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A reduced chemical kinetic model by Li et al. [1]* for predicting primary reference fuels' reactivity and autoignition behavior was modified to apply to the butanes, and it was correlated to experimental results from the non-fired engine cycles under skip fired conditions. The fuels examined in this work were neat n-butane and n-butane/iso-butane blends (10, 20, and 48 percent by volume iso-butane). In our initial work using measured pressure data from the first skip cycle, we modified Li et al.'s model by only adjusting the fuel specific rate parameters of the alkylperoxy radical (RO2·) isomerization reaction, the reaction of aldehydes with OH·, and the reaction forming cyclic ethers. In this work, analysis was extended to the second skip cycle and additional oxidation rate parameters with high fuel sensitivity were adjusted. Several reactions, which are not significant in butane oxidation, were temporarily made to be inactive in the model.

In Homogeneous Charge Compression Ignition (HCCI) engines, fuel oxidation chemistry determines the auto-ignition timing, the heat release, the reaction intermediates, and the ultimate products of combustion. Therefore a model that correctly simulates fuel oxidation at these conditions would be a useful design tool. Detailed models of hydrocarbon fuel oxidation, consisting of hundreds of chemical species and thousands of reactions, when coupled with engine transport process models, require tremendous computational resources. A way to lessen the burden is to use a “skeletal” reaction model, containing only tens of species and reactions. This paper reports an initial effort to extend our skeletal chemical kinetic model of pre-ignition through the entire HCCI combustion process. The model was developed from our existing preignition model, which has 29 reactions and 20 active species, to yield a new model with 69 reactions and 45 active species.

We investigated the ability of a reduced chemical kinetic model of 18 reactions and 13 active species to predict the heat release for a blend of primary reference fuels with octane rating 63 in a motored research engine. Given the initial fuel-air mixture concentration and temperature, the chemical kinetic model is used to predict temperature, heat release and species concentrations as a function of time or crank angle by integrating the coupled rate and energy equations. For comparison, we independently calculated heat release from measured pressure data using a standard thermodynamic model.

Inevitably a fraction of the hydrocarbon fuel in spark ignition engines escapes in-cylinder combustion and flows out with the burned products. Post combustion oxidation in the cylinder and exhaust port may consume a part of this fuel and plays an important role in determining exhaust emission levels. This paper presents results from experiments designed to identify the factors that control post-combustion oxidation. Regulated exhaust components and detailed hydrocarbon species were measured using seven neat hydrocarbons and four blends as fuel. The fuels were selected to compare the relative rates of mixing and chemical kinetics. The results indicate that exhaust temperature, diffusion rates and fuel kinetics each play a complicated role in determining emission levels.

This paper examines the similarity in the pre-ignition chemistry and reactivity behavior of two and four-stoke homogenous charge engines, analyzes the sources of UHC and CO, and describes an approach with the potential to substantially reduce UHC and CO in these systems. The approach is based on experiments on a two-stroke engine at no load conditions and on a four-stroke engine both with high levels of internal exhaust gas recirculation (EGR). By increasing internal EGR in an unloaded spark ignited two-stroke engine, UHC was reduced from 7800 ppm to 3000 ppm, CO decreased from 3% to 0.2%, and cyclic variability was diminished. These results demonstrate that stable engine operation can be obtained with additional internal EGR. Similar improvements were obtained at stoichiometric and lean conditions. Further experiments and modeling indicate that the main source of UHC and CO emissions is the fuel trapped in crevices.

This experimental study was conducted in a motored research engine to investigate the effect of blending methanol and ethanol on hydrocarbon oxidation and autoignition. An 87 octane mixture of primary reference fuels, 87 PRF, was blended with small percentages of the alcohols to yield a constant gravimetric oxygen percentage in the fuel. The stoichiometric fuel mixtures and neat methanol and ethanol were tested in a modified single-cylinder engine at a compression ratio of 8.2. Supercharging and heating of the intake charge were used to control reactivity. The inlet gas temperature was increased from 325 K to the point of autoignition or the maximum achievable temperature of 500 K. Exhaust carbon monoxide levels and in-cylinder pressure histories were monitored in order to determine and quantify reactivity.

This paper presents results of studies investigating the effect of octane enhancing ethers on the reactivity of an 87 octane mixture of primary reference fuels, 87 PRF, in a motored engine. 87 PRF was blended with small percentages of MTBE, ETBE, TAME and DIPE based on a constant gravimetric oxygen percentage in the fuel. The experiments were conducted in a modified single-cylinder Wisconsin AENL engine at compression ratios of 5.2 and 8.2. Supercharging and heating of the intake charge were used to control reactivity. The inlet gas temperature was increased from 320 K, where no reactivity occurred, until either autoignition occurred or the maximum temperature of the facility was reached. Exhaust carbon monoxide levels and in-cylinder pressure histories were monitored in order to determine and quantify reactivity.

The role of post-combustion oxidation in influencing exhaust hydrocarbon emissions from spark ignition engines has been identified as one of the major uncertainties in hydrocarbon emissions research [l]*. While we know that post-combustion oxidation plays a significant role, the factors that control the oxidation are not well known. In order to address some of these issues a research program has been initiated at Drexel University. In preliminary studies, seven gaseous fuels: methane, ethane,ethene,propane,propene, n-butane, 1-butene and their blends were used to examine the effect of fuel structure on exhaust emissions. The results of the studies presented in an earlier paper [2] showed that the effect of fuel structure is manifested through its effect on the post-combustion environment and the associated oxidation process. A combination of factors like temperatures, fuel diffusion and reaction rates were used to examine and explain the exhaust hydrocarbon emission levels.

Time resolved exhaust port sampling results show that the gas mixture in the port at exhaust valve closing contains high concentrations of hydrocarbons. These hydrocarbons are mixed with hot in-cylinder gases during blowdown and can react either via gas phase kinetics in the exhaust port/runner system or subsequently on the exhaust catalyst before they are emitted. Studies were conducted on a single cylinder, four stroke engine in our laboratory to determine the interaction between the hot blowdown gases and the hydrocarbons which remain in the exhaust port. A preselected concentration and volume of hydrocarbon tracers (propane, propene, n-butane, and 1-butene) in either oxygen/nitrogen mixtures or pure nitrogen were injected into the exhaust port just behind the exhaust valve to control the initial conditions for any potential oxidation in the port.

Recently, studies were conducted on a single cylinder, four stroke engine to investigate the effect of temperature and local mixedness on exhaust port hydrocarbon oxidation. To examine the effect of temperature, hydrocarbon tracers (propane, propene, 1-butene, n-butane, and n-pentane) were individually injected into the exhaust port just behind the exhaust valve for operating conditions that provided different exhaust port temperatures. For the local mixedness experiments, tracer mixtures (propane + n-butane, 1-butene + n-butane, propene + n-butane) were injected into the exhaust port just behind either a normal exhaust valve or a shrouded exhaust valve. The concentration of tracers and their reaction products were measured using gas chromatography of samples withdrawn from the exhaust stream. The tracer consumption behavior with changing port temperature confirmed that there is a minimum port temperature for hydrocarbon oxidation.