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For several years, a single-cylinder, spark-ignited engine without catalyst has been operated at Ford on single-component fuels that are constituents of gasoline as well as on simple fuel mixtures. This paper presents a review of these experiments as well as others pertinent to understanding hydrocarbon emissions. The engine was run at four steady-state conditions which are typical of normal operation. The fuel structure and the engine operating conditions affected both the total HC emissions and the reactivity of these emissions for forming photochemical smog in the atmosphere. These experiments identified major precursor species of the toxic HC emissions benzene and 1,3-butadiene to be alkylated benzenes and either straight chain terminal olefins or cyclic alkanes, respectively. In new data presented, the primary exhaust hydrocarbon species from MTBE combustion is identified as isobutene.

As vehicle tailpipe emission levels decrease with improvements in emission control technology and reformulation of gasolines, exhaust hydrocarbon levels begin to approach the levels in ambient air. Hydrocarbon speciation at these low levels requires high sensitivity capillary gas chromatography methods. In this study, a mixture of “synthetic” exhaust was prepared at two concentration levels (approximately 5 ppm C and 10 ppm C), and was analyzed by the widely-used Auto/Oil Air Quality Improvement Research Program (AQIRP) Phase II (gas chromatography) speciation method with a sensitivity of 0.005 ppm C for individual species. The mixture at each concentration level, along with a sample of ambient air, was analyzed a total of 20 times on 10 separate days over a 2½ week period. Concentrations of total hydrocarbons (HCs) and individual species (using the AQIRP library) were measured; averages and standard deviations were calculated.

The effects of operating parameters (speed, load, spark-timing, EGR, and end of fuel injection timing [EOI]) on engine-out, regulated (total HC, NOx, and CO) and speciated HC emissions have been investigated for a 1.83 L direct-injection, spark-ignition (DISI) engine. As the EOI is varied over the range from high to low stratification with other engine parameters held constant, the mole fractions of all regulated emissions vary sharply over relatively small (10-20 crank angle degrees [CAD]) changes in EOI, suggesting that emissions are very sensitive to the evaporation, mixing, and motion of the stratified fuel cloud prior to ignition. The contribution of unburned fuel to the HC emissions decreases while the olefinic partial oxidation products increase as the fuel stratification increases, increasing the smog reactivity of the HC in the exhaust gas by 25%.

Speciated HC emissions from the exhaust system of a production engine without an active catalyst have been obtained with 3 sec time resolution during a 70°F cold start using two control strategies. For the conventional cold start, the emissions were initially enriched in light fuel alkanes and depleted in heavy aromatic species. The light alkanes fell rapidly while the lower vapor pressure aromatics increased over a period of 50 sec. These results indicate early retention of low vapor pressure fuel components in the intake manifold and exhaust system. Loss of higher molecular weight HC species does occur in the exhaust system as shown by experiments in which the exhaust system was preheated to 100° C. The atmospheric reactivity of the exhaust HC emissions for photochemical smog formation increases as the engine warms.