A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure
Abstract
Particulate matter emissions negatively affect public health and global climate, yet newer fuel-efficient gasoline direct injection engines tend to produce more soot than their port-fuel injection counterparts. Fortunately, the search for sustainable biomass-based fuel blendstocks provides an opportunity to develop fuels that suppress soot formation in more efficient engine designs. However, as emissions tests are experimentally cumbersome and the search space for potential bioblendstocks is vast, new techniques are needed to estimate the sooting tendency of a diverse range of compounds. In this study, we develop a quantitative structure-activity relationship (QSAR) model of sooting tendency based on the experimental yield sooting index (YSI), which ranks molecules on a scale from n-hexane, 0, to benzene, 100. The model includes a rigorously defined applicability domain, and the predictive performance is checked using both internal and external validation. Model predictions for compounds in the external test set had a median absolute error of ~3 YSI units. An investigation of compounds that are poorly predicted by the model lends new insight into the complex mechanisms governing soot formation. Predictive models of soot formation can therefore be expected to play an increasingly important role in the screening and development of next-generation biofuels.
- Authors:
-
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Yale Univ., New Haven, CT (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (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), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Science Foundation (NSF)
- OSTI Identifier:
- 1394743
- Report Number(s):
- NREL/JA-2700-69123
Journal ID: ISSN 0887-0624
- Grant/Contract Number:
- AC36-08GO28308; ACI-1053575
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Energy and Fuels
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 9; Journal ID: ISSN 0887-0624
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; 54 ENVIRONMENTAL SCIENCES; sooting tendency; emissions
Citation Formats
St. John, Peter C., Kairys, Paul, Das, Dhrubajyoti D., McEnally, Charles S., Pfefferle, Lisa D., Robichaud, David J., Nimlos, Mark R., Zigler, Bradley T., McCormick, Robert L., Foust, Thomas D., Bomble, Yannick J., and Kim, Seonah. A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure. United States: N. p., 2017.
Web. doi:10.1021/acs.energyfuels.7b00616.
St. John, Peter C., Kairys, Paul, Das, Dhrubajyoti D., McEnally, Charles S., Pfefferle, Lisa D., Robichaud, David J., Nimlos, Mark R., Zigler, Bradley T., McCormick, Robert L., Foust, Thomas D., Bomble, Yannick J., & Kim, Seonah. A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure. United States. https://doi.org/10.1021/acs.energyfuels.7b00616
St. John, Peter C., Kairys, Paul, Das, Dhrubajyoti D., McEnally, Charles S., Pfefferle, Lisa D., Robichaud, David J., Nimlos, Mark R., Zigler, Bradley T., McCormick, Robert L., Foust, Thomas D., Bomble, Yannick J., and Kim, Seonah. 2017.
"A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure". United States. https://doi.org/10.1021/acs.energyfuels.7b00616. https://www.osti.gov/servlets/purl/1394743.
@article{osti_1394743,
title = {A Quantitative Model for the Prediction of Sooting Tendency from Molecular Structure},
author = {St. John, Peter C. and Kairys, Paul and Das, Dhrubajyoti D. and McEnally, Charles S. and Pfefferle, Lisa D. and Robichaud, David J. and Nimlos, Mark R. and Zigler, Bradley T. and McCormick, Robert L. and Foust, Thomas D. and Bomble, Yannick J. and Kim, Seonah},
abstractNote = {Particulate matter emissions negatively affect public health and global climate, yet newer fuel-efficient gasoline direct injection engines tend to produce more soot than their port-fuel injection counterparts. Fortunately, the search for sustainable biomass-based fuel blendstocks provides an opportunity to develop fuels that suppress soot formation in more efficient engine designs. However, as emissions tests are experimentally cumbersome and the search space for potential bioblendstocks is vast, new techniques are needed to estimate the sooting tendency of a diverse range of compounds. In this study, we develop a quantitative structure-activity relationship (QSAR) model of sooting tendency based on the experimental yield sooting index (YSI), which ranks molecules on a scale from n-hexane, 0, to benzene, 100. The model includes a rigorously defined applicability domain, and the predictive performance is checked using both internal and external validation. Model predictions for compounds in the external test set had a median absolute error of ~3 YSI units. An investigation of compounds that are poorly predicted by the model lends new insight into the complex mechanisms governing soot formation. Predictive models of soot formation can therefore be expected to play an increasingly important role in the screening and development of next-generation biofuels.},
doi = {10.1021/acs.energyfuels.7b00616},
url = {https://www.osti.gov/biblio/1394743},
journal = {Energy and Fuels},
issn = {0887-0624},
number = 9,
volume = 31,
place = {United States},
year = {Mon Jul 24 00:00:00 EDT 2017},
month = {Mon Jul 24 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Airborne Particulate Matter and Human Health: Toxicological Assessment and Importance of Size and Composition of Particles for Oxidative Damage and Carcinogenic Mechanisms
journal, November 2008
- Valavanidis, Athanasios; Fiotakis, Konstantinos; Vlachogianni, Thomais
- Journal of Environmental Science and Health, Part C, Vol. 26, Issue 4
Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols
journal, February 2001
- Jacobson, Mark Z.
- Nature, Vol. 409, Issue 6821
Ash Effects on Diesel Particulate Filter Pressure Drop Sensitivity to Soot and Implications for Regeneration Frequency and DPF Control
journal, April 2010
- Sappok, Alexander; Wong, Victor W.
- SAE International Journal of Fuels and Lubricants, Vol. 3, Issue 1
Strategies Towards Meeting Future Particulate Matter Emission Requirements in Homogeneous Gasoline Direct Injection Engines
journal, April 2011
- Piock, Walter; Hoffmann, Guy; Berndorfer, Axel
- SAE International Journal of Engines, Vol. 4, Issue 1
Assessing the Climate Trade-Offs of Gasoline Direct Injection Engines
journal, July 2016
- Zimmerman, Naomi; Wang, Jonathan M.; Jeong, Cheol-Heon
- Environmental Science & Technology, Vol. 50, Issue 15
Particulate matter indices using fuel smoke point for vehicle emissions with gasoline, ethanol blends, and butanol blends
journal, May 2016
- Barrientos, Eduardo J.; Anderson, James E.; Maricq, M. Matti
- Combustion and Flame, Vol. 167
Effect of molecular structure on incipient soot formation
journal, January 1983
- Calcote, H. F.; Manos, D. M.
- Combustion and Flame, Vol. 49, Issue 1-3
Group additivity in soot formation for the example of C-5 oxygenated hydrocarbon fuels
journal, August 2013
- Barrientos, Eduardo J.; Lapuerta, Magín; Boehman, André L.
- Combustion and Flame, Vol. 160, Issue 8
Novel Micropyrolyis Index (MPI) to Estimate the Sooting Tendency of Fuels
journal, July 2008
- Crossley, Steven P.; Alvarez, Walter E.; Resasco, Daniel E.
- Energy & Fuels, Vol. 22, Issue 4
Improved sooting tendency measurements for aromatic hydrocarbons and their implications for naphthalene formation pathways
journal, March 2007
- Mcenally, C.; Pfefferle, L.
- Combustion and Flame, Vol. 148, Issue 4
Sooting tendencies of nonvolatile aromatic hydrocarbons
journal, January 2009
- McEnally, Charles S.; Pfefferle, Lisa D.
- Proceedings of the Combustion Institute, Vol. 32, Issue 1
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
Sooting tendencies of unsaturated esters in nonpremixed flames
journal, April 2015
- Das, Dhrubajyoti D.; McEnally, Charles S.; Pfefferle, Lisa D.
- Combustion and Flame, Vol. 162, Issue 4
Computational Methods in Developing Quantitative Structure-Activity Relationships (QSAR): A Review
journal, March 2006
- Dudek, Arkadiusz; Arodz, Tomasz; Galvez, Jorge
- Combinatorial Chemistry & High Throughput Screening, Vol. 9, Issue 3
Principles of QSAR models validation: internal and external
journal, May 2007
- Gramatica, Paola
- QSAR & Combinatorial Science, Vol. 26, Issue 5
QSPR Models for Octane Number Prediction
journal, August 2014
- Al-Fahemi, Jabir H.; Albis, Nahla A.; Gad, Elshafie A. M.
- Journal of Theoretical Chemistry, Vol. 2014
Flash Point and Cetane Number Predictions for Fuel Compounds Using Quantitative Structure Property Relationship (QSPR) Methods
journal, September 2011
- Saldana, Diego Alonso; Starck, Laurie; Mougin, Pascal
- Energy & Fuels, Vol. 25, Issue 9
Relation of Smoke Point to Molecular Structure
journal, March 1953
- Hunt, Russell A.
- Industrial & Engineering Chemistry, Vol. 45, Issue 3
Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties
journal, September 1958
- Benson, Sidney W.; Buss, Jerry H.
- The Journal of Chemical Physics, Vol. 29, Issue 3
Structural group analysis for soot reduction tendency of oxygenated fuels
journal, July 2008
- Pepiotdesjardins, P.; Pitsch, H.; Malhotra, R.
- Combustion and Flame, Vol. 154, Issue 1-2
Prediction of Sooting Tendency for Hydrocarbon Liquids in Diffusion Flames
journal, November 2005
- Yan, Shihong; Eddings, Eric G.; Palotas, Arpad B.
- Energy & Fuels, Vol. 19, Issue 6
Two-dimensional soot volume fraction measurements in flames doped with large hydrocarbons
journal, January 2017
- Das, Dhrubajyoti D.; Cannella, William J.; McEnally, Charles S.
- Proceedings of the Combustion Institute, Vol. 36, Issue 1
SMILES, a chemical language and information system. 1. Introduction to methodology and encoding rules
journal, February 1988
- Weininger, David
- Journal of Chemical Information and Modeling, Vol. 28, Issue 1
Computational and experimental study of soot formation in a coflow, laminar ethylene diffusion flame
journal, January 1998
- McEnally, C. S.; Schaffer, A. M.; Long, M. B.
- Symposium (International) on Combustion, Vol. 27, Issue 1
Does Rational Selection of Training and Test Sets Improve the Outcome of QSAR Modeling?
journal, September 2012
- Martin, Todd M.; Harten, Paul; Young, Douglas M.
- Journal of Chemical Information and Modeling, Vol. 52, Issue 10
Relationships between Molecular Complexity, Biological Activity, and Structural Diversity
journal, March 2006
- Schuffenhauer, Ansgar; Brown, Nathan; Selzer, Paul
- Journal of Chemical Information and Modeling, Vol. 46, Issue 2
QSAR Applicability Domain Estimation by Projection of the Training Set in Descriptor Space: A Review
journal, October 2005
- Jaworska, Joanna; Nikolova-Jeliazkova, Nina; Aldenberg, Tom
- Alternatives to Laboratory Animals, Vol. 33, Issue 5
Isolation Forest
conference, December 2008
- Liu, Fei Tony; Ting, Kai Ming; Zhou, Zhi-Hua
- 2008 Eighth IEEE International Conference on Data Mining (ICDM)
Reaction mechanism of soot formation in flames
journal, February 2002
- Frenklach, Michael
- Physical Chemistry Chemical Physics, Vol. 4, Issue 11
Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study
journal, April 2006
- Wang, Dong; Violi, Angela; Kim, Do Hyong
- The Journal of Physical Chemistry A, Vol. 110, Issue 14
Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis
journal, March 2012
- Cavallotti, Carlo; Polino, Daniela; Frassoldati, Alessio
- The Journal of Physical Chemistry A, Vol. 116, Issue 13
Mechanism of the Pyrolysis of Bicyclo [2.2.1]heptadiene. Kinetics of the Bicyclo [2.2.1]heptadiene to Toluene Isomerization
journal, May 1964
- Herndon, William C.; Lowry, Lyle L.
- Journal of the American Chemical Society, Vol. 86, Issue 10
The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical
journal, July 2016
- Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg
- The Journal of Chemical Physics, Vol. 145, Issue 1
Radical Chemistry in the Thermal Decomposition of Anisole and Deuterated Anisoles: An Investigation of Aromatic Growth
journal, September 2010
- Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.
- The Journal of Physical Chemistry A, Vol. 114, Issue 34
The Effect of Compression Ratio, Fuel Octane Rating, and Ethanol Content on Spark-Ignition Engine Efficiency
journal, July 2015
- Leone, Thomas G.; Anderson, James E.; Davis, Richard S.
- Environmental Science & Technology, Vol. 49, Issue 18
The ChEBI reference database and ontology for biologically relevant chemistry: enhancements for 2013
journal, November 2012
- Hastings, Janna; de Matos, Paula; Dekker, Adriano
- Nucleic Acids Research, Vol. 41, Issue D1
Estimation of Soot Thresholds for Fuel Mixtures
journal, September 1984
- Gill, R. J.; Olson, D. B.
- Combustion Science and Technology, Vol. 40, Issue 5-6
Development of a Predictive Model for Gasoline Vehicle Particulate Matter Emissions
journal, August 2010
- Aikawa, Koichiro; Sakurai, Takayuki; Jetter, Jeff J.
- SAE International Journal of Fuels and Lubricants, Vol. 3, Issue 2
Knock Resistance and Fine Particle Emissions for Several Biomass-Derived Oxygenates in a Direct-Injection Spark-Ignition Engine
journal, April 2016
- Ratcliff, Matthew A.; Burton, Jonathan; Sindler, Petr
- SAE International Journal of Fuels and Lubricants, Vol. 9, Issue 1
Works referencing / citing this record:
Message-passing neural networks for high-throughput polymer screening
journal, June 2019
- St. John, Peter C.; Phillips, Caleb; Kemper, Travis W.
- The Journal of Chemical Physics, Vol. 150, Issue 23
Performance-advantaged ether diesel bioblendstock production by a priori design
journal, December 2019
- Huq, Nabila A.; Huo, Xiangchen; Hafenstine, Glenn R.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 52