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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.

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.

Analytical procedures for the speciation of hydrocarbons and oxygenates (ethers, aldehydes, ketones and alcohols) in vehicle evaporative and tailpipe exhaust emissions have been improved for Phase II studies of the Auto/Oil Air Quality Improvement Research Program (AQIRP). One gas chromatograph (GC) was used for measurement of C1-C4 species and a second GC for C4-C12 species. Detection limits for this technique are 0.005 ppm C or 0.1 mg/mile exhaust emission level at a chromatographic signal-to-noise ratio of 3/1, a ten-fold improvement over the Phase I technique. The Phase I library was modified to include additional species for a total of 154 species. A 23-component gas standard was used to establish a calibration scale for automated computer identification of species. This method identifies 95±3% of the total hydrocarbon mass measured by GC for a typical exhaust sample. Solid adsorbent cartridges or impingers were used to collect aldehydes and ketones.

An analytical method for the determination of hydrocarbon and ether emissions from gasoline-, methanol-, and flexible-fueled vehicles is described. This method was used in Phase I of the Auto/Oil Air Quality Improvement Research Program to provide emissions data for various vehicles using individual reformulated gasolines and alternate fuels. These data would then be used for air modeling studies. Emission samples for tailpipe, evaporative, and running loss were collected in Tedlar bags. Gas chromatographic analysis of the emissions samples included 140 components (hydrocarbons, ethers, alcohols and aldehydes) between C1 and C12 in a single analysis of 54-minutes duration. Standardization, quality control procedures, and inter-laboratory comparisons developed and completed as part of this program are also described.