A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil
This dissertation addresses the hydrodeoxygenation (HDO) of the model compound 4-methylphenol and pyrolysis oil, over alternative, non-sulfided catalysts. The HDO of 4-methylphenol was studied over unsupported, low surface area MoS₂, MoO₂, MoO₃, and MoP catalysts. The initial turn over frequency (TO...
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ndltd-LACETR-oai-collectionscanada.gc.ca-BVAU.2429-446622014-03-26T03:39:50Z A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil Whiffen, Victoria This dissertation addresses the hydrodeoxygenation (HDO) of the model compound 4-methylphenol and pyrolysis oil, over alternative, non-sulfided catalysts. The HDO of 4-methylphenol was studied over unsupported, low surface area MoS₂, MoO₂, MoO₃, and MoP catalysts. The initial turn over frequency (TOF) for the HDO of 4-methylphenol decreased in the order MoP > MoS₂ > MoO₂ > MoO₃. Among the catalysts examined, MoP had the highest hydrogenating selectivity, lowest activation energy, and per site activity (TOF) for the HDO of 4-methylphenol. However, the observed conversion over MoP was limited by its low surface area and CO uptake. Addition of citric acid (CA) improved the properties of unsupported MoP. CA acted as a structural promoter and formed a metal citrate during the catalyst preparation, which increased the surface area and CO uptake of the MoP. High surface area Ni₂P catalysts were prepared similarly and based on initial TOFs, Ni₂P was 6 times more active than MoP for the HDO of 4-methylphenol. The HDO of 4-methylphenol was found to be structure insensitive over both MoP and Ni₂P. However, the Ni₂P catalysts deactivated due to C deposition on the catalyst surface. A kinetic model of the direct deoxygenation and hydrogenation reaction pathways for the HDO reaction over MoP showed the former to have a higher barrier energy (Ea = 106 kJ/mol) than the latter (Ea = 85 kJ/mol). Finally, to validate the use of model compounds to screen catalysts, the HDO of 4-methylphenol was compared to the HDO of pyrolysis oil over sulfide, oxide, and phosphide catalysts. MoP was found to have the highest yield of O-free liquid and the lowest coke yield, followed by Ni₂P, NiMoS/Al₂O₃, MoS₂, and MoO₃ for the HDO of pyrolysis oil. Those catalysts displaying high hydrogenating abilities had a high degree of O free liquid and a low yield of coke (MoP), while those catalysts displaying high isomerization abilities (MoO₃) had a high coke yield. Overall, this thesis identified phosphide catalysts as a new class of catalysts for HDO reactions with strong hydrogenating abilities, and their activity was superior to commercial NiMoS/Al₂O₃ for the HDO of pyrolysis oil. 2013-07-16T14:20:53Z 2013-07-17T09:12:14Z 2013 2013-07-16 2013-11 Electronic Thesis or Dissertation http://hdl.handle.net/2429/44662 eng University of British Columbia |
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English |
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description |
This dissertation addresses the hydrodeoxygenation (HDO) of the model compound 4-methylphenol and pyrolysis oil, over alternative, non-sulfided catalysts. The HDO of 4-methylphenol was studied over unsupported, low surface area MoS₂, MoO₂, MoO₃, and MoP catalysts. The initial turn over frequency (TOF) for the HDO of 4-methylphenol decreased in the order MoP > MoS₂ > MoO₂ > MoO₃. Among the catalysts examined, MoP had the highest hydrogenating selectivity, lowest activation energy, and per site activity (TOF) for the HDO of 4-methylphenol. However, the observed conversion over MoP was limited by its low surface area and CO uptake.
Addition of citric acid (CA) improved the properties of unsupported MoP. CA acted as a structural promoter and formed a metal citrate during the catalyst preparation, which increased the surface area and CO uptake of the MoP. High surface area Ni₂P catalysts were prepared similarly and based on initial TOFs, Ni₂P was 6 times more active than MoP for the HDO of 4-methylphenol. The HDO of 4-methylphenol was found to be structure insensitive over both MoP and Ni₂P. However, the Ni₂P catalysts deactivated due to C deposition on the catalyst surface. A kinetic model of the direct deoxygenation and hydrogenation reaction pathways for the HDO reaction over MoP showed the former to have a higher barrier energy (Ea = 106 kJ/mol) than the latter (Ea = 85 kJ/mol).
Finally, to validate the use of model compounds to screen catalysts, the HDO of 4-methylphenol was compared to the HDO of pyrolysis oil over sulfide, oxide, and phosphide catalysts. MoP was found to have the highest yield of O-free liquid and the lowest coke yield, followed by Ni₂P, NiMoS/Al₂O₃, MoS₂, and MoO₃ for the HDO of pyrolysis oil. Those catalysts displaying high hydrogenating abilities had a high degree of O free liquid and a low yield of coke (MoP), while those catalysts displaying high isomerization abilities (MoO₃) had a high coke yield. Overall, this thesis identified phosphide catalysts as a new class of catalysts for HDO reactions with strong hydrogenating abilities, and their activity was superior to commercial NiMoS/Al₂O₃ for the HDO of pyrolysis oil. |
author |
Whiffen, Victoria |
spellingShingle |
Whiffen, Victoria A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
author_facet |
Whiffen, Victoria |
author_sort |
Whiffen, Victoria |
title |
A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
title_short |
A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
title_full |
A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
title_fullStr |
A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
title_full_unstemmed |
A study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
title_sort |
study of metal phosphides for the hydrodeoxygenation of phenols and pyrolysis oil |
publisher |
University of British Columbia |
publishDate |
2013 |
url |
http://hdl.handle.net/2429/44662 |
work_keys_str_mv |
AT whiffenvictoria astudyofmetalphosphidesforthehydrodeoxygenationofphenolsandpyrolysisoil AT whiffenvictoria studyofmetalphosphidesforthehydrodeoxygenationofphenolsandpyrolysisoil |
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