Search Results

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.

Homogeneous Charge Compression Ignition (HCCI) engines have the possibility of low NOx and particulate emissions and high fuel efficiencies. In HCCI the oxidation chemistry determines the auto-ignition timing, the heat release rate, the reaction intermediates, and the ultimate products of combustion. This paper reports an initial effort to apply our reduced chemical kinetic model to HCCI processes. The model was developed to study the pre-ignition characteristics (pre-ignition heat release and start of ignition) of primary reference fuels (PRF) and includes 29 reactions and 20 active species. The only modifications to the model were to make the proscribed adjustments to the fuel specific rate constants, and to enhance the H2O2 decomposition rate to agree with published data.

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.

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.

A reduced chemical kinetic model has been developed for the prediction of major oxidation behavior of primary reference fuels (PRF's) in a motored engine, including ignition delay, preignition heat release, fuel consumption, CO formation and production of other species classes. This model consists of 29 reactions with 20 active species and was tuned to be applicable for the neat PRF's, 87 PRF and 63 PRF, and at various engine conditions. At the motored engine condition where detailed species data were generated, the model reproduces the ignition delay and the preignition heat release quite well (to within 15%). Fuel consumption and CO formation predictions differed from experiments by at most 25% for all of the four fuels. Predictions for other species classes generally agreed with experiments. As inlet temperature was varied, the experimentally observed negative temperature coefficient (NTC) behavior of iso-octane and 87 PRF was reproduced by the model.

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.

Recently, we reported the development of a new reduced chemical kinetic model for predicting reactivity and autoignition behavior of primary reference fuels in a motored research engine. The predicted oxidation behavior (ignition delay, preignition heat release, and evolution of key chemical species) is in fairly good agreement with experiments. In addition, the model reproduced the experimentally observed dependence of overall reactivity on charge density and manifold inlet conditions. This paper reports our initial effort to apply this new reduced chemical kinetic model to other fuels. Specifically, the model was tested using neat n-butane and n-butane/iso-butane blends (10, 20, and 48 percent by volume iso-butane) under skip fired conditions. The only adjustments made in the model were to the fuel specific rate parameters of the RO2· isomerization reaction, the reaction of aldehydes with OH·, and the reaction forming cyclic ethers.

One option for ignition control of Homogeneous Charge Compression Ignition (HCCI) engines is to use small amounts of ignition-enhancing additives to alter the ignition properties. Di-tertiary Butyl Peroxide (DTBP) is one such additive and it has been suggested as a cetane improver in diesel engines. In this study, the effects of DTBP on spark ignition (SI) primary reference fuels (PRFs, n-heptane and iso-octane) and their blends (PRF20, PRF50, PRF63, PRF87 and PRF92) were investigated during HCCI engine operation. Experiments were run in a single cylinder CFR research engine for three inlet temperatures (410, 450 and 500 K) and several equivalence ratios (0.28 - 0.57) at a constant speed of 800 rpm and a compression ratio of 16.0. Experimental results show that ignition delay time, cycle to cycle variation, and stable operating range were all improved with the addition of less than 2.5% DTBP by volume.

The generally accepted explanation of autoignition in engines is that the reactivity is driven by temperature, where autoignition occurs after the mixture has reached some critical temperature (approx. 1000 K) by a combination of self-heating due to preignition reactions and compression heating due to piston motion and flame propagation. During the course of our investigations into autoignition processes and homogeneous charge compression ignition we have observed some ignitions that begin at much lower temperature (< 550 K). In this paper we describe these observations, our attempts to investigate their origins, and an alternative explanation that proposes that traditional models may be missing the chemistry that explains this behavior. Finally, applications of lower temperature chemical reactions are discussed.