The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study

Falbo, Leonardo; Visconti, Carlo G.; Lietti, Luca; Szanyi, Janos

doi:10.1016/j.apcatb.2019.117791

Title: The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study

Journal Article · Tue Nov 05 00:00:00 EST 2019 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2019.117791· OSTI ID:1776575

Falbo, Leonardo ^[1]; Visconti, Carlo G. ^[1]; Lietti, Luca ^[1]; Szanyi, Janos ^[2]

Politecnico di Milano
BATTELLE (PACIFIC NW LAB)

The reactivity of Ru/Al2O3 catalysts in the hydrogenation of CO/CO2 gas mixtures is investigated in this work. Accordingly kinetic measurements are carried out at process conditions of industrial interest (i.e., at high COx per-pass conversion and with concentrated COx/H2 streams), and the surface species on the catalyst are investigated through transient DRIFTS-MS analysis. The catalyst shows gradual deactivation when the methanation is carried out in the presence of CO in the gas feed at low temperatures (200-300 °C). However, stable performance is observed at higher temperatures, showing CH4 yields even higher than those observed during methanation of a pure CO2 feed. The catalyst deactivation at low temperature is reversible as thermal treatments at temperatures above 350 °C are able to restore the catalytic activity. DRIFTS-MS experiments revealed that CO2 methanation involves a reaction pathway where CO2 is adsorbed as bicarbonate on Al2O3 and successively hydrogenated to methane on Ru, passing through formate and carbonyl intermediates. In the presence of CO at low temperatures, the catalyst shows a higher CO coverage of the Ru sites, a larger formate coverage of alumina sites and the presence of adsorbed carbonaceous species, identified as hydrocarbon and carboxylate species. Carboxylates remain on the surface, effectively blocking adsorption sites thus leading to catalyst deactivation. However, working above the carboxylate decomposition temperature ensures a clean catalyst surface, resulting in stable and high performance in CO/CO2 methanation. Catalyst preparation, characterization and testing activity were carried out with a joint project between the Politecnico di Milano and the Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), which is gratefully acknowledged. The authors gratefully acknowledge the financial support of the DRIFTS experiments by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. L.F. also acknowledges the Pacific Northwest National Laboratory (PNNL) for the financial support during his permanence as visiting student.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1776575

Report Number(s):: PNNL-SA-134496

Journal Information:: Applied Catalysis B: Environmental, Vol. 256

Country of Publication:: United States

Language:: English

References (69)

Recent Advances in CO ₂ Capture and Utilization Yu, Kai Man Kerry; Curcic, Igor; Gabriel, Joseph ChemSusChem, Vol. 1, Issue 11 https://doi.org/10.1002/cssc.200800169	journal	November 2008
Catalysis for the Valorization of Exhaust Carbon: from CO ₂ to Chemicals, Materials, and Fuels. Technological Use of CO ₂ Aresta, Michele; Dibenedetto, Angela; Angelini, Antonella Chemical Reviews, Vol. 114, Issue 3 https://doi.org/10.1021/cr4002758	journal	November 2013
New trends in the development of heterogeneous catalysts for electrochemical CO 2 reduction Kumar, Bijandra; Brian, Joseph P.; Atla, Veerendra Catalysis Today, Vol. 270 https://doi.org/10.1016/j.cattod.2016.02.006	journal	July 2016
Recent advances in catalytic hydrogenation of carbon dioxide Wang, Wei; Wang, Shengping; Ma, Xinbin Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c1cs15008a	journal	January 2011
A critical review of CO2 photoconversion: Catalysts and reactors Li, Kimfung; An, Xiaoqiang; Park, Kyeong Hyeon Catalysis Today, Vol. 224 https://doi.org/10.1016/j.cattod.2013.12.006	journal	April 2014
Recent advances in methanation catalysts for the production of synthetic natural gas Gao, Jiajian; Liu, Qing; Gu, Fangna RSC Advances, Vol. 5, Issue 29 https://doi.org/10.1039/C4RA16114A	journal	January 2015
CO ₂ methanation over heterogeneous catalysts: recent progress and future prospects Aziz, M. A. A.; Jalil, A. A.; Triwahyono, S. Green Chemistry, Vol. 17, Issue 5 https://doi.org/10.1039/C5GC00119F	journal	January 2015
Power to Gas projects review: Lab, pilot and demo plants for storing renewable energy and CO2 Bailera, Manuel; Lisbona, Pilar; Romeo, Luis M. Renewable and Sustainable Energy Reviews, Vol. 69 https://doi.org/10.1016/j.rser.2016.11.130	journal	March 2017
Review on methanation – From fundamentals to current projects Rönsch, Stefan; Schneider, Jens; Matthischke, Steffi Fuel, Vol. 166 https://doi.org/10.1016/j.fuel.2015.10.111	journal	February 2016
Renewable Power-to-Gas: A technological and economic review Götz, Manuel; Lefebvre, Jonathan; Mörs, Friedemann Renewable Energy, Vol. 85 https://doi.org/10.1016/j.renene.2015.07.066	journal	January 2016
Material constraints related to storage of future European renewable electricity surpluses with CO2 methanation Meylan, Frédéric D.; Moreau, Vincent; Erkman, Suren Energy Policy, Vol. 94 https://doi.org/10.1016/j.enpol.2016.04.012	journal	July 2016
Methanation of CO2 - storage of renewable energy in a gas distribution system Schaaf, Tanja; Grünig, Jochen; Schuster, Markus Roman Energy, Sustainability and Society, Vol. 4, Issue 1 https://doi.org/10.1186/s13705-014-0029-1	journal	December 2014
Production of synthetic natural gas (SNG) from coal and dry biomass – A technology review from 1950 to 2009 Kopyscinski, Jan; Schildhauer, Tilman J.; Biollaz, Serge M. A. Fuel, Vol. 89, Issue 8 https://doi.org/10.1016/j.fuel.2010.01.027	journal	August 2010
A review of the technologies, economics and policy instruments for decarbonising energy-intensive manufacturing industries Napp, T. A.; Gambhir, A.; Hills, T. P. Renewable and Sustainable Energy Reviews, Vol. 30 https://doi.org/10.1016/j.rser.2013.10.036	journal	February 2014
Catalytic Methanation Mills, G. Alex; Steffgen, Fred W. Catalysis Reviews, Vol. 8, Issue 1 https://doi.org/10.1080/01614947408071860	journal	January 1974
Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS) Czekaj, Izabela; Loviat, Francois; Raimondi, Fabio Applied Catalysis A: General, Vol. 329 https://doi.org/10.1016/j.apcata.2007.06.027	journal	October 2007
Deactivation of nickel-based catalysts during CO methanation and disproportionation Mirodatos, C. Journal of Catalysis, Vol. 107, Issue 2 https://doi.org/10.1016/0021-9517(87)90294-6	journal	October 1987
Catalysis mechanisms of CO ₂ and CO methanation Miao, Bin; Ma, Su Su Khine; Wang, Xin Catalysis Science & Technology, Vol. 6, Issue 12 https://doi.org/10.1039/C6CY00478D	journal	January 2016
Hydrogenation of surface carbon on alumina-supported nickel Mccarty, J. Journal of Catalysis, Vol. 57, Issue 3 https://doi.org/10.1016/0021-9517(79)90007-1	journal	May 1979
Atomic-scale imaging of carbon nanofibre growth Helveg, Stig; López-Cartes, Carlos; Sehested, Jens Nature, Vol. 427, Issue 6973 https://doi.org/10.1038/nature02278	journal	January 2004
Catalytic and adsorption studies for the hydrogenation of CO2 to methane Janke, C.; Duyar, M. S.; Hoskins, M. Applied Catalysis B: Environmental, Vol. 152-153 https://doi.org/10.1016/j.apcatb.2014.01.016	journal	June 2014
CO ₂ Reduction on Supported Ru/Al ₂ O ₃ Catalysts: Cluster Size Dependence of Product Selectivity Kwak, Ja Hun; Kovarik, Libor; Szanyi, János ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400381f	journal	October 2013
Transient drift spectroscopy for the determination of the surface reaction kinetics of CO2 methanation Marwood, Michel; Doepper, Ralf; Prairie, Michael Chemical Engineering Science, Vol. 49, Issue 24 https://doi.org/10.1016/S0009-2509(05)80060-0	journal	January 1994
Mechanistic Study of the Selective Methanation of CO over Ru/TiO ₂ Catalysts: Effect of Metal Crystallite Size on the Nature of Active Surface Species and Reaction Pathways Panagiotopoulou, Paraskevi; Verykios, Xenophon E. The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b12091	journal	February 2017
CO2 methanation on Ru-doped ceria Sharma, Sudhanshu; Hu, Zhenpeng; Zhang, Peng Journal of Catalysis, Vol. 278, Issue 2 https://doi.org/10.1016/j.jcat.2010.12.015	journal	March 2011
CO ₂ methanation by Ru-doped ceria: the role of the oxidation state of the surface Upham, D. Chester; Derk, Alan R.; Sharma, Sudanshu Catalysis Science & Technology, Vol. 5, Issue 3 https://doi.org/10.1039/C4CY01106F	journal	January 2015
Kinetics of CO2 methanation on a Ru-based catalyst at process conditions relevant for Power-to-Gas applications Falbo, Leonardo; Martinelli, Michela; Visconti, Carlo Giorgio Applied Catalysis B: Environmental, Vol. 225 https://doi.org/10.1016/j.apcatb.2017.11.066	journal	June 2018
Methanation of carbon dioxide on Ru/Al2O3: Catalytic activity and infrared study Garbarino, Gabriella; Bellotti, Daria; Finocchio, Elisabetta Catalysis Today, Vol. 277 https://doi.org/10.1016/j.cattod.2015.12.010	journal	November 2016
CO2 hydrogenation reaction over pristine Fe, Co, Ni, Cu and Al2O3 supported Ru: Comparison and determination of the activation energies Mutschler, Robin; Moioli, Emanuele; Luo, Wen Journal of Catalysis, Vol. 366 https://doi.org/10.1016/j.jcat.2018.08.002	journal	October 2018
Hydrogenation of Carbon Monoxide and Carbon Dioxide on Supported Ruthenium Catalysts at Moderate Pressures Karn, F. S.; Shultz, J. F.; Anderson, R. B. Industrial & Engineering Chemistry Product Research and Development, Vol. 4, Issue 4 https://doi.org/10.1021/i360016a014	journal	December 1965
Insights into the deactivation and reactivation of Ru/TiO2 during Fischer–Tropsch synthesis Carballo, Juan María González; Finocchio, Elisabetta; García-Rodriguez, Sergio Catalysis Today, Vol. 214 https://doi.org/10.1016/j.cattod.2012.09.018	journal	October 2013
Mechanisms of catalyst deactivation Bartholomew, Calvin H. Applied Catalysis A: General, Vol. 212, Issue 1-2 https://doi.org/10.1016/S0926-860X(00)00843-7	journal	April 2001
Structure sensitive reactions over supported ruthenium catalysts during Fischer-Tropsch synthesis Abrevaya, H.; Cohn, M. J.; Targos, W. M. Catalysis Letters, Vol. 7, Issue 1-4 https://doi.org/10.1007/BF00764501	journal	January 1991
Reactive metal volatilization from Ru/Al2O3 as a result of ruthenium carbonyl formation Goodwin, J. G.; Goa, D. O.; Erdal, S. Applied Catalysis, Vol. 24, Issue 1-2 https://doi.org/10.1016/S0166-9834(00)81268-3	journal	July 1986
Heterogeneous methanation: Steady-state rate of CO hydrogenation on supported ruthenium, nickel and rhenium Dallabetta, R. Journal of Catalysis, Vol. 40, Issue 2 https://doi.org/10.1016/0021-9517(75)90244-4	journal	November 1975
Deactivation by carbon of Ru/Al2O3 during CO hydrogenation Bowman, Richard M.; Bartholomew, Calvin H. Applied Catalysis, Vol. 7, Issue 2 https://doi.org/10.1016/0166-9834(83)80006-2	journal	August 1983
Heterogeneous methanation: In situ infrared spectroscopic study of Ru/Al2O3 during the hydrogenation of CO Betta, R. Journal of Catalysis, Vol. 48, Issue 1-3 https://doi.org/10.1016/0021-9517(77)90082-3	journal	June 1977
Synthesis of hydrocarbons from CO and H2 over silica-supported Ru: Reaction rate measurements and infrared spectra of adsorbed species Ekerdt, J. Journal of Catalysis, Vol. 58, Issue 2 https://doi.org/10.1016/0021-9517(79)90255-0	journal	June 1979
CO Chemisorption and Dissociation at High Coverages during CO Hydrogenation on Ru Catalysts Loveless, Brett T.; Buda, Corneliu; Neurock, Matthew Journal of the American Chemical Society, Vol. 135, Issue 16 https://doi.org/10.1021/ja311848e	journal	April 2013
An in situ infrared study of CO hydrogenation over silica and alumina-supported ruthenium and silica-supported iron King, D. Journal of Catalysis, Vol. 61, Issue 1 https://doi.org/10.1016/0021-9517(80)90341-3	journal	January 1980
Studies of carbon monoxide hydrogenation over ruthenium using transient response techniques Cant, N. Journal of Catalysis, Vol. 73, Issue 2 https://doi.org/10.1016/0021-9517(82)90099-9	journal	February 1982
Mechanistic Study of the Selective Methanation of CO over Ru/TiO ₂ Catalyst: Identification of Active Surface Species and Reaction Pathways Panagiotopoulou, Paraskevi; Kondarides, Dimitris I.; Verykios, Xenophon E. The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp106538z	journal	September 2010
Mechanistic Studies of Hydrocarbon Combustion and Synthesis on Noble Metals Inderwildi, Oliver R.; Jenkins, Stephen J.; King, David A. Angewandte Chemie International Edition, Vol. 47, Issue 28 https://doi.org/10.1002/anie.200800685	journal	June 2008
Reaction Intermediates and Side Products in the Methanation of CO and CO ₂ over Supported Ru Catalysts in H ₂ -Rich Reformate Gases Eckle, Stephan; Anfang, Hans-Georg; Behm, R. Jürgen The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp108106t	journal	September 2010
Carbon dioxide adsorption and methanation on ruthenium Zali, E. Journal of Catalysis, Vol. 69, Issue 1 https://doi.org/10.1016/0021-9517(81)90122-6	journal	May 1981
Hydrogenation of CO2 on group VIII metals II. Kinetics and mechanism of CO2 hydrogenation on nickel Weatherbee, G. Journal of Catalysis, Vol. 77, Issue 2 https://doi.org/10.1016/0021-9517(82)90186-5	journal	October 1982
The transient species formed over Ru$z.sbnd;RuOx/TiO2 catalyst in the CO and CO + H2 interaction: FTIR spectroscopic study Gupta, N. Journal of Catalysis, Vol. 137, Issue 2 https://doi.org/10.1016/0021-9517(92)90174-G	journal	October 1992
In-situ surface and gas phase analysis for kinetic studies under transient conditions The catalytic hydrogenation of CO2 Marwood, Michel; Doepper, Ralf; Renken, Albert Applied Catalysis A: General, Vol. 151, Issue 1 https://doi.org/10.1016/S0926-860X(96)00267-0	journal	March 1997
Kinetic modeling and transient DRIFTS–MS studies of CO2 methanation over Ru/Al2O3 catalysts Wang, Xiang; Hong, Yongchun; Shi, Hui Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2016.02.001	journal	November 2016
Kinetics of the Methanation of Carbon Dioxide over Ruthenium on Titania Traa, Yvonne; Weitkamp, Jens Chemical Engineering & Technology, Vol. 22, Issue 4 https://doi.org/10.1002/(SICI)1521-4125(199904)22:4<291::AID-CEAT291>3.0.CO;2-L	journal	April 1999
Quantitative Analysis of Adsorbate Concentrations by Diffuse Reflectance FT-IR Sirita, Jinda; Phanichphant, Sukon; Meunier, Frederic C. Analytical Chemistry, Vol. 79, Issue 10 https://doi.org/10.1021/ac0702802	journal	May 2007
Effective bulk and surface temperatures of the catalyst bed of FT-IR cells used for in situ and operando studies Li, Haoguang; Rivallan, Mickael; Thibault-Starzyk, Frederic Physical Chemistry Chemical Physics, Vol. 15, Issue 19 https://doi.org/10.1039/c3cp50442e	journal	January 2013
Isotopic tracer and NMR studies of carbonaceous species present during CO hydrogenation over Ru/TiO2 Yokomizo, G. Journal of Catalysis, Vol. 119, Issue 2 https://doi.org/10.1016/0021-9517(89)90175-9	journal	October 1989
An isotopic tracer study of the deactivation of Ru/Ti02 catalysts during Fischer-Tropsch synthesis Krishna, K. Journal of Catalysis, Vol. 130, Issue 2 https://doi.org/10.1016/0021-9517(91)90139-U	journal	August 1991
Gas-Uptake, Methanation, and Microcalorimetric Measurements on the Coadsorption of CO and H2over Polycrystalline Ru and a Ru/TiO2Catalyst Gupta, N. M.; Londhe, V. P.; Kamble, V. S. Journal of Catalysis, Vol. 169, Issue 2 https://doi.org/10.1006/jcat.1997.1718	journal	July 1997
Dissecting the steps of CO ₂ reduction: 1. The interaction of CO and CO ₂ with γ-Al ₂ O ₃ : an in situ FTIR study Szanyi, János; Kwak, Ja Hun Phys. Chem. Chem. Phys., Vol. 16, Issue 29 https://doi.org/10.1039/C4CP00616J	journal	January 2014
Basic catalysis and catalysis assisted by basicity: FT-IR and TPD characterization of potassium-doped alumina Montanari, Tania; Castoldi, Lidia; Lietti, Luca Applied Catalysis A: General, Vol. 400, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.04.016	journal	June 2011
I.r. spectroscopic study of CO2 adsorption onto η-Al2O3 Morterra, Claudio; Zecchina, Adriano; Coluccia, Salvatore Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777301544	journal	January 1977
A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species Morterra, Claudio; Magnacca, Giuliana Catalysis Today, Vol. 27, Issue 3-4 https://doi.org/10.1016/0920-5861(95)00163-8	journal	February 1996
FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces Busca, Guido; Lamotte, Jean; Lavalley, Jean Claude Journal of the American Chemical Society, Vol. 109, Issue 17 https://doi.org/10.1021/ja00251a025	journal	August 1987
Carbon monoxide adsorption on supported ruthenium Dalla Betta, R. A. The Journal of Physical Chemistry, Vol. 79, Issue 23 https://doi.org/10.1021/j100590a015	journal	November 1975
FTIR spectroscopic study of the interaction of CO2 and CO2 + H2 over partially oxidized Ru/TiO2 catalyst Gupta, N.; Kamble, V.; Kartha, V. Journal of Catalysis, Vol. 146, Issue 1 https://doi.org/10.1016/0021-9517(94)90020-5	journal	March 1994
FTIR Studies of CO Adsorption on Al ₂ O ₃ - and SiO ₂ -Supported Ru Catalysts Chin, Soo Yin; Williams, Christopher T.; Amiridis, Michael D. The Journal of Physical Chemistry B, Vol. 110, Issue 2 https://doi.org/10.1021/jp053908q	journal	January 2006
Determination of formate decomposition rates and relation to product formation during CO hydrogenation over supported cobalt Lorito, D.; Paredes-Nunez, A.; Mirodatos, C. Catalysis Today, Vol. 259 https://doi.org/10.1016/j.cattod.2015.06.027	journal	January 2016
Infrared Study of Coke on Alumina and Zeolite Datka, J.; Sarbak, Z.; Eischens, R. P. Journal of Catalysis, Vol. 145, Issue 2 https://doi.org/10.1006/jcat.1994.1065	journal	February 1994
Chemical adsorption of acetic acid and deuterated acetic acid on Ru(0001), by RAIRS Garcia, A. R.; da Silva, J. L.; Ilharco, L. M. Surface Science, Vol. 415, Issue 1-2 https://doi.org/10.1016/S0039-6028(98)00590-1	journal	September 1998
Mechanistic aspects of the selective methanation of CO over Ru/TiO2 catalyst Panagiotopoulou, Paraskevi; Kondarides, Dimitris I.; Verykios, Xenophon E. Catalysis Today, Vol. 181, Issue 1 https://doi.org/10.1016/j.cattod.2011.05.030	journal	February 2012
Influence of the oxide support reducibility on the CO2 methanation over Ru-based catalysts Dreyer, Jochen A. H.; Li, Peixin; Zhang, Linghai Applied Catalysis B: Environmental, Vol. 219 https://doi.org/10.1016/j.apcatb.2017.08.011	journal	December 2017
Nature and reactivity of the surface species observed over a supported cobalt catalyst under CO/H2 mixtures Paredes-Nunez, Anaëlle; Lorito, Davide; Guilhaume, Nolven Catalysis Today, Vol. 242 https://doi.org/10.1016/j.cattod.2014.04.033	journal	March 2015

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Title: The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study

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