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Title: An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh2P

Abstract

Here, the production of hydrocarbon fuels from biomass pyrolysis requires the development of effective deoxygenation catalysts, and insight into how the properties of the support influence performance is critical for catalyst design. In this report, nanoparticles of Ni and Rh2P were synthesized using solution-phase techniques and dispersed on high surface area supports. The supports included a relatively inert material (C), an acidic reducible metal-oxide (TiO2), an acidic irreducible metal-oxide (Al2O3), and a basic irreducible metal-oxide (MgO). The eight active phase/support combinations were investigated for the deoxygenation of guaiacol, a pyrolysis vapor model compound, under ex situ catalytic fast pyrolysis conditions (350 °C, 0.44 MPa H2). Compared to the baseline performance of the C-supported catalysts, Ni/TiO2 and Rh2P/TiO2 exhibited higher guaiacol conversion and lower O : C ratios for C5+ products, highlighting the enhanced activity and greater selectivity to deoxygenated products derived from the use of an acidic reducible metal-oxide support. The Al2O3-supported catalysts also exhibited higher conversion than the C-supported catalysts and promoted alkylation reactions, which improve carbon efficiency and increase the carbon number of the C5+ products. However, Ni/Al2O3 and Rh2P/Al2O3 were less selective towards deoxygenated products than the C-supported catalysts. The MgO-supported catalyst exhibited lower conversion and decreasedmore » yield of deoxygenated products compared to the C-supported catalysts. The results reported here suggest that basic metal-oxide supports may inhibit deoxygenation of phenolics under CFP conditions. Contrastingly, support acidity and reducibility were demonstrated to promote conversion and selectivity to deoxygenated products, respectively.« less

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1372621
Report Number(s):
NREL/JA-5100-67975
Journal ID: ISSN 2044-4753; CSTAGD
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 7; Journal Issue: 14; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; catalytic fast pyrolysis; deoxygenation; nanoparticle; metal phosphide; support effect

Citation Formats

Griffin, Michael B., Baddour, Frederick G., Habas, Susan E., Nash, Connor P., Ruddy, Daniel A., and Schaidle, Joshua A. An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh2P. United States: N. p., 2017. Web. doi:10.1039/C7CY00261K.
Griffin, Michael B., Baddour, Frederick G., Habas, Susan E., Nash, Connor P., Ruddy, Daniel A., & Schaidle, Joshua A. An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh2P. United States. doi:10.1039/C7CY00261K.
Griffin, Michael B., Baddour, Frederick G., Habas, Susan E., Nash, Connor P., Ruddy, Daniel A., and Schaidle, Joshua A. Tue . "An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh2P". United States. doi:10.1039/C7CY00261K. https://www.osti.gov/servlets/purl/1372621.
@article{osti_1372621,
title = {An investigation into support cooperativity for the deoxygenation of guaiacol over nanoparticle Ni and Rh2P},
author = {Griffin, Michael B. and Baddour, Frederick G. and Habas, Susan E. and Nash, Connor P. and Ruddy, Daniel A. and Schaidle, Joshua A.},
abstractNote = {Here, the production of hydrocarbon fuels from biomass pyrolysis requires the development of effective deoxygenation catalysts, and insight into how the properties of the support influence performance is critical for catalyst design. In this report, nanoparticles of Ni and Rh2P were synthesized using solution-phase techniques and dispersed on high surface area supports. The supports included a relatively inert material (C), an acidic reducible metal-oxide (TiO2), an acidic irreducible metal-oxide (Al2O3), and a basic irreducible metal-oxide (MgO). The eight active phase/support combinations were investigated for the deoxygenation of guaiacol, a pyrolysis vapor model compound, under ex situ catalytic fast pyrolysis conditions (350 °C, 0.44 MPa H2). Compared to the baseline performance of the C-supported catalysts, Ni/TiO2 and Rh2P/TiO2 exhibited higher guaiacol conversion and lower O : C ratios for C5+ products, highlighting the enhanced activity and greater selectivity to deoxygenated products derived from the use of an acidic reducible metal-oxide support. The Al2O3-supported catalysts also exhibited higher conversion than the C-supported catalysts and promoted alkylation reactions, which improve carbon efficiency and increase the carbon number of the C5+ products. However, Ni/Al2O3 and Rh2P/Al2O3 were less selective towards deoxygenated products than the C-supported catalysts. The MgO-supported catalyst exhibited lower conversion and decreased yield of deoxygenated products compared to the C-supported catalysts. The results reported here suggest that basic metal-oxide supports may inhibit deoxygenation of phenolics under CFP conditions. Contrastingly, support acidity and reducibility were demonstrated to promote conversion and selectivity to deoxygenated products, respectively.},
doi = {10.1039/C7CY00261K},
journal = {Catalysis Science and Technology},
number = 14,
volume = 7,
place = {United States},
year = {2017},
month = {6}
}

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    Works referencing / citing this record:

    Role of Sn promoter in Ni/Al 2 O 3 catalyst for the deoxygenation of stearic acid and coke formation: experimental and theoretical studies
    journal, January 2019

    • Reangchim, Promporn; Saelee, Tinnakorn; Itthibenchapong, Vorranutch
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