Structure–Reactivity Relationships in Fuel Stability: Experimental and Kinetic Modeling Study of Isoparaffin Autoxidation

Liquid phase stability is a major concern in the transportation and the energy field where fuels, lubricants, and additives have to be stable from their production site to their application (engine, combustors). Although alkanes are major constituents of commercial fuels and well-documented solvents, their respective reactivities and selectivities in autoxidation are poorly understood. This experimental and modeling study aims at (i) enhancing the current knowledge on alkane autoxidation and (ii) reviewing and correcting the previously established structure reactivity relationships in alkane autoxidation. Experimentally, this study investigates the influence of branching [0–3] and temperature [373–433 K] on the autoxidation of alkanes using four octane isomers: n-octane (C8), 2-methylheptane (MH), 2,5-dimethylhexane (DMH), and the 2,2,4-trimethylpentane (TMP). Induction Period (IP) and qualitative species identification are used to characterize the autoxidation processes of alkanes. The present study also...

[1]  S. M. Sarathy,et al.  Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds , 2017, Proceedings of the National Academy of Sciences.

[2]  Arij Ben Amara,et al.  Toward the Accurate Prediction of Liquid Phase Oxidation of Aromatics: A Detailed Kinetic Mechanism for Toluene Autoxidation , 2017 .

[3]  K. Chatelain.  Oxidation stability of fuels in liquid phase , 2016 .

[4]  T. Bruin,et al.  First-principle based modeling of urea decomposition kinetics in aqueous solutions , 2016 .

[5]  M. Nardin,et al.  Original Experimental Approach for Assessing Transport Fuel Stability , 2016, Journal of visualized experiments : JoVE.

[6]  S. Mani Sarathy,et al.  Predicting Fuel Ignition Quality Using 1H NMR Spectroscopy and Multiple Linear Regression , 2016 .

[7]  Arij Ben Amara,et al.  Toward an optimal formulation of alternative jet fuels: Enhanced Oxidation and Thermal Stability by the addition of cyclic molecules , 2016 .

[8]  Arij Ben Amara,et al.  Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact on n-Alkanes Autoxidation , 2016 .

[9]  Wolfgang Marquardt,et al.  A Novel Group Contribution Method for the Prediction of the Derived Cetane Number of Oxygenated Hydrocarbons , 2015 .

[10]  M. Nardin,et al.  Oxidation Stability of Diesel/Biodiesel Fuels Measured by a PetroOxy Device and Characterization of Oxidation Products , 2015 .

[11]  M. Skolniak,et al.  Analysis of Changes in the Properties of Selected Chemical Compounds and Motor Fuels Taking Place During Oxidation Processes , 2015 .

[12]  Carl E. Brown,et al.  Storage stability of commercially available biodiesels and their blends under different storage conditions , 2014 .

[13]  Olaf Erik Herrmann,et al.  The New Denso Common Rail Diesel Solenoid Injector , 2013, MTZ worldwide.

[14]  F. Ser,et al.  OXIDATION STABILITY OF JET FUEL MODEL MOLECULES EVALUATED BY RAPID SMALL SCALE OXIDATION TESTS , 2013 .

[15]  Arij Ben Amara,et al.  Toward Predictive Modeling of Petroleum and Biobased Fuel Stability: Kinetics of Methyl Oleate/n-Dodecane Autoxidation , 2013 .

[16]  Diego Saldana Miranda,et al.  Prediction of Flash Points for Fuel Mixtures Using Machine Learning and a Novel Equation , 2013 .

[17]  Jean-Marie Aubry,et al.  Oxidative degradation of fragrant aldehydes. Autoxidation by molecular oxygen , 2013 .

[18]  William H. Green,et al.  An extensible framework for capturing solvent effects in computer generated kinetic models. , 2013, The journal of physical chemistry. B.

[19]  Pascal Mougin,et al.  Prediction of Density and Viscosity of Biofuel Compounds Using Machine Learning Methods , 2012 .

[20]  Ludivine Pidol,et al.  Flash Point and Cetane Number Predictions for Fuel Compounds Using Quantitative Structure Property Relationship (QSPR) Methods , 2011 .

[21]  J. J. Wilkinson,et al.  Autoxidation of Branched Alkanes in the Liquid Phase , 2011 .

[22]  J. Afonso,et al.  OXIDATIVE CRACKING OF LINEAR HYDROCARBONS AT LOW TEMPERATURES , 2010 .

[23]  W. Green,et al.  Predicting solvation energies for kinetic modeling , 2010 .

[24]  M. Abraham,et al.  Enthalpy of solvation correlations for organic solutes and gases dissolved in acetonitrile and acetone , 2009 .

[25]  Robert J. Santoro,et al.  Development of an advanced, thermally stable, coal-based jet fuel , 2008 .

[26]  L. Broadbelt,et al.  Mechanistic Modeling of Lubricant Degradation. 2. The Autoxidation of Decane and Octane , 2008 .

[27]  Yan Yang,et al.  Database Tools for Evaluating Thermophysical Property Data , 2007 .

[28]  M. Abraham.  Solvent Effects on Transition States and Reaction Rates , 2007 .

[29]  J. Ervin,et al.  Use of Measured Species Class Concentrations with Chemical Kinetic Modeling for the Prediction of Autoxidation and Deposition of Jet Fuels , 2007 .

[30]  Hans-Heinrich Carstensen,et al.  Rate constants for the abstraction reactions RO2 + C2H6; R = H, CH3, and C2H5 , 2005 .

[31]  Thomas R. Sem,et al.  Investigation of Injector Tip Deposits on Transport Refrigeration Units Running on Biodiesel Fuel , 2004 .

[32]  J. Ervin,et al.  Simulation of the Effect of Metal-Surface Catalysis on the Thermal Oxidation of Jet Fuel , 2004 .

[33]  Qing-xiang Guo,et al.  Isokinetic relationship, isoequilibrium relationship, and enthalpy-entropy compensation. , 2001, Chemical reviews.

[34]  A. J. Lusztyk,et al.  Kinetic Solvent Effects on Hydrogen-Atom Abstractions: Reliable, Quantitative Predictions via a Single Empirical Equation1 , 2001 .

[35]  J. Ervin,et al.  Computational Fluid Dynamics Simulations of Jet Fuel Oxidation Incorporating Pseudo-Detailed Chemical Kinetics , 1998 .

[36]  Steven Zabarnick,et al.  Chemical kinetic modeling of jet fuel autoxidation and antioxidant chemistry , 1993 .

[37]  F. García-Ochoa,et al.  Modeling of the thermal n-octane oxidation in the liquid phase , 1989 .

[38]  G. Just,et al.  Estimation of relative Autoxidation Rates of Normal Paraffins, secondary alcohols, and ketones by competitive reactions , 1986 .

[39]  C. F. Cullis,et al.  The oxidation of decane in the liquid and gaseous phases , 1981, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[40]  S. Korcek,et al.  Liquid-phase autoxidation of organic compounds at elevated temperatures. 1. The stirred flow reactor technique and analysis of primary products from n-hexadecane autoxidation at 120-180.degree.C , 1979 .

[41]  J. Howard,et al.  Absolute rate constants for hydrocarbon autoxidation. 25. Rate constants for hydrogen atom abstraction from alkanes by the tert-butylperoxy radical , 1978 .

[42]  A. M. Syroezhko,et al.  UMWANDLUNGEN VON DECANON-(2) UND DECANON-(3) BEI DER KATALYSIERTEN LUFTOXIDATION VON N-DECAN , 1974 .

[43]  T. Mill,et al.  Intramolecular propagation in the oxidation of n-alkanes. Autoxidation of n-pentane and n-octane , 1973 .

[44]  D. Sickle.  Oxidation of 2,4,6-trimethylheptane , 1972 .

[45]  R. Hazlett,et al.  Oxidation of hydrocarbons in the liquid phase: n-dodecane in a borosilicate glass chamber at 200 °C , 1969 .

[46]  G. Hearne,et al.  Liquid Phase Oxidation of Isobutane , 1961 .