 2. Diffusivities of organic compounds, pressure-normalised mean free paths, and average Knudsen numbers for gas uptake calculations Tang, M. J.; Shiraiwa, M.; Pöschl, U. Atmospheric Chemistry and Physics, Vol. 15, Issue 10 https://doi.org/10.5194/acp-15-5585-2015	journal	January 2015
Catalytic combustion of ventilation air methane (VAM) – long term catalyst stability in the presence of water vapour and mine dust Setiawan, Adi; Friggieri, Jarrod; Kennedy, Eric M. Catal. Sci. Technol., Vol. 4, Issue 6 https://doi.org/10.1039/C4CY00120F	journal	January 2014
The effect of water on methane oxidation over Pd/Al 2 O 3 under lean, stoichiometric and rich conditions Mihai, Oana; Smedler, Gudmund; Nylén, Ulf Catalysis Science & Technology, Vol. 7, Issue 14 https://doi.org/10.1039/C6CY02329K	journal	January 2017
Characterization of well faceted palladium nanoparticles supported on alumina by transmission electron microscopy and FT-IR spectroscopy of CO adsorption Di Gregorio, F.; Bisson, L.; Armaroli, T. Applied Catalysis A: General, Vol. 352, Issue 1-2 https://doi.org/10.1016/j.apcata.2008.09.034	journal	January 2009
DRIFTS study of CO adsorption on praseodymium modified Pt/Al2O3 Tankov, I.; Cassinelli, W. H.; Bueno, J. M. C. Applied Surface Science, Vol. 259 https://doi.org/10.1016/j.apsusc.2012.07.138	journal	October 2012
Kinetics of methane combustion over Pt and Pt–Pd catalysts Abbasi, R.; Wu, L.; Wanke, S. E. Chemical Engineering Research and Design, Vol. 90, Issue 11 https://doi.org/10.1016/j.cherd.2012.03.003	journal	November 2012
Vacancy-Mediated Processes in the Oxidation of CO on PdO(101) Weaver, Jason F.; Zhang, Feng; Pan, Li Accounts of Chemical Research, Vol. 48, Issue 5 https://doi.org/10.1021/acs.accounts.5b00101	journal	May 2015
Spatially-resolved investigation of the water inhibition of methane oxidation over palladium Coney, Ciaran; Stere, Cristina; Millington, Paul Catalysis Science & Technology, Vol. 10, Issue 6 https://doi.org/10.1039/D0CY00154F	journal	January 2020
Irreversible Catalyst Deactivation Mechanisms of PdO/γ-Al₂O₃ Catalysts for Lean Methane Oxidation Chen, Hai-Ying; Lugo-Jose, Yuliana; Fedeyko, Joseph M. ACS Catalysis, Vol. 14, Issue 20 https://doi.org/10.1021/acscatal.4c03690	journal	October 2024
Spectroscopic study of the interaction of carbon monoxide with cationic and metallic palladium in palladium–alumina catalysts Tessier, Didier; Rakai, Ahmed; Bozon-Verduraz, François J. Chem. Soc., Faraday Trans., Vol. 88, Issue 5 https://doi.org/10.1039/FT9928800741	journal	January 1992
Surface reaction kinetics of methane oxidation over PdO Stotz, H.; Maier, L.; Boubnov, A. Journal of Catalysis, Vol. 370 https://doi.org/10.1016/j.jcat.2018.12.007	journal	February 2019
Mine ventilation air methane as a sustainable energy source Karakurt, Izzet; Aydin, Gokhan; Aydiner, Kerim Renewable and Sustainable Energy Reviews, Vol. 15, Issue 2 https://doi.org/10.1016/j.rser.2010.11.030	journal	February 2011
Temperature Dependence of the Kinetics for the Complete Oxidation of Methane on Palladium and Palladium Oxide ^† Zhu, Guanghui; Han, Jinyi; Zemlyanov, Dmitri Yu. The Journal of Physical Chemistry B, Vol. 109, Issue 6 https://doi.org/10.1021/jp0488665	journal	February 2005
Site Trials and Demonstration of a Novel Pilot Ventilation Air Methane Mitigator Yin, Junjun; Su, Shi; Yu, Xinxiang Energy & Fuels, Vol. 34, Issue 8 https://doi.org/10.1021/acs.energyfuels.0c01681	journal	July 2020
Enrichment experiment of ventilation air methane (0.5%) by the mechanical tower Wang, Wen; Ren, Jiandong; Li, Xiaojun Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-63698-x	journal	April 2020
Kinetics of Low-Temperature Methane Oxidation over SiO₂-Encapsulated Bimetallic Pd–Pt Nanoparticles Habibi, Amir H.; Semagina, Natalia; Hayes, Robert E. Industrial & Engineering Chemistry Research, Vol. 57, Issue 24 https://doi.org/10.1021/acs.iecr.8b01338	journal	May 2018
Progress and key challenges in catalytic combustion of lean methane Feng, Xiangbo; Jiang, Lei; Li, Danyang Journal of Energy Chemistry, Vol. 75 https://doi.org/10.1016/j.jechem.2022.08.001	journal	December 2022
Structured reactors for kinetic measurements in catalytic combustion Groppi, Gianpiero; Ibashi, Watari; Tronconi, Enrico Chemical Engineering Journal, Vol. 82, Issue 1-3 https://doi.org/10.1016/S1385-8947(00)00342-9	journal	March 2001
First-Principles Microkinetic Modeling of Methane Oxidation over Pd(100) and Pd(111) Jørgensen, Mikkel; Grönbeck, Henrik ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01752	journal	September 2016
Understanding of Active Sites and Interconversion of Pd and PdO during CH4 Oxidation Oh, Dong Gun; Aleksandrov, Hristiyan A.; Kim, Haneul Molecules, Vol. 28, Issue 4 https://doi.org/10.3390/molecules28041957	journal	February 2023
Palladium Catalysts for Methane Oxidation: Old Materials, New Challenges Oh, Jinwon; Boucly, Anthony; van Bokhoven, Jeroen Anton Accounts of Chemical Research, Vol. 57, Issue 1 https://doi.org/10.1021/acs.accounts.3c00454	journal	December 2023
CH ₄ Oxidation Activity in Pd and Pt–Pd Bimetallic Catalysts: Correlation with Surface PdO _x Quantified from the DRIFTS Study Jang, Eun Jeong; Lee, Jaekyoung; Oh, Dong Gun ACS Catalysis, Vol. 11, Issue 10 https://doi.org/10.1021/acscatal.1c00156	journal	April 2021
Development of Combustion Technology for Methane Emitted from Coal-Mine Ventilation Air Systems Setiawan, Adi; Kennedy, Eric M.; Stockenhuber, Michael Energy Technology, Vol. 5, Issue 4 https://doi.org/10.1002/ente.201600490	journal	January 2017
DRIFTS study of CO adsorption on Pt nanoparticles supported by DFT calculations Lentz, Claudia; Jand, Sara Panahian; Melke, Julia Journal of Molecular Catalysis A: Chemical, Vol. 426 https://doi.org/10.1016/j.molcata.2016.10.002	journal	January 2017
Catalytic Oxidation of Methane: Pd and Beyond: Catalytic Oxidation of Methane: Pd and Beyond Monai, Matteo; Montini, Tiziano; Gorte, Raymond J. European Journal of Inorganic Chemistry, Vol. 2018, Issue 25 https://doi.org/10.1002/ejic.201800326	journal	June 2018
CO Adsorption on Clean and Oxidized Pd(111) Martin, N. M.; Van den Bossche, M.; Grönbeck, H. The Journal of Physical Chemistry C, Vol. 118, Issue 2 https://doi.org/10.1021/jp410895c	journal	December 2013
Kinetics of the Complete Oxidation of Methane over Supported Palladium Catalysts Ribeiro, F. H.; Chow, M.; Dallabetta, R. A. Journal of Catalysis, Vol. 146, Issue 2 https://doi.org/10.1006/jcat.1994.1092	journal	April 1994
Structure and Reactivity of PdOx/ZrO2Catalysts for Methane Oxidation at Low Temperatures Fujimoto, Ken-ichiro; Ribeiro, Fabio H.; Avalos-Borja, Miguel Journal of Catalysis, Vol. 179, Issue 2 https://doi.org/10.1006/jcat.1998.2178	journal	October 1998
Catalytic Combustion of Methane over Palladium-Based Catalysts Ciuparu, Dragos; Lyubovsky, Maxim R.; Altman, Eric Catalysis Reviews, Vol. 44, Issue 4 https://doi.org/10.1081/CR-120015482	journal	December 2002

Similar Records

Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H₂O₂ over Tungsten Oxide Catalysts

Journal Article · Wed Feb 24 00:00:00 EST 2021 · ACS Catalysis · OSTI ID:1807582

Yun, Danim; Ayla, E. Zeynep; Bregante, Daniel T.; +1 more

A study of Ni/La-Al₂O₃ catalysts: A competitive system for CO₂ methanation

Journal Article · Tue Dec 25 00:00:00 EST 2018 · Applied Catalysis. B, Environmental · OSTI ID:1609623

Garbarino, Gabriella; Wang, Chongyang; Cavattoni, Tullio; +4 more

Related Subjects

methane oxidation
Pd-based catalysts
kinetic model
H2O inhibition effect
self-inhibition
surface reconstruction

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al2O3 Catalyst

Citation Formats

References (46)

Similar Records

Related Subjects

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al₂O₃ Catalyst