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Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel.

Abstract: Laminar flame speeds and extinction strain rates of cyclopentadiene/air mixture were determined in the counterflow configuration at atmospheric pressure, unburned mixture temperature of 353K, and for a wide range of equivalence ratios. The experiments were modeled using recently developed kinetic models. Sensitivity analyses showed that both flame propagation and extinction of cyclopentadiene/air mixtures flames depend notably on the fuel kinetics and subsequent intermediates such as cyclopentadienyl, cyclopentadienone, and cyclopentadienoxy. Analyses of the computed flame structures revealed that the high temperature oxidation of cyclopentadiene depends in general on the kinetics of first few intermediates in the oxidation process following the fuel consumption. The potential reaction pathways of the consumption of cyclopentadienyl radicals were discussed and further investigation and validation is recommended for two relevant reactions that could improve the high temperature oxidation kinetic model of cyclopentadiene. The experimental flame data of this study are the first ones to be reported. [Copyright &y& Elsevier]

The HyChem (hy brid chem istry) approach is utilized for modeling the combustion behaviors of gasoline fuels. The approach combines an experimentally constrained, lumped-step model for fuel pyrolysis under the high-temperature combustion condition and a detailed foundation fuel chemistry model to describe the subsequent oxidation of the pyrolysis products. We present results obtained for two Shell gasoline fuels as examples. The results show that with the parameters in the lumped reactions determined by matching the experiment time history data of key products of gasoline pyrolysis, the HyChem reaction models capture the ignition delay times and laminar flame speeds over a wide range of thermodynamic conditions. The HyChem approach is also extended to model the negative-temperature coefficient (NTC) behaviors for the gasoline fuels. The results show that the NTC-enabled models are capable of capturing the ignition delays under both high-temperature conditions and the conditions under which the NTC behaviors are important. The relationship between fuel composition and combustion properties is analyzed. Finally, the HyChem models are reduced to about 40 species to enable turbulent combustion modeling of gasoline fuels in practical engine simulations. [ABSTRACT FROM AUTHOR]

Abstract The Hybrid Chemistry (HyChem) approach has been proposed previously for combustion chemistry modeling of real, liquid fuels of a distillate origin. In this work, the applicability of the HyChem approach is tested for single-component fuels using JP10 as the model fuel. The method remains the same: an experimentally constrained, lumped single-fuel model describing the kinetics of fuel pyrolysis is combined with a detailed foundational fuel chemistry model. Due to the multi-ring molecular structure of JP10, the pyrolysis products were found to be somewhat different from those of conventional jet fuels. The lumped reactions were therefore modified to accommodate the fuel-specific pyrolysis products. The resulting model shows generally good agreement with experimental data, which suggests that the HyChem approach is also applicable for developing combustion reaction kinetic models for single-component fuels. [ABSTRACT FROM AUTHOR]

Real distillate fuels usually contain thousands of hydrocarbon components. Over a wide range of combustion conditions, large hydrocarbon molecules undergo thermal decomposition to form a small set of low molecular weight fragments. In the case of conventional petroleum-derived fuels, the composition variation of the decomposition products is washed out due to the principle of large component number in real, multicomponent fuels. From a joint consideration of elemental conservation, thermodynamics and chemical kinetics, it is shown that the composition of the thermal decomposition products is a weak function of the thermodynamic condition, the fuel-oxidizer ratio and the fuel composition within the range of temperatures of relevance to flames and high temperature ignition. Based on these findings, we explore a hybrid chemistry (HyChem) approach to modeling the high-temperature oxidation of real, distillate fuels. In this approach, the kinetics of thermal and oxidative pyrolysis of the fuel is modeled using lumped kinetic parameters derived from experiments, while the oxidation of the pyrolysis fragments is described by a detailed reaction model. Sample model results are provided to support the HyChem approach. [ABSTRACT FROM AUTHOR]

We propose and test an alternative approach to modeling high-temperature combustion chemistry of multicomponent real fuels. The hy brid chem istry (HyChem) approach decouples fuel pyrolysis from the oxidation of fuel pyrolysis products. The pyrolysis (or oxidative pyrolysis) process is modeled by seven lumped reaction steps in which the stoichiometric and reaction rate coefficients are derived from experiments. The oxidation process is described by detailed chemistry of foundational hydrocarbon fuels. We present results obtained for three conventional jet fuels and two rocket fuels as examples. Modeling results demonstrate that HyChem models are capable of predicting a wide range of combustion properties, including ignition delay times, laminar flame speeds, and non-premixed flame extinction strain rates of all five fuels. Sensitivity analysis shows that for conventional, petroleum-derived real fuels, the uncertainties in the experimental measurements of C 2 H 4 and CH 4 impact model predictions to an extent, but the largest influence of the model predictability stems from the uncertainties of the foundational fuel chemistry model used (USC Mech II). In addition, we introduce an approach in the realm of the HyChem approach to address the need to predict the negative-temperature coefficient (NTC) behaviors of jet fuels, in which the CH 2 O speciation history is proposed to be a viable NTC-activity marker for model development. Finally, the paper shows that the HyChem model can be reduced to about 30 species in size to enable turbulent combustion modeling of real fuels with a testable chemistry model. [ABSTRACT FROM AUTHOR]

Abstract: Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (n-butyraldehyde) and iso-butanal (iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. [Copyright &y& Elsevier]