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This paper provides an overview of spark-ignition engine unburned hydrocarbon emissions mechanisms, and then uses this framework to relate measured engine-out hydrocarbon emission levels to the processes within the engine from which they result. Typically, spark-ignition engine-out HC levels are 1.5 to 2 percent of the gasoline fuel flow into the engine; about half this amount is unburned fuel and half is partially reacted fuel components. The different mechanisms by which hydrocarbons in the gasoline escape burning during the normal engine combustion process are described and approximately quantified. The in-cylinder oxidation of these HC during the expansion and exhaust processes, the fraction which exit the cylinder, and the fraction oxidized in the exhaust port and manifold are also estimated.

The in-cylinder hydrocarbon (HC) mole fraction was measured on a cycle-resolved basis during simulated starting and warm-up of a port-injected single-cylinder SI research engine on a dynamometer. The measurements were made with a fast-response flame ionization detector with a heated sample line. The primary parameters that influence how rapidly a combustible mixture builds up in the cylinder are the inlet pressure and the amount of fuel injected; engine speed and fuel injection schedule have smaller effects. When a significant amount of liquid fuel is present at the intake port in the starting process, the first substantial firing cycle is often preceded by a cycle with abnormally high in-cylinder HC and low compression pressure. An energy balance analysis suggests that a large amount of liquid vaporization occurs within the cylinder in this cycle.

An analysis method for characterizing fuel behavior during spark-ignition engine starting has been developed and applied to several sets of start-up data. The data sets were acquired from modern production vehicles during room temperature engine start-up. Two different engines, two control schemes, and two engine temperatures (cold and hot) were investigated. A cycle-by-cycle mass balance for the fuel was used to compare the amount of fuel injected with the amount burned or exhausted as unburned hydrocarbons. The difference was measured as “fuel unaccounted for”. The calculation for the amount of fuel burned used an energy release analysis of the cylinder pressure data. The results include an overview of starting behavior and a fuel accounting for each data set Overall, starting occurred quickly with combustion quality, manifold pressure, and engine speed beginning to stabilize by the seventh cycle, on average.

Recent studies have shown that for a given RON, fuels with a higher sensitivity (RON-MON) tend to have better antiknock performance at most knock-limited conditions in modern engines. The underlying chemistry behind fuel sensitivity was therefore investigated to understand why this trend occurs. Chemical kinetic models were used to study fuels of varying sensitivities; in particular their autoignition delay times and chemical intermediates were compared. As is well known, non-sensitive fuels tend to be paraffins, while the higher sensitivity fuels tend to be olefins, aromatics, diolefins, napthenes, and alcohols. A more exact relationship between sensitivity and the fuel's chemical structure was not found to be apparent. High sensitivity fuels can have vastly different chemical structures. The results showed that the autoignition delay time (τ) behaved differently at different temperatures. At temperatures below 775 K and above 900 K, τ has a strong temperature dependence.