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Title: Role of ZrO2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts

Abstract

The effects of Zr promotion on the structure and performance of Co-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. Inclusion of Zr in the catalysts was found to increase the FTS turnover frequency and the selectivity to C5+ hydrocarbons and to decrease the selectivity to methane under most operating conditions. These improvements to the catalytic performance are a function of Zr loading up to an atomic ratio of Zr/Co = 1.0, above which the product selectivity is insensitive to higher concentrations of the promoter. Characterization of the Co nanoparticles by different methods demonstrated that the optimal Zr loading corresponds to half monolayer coverage of the Co surface by the promoter. Measurements of the rate of FTS at different pressures and temperatures established that the kinetics data for both the Zr-promoted and unpromoted catalysts are described by a two-parameter Langmuir-Hinshelwood expression. The parameters used to fit this rate law to the experimental data indicate that the apparent rate coefficient and the CO adsorption constant for the Zr-promoted catalysts are higher than those for the unpromoted catalyst. Elemental mapping by means of STEM-EDS provided evidence that Zr is highly dispersed over the catalyst surface and has limited preference for association with the Comore » nanoparticles. In situ X-ray absorption spectroscopy confirmed the absence of mixing between the Zr and Co in the nanoparticles. Here, these results suggest that Zr exists as a partial layer of ZrO2 on the surface of the Co metal nanoparticles. Accordingly, it is proposed that Zr promotion effects originate from sites of enhanced activity at the interface between Co and ZrO2. The possibility that ZrO2 acts as a Lewis acid to assist in CO dissociation as well as to increase the ratio of CO to H adsorbed on the catalyst surface is discussed.« less

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1418287
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cobalt; Fischer−Tropsch synthesis; heterogeneous catalysis; promotion; zirconium

Citation Formats

Johnson, Gregory R., and Bell, Alexis T. Role of ZrO2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b02205.
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Johnson, Gregory R., & Bell, Alexis T. Role of ZrO2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts. United States. https://doi.org/10.1021/acscatal.5b02205
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Johnson, Gregory R., and Bell, Alexis T. Tue . "Role of ZrO2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts". United States. https://doi.org/10.1021/acscatal.5b02205. https://www.osti.gov/servlets/purl/1418287.
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@article{osti_1418287,
title = {Role of ZrO2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts},
author = {Johnson, Gregory R. and Bell, Alexis T.},
abstractNote = {The effects of Zr promotion on the structure and performance of Co-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. Inclusion of Zr in the catalysts was found to increase the FTS turnover frequency and the selectivity to C5+ hydrocarbons and to decrease the selectivity to methane under most operating conditions. These improvements to the catalytic performance are a function of Zr loading up to an atomic ratio of Zr/Co = 1.0, above which the product selectivity is insensitive to higher concentrations of the promoter. Characterization of the Co nanoparticles by different methods demonstrated that the optimal Zr loading corresponds to half monolayer coverage of the Co surface by the promoter. Measurements of the rate of FTS at different pressures and temperatures established that the kinetics data for both the Zr-promoted and unpromoted catalysts are described by a two-parameter Langmuir-Hinshelwood expression. The parameters used to fit this rate law to the experimental data indicate that the apparent rate coefficient and the CO adsorption constant for the Zr-promoted catalysts are higher than those for the unpromoted catalyst. Elemental mapping by means of STEM-EDS provided evidence that Zr is highly dispersed over the catalyst surface and has limited preference for association with the Co nanoparticles. In situ X-ray absorption spectroscopy confirmed the absence of mixing between the Zr and Co in the nanoparticles. Here, these results suggest that Zr exists as a partial layer of ZrO2 on the surface of the Co metal nanoparticles. Accordingly, it is proposed that Zr promotion effects originate from sites of enhanced activity at the interface between Co and ZrO2. The possibility that ZrO2 acts as a Lewis acid to assist in CO dissociation as well as to increase the ratio of CO to H adsorbed on the catalyst surface is discussed.},
doi = {10.1021/acscatal.5b02205},
journal = {ACS Catalysis},
number = 1,
volume = 6,
place = {United States},
year = {Tue Nov 17 00:00:00 EST 2015},
month = {Tue Nov 17 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acscatal.5b02205
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