TY - JOUR
T1 - Properties of Oxygenates Found in Upgraded Biomass Pyrolysis Oil as Components of Spark and Compression Ignition Engine Fuels
AU - McCormick, Robert L.
AU - Ratcliff, Matthew A.
AU - Christensen, Earl
AU - Fouts, Lisa
AU - Luecke, Jon
AU - Chupka, Gina M.
AU - Yanowitz, Janet
AU - Tian, Miao
AU - Boot, Michael
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015
Y1 - 2015
N2 - Oxygenates present in partially hydroprocessed lignocellulosic-biomass pyrolysis oils were examined for their impact on the performance properties of gasoline and diesel. These included: methyltetrahydrofuran, 2,5-dimethylfuran (DMF), 2-hexanone, 4-methylanisole, phenol, p-cresol, 2,4-xylenol, guaiacol, 4-methylguaiacol, 4-methylacetophenone, 4-propylphenol, and 4-propylguaiacol. Literature values indicate that acute toxicity for these compounds falls within the range of the components in petroleum-derived fuels. On the basis of the available data, 4-methylanisole and by extension other methyl aryl ethers appear to be the best drop-in fuel components for gasoline because they significantly increase research octane number and slightly reduce vapor pressure without significant negative fuel property effects. A significant finding is that DMF can produce high levels of gum under oxidizing conditions. If the poor stability results observed for DMF could be addressed with a stabilizer additive or removal of impurities, it could also be considered a strong drop-in fuel candidate. The low solubility of phenol and p-cresol (and by extension, the two other cresol isomers) in hydrocarbons and the observation that phenol is also highly extractable into water suggest that these molecules cannot likely be present above trace levels in drop-in fuels. The diesel boiling range oxygenates all have low cetane numbers, which presents challenges for blending into diesel fuel. There were some beneficial properties observed for the phenolic oxygenates in diesel, including increasing conductivity, lubricity, and oxidation stability of the diesel fuel. Oxygenates other than phenol and cresol, including other phenolic compounds, showed no negative impacts at the low blend levels examined here and could likely be present in an upgraded bio-oil gasoline or diesel blendstock at low levels to make a drop-in fuel. On the basis of solubility parameter theory, 4-methylanisole and DMF showed less interaction with elastomers than ethanol, while phenolic compounds showed somewhat greater interaction. This effect is not large, especially at low blend levels, and is also less significant as the size and number of alkyl substituents on the phenol ring increase.
AB - Oxygenates present in partially hydroprocessed lignocellulosic-biomass pyrolysis oils were examined for their impact on the performance properties of gasoline and diesel. These included: methyltetrahydrofuran, 2,5-dimethylfuran (DMF), 2-hexanone, 4-methylanisole, phenol, p-cresol, 2,4-xylenol, guaiacol, 4-methylguaiacol, 4-methylacetophenone, 4-propylphenol, and 4-propylguaiacol. Literature values indicate that acute toxicity for these compounds falls within the range of the components in petroleum-derived fuels. On the basis of the available data, 4-methylanisole and by extension other methyl aryl ethers appear to be the best drop-in fuel components for gasoline because they significantly increase research octane number and slightly reduce vapor pressure without significant negative fuel property effects. A significant finding is that DMF can produce high levels of gum under oxidizing conditions. If the poor stability results observed for DMF could be addressed with a stabilizer additive or removal of impurities, it could also be considered a strong drop-in fuel candidate. The low solubility of phenol and p-cresol (and by extension, the two other cresol isomers) in hydrocarbons and the observation that phenol is also highly extractable into water suggest that these molecules cannot likely be present above trace levels in drop-in fuels. The diesel boiling range oxygenates all have low cetane numbers, which presents challenges for blending into diesel fuel. There were some beneficial properties observed for the phenolic oxygenates in diesel, including increasing conductivity, lubricity, and oxidation stability of the diesel fuel. Oxygenates other than phenol and cresol, including other phenolic compounds, showed no negative impacts at the low blend levels examined here and could likely be present in an upgraded bio-oil gasoline or diesel blendstock at low levels to make a drop-in fuel. On the basis of solubility parameter theory, 4-methylanisole and DMF showed less interaction with elastomers than ethanol, while phenolic compounds showed somewhat greater interaction. This effect is not large, especially at low blend levels, and is also less significant as the size and number of alkyl substituents on the phenol ring increase.
KW - biomass
KW - diesel
KW - gasoline
KW - oxygenates
KW - pyrolysis
UR - http://www.scopus.com/inward/record.url?scp=84928136775&partnerID=8YFLogxK
U2 - 10.1021/ef502893g
DO - 10.1021/ef502893g
M3 - Article
AN - SCOPUS:84928136775
SN - 0887-0624
VL - 29
SP - 2453
EP - 2461
JO - Energy and Fuels
JF - Energy and Fuels
IS - 4
ER -