skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on December 26, 2020

Title: Performance-advantaged ether diesel bioblendstock production by a priori design

Abstract

Lignocellulosic biomass provides a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. In this report, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C 2and C 4carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C 11branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers tomore » guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [2];  [1];  [3];  [1];  [4];  [4]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1] more »; ORCiD logo [1] « less
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Yale Univ., New Haven, CT (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (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); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1580492
Alternate Identifier(s):
OSTI ID: 1579571
Report Number(s):
NREL/JA-5100-74902
Journal ID: ISSN 0027-8424
Grant/Contract Number:  
AC36-08GO28308; AC36-99GO10337; EE0007983
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 52; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; biooxygenate; biofuel; solvent-free; technoeconomic analysis; life-cycle analysis; OPPL

Citation Formats

Huq, Nabila A., Huo, Xiangchen, Hafenstine, Glenn R., Tifft, Stephen M., Stunkel, Jim, Christensen, Earl D., Fioroni, Gina M., Fouts, Lisa, McCormick, Robert L., Cherry, Patrick A., McEnally, Charles S., Pfefferle, Lisa D., Wiatrowski, Matthew R., Benavides, P. Thathiana, Biddy, Mary J., Connatser, Raynella M., Kass, Michael D., Alleman, Teresa L., St. John, Peter C., Kim, Seonah, and Vardon, Derek R. Performance-advantaged ether diesel bioblendstock production by a priori design. United States: N. p., 2019. Web. doi:10.1073/pnas.1911107116.
Huq, Nabila A., Huo, Xiangchen, Hafenstine, Glenn R., Tifft, Stephen M., Stunkel, Jim, Christensen, Earl D., Fioroni, Gina M., Fouts, Lisa, McCormick, Robert L., Cherry, Patrick A., McEnally, Charles S., Pfefferle, Lisa D., Wiatrowski, Matthew R., Benavides, P. Thathiana, Biddy, Mary J., Connatser, Raynella M., Kass, Michael D., Alleman, Teresa L., St. John, Peter C., Kim, Seonah, & Vardon, Derek R. Performance-advantaged ether diesel bioblendstock production by a priori design. United States. doi:10.1073/pnas.1911107116.
Huq, Nabila A., Huo, Xiangchen, Hafenstine, Glenn R., Tifft, Stephen M., Stunkel, Jim, Christensen, Earl D., Fioroni, Gina M., Fouts, Lisa, McCormick, Robert L., Cherry, Patrick A., McEnally, Charles S., Pfefferle, Lisa D., Wiatrowski, Matthew R., Benavides, P. Thathiana, Biddy, Mary J., Connatser, Raynella M., Kass, Michael D., Alleman, Teresa L., St. John, Peter C., Kim, Seonah, and Vardon, Derek R. Thu . "Performance-advantaged ether diesel bioblendstock production by a priori design". United States. doi:10.1073/pnas.1911107116.
@article{osti_1580492,
title = {Performance-advantaged ether diesel bioblendstock production by a priori design},
author = {Huq, Nabila A. and Huo, Xiangchen and Hafenstine, Glenn R. and Tifft, Stephen M. and Stunkel, Jim and Christensen, Earl D. and Fioroni, Gina M. and Fouts, Lisa and McCormick, Robert L. and Cherry, Patrick A. and McEnally, Charles S. and Pfefferle, Lisa D. and Wiatrowski, Matthew R. and Benavides, P. Thathiana and Biddy, Mary J. and Connatser, Raynella M. and Kass, Michael D. and Alleman, Teresa L. and St. John, Peter C. and Kim, Seonah and Vardon, Derek R.},
abstractNote = {Lignocellulosic biomass provides a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. In this report, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C2and C4carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C11branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers to guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.},
doi = {10.1073/pnas.1911107116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 52,
volume = 116,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on December 26, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Net-zero emissions energy systems
journal, June 2018


Synthesis of Ethyl-4-ethoxy Pentanoate by Reductive Etherification of Ethyl Levulinate in Ethanol on Pd/SiO 2 -C Catalysts
journal, October 2018


Model-Based Design of Tailor-Made Biofuels
journal, February 2016


Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d

High cetane renewable diesel fuels prepared from bio-based methyl ketones and diols
journal, January 2018

  • Harrison, Kale W.; Harvey, Benjamin G.
  • Sustainable Energy & Fuels, Vol. 2, Issue 2
  • DOI: 10.1039/C7SE00415J

Water-Tolerant Solid Acid Catalysts
journal, October 2002


p-Sulfonic acid calix[n]arenes: the most active and water tolerant organocatalysts in esterification reactions
journal, January 2014

  • Natalino, R.; Varejão, E. V. V.; da Silva, M. J.
  • Catal. Sci. Technol., Vol. 4, Issue 5
  • DOI: 10.1039/C3CY01081C

Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia
journal, August 2018


Convergence on climate warming by black carbon aerosols
journal, April 2016

  • Gustafsson, Örjan; Ramanathan, Veerabhadran
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 16
  • DOI: 10.1073/pnas.1603570113

Catalytic etherification of glycerol by tert-butyl alcohol to produce oxygenated additives for diesel fuel
journal, October 2009


Production of alkanes from biomass derived carbohydrates on bi-functional catalysts employing niobium-based supports
journal, July 2009


Prediction of Flash Points of Middle Distillates
journal, April 1956

  • Butler, R. M.; Cooke, G. M.; Lukk, G. G.
  • Industrial & Engineering Chemistry, Vol. 48, Issue 4
  • DOI: 10.1021/ie50556a041

A Review of Flash Point Prediction Models for Flammable Liquid Mixtures
journal, July 2014

  • Phoon, Li Yee; Mustaffa, Azizul Azri; Hashim, Haslenda
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 32
  • DOI: 10.1021/ie501233g

Artificial neural network based predictions of cetane number for furanic biofuel additives
journal, October 2017


An alternative catalytic method to the Williamson's synthesis of ethers
journal, June 1995


Mechanism and kinetics of 1-dodecanol etherification over tungstated zirconia
journal, October 2017


Estimation of flash point temperature
journal, February 1973


A Novel Group Contribution Method for the Prediction of the Derived Cetane Number of Oxygenated Hydrocarbons
journal, August 2015


Chemical Structure–Based Predictive Model for Methanogenic Anaerobic Biodegradation Potential
journal, January 2007

  • Meylan, William; Boethling, Robert; Aronson, Dallas
  • Environmental Toxicology and Chemistry, Vol. 26, Issue 9
  • DOI: 10.1897/06-579R.1

Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification
journal, January 2019

  • Eagan, Nathaniel M.; Moore, Benjamin M.; McClelland, Daniel J.
  • Green Chemistry, Vol. 21, Issue 12
  • DOI: 10.1039/C9GC01290G

Lignin-Derived Carbon Fiber as a Co-Product of Refining Cellulosic Biomass
journal, January 2014

  • Langholtz, Matthew; Downing, Mark; Graham, Robin
  • SAE International Journal of Materials and Manufacturing, Vol. 7, Issue 1
  • DOI: 10.4271/2013-01-9092

Role of Lewis and Brønsted Acidity in Metal Chloride Catalysis in Organic Media: Reductive Etherification of Furanics
journal, September 2017


Bio-based volatile fatty acid production and recovery from waste streams: Current status and future challenges
journal, November 2018


Safety and Industrial Hygiene Issues Related to the Use of Oxygenates in Diesel Fuel
conference, May 1999

  • Murphy, Michael J.
  • International Fuels & Lubricants Meeting & Exposition, SAE Technical Paper Series
  • DOI: 10.4271/1999-01-1473

Oxygenates: An Evaluation of their Effects on Diesel Emissions
conference, May 2001

  • Yeh, L. I.; Rickeard, D. J.; Duff, J. L. C.
  • International Spring Fuels & Lubricants Meeting, SAE Technical Paper Series
  • DOI: 10.4271/2001-01-2019

Effects of ethanol–diesel fuel blends on the performance and exhaust emissions of heavy duty DI diesel engine
journal, November 2008


Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach
journal, January 2019

  • Huo, Xiangchen; Huq, Nabila A.; Stunkel, Jim
  • Green Chemistry, Vol. 21, Issue 21
  • DOI: 10.1039/C9GC01820D

Glycerol etherification with benzyl alcohol over sulfated zirconia catalysts
journal, September 2015


Wet waste-to-energy resources in the United States
journal, October 2018


Biogenous ethers: production and operation in a diesel engine
journal, April 2018

  • Damyanov, Aleksandar; Hofmann, Peter; Geringer, Bernhard
  • Automotive and Engine Technology, Vol. 3, Issue 1-2
  • DOI: 10.1007/s41104-018-0028-x

Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review focusing on acidogenic metabolic pathways
journal, January 2018


Production of Biomass-Based Automotive Lubricants by Reductive Etherification
journal, May 2017

  • Jadhav, Deepak; Grippo, Adam M.; Shylesh, Sankaranarayanapillai
  • ChemSusChem, Vol. 10, Issue 11
  • DOI: 10.1002/cssc.201700427

Direct Atom-Efficient Esterification between Carboxylic Acids and Alcohols Catalyzed by Amphoteric, Water-Tolerant TiO(acac) 2
journal, October 2005

  • Chen, Chien-Tien; Munot, Yogesh S.
  • The Journal of Organic Chemistry, Vol. 70, Issue 21
  • DOI: 10.1021/jo051337s

New group contribution method for estimating properties of pure compounds
journal, October 1994


Global estimates of mortality associated with long-term exposure to outdoor fine particulate matter
journal, September 2018

  • Burnett, Richard; Chen, Hong; Szyszkowicz, Mieczysław
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 38
  • DOI: 10.1073/pnas.1803222115

Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale
journal, April 2018


Retardation of oxidation and material degradation in biodiesel: a review
journal, January 2016

  • Sazzad, B. S.; Fazal, M. A.; Haseeb, A. S. M. A.
  • RSC Advances, Vol. 6, Issue 65
  • DOI: 10.1039/C6RA10016C

Direct Hydrogenation of Biomass-Derived Butyric Acid to n -Butanol over a Ruthenium-Tin Bimetallic Catalyst
journal, August 2014


Early-Stage Capital Cost Estimation of Biorefinery Processes: A Comparative Study of Heuristic Techniques
journal, August 2016

  • Tsagkari, Mirela; Couturier, Jean-Luc; Kokossis, Antonis
  • ChemSusChem, Vol. 9, Issue 17
  • DOI: 10.1002/cssc.201600309

Economic analysis of wet waste-to-energy resources in the United States
journal, June 2019


Why Are Some Properties More Difficult To Predict than Others? A Study of QSPR Models of Solubility, Melting Point, and Log P
journal, December 2007

  • Hughes, Laura D.; Palmer, David S.; Nigsch, Florian
  • Journal of Chemical Information and Modeling, Vol. 48, Issue 1
  • DOI: 10.1021/ci700307p

Volatile fatty acids production from food wastes for biorefinery platforms: A review
journal, November 2018

  • Strazzera, Giuseppe; Battista, Federico; Garcia, Natalia Herrero
  • Journal of Environmental Management, Vol. 226
  • DOI: 10.1016/j.jenvman.2018.08.039

Applying thermodynamics to fossil fuels: Heats of combustion from elemental compositions
journal, January 1980

  • Lloyd, William G.; Davenport, Derek A.
  • Journal of Chemical Education, Vol. 57, Issue 1
  • DOI: 10.1021/ed057p56

One-Pot Synthesis of Alkyl 4-Alkoxypentanoates by Esterification and Reductive Etherification of Levulinic Acid in Alcoholic Solutions
journal, July 2016


Introduction: A smouldering public-health crisis
journal, June 2011


Efficient Hydrogenation of Ketones Catalyzed by an Iron Pincer Complex
journal, January 2011

  • Langer, Robert; Leitus, Gregory; Ben-David, Yehoshoa
  • Angewandte Chemie International Edition, Vol. 50, Issue 9
  • DOI: 10.1002/anie.201007406

Renewable Gasoline, Solvents, and Fuel Additives from 2,3-Butanediol
journal, June 2016

  • Harvey, Benjamin G.; Merriman, Walter W.; Quintana, Roxanne L.
  • ChemSusChem, Vol. 9, Issue 14
  • DOI: 10.1002/cssc.201600225

Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment
journal, June 2015

  • Balakrishnan, Madhesan; Sacia, Eric R.; Sreekumar, Sanil
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1508274112

Water-tolerant heteropolyacid on magnetic nanoparticles as efficient catalysts for esterification of free fatty acid
journal, January 2013

  • Duan, Xixin; Liu, Yue; Zhao, Qian
  • RSC Advances, Vol. 3, Issue 33
  • DOI: 10.1039/c3ra40219c

Upgraded Acidic Components of Bio-oil through Catalytic Ketonic Condensation
journal, January 2009

  • Deng, Li; Fu, Yao; Guo, Qing-Xiang
  • Energy & Fuels, Vol. 23, Issue 1
  • DOI: 10.1021/ef800692a

Long-term storage stability of biodiesel and biodiesel blends
journal, December 2014


A review of the production and applications of waste-derived volatile fatty acids
journal, January 2014

  • Lee, Wee Shen; Chua, Adeline Seak May; Yeoh, Hak Koon
  • Chemical Engineering Journal, Vol. 235
  • DOI: 10.1016/j.cej.2013.09.002

Screening of Potential Biomass-Derived Streams as Fuel Blendstocks for Mixing Controlled Compression Ignition Combustion
conference, April 2019

  • Fioroni, Gina; Fouts, Lisa; Luecke, Jon
  • WCX SAE World Congress Experience, SAE Technical Paper Series
  • DOI: 10.4271/2019-01-0570

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions
journal, August 2017


Estimation of a Lower Heating Value of Vegetable Oil and Biodiesel Fuel
journal, August 2009

  • Mehta, Pramod S.; Anand, K.
  • Energy & Fuels, Vol. 23, Issue 8
  • DOI: 10.1021/ef900196r

Ether synthesis from alcohol and aldehyde in the presence of hydrogen and palladium deposited on charcoal
journal, March 2000


REVIEW OF THE ENVIRONMENTAL BEHAVIOR AND FATE OF METHYL tert-BUTYL ETHER
journal, January 1997


Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion
journal, October 2013

  • Pham, Tu N.; Sooknoi, Tawan; Crossley, Steven P.
  • ACS Catalysis, Vol. 3, Issue 11
  • DOI: 10.1021/cs400501h

Life cycle assessment of adipic acid production from lignin
journal, January 2018

  • Corona, Andrea; Biddy, Mary J.; Vardon, Derek R.
  • Green Chemistry, Vol. 20, Issue 16
  • DOI: 10.1039/C8GC00868J

Integrated catalytic sequences for catalytic upgrading of bio-derived carboxylic acids to fuels, lubricants and chemical feedstocks
journal, January 2017

  • Shylesh, Sankaranarayanapillai; Gokhale, Amit A.; Sun, Keyang
  • Sustainable Energy & Fuels, Vol. 1, Issue 8
  • DOI: 10.1039/C7SE00359E

A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure
journal, August 2017


Sooting tendencies of diesel fuels, jet fuels, and their surrogates in diffusion flames
journal, June 2017


Sooting Tendencies of Oxygenated Hydrocarbons in Laboratory-Scale Flames
journal, March 2011

  • McEnally, Charles S.; Pfefferle, Lisa D.
  • Environmental Science & Technology, Vol. 45, Issue 6
  • DOI: 10.1021/es103733q

Solid Acid Catalysts for Biodiesel Production –-Towards Sustainable Energy
journal, January 2006

  • Kiss, Anton A.; Dimian, Alexandre C.; Rothenberg, Gadi
  • Advanced Synthesis & Catalysis, Vol. 348, Issue 1-2
  • DOI: 10.1002/adsc.200505160