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Title: Barium-Promoted Ruthenium Catalysts on Yittria-Stabilized Zirconia Supports for Ammonia Synthesis

Abstract

The cost-effective, small-scale, distributed synthesis of ammonia depends on effective catalysts and processes that operate under modest elevated pressure (i.e., p < 20 bar) conditions. The present paper considers Ru as the active catalyst supported on yittria-stabilized zirconia (YSZ). The addition of alkali and alkaline-earth metal promoters is found to increase synthesis rates by an order of magnitude. The rate enhancement is largely insensitive to the promoter concentration, with Cs outperforming Ba and K by a factor of 2. However, Ba is found to be stable whereas Cs degrades more rapidly, which is attributed to the low melting point of its oxide. At 400 °C and 1.0 MPa, the specific synthesis rate over Ba–Ru is measured to be approximately 1410 mmol gRu–1 h–1, higher than the most active oxide-supported Ru catalysts reported in the literature. The rate becomes inhibited by H2 absorption at low temperature (below 350 °C), but lower H2/N2 ratios enable the rate to remain comparable to what is observed in stoichiometric mixtures at temperatures below 400 °C. The paper reports a new detailed microkinetic model that accurately captures the observed behavior, revealing that adsorption is coverage dependent. Furthermore, these results provide insight and direction into developing alternativesmore » to Haber–Bosch for distributed synthesis of green ammonia.« less

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
Colorado School of Mines, Golden, CO (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1779197
Grant/Contract Number:  
AR0001004; AR0000808
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 7; Journal Issue: 21; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ammonia synthesis; Heterogeneous catalysis; Ru/YSZ; Microkinetics; Catalysts; Oxides; Reaction rates; Equilibrium; Ammonia

Citation Formats

Zhang, Zhenyu, Karakaya, Canan, Kee, Robert J., Way, J. Douglas, and Wolden, Colin A. Barium-Promoted Ruthenium Catalysts on Yittria-Stabilized Zirconia Supports for Ammonia Synthesis. United States: N. p., 2019. Web. doi:10.1021/acssuschemeng.9b04929.
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Zhang, Zhenyu, Karakaya, Canan, Kee, Robert J., Way, J. Douglas, & Wolden, Colin A. Barium-Promoted Ruthenium Catalysts on Yittria-Stabilized Zirconia Supports for Ammonia Synthesis. United States. https://doi.org/10.1021/acssuschemeng.9b04929
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Zhang, Zhenyu, Karakaya, Canan, Kee, Robert J., Way, J. Douglas, and Wolden, Colin A. Mon . "Barium-Promoted Ruthenium Catalysts on Yittria-Stabilized Zirconia Supports for Ammonia Synthesis". United States. https://doi.org/10.1021/acssuschemeng.9b04929. https://www.osti.gov/servlets/purl/1779197.
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@article{osti_1779197,
title = {Barium-Promoted Ruthenium Catalysts on Yittria-Stabilized Zirconia Supports for Ammonia Synthesis},
author = {Zhang, Zhenyu and Karakaya, Canan and Kee, Robert J. and Way, J. Douglas and Wolden, Colin A.},
abstractNote = {The cost-effective, small-scale, distributed synthesis of ammonia depends on effective catalysts and processes that operate under modest elevated pressure (i.e., p < 20 bar) conditions. The present paper considers Ru as the active catalyst supported on yittria-stabilized zirconia (YSZ). The addition of alkali and alkaline-earth metal promoters is found to increase synthesis rates by an order of magnitude. The rate enhancement is largely insensitive to the promoter concentration, with Cs outperforming Ba and K by a factor of 2. However, Ba is found to be stable whereas Cs degrades more rapidly, which is attributed to the low melting point of its oxide. At 400 °C and 1.0 MPa, the specific synthesis rate over Ba–Ru is measured to be approximately 1410 mmol gRu–1 h–1, higher than the most active oxide-supported Ru catalysts reported in the literature. The rate becomes inhibited by H2 absorption at low temperature (below 350 °C), but lower H2/N2 ratios enable the rate to remain comparable to what is observed in stoichiometric mixtures at temperatures below 400 °C. The paper reports a new detailed microkinetic model that accurately captures the observed behavior, revealing that adsorption is coverage dependent. Furthermore, these results provide insight and direction into developing alternatives to Haber–Bosch for distributed synthesis of green ammonia.},
doi = {10.1021/acssuschemeng.9b04929},
journal = {ACS Sustainable Chemistry & Engineering},
number = 21,
volume = 7,
place = {United States},
year = {Mon Oct 07 00:00:00 EDT 2019},
month = {Mon Oct 07 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acssuschemeng.9b04929
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