Jet fuels, like typical transportation fuels, are mixtures of several hundreds of compounds belonging to different hydrocarbon classes. Their composition varies from one source to another, and only average fuel properties are known at best. In order to understand the combustion characteristics of the real fuels, and to address the problem of combustion control, computational studies using a detailed kinetic model to represent the real fuel, serves as a highly useful tool. However, the complexity of the real fuels makes it infeasible to simulate their combustion characteristics directly, requiring a simplified fuel representation to circumvent this difficulty. Typically, the real fuels are modeled using a representative surrogate mixture, i.e. a well-defined mixture comprised of a few components chosen to mimic the desired physical and chemical properties of the real fuel under consideration. Surrogates have been proposed for transportation fuels, including aviation fuels, and several kinetic modeling attempts for the proposed surrogates have also been made. However, (i) the fundamental kinetics of individual fuels, which make up the surrogate mixtures is not understood well, (ii) their combustion behavior at low through high temperatures has not been comprehensively validated, and this directly impacts the (iii) reliability of the multi-component reaction mechanism for a surrogate made up of these individual components. The present work is aimed at addressing the afore-mentioned concerns. The objective of this work is to develop a single, reliable kinetic model that can describe the oxidation of a few representative fuels, which are important components of transportation fuel surrogates, and thereby capture the specificities of the simpler, but still multi-component surrogates. The reaction mechanism is intended to well-represent the individual components as well as a multi-component surrogate for jet fuel made up of these fuel components. Further, this reaction mechanism is desired to be applicable at low through high temperatures, and be compact enough that chemical kinetic analysis is feasible. First, a representative compound for each of the major hydrocarbon classes found in the real jet fuel is identified. A surrogate for jet fuels is chosen to be comprised of n-dodecane (to represent normal alkanes), methylcyclohexane (to represent cyclic alkanes), and m-xylene (to represent aromatics). A Component Library approach is invoked for the development of a single, consistent, and reliable chemical scheme to accurately model this multi-component surrogate mixture. The chemical model is assembled in stages, starting with a base model and adding to it sub-mechanisms for the individual components of the surrogate, namely m- xylene, n-dodecane, and methylcyclohexane. The chemical model is validated comprehensively every time the oxidation pathways of a new component are incorporated into it and the experimental data is well captured by the simulations. In addition to the jet fuel surrogate, with the number of fuels described in the proposed reaction mechanism, a surrogate for the alternative Fischer-Tropsch fuels is also considered. Surrogates are defined for jet fuels and Fischer-Tropsch fuels by matching target properties important for combustion applications between the surrogate and the real fuel. The simulations performed using the proposed reaction mechanism, with the surrogates defined as fuels, are compared against global targets, such as ignition delays, flow reactor profiles, and flame speed measurements for representative jet fuels and Fischer-Tropsch fuels. The computations show promising agreement with these experimental data sets. The proposed reaction mechanism is well-suited to be used in real flow simulations of jet fuels. The proposed reaction mechanism has the ability to describe the kinetics of n- heptane, iso-octane, substituted aromatics, n-dodecane, and methylcyclohexane, all of which are important components of transportation fuel surrogates. Considering the large number of hydrocarbons whose kinetics are well described by this reaction mechanism, there are avenues for this reaction mechanism to be used to model other transportation fuels, such as gasoline, diesel, and alternative fuels, in addition to the jet and Fischer-Tropsch fuels discussed in the present study.

The chemistries of aviation fuels are invariably complex due to largehydrocarbon molecules. There are also large variations for a given fuel type. Furthermore, flow timescales encountered in high performance propulsion devicesincreasingly lead to difficulties associated with kinetically controlled or influencedphenomena such as flame stability, extinction and re-light. Current indications alsosuggest that fuel sources will become significantly more diverse in the future andmay, for example, encompass Fischer-Tropsch and/or bio-derived components. Thecombustion properties of such fuels can vary significantly from those in current useand this work outlines a route towards surrogate fuel mechanisms of sufficientaccuracy and generality to support the development of practical devices. A reaction class based route to the derivation of detailed chemical kineticmechanisms for alkyl-substituted aromatics is outlined and applied to thecyclopentadiene/indene, benzene/naphthalene, toluene/1-methyl naphthalenesystems. Work has also been extended to the n-propyl benzene system as well. These reaction classes were applied to model the oxidation of the above fuels withencouraging results. Important reaction channels during oxidation were identifiedand specifically, the methyl groups on aromatic rings have been identified asimportant in the context of radical scavenging. Furthermore, 1-methyl naphthalenemay also be used to modulate sooting tendencies in aviation and Diesel surrogates. Results obtained from chemical kinetic modelling of cyclopentadiene, toluene, npropylbenzene, naphthalene and 1-methyl naphthalene oxidation in shock tubes, jet-stirred and plug-flow reactors at various sets of representative stoichiometriesand temperatures are reported.

Gasoline consists of many different classes of hydrocarbons, such as paraffins, olefins, aromatics, and cycloalkanes. In this study, a surrogate gasoline reaction mechanism is developed, and it has one representative fuel constituent from each of these classes. These selected constituents are iso-octane, n-heptane, 1-pentene, toluene, and methyl-cyclohexane. The mechanism was developed in a step-wise fashion, adding submechanisms to treat each fuel component. Reactions important for low temperature oxidation (

Gasoline, diesel, and other alternative transportation fuels contain hundreds to thousands of compounds. It is currently not possible to represent all these compounds in detailed chemical kinetic models. Instead, these fuels are represented by surrogate fuel models which contain a limited number of representative compounds. We have been extending the list of compounds for detailed chemical models that are available for use in fuel surrogate models. Detailed models for components with larger and more complicated fuel molecular structures are now available. These advancements are allowing a more accurate representation of practical and alternative fuels. We have developed detailed chemical kinetic models for fuels with higher molecular weight fuel molecules such as n-hexadecane (C16). Also, we can consider more complicated fuel molecular structures like cyclic alkanes and aromatics that are found in practical fuels. For alternative fuels, the capability to model large biodiesel fuels that have ester structures is becoming available. These newly addressed cyclic and ester structures in fuels profoundly affect the reaction rate of the fuel predicted by the model. Finally, these surrogate fuel models contain large numbers of species and reactions and must be reduced for use in multi-dimensional models for spark-ignition, HCCI and diesel engines.

Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. It is generally agreed that their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. In this work, a recently revised version of the kinetic model by the authors is used to analyze the combustion behavior of several components relevant to gasoline surrogate formulation. Particular attention is devoted to linear and branched saturated hydrocarbons (PRF mixtures), olefins (1-hexene) and aromatics (toluene). Model predictions for pure components, binary mixtures and multi-component gasoline surrogates are compared with recent experimental information collected in rapid compression machine, shock tube and jet stirred reactors covering a wide range of conditions pertinent to internal combustion engines. Simulation results are discussed focusing attention on the mixing effects of the fuel components.

The removal of the high Damkohler number assumption from modeling approaches is essential for the computational simulation of combusting flows where strong direct kinetic effects are present. Examples of relevant physical phenomena include flame extinction and re-light as well as pollutant emissions. Calculation methods (e.g. LES/FMDF) aimed at including such effects are computationally demanding and simplified reaction mechanisms that represent the desired chemical features with sufficient accuracy are required. Difficulties are augmented for aviation fuels due to the wide range of fuel components and sufficiently accurate detailed surrogate mechanisms are required for the subsequent derivation of further simplifications under actual operating conditions prior to the implementation into calculation methods for turbulent flows. The present paper addresses the issue of substituted aromatics and outlines a reaction class based route to the derivation of detailed chemical kinetic mechanisms. The example given considers the toluene/1-methyl naphthalene system.

There has been much recent progress in the area of surrogate fuels for diesel. In the last few years, experiments and modeling have been performed on higher molecular weight components of relevance to diesel fuel such as n-hexadecane (n-cetane) and 2,2,4,4,6,8,8-heptamethylnonane (iso-cetane). Chemical kinetic models have been developed for all the n-alkanes up to 16 carbon atoms. Also, there has been much experimental and modeling work on lower molecular weight surrogate components such as n-decane and do-decane which are most relevant to jet fuel surrogates, but are also relevant to diesel surrogates where simulation of the full boiling point range is desired. For the cycloalkanes, experimental work on decalin and tetralin recently has been published. For multi-component surrogate fuel mixtures, recent work on modeling of these mixtures and comparisons to real diesel fuel is reviewed. Detailed chemical kinetic models for surrogate fuels are very large in size. Significant progress also has been made in improving the mechanism reduction tools that are needed to make these large models practicable in multidimensional reacting flow simulations of diesel combustion. Nevertheless, major research gaps remain. In the case of iso-alkanes, there are experiments and modeling work on only one of relevance to diesel: iso-cetane. Also, the iso-alkanes in diesel are lightly branched and no detailed chemical kinetic models or experimental investigations are available for such compounds. More components are needed to fill out the iso-alkane boiling point range. For the aromatic class of compounds, there has been no new work for compounds in the boiling point range of diesel. Most of the new work has been on alkyl aromatics that are of the range C7 to C8, below the C10 to C20 range that is needed. For the chemical class of cycloalkanes, experiments and modeling on higher molecular weight components are warranted. Finally for multi-component surrogates needed to treat real diesel, the inclusion of higher molecular weight components is needed in models and experimental investigations.