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A literature review was conducted to survey recent research on the effects of fuel properties on exhaust emissions from gasoline and diesel vehicles, on-road and off-road. Most of the literature has been published in SAE papers, although data have also been reported in other journals and government reports. A full report and database are available from the Coordinating Research Council (www.crcao.org). The review identified areas of agreement and disagreement in the literature and evaluated the adequacy of experimental design and analysis of results. Areas where additional research would be helpful in defining fuel effects are also identified. In many of the research programs carried out to evaluate the effect of new blendstocks, the fuel components were splash blended in fully formulated fuels. This approach makes it extremely difficult to determine the exact cause of the emissions benefit or debit.

Four vehicle fleets, consisting of 3 to 4 vehicles each, were emission tested on a 48″ roll chassis dynamometer using both the FTP urban dynamometer driving cycle and the REP05 driving cycle. The REP05 cycle was developed to test vehicles under high speed and high load conditions not included in the FTP. The vehicle fleets consisted of 1989 light-duty gasoline vehicles, 1992-93 limited production FFV/VFV methanol vehicles, 1992-93 compressed natural gas (CNG) vehicles and their gasoline counterparts, and a 1992 production and two prototype ethanol FFV/VFV vehicles. All vehicles (except the dedicated CNG vehicles) were tested using Auto/Oil AQIRP fuels A and C2. Other fuels used were M85 blended from A and C2, E85 blended from C1, which is similar to C2 but without MTBE, and four CNG fuels representing the range of in-use CNG fuels. In addition to bag measurements, tailpipe exhaust concentration and A/F data were collected once per second throughout every test.

Exhaust emissions of three vehicles fueled with compressed natural gas (CNG) were compared with emissions of three counterpart gasoline vehicles. The natural gas vehicles were tested on four CNG fuels covering a wide range of pipeline natural gas compositions. The gasoline vehicles were tested on AQIRP Industry Average gasoline and a reformulated gasoline meeting California 1996 regulatory requirements. Nonmethane hydrocarbon (NMHC) and toxic air pollutant emissions of the CNG vehicles were about one-tenth those of their counterpart gasoline vehicles, while methane emissions were about ten times those of the gasoline vehicles. Carbon monoxide (CO) and nitrogen oxides (NOx) emissions were more variable among the three vehicle pairs. CO emissions ranged from 20 to 80% lower with CNG than with gasoline, and NOx ranged from 80% lower with CNG to equivalent to gasoline.

Exhaust and evaporative emissions from three flexible/variable fuel vehicles (FFV/VFV) were measured as the vehicles operated on E85 fuel (a mixture of 85% ethanol and 15% gasoline) or on gasoline. One vehicle was a production vehicle designed for ethanol fuels and sold in 1992-93 and the other two vehicles were prototypes which were recalibrated 1992 model year methanol FFV's. The gasolines tested were Industry Average Fuel A and a reformulated gasoline Fuel C2 that met California 1996 regulatory requirements. The gasoline component of Fuel E85 was based on the reformulated gasoline. The major findings from this three-vehicle program were that E85 reduced NOx 49% compared to Fuel A and 37% compared to Fuel C2, but increased total toxics 108% (5 mg/mi) and 255% (20 mg/mi), respectively, primarily by increasing acetaldehyde. The NOx effect was significant for both engine-out and tailpipe emissions.

Exhaust and hot soak evaporative emissions were measured in a fleet of 1993 production flexible/variable-fueled vehicles on methanol fuels blended with a reformulated gasoline. A fleet of 1993 California Tier 1 gasoline vehicles was also tested on the same reformulated gasoline blended to meet the specifications of California Phase 2 fuel. Ozone-forming reactivity, expressed as reactivity weighted emissions and specific reactivity, was calculated using 1991 SAPRC and 1994 CBM MIR and MOR factors. Within the FFV/VFV fleet, FTP exhaust and reactivity weighted emissions were significantly lower by 18 to 32% with Phase 2 gasoline relative to Industry Average gasoline. With the exception of greater NMOG emissions with the M85 blends, and lower OMHCE emissions with M85 blended with Industry Average gasoline, exhaust organic emissions, CO and NOx with the methanol fuels were not significantly different than their base gasolines.

The effect of gasoline olefin composition and content on urban ozone was estimated using the Urban Airshed Model (UAM), emission measurements for a base fuel, and projected emissions for two hypothetical fuels with reduced olefin content. The projected emissions for the hypothetical fuels were developed using regressions developed from Auto/Oil Air Quality Improvement Research Program (AQIRP) Phase I testing, a vapor headspace model and other information. Ozone modeling was conducted for Los Angeles in year 2010 and Dallas-Fort Worth and New York in year 2005. When all olefins were removed from the base fuel, the light-duty vehicle contribution to peak hourly ozone was reduced by 8 to 12%. This corresponds to a projected reduction of 0.6 to 0.8% in total peak ozone from all sources. Removing only light (C5) olefins provided 67 to 78% of the peak ozone benefit from removal of all olefins.

The analysis of data from the Auto/Oil Air Quality Improvement Research Program (AQIRP) study of the effect of aromatics, MTBE, olefins, and T90 on mass exhaust emissions from current (1989) vehicles was extended to include individual vehicles during individual operating modes. The results of the modal data analysis agree with and complement results which have been reported previously by AQIRP. Beyond this, attention is focused on three fuel compositional changes where the effect on emissions shows a reversal in sign depending on the vehicle operating mode chosen.

Fuel economy measurements from portions of Phase I of the Auto/Oil Air Quality Improvement Research Program were analyzed. The following fuel variables were examined: aromatics, olefins, T90, RVP, and various oxygenates (MTBE, ETBE and ethanol). Two vehicle fleets were tested: twenty 1989 vehicles and fourteen 1983-1985 vehicles. Three measures of fuel economy were analyzed. EPA Fuel Economy used the calculation defined in the Federal Register and is an attempt to correct for changes in fuel properties. Volumetric Fuel Economy is based on a carbon balance calculation and is a measure of the actual volume of gasoline burned. Energy Specific Fuel Economy is a measure of fuel economy based on energy content. The following fuel changes resulted in reductions of Volumetric Fuel Economy in both fleets: reduced aromatics, reduced olefins, reduced T90, and addition of oxygenates. Changes in RVP did not have a significant effect on fuel economy.

The chemistries controlling autoignition of primary reference fuels (n-heptane/isooctane binary mixtures) and binary olefin/paraffin mixtures have been inferred from experimental motored-engine measurements. For all n-heptane/isooctane and olefin/paraffin mixtures, each component of the mixture reacted via parallel intramolecular mechanisms with the only interactions being via small labile radicals. The octane qualities of the neat components appears to be dictated not by the initial reaction rate of the fuel, but by the reaction rate of the subsequent fuel-product reactions. In contrast, the blending octane quality of a component appears to be dictated more by the rate of the initial fuel reactions. The abnormally high blending octane qualities of olefins result from them having high rates of initial fuel reaction combined with slow rates of subsequent fuel-product reactions.

Speciated exhaust emission data from Phase I of the Auto/Oil Air Quality Improvement Research Program are presented and analyzed. Eighteen fuels were tested which varied in four fuel parameters: aromatics, MTBE content, olefins, and T90. These fuels were tested in two fleets of vehicles. One consisted of twenty 1989 vehicles and the other consisted of fourteen 1983-1985 vehicles. The 1990 version of Carter reactivity factors were used to calculate reactivities for each of these tests. Two types of reactivities were calculated. The first was Specific Reactivity and has units of grams ozone per gram NMOG (non-methane organic gas). The second was Ozone Forming Potential and has units of grams ozone per mile. Both types of reactivities were calculated using Carter's MIR (Maximum Incremental Reactivity) as well as MOR (Maximum Ozone Reactivity) factors.

This report presents the Auto/Oil AQIRP results of a methanol fueled vehicle emission study. Nineteen early prototype flexible/variable fueled vehicles (FFV/VFV) were emission tested with industry average gasoline (M0), an 85% methanol-gasoline blend (M85), and a splash-blend of M85 with M0 (gasoline) giving 10% methanol (M10). Vehicle emissions were analyzed for the FTP exhaust emissions, SHED diurnal and hot soak evaporative emissions, and running loss evaporative emissions. Measurements were made for HC, CO and NOx emissions and up to 151 organic emission species, including air toxic components. M0 and M10 emissions were very similar except for elevated M10 evaporative emissions resulting from the high M10 fuel vapor pressure. M85 showed lower exhaust emissions than M0 for NMHC (non-methane hydrocarbon), OMHCE (organic material hydrocarbon equivalent), CO and most species. M85 had higher exhaust emissions for NMOG (non-methane organic gases), NOx, methanol and formaldehyde.

Exhaust and evaporative emissions were measured as a function of gasoline composition and fuel vapor pressure in a fleet of 20 1989 vehicles. Eleven fuels were evaluated; four hydrocarbon only, four splash blended ethanol fuels (10 vol %), two methyl tertiary-butyl ether (MTBE) blends (15 vol %) and one ethyl tertiary-butyl ether (ETBE) blend (17 vol %). Reid vapor pressures were between 7.8 and 9.6 psi. Exhaust emission results indicated that a reduction in fuel Reid vapor pressure of one psi reduced exhaust HC and CO. Adding oxygenates reduced exhaust HC and CO but increased NOx. Results of evaporative emissions tests on nineteen vehicles indicated a reduction in diurnal emissions with reduced Reid vapor pressure in the non-oxygenated and ethanol blended fuels. However, no reduction in diurnal emissions with the MTBE fuel due to Reid vapor pressure reduction was observed. Reducing Reid vapor pressure had no statistically significant effect on hot soak emissions.

In this pilot study conducted by the Auto/Oil Air Quality Improvement Research Program, engine-out and tailpipe speciated hydrocarbon emissions were obtained for three vehicles operated over the Federal Test Procedure on two different fuels, both of which were speciated. The fates of the fuel species were traced across the engine and across the catalyst, and relationships were developed between engine-out and tailpipe hydrocarbon emissions and fuel composition. These relationships allowed separating the fuel's contribution to engine-out and tailpipe hydrocarbon emissions into two parts, unreacted fuel and partial oxidation products. Specific ozone reactivities and toxic air pollutants were analyzed for both engine-out and tailpipe emissions. Vehicle-to-vehicle, fuel-to-fuel, and bag-to-bag differences have been highlighted.

Prior studies of the effect of gasoline composition and physical properties on automotive exhaust and evaporative emissions have been reviewed. The prior work shows that the parameters selected for investigation in the Auto/Oil Air Quality Improvement Research Program (AQIRP) - gasoline aromatics content, addition of oxygenated compounds, olefins content, 90% distillation temperature, Reid vapor pressure, and sulfur content - can affect emissions. Effects have been observed on the mass of hydrocarbon, CO, and NOx emissions; on the reactivity of emissions toward ozone formation; and on the emissions of designated toxic air pollutants. The individual effects of some of the AQIRP parameters have been studied extensively in modern vehicles, but the most comprehensive studies of gasoline composition were conducted in early 1970 vehicles, and comparing the various studies shows that fuel effects can vary among vehicles with different control technology.

In this portion of the Auto/Oil Air Quality Improvement Research Program, ten 1989 model vehicles were tested using two fuels with different sulfur levels. These tests were run to determine instantaneous effects on exhaust emissions, not long-term durability effects. The high- and low-sulfur fuels contained 466 ppm and 49 ppm sulfur, respectively. Mass exhaust emissions of the fleet decreased as fuel sulfur level was reduced. Overall, HC, CO, and NOx were reduced by 16, 13, and 9 percent, respectively, when fuel sulfur level decreased. This effect appeared to be immediately reversible. Engine-out mass emissions were unaffected by changes in the fuel sulfur content, therefore, tailpipe emissions reductions were attributed to increased catalyst activity as the sulfur level was reduced.

An overview of Phase 1 of the Auto/Oil Air Quality Improvement Research Program is presented. Specific information is provided on each of the individual test fuel matrices that were conducted to investigate vehiclelfuel “system” effects on emissions. Procedures for sampling exhaust, evaporative, and running loss vehicle emissions are described, as well as techniques developed for speciation of individual hydrocarbons. Air quality models to project ozone reduction potential of reformulated gasolines and methanol, and economic studies to estimate the relative cost-effectiveness of the vehiclelfuel alternatives are also briefly explained.

Autoignition chemistries of several paraffins, olefins, and aromatics were examined in a motored engine at different engine conditions. Paraffin chemistry was dominated by “negative-temperature coefficient” (NTC) behavior which became more pronounced at lower pressures, higher temperatures, and shorter reaction times. In contrast, olefin and aromatic chemistries did not exhibit NTC behavior. Measured pressures and calculated temperatures at fired octane rating conditions showed slightly lower pressures, higher temperatures, and lower reaction times at Motor octane rating conditions when compared to Research conditions. Therefore, paraffins would have a more pronounced NTC behavior under Motor rating conditions than under Research conditions.

The autoignition chemistries of the olefins 1-butene, 2-butene, isobutene, 2-methyl-2-butene, and 1-hexene and their corresponding paraffins were examined in a motored, single-cylinder engine by measuring stable intermediate species and performing heat-release analyses. The same engine conditions were used for each olefin-paraffin pair, and compression ratio was varied to affect different levels of chemical activity. Paraffin autoignition chemistry is dominated by hydrogen abstraction from the fuel, followed by the intramolecular alkylperoxy isomerization mechanism. Olefin autoignition chemistry differs markedly being controlled by radical addition to the double bond. Hydroxyl radical addition is followed by oxygen addition to the adjacent radical site, followed by scission forming two carbonyls. Hydroperoxyl radical addition yields an epoxy directly. Experimental measurements for each olefin-paraffin pair are compared with each other and with literature values.