Title: Properties of Oxygenates Found in Upgraded Biomass Pyrolysis Oil as Components of Spark and Compression Ignition Engine Fuels

Abstract

We examined xxygenates present in partially hydroprocessed lignocellulosic-biomass pyrolysis oils 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 blendingmore » into diesel fuel. Moreover, 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.« less

Authors:

McCormick, Robert L. ^[1]; Ratcliff, Matthew A. ^[1]; Christensen, Earl ^[1]; Fouts, Lisa ^[1]; Luecke, Jon ^[1]; Chupka, Gina M. ^[1]; Yanowitz, Janet ^[2]; Tian, Miao ^[3]; Boot, Michael ^[3]

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+ Show Author Affiliations

1. National Renewable Energy Laboratory, Golden, Colorado 80401, United States
2. EcoEngineering, Inc., Boulder, Colorado 80304, United States
3. Eindhoven Technical University, 5612AZ Eindhoven, Netherlands

Publication Date:

2015-03-19

Research Org.:

National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

OSTI Identifier:

1178174

Alternate Identifier(s):

OSTI ID: 1220653

Report Number(s):

NREL/JA-5400-63352
Journal ID: ISSN 0887-0624

Grant/Contract Number:  

FOA-0000239; DE347AC36-99GO10337; AC36-08GO28308; 347-AC36-99GO10337

Resource Type:

Published Article

Journal Name:

Energy and Fuels

Additional Journal Information:

Journal Name: Energy and Fuels Journal Volume: 29 Journal Issue: 4; Journal ID: ISSN 0887-0624

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

09 BIOMASS FUELS; biomass; pyrolysis; oxygenates; gasoline; diesel