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Title: Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

Abstract

We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from aceticmore » acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Energy and Environmental Directorate, Institute for Integrated Catalysis, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1398169
Report Number(s):
PNNL-SA-125545
Journal ID: ISSN 2168-0485; 49656; BM0102060
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Davidson, Stephen D., Spies, Kurt A., Mei, Donghai, Kovarik, Libor, Kutnyakov, Igor, Li, Xiaohong S., Lebarbier Dagle, Vanessa, Albrecht, Karl O., and Dagle, Robert A. Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability. United States: N. p., 2017. Web. doi:10.1021/acssuschemeng.7b02052.
Davidson, Stephen D., Spies, Kurt A., Mei, Donghai, Kovarik, Libor, Kutnyakov, Igor, Li, Xiaohong S., Lebarbier Dagle, Vanessa, Albrecht, Karl O., & Dagle, Robert A. Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability. United States. doi:10.1021/acssuschemeng.7b02052.
Davidson, Stephen D., Spies, Kurt A., Mei, Donghai, Kovarik, Libor, Kutnyakov, Igor, Li, Xiaohong S., Lebarbier Dagle, Vanessa, Albrecht, Karl O., and Dagle, Robert A. Mon . "Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability". United States. doi:10.1021/acssuschemeng.7b02052.
@article{osti_1398169,
title = {Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability},
author = {Davidson, Stephen D. and Spies, Kurt A. and Mei, Donghai and Kovarik, Libor and Kutnyakov, Igor and Li, Xiaohong S. and Lebarbier Dagle, Vanessa and Albrecht, Karl O. and Dagle, Robert A.},
abstractNote = {We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, and activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.},
doi = {10.1021/acssuschemeng.7b02052},
journal = {ACS Sustainable Chemistry & Engineering},
issn = {2168-0485},
number = 10,
volume = 5,
place = {United States},
year = {2017},
month = {9}
}