Multi-fuel surrogate chemical kinetic mechanisms for real world applications.

The most important driving force for development of detailed chemical kinetic reaction mechanisms in combustion is the desire by researchers to simulate practical systems. This paper reviews the parallel evolution of kinetic reaction mechanisms and applications of those models to practical, real engines. Early, quite simple, kinetic models for small fuel molecules were extremely valuable in analyzing long-standing, poorly understood applied ignition and flame quenching problems, and later kinetic models have been applied to much more complex flame propagation, problems including autoignition in spark-ignition engines and issues related to octane numbers and knock in modern, high compression ratio and other engines. The recent emergence of very large, multi-fuel surrogate kinetic mechanisms that can address many different fuel types and real engine applications is discussed as a modern analytical tool that can be used for a wide variety of practical applications.

Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition.

Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. Calculated thermodynamic and kinetic data are presented for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. These radicals can be formed via H atom abstraction reactions by H and Ö atoms and È®H, HÈ®2, and CH3 radicals, the rate constants of which have been calculated. Abstraction from the ß-hydrogen atom is the dominant process when È®H is involved, but the reverse holds true for HÈ®2 radicals. The subsequent ß-scission of the radicals formed is also determined, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.

Diesel Surrogate Fuels for Engine Testing and Chemical-Kinetic Modeling: Compositions and Properties.

The primary objectives of this work were to formulate, blend, and characterize a set of four ultralow-sulfur diesel surrogate fuels in quantities sufficient to enable their study in single-cylinder-engine and combustion-vessel experiments. The surrogate fuels feature increasing levels of compositional accuracy (i.e., increasing exactness in matching hydrocarbon structural characteristics) relative to the single target diesel fuel upon which the surrogate fuels are based. This approach was taken to assist in determining the minimum level of surrogate-fuel compositional accuracy that is required to adequately emulate the performance characteristics of the target fuel under different combustion modes. For each of the four surrogate fuels, an approximately 30 L batch was blended, and a number of the physical and chemical properties were measured. This work documents the surrogate-fuel creation process and the results of the property measurements.

Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics.

Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (ϕ = 0.5), stoichiometric (ϕ = 1.0), and fuel-rich (ϕ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C-H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce "cool flames" or negative temperature coefficient behavior. The connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low-temperature reactivity, and the gasoline engine concept of octane sensitivity are discussed.

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame.

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

Detailed chemical kinetic modeling of cyclohexane oxidation.

A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Rules for reaction rate constants are developed for the low-temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Because cyclohexane produces only one type of cyclohexyl radical, much of the low-temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical with O2 through five-, six-, and seven-membered-ring transition states. The direct elimination of cyclohexene and HO2 from RO2 is included in the treatment using a modified rate constant of Cavallotti et al. (Proc. Combust. Inst. 2007, 31, 201). Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data, are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments cannot be simulated according to the current understanding of low-temperature chemistry. Possible "alternative" H-atom isomerizations leading to different products from the parent O2QOOH radical were included in the low-temperature chemical kinetic mechanism and were found to play a significant role.

Chemical kinetic modeling study of the effects of oxygenated hydrocarbons on soot emissions from diesel engines.

A detailed chemical kinetic modeling approach is used to examine the phenomenon of suppression of sooting in diesel engines by the addition of oxygenated hydrocarbon species to the fuel. This suppression, which has been observed experimentally for a few years, is explained kinetically as a reduction in concentrations of soot precursors present in the hot products of a fuel-rich diesel ignition zone when oxygenates are included. The kinetic model is also used to show how different oxygenates, ester structures in particular, can have different soot-suppression efficiencies due to differences in the molecular structure of the oxygenated species.