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Controlling start of ignition in Homogenous Charge Compression Ignition (HCCI) engines remains a major challenge. Here we have investigated changes in intake charge composition and its effects on ignition delay for natural gas based HCCI engine operation. In particular, we have investigated the effects of small amounts of nitrogen dioxide (NO2) on operating characteristics. Previous research had shown that NOx presence might attenuate natural gas ignition. The hypothesized catalytic effect of NOx on methane ignition at HCCI conditions was experimentally confirmed in a custom built engine. The problem was further studied in both zero and multidimensional numerical engine simulations with detailed chemistry. The simulations were used to complete a reaction rate sensitivity analysis to elucidate the controlling chemistry, and further confirm that a significant shift in ignition phasing is produced with the addition of just several ppm by volume of NO2 or NOx (NO + NO2).

Computational fluid dynamic (CFD) simulations that include realistic combustion/emissions chemistry hold the promise of significantly shortening the development time for advanced high-efficiency, low-emission engines. However, significant challenges must be overcome to realize this potential. This paper discusses these challenges in the context of diesel combustion and outlines a technical program based on the use of surrogate fuels that sufficiently emulate the chemical complexity inherent in conventional diesel fuel.

The development of surrogate mixtures that represent gasoline combustion behavior is reviewed. Combustion chemistry behavioral targets that a surrogate should accurately reproduce, particularly for emulating homogeneous charge compression ignition (HCCI) operation, are carefully identified. Both short and long term research needs to support development of more robust surrogate fuel compositions are described. Candidate component species are identified and the status of present chemical kinetic models for these components and their interactions are discussed. Recommendations are made for the initial components to be included in gasoline surrogates for near term development. Components that can be added to refine predictions and to include additional behavioral targets are identified as well. Thermodynamic, thermochemical and transport properties that require further investigation are discussed.

The influence of the addition of oxygenated hydrocarbons to diesel fuels has been studied, using a detailed chemical kinetic model. Resulting changes in ignition and soot precursor production have been examined. N-heptane was used as a representative diesel fuel, and methanol, ethanol, dimethyl ether, dimethoxymethane and methyl butanoate were used as oxygenated fuel additives. It was found that addition of oxygenated hydrocarbons reduced the production of soot precursors. When the overall oxygen content in the fuel reached approximately 30-40 % by mass, production of soot precursors fell effectively to zero, in agreement with experimental studies. The kinetic factors responsible for these observations are discussed.