Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.

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.

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 book on Advanced Chemical Kinetics gives insight into different aspects of chemical reactions both at the bulk and nanoscale level and covers topics from basic to high class. This book has been divided into three sections: (i) "Kinetics Modeling and Mechanism," (ii) "Kinetics of Nanomaterials," and (iii) "Kinetics Techniques." The first section consists of six chapters with a variety of topics like activation energy and complexity of chemical reactions; the measurement of reaction routes; mathematical modeling analysis and simulation of enzyme kinetics; mechanisms of homogeneous charge compression ignition combustion for the fuels; photophysical processes and photochemical changes; the mechanism of hydroxyl radical, hydrate electron, and hydrogen atom; and acceptorless alcohol dehydrogenation. The understanding of the kinetics of nanomaterials, to bridge the knowledge gap, is presented in the second section. The third section highlights an overview of experimental techniques used to study the mechanism of reactions.

Predictive engine simulation models are needed to make rapid progress towards DOE's goals of increasing combustion engine efficiency and reducing pollutant emissions. These engine simulation models require chemical kinetic submodels to allow the prediction of the effect of fuel composition on engine performance and emissions. Chemical kinetic models for conventional and next-generation transportation fuels need to be developed so that engine simulation tools can predict fuel effects. The objectives are to: (1) Develop detailed chemical kinetic models for fuel components used in surrogate fuels for diesel and HCCI engines; (2) Develop surrogate fuel models to represent real fuels and model low temperature combustion strategies in HCCI and diesel engines that lead to low emissions and high efficiency; and (3) Characterize the role of fuel composition on low temperature combustion modes of advanced combustion engines.

This book covers the origin and chemical structure of sedimentary organic matter, how that structure relates to appropriate chemical reaction models, how to obtain reaction data uncontaminated by heat and mass transfer, and how to convert that data into global kinetic models that extrapolate over wide temperature ranges. It also shows applications for in-situ and above-ground processing of oil shale, coal and other heavy fossil fuels. It is essential reading for anyone who wants to develop and apply reliable chemical kinetic models for natural petroleum formation and fossil fuel processing and is designed for course use in petroleum systems modelling. Problem sets, examples and case studies are included to aid in teaching and learning. It presents original work and contains an extensive reanalysis of data from the literature.

The objectives for this project are as follows: Develop detailed chemical kinetic models for fuel components used in surrogate fuels for compression ignition (CI), homogeneous charge compression ignition (HCCI) and reactivity-controlled compression-ignition (RCCI) engines; and Combine component models into surrogate fuel models to represent real transportation fuels. Use them to model low-temperature combustion strategies in HCCI, RCCI, and CI engines that lead to low emissions and high efficiency.