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CO2 methanation reaction pathways over unpromoted and NaNO3-promoted Ru/Al2O3 catalysts

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/d2cy00515h· OSTI ID:1885245

Catalytic CO2 sorbents, materials that adsorb and pre-concentrate CO2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO2 capture and utilization. In this work, a prototypical CO2 methanation catalyst – Ru/Al2O3 – and a related catalytic sorbent – NaNO3/Ru/Al2O3 – are used for CO2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO3/Ru/Al2O3 material are slightly higher than unpromoted Ru/Al2O3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al2O3, while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO3/Ru/Al2O3. Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. In conclusion, results suggest that the pathway over the NaNO3/Ru/Al2O3 catalyst likely has an additional kinetically relevant irreversible step in the CO2 methanation reaction pathway.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Center (EFRC) (United States). Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; SC0012577
OSTI ID:
1885245
Alternate ID(s):
OSTI ID: 1872484
Journal Information:
Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 14 Vol. 12; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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