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

Journal Article · · Energy and Fuels
DOI:https://doi.org/10.1021/ef502893g· OSTI ID:1178174
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3]
  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

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 blending 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.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
FOA-0000239; DE347AC36-99GO10337; AC36-08GO28308; 347-AC36-99GO10337
OSTI ID:
1178174
Alternate ID(s):
OSTI ID: 1220653
Report Number(s):
NREL/JA-5400-63352
Journal Information:
Energy and Fuels, Journal Name: Energy and Fuels Vol. 29 Journal Issue: 4; ISSN 0887-0624
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 70 works
Citation information provided by
Web of Science

References (28)

The flash pyrolysis of aspen-poplar wood journal October 1982
A review and perspective of recent bio-oil hydrotreating research journal January 2014
Renewable Oxygenate Blending Effects on Gasoline Properties journal October 2011
Bio-oil Stabilization and Upgrading by Hot Gas Filtration journal May 2013
Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review journal May 2006
Performance of lignin derived aromatic oxygenates in a heavy-duty diesel engine journal January 2014
Prediction of Hansen Solubility Parameters with a New Group-Contribution Method journal April 2008
Biomass feedstocks for renewable fuel production: a review of the impacts of feedstock and pretreatment on the yield and product distribution of fast pyrolysis bio-oils and vapors journal January 2014
Fuel Oil Quality of Biomass Pyrolysis OilsState of the Art for the End Users journal July 1999
Solubility and Equilibrium Data of Phenol-Water-n-Butyl Acetate System at 30° C. journal July 1962
Selective O-Alkylation of Phenol with Methanol over Sulfates Supported on γ-Al2O3 journal March 1995
Real-Time Viscosity Measurements during the Accelerated Aging of Biomass Pyrolysis Oil journal July 2011
Hansen Solubility Parameters book June 2007
Advanced bio-fuels from pyrolysis oil: The impact of economies of scale and use of existing logistic and processing capabilities journal December 2012
Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds journal April 2013
Anisole production by alkylation of phenol over ZSM5 journal October 1986
Ignition characteristics of a bio-derived class of saturated and unsaturated furans for engine applications journal January 2015
A perspective on oxygenated species in the refinery integration of pyrolysis oil journal January 2014
Methyl aryl ethers from coal liquids as gasoline extenders and octane improvers report November 1980
Utilization of Renewable Oxygenates as Gasoline Blending Components report August 2011
Air-Water Partitioning and Aqueous Solubility of Phenols journal March 1995
Identification and classification of components in flash pyrolysis oil and hydrodeoxygenated oils by two-dimensional gas chromatography and time-of-flight mass spectrometry journal April 2008
Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil Distillate Fractions journal November 2011
Combustion and Emissions of 2,5-Dimethylfuran in a Direct-Injection Spark-Ignition Engine journal May 2010
Experimental Study of Biomass Pyrolysis Based on Three Major Components: Hemicellulose, Cellulose, and Lignin journal September 2011
Additives To Lower and Stabilize the Viscosity of Pyrolysis Oils during Storage journal September 1997
Overview of Applications of Biomass Fast Pyrolysis Oil journal March 2004
Mild Hydrotreating of Bio-Oil: Effect of Reaction Severity and Fate of Oxygenated Species journal July 2011