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Technical Paper

Autoignition Chemistry of the Hexane Isomers: An Experimental and Kinetic Modeling Study

1995-10-01
952406
Autoignition of the five distinct isomers of hexane is studied experimentally under motored engine conditions and computationally using a detailed chemical kinetic reaction mechanism. Computed and experimental results are compared and used to help understand the chemical factors leading to engine knock in spark-ignited engines and the molecular structure factors contributing to octane rating for hydrocarbon fuels. The kinetic model reproduces observed variations in critical compression ratio with fuel structure, and it also provides intermediate and final product species concentrations in much better agreement with observed results than has been possible previously. In addition, the computed results provide insights into the kinetic origins of fuel octane sensitivity.
Technical Paper

Gasoline Reformulation and Vehicle Technology Effects on Emissions - Auto/Oil Air Quality Improvement Research Program

1995-10-01
952509
Engine-out and tailpipe exhaust, and hot soak evaporative emissions of two reformulated test gasolines and an Industry Average reference gasoline were compared in four vehicle fleets designed for progressively lower emission standards. The two reformulated gasolines included: 1) a gasoline meeting 1996 California Phase 2 regulatory requirements, and 2) a gasoline blended to the same specifications but without an oxygenated component. These two gasolines were compared with the Auto-Oil Air Quality Improvement Research Program's (AQIRP) Industry Average gasoline representing 1988 national average composition. The vehicle fleets were the AQIRP Older (1983 to 85MY) and Current (1989MY) vehicle fleets used in prior studies, and two new AQIRP test fleets, one designed to 1994 Federal Tier 1 standards and a prototype Advanced Technology fleet designed for lower emission levels of 1995 and later.
Technical Paper

Effects of Gasoline Properties on Emissions of Current and Future Vehicles - T50, T90, and Sulfur Effects - Auto/Oil Air Quality Improvement Research Program

1995-10-01
952510
Exhaust emissions were measured using a matrix of fuels designed to expand on prior AQIRP work by investigating potential interactive effects of fuel distillation parameters T50 and T90, and of T90 and fuel sulfur content. (T50 and T90 represent the temperature at which 50 or 90% of the fuel distills in a standard test.) This fuel matrix was used also to investigate whether fuel effects found in prior work with then-current vehicle technology can be expected to continue in future lower emission vehicles. An additional pair of fuels was included to extend the range of T50. The vehicles were half of the AQIRP Current fleet (ten vehicles) used in prior studies, and two new fleets of six vehicles each. One of the new fleets was designed to 1994 Federal Tier 1 standards, and the other was Advanced Technology prototypes targeted for lower emission levels of 1995 and later. A set of six fuels was tested in all three fleets.
Technical Paper

Emissions with E85 and Gasolines in Flexible/Variable Fuel Vehicles - The Auto/Oil Air Quality Improvement Research Program

1995-10-01
952508
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.
Technical Paper

Effects of Gasoline Properties (T50, T90, and Sulfur) on Exhaust Hydrocarbon Emissions of Current and Future Vehicles: Modal Analysis - The Auto/Oil Air Quality Improvement Research Program

1995-10-01
952504
Modal analyses have been performed on engine-out and tailpipe hydrocarbon mass emissions to help understand why fuels with higher T50 and/or T90 distillation temperatures produce somewhat higher engine-out hydrocarbon emissions and substantially higher tailpipe hydrocarbon emissions. Modal analyses were also performed to examine how increased fuel sulfur increases tailpipe hydrocarbon emissions and to identify which gasoline properties in this study are responsible for the lower tailpipe hydrocarbon emissions with reformulated gasolines. These analyses were performed on three different test vehicle fleets representing varying levels of emissions control technology. The modal analyses showed that the substantially higher tailpipe hydrocarbon emissions from fuels with high T50 and/or T90 distillation temperatures result primarily from these fuels producing substantially higher engine-out hydrocarbon emissions during the first cycle of the Federal Test Procedure (FTP).
Technical Paper

Effects of Gasoline Properties (T50, T90, and Sulfur) on Exhaust Hydrocarbon Emissions of Current and Future Vehicles: Speciation Analysis - The Auto/Oil Air Quality Improvement Research Program

1995-10-01
952505
Species analyses have been performed on engine-out and tailpipe hydrocarbon mass emissions to help understand why fuels with higher T50 and/or T90 distillation temperatures produce higher engine-out and tailpipe hydrocarbon emissions and why fuels with higher T90 distillation temperatures produce higher engine-out and tailpipe specific reactivities. Species analyses were also performed to examine the effects of fuel sulfur level on engine-out and tailpipe species and specific reactivities. These analyses were performed on three different test-vehicle fleets representing varying levels of emissions control technology and the effect of emissions control technology was examined. Individual hydrocarbon species concentrations in both the engine-out and tailpipe were found to correlate linearly with the concentrations of the same species in the fuel, implying that a small fraction of the fuel escapes the combustion process and conversion over the catalyst.
Technical Paper

Comparison of CNG and Gasoline Vehicle Exhaust Emissions: Mass and Composition - The Auto/Oil Air Quality Improvement Research Program

1995-10-01
952507
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.
Technical Paper

Effect of Gasoline Olefin Composition on Predicted Ozone in 2005/2010 - Auto/Oil Air Quality Improvement Research Program

1994-03-01
940579
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.
Technical Paper

Comparison of Effects of MTBE and TAME on Exhaust and Evaporative Emissions — Auto/Oil Air Quality Improvement Research Program

1993-10-01
932730
Effects of methyl tertiary-butyl ether (MTBE) and tertiary-amyl methyl ether (TAME) on emissions were compared in a fleet of ten 1989 model year vehicles. Test fuels containing 11.5 vol.% MTBE or 12.7 vol.% TAME were blended in a base fuel representing federal emission certification fuel. The oxygen content of both fuels was about 2.0 wt.%. No significant differences were found between the two fuels in exhaust mass HC, NMHC, CO, or NOx; in exhaust or evaporative toxic air pollutants, benzene, 1,3-butadiene, acetaldehyde, or total toxic emissions; or in evaporative hot soak emissions. The only differences found to be significant at the 95% level were in mass and estimated reactivity-weighted diurnal evaporative emissions, for both of which the TAME fuel was about 24% lower than the MTBE fuel; and in formaldehyde emissions, which were 28% higher with the TAME fuel.
Technical Paper

Effects of Gasoline Sulfur Level on Exhaust Mass and Speciated Emissions: The Question of Linearity - Auto/Oil Air Quality Improvement Program

1993-10-01
932727
Effects of gasoline sulfur content on emissions were measured in a fleet of ten 1989 model year vehicles. Two ranges of sulfur content were examined. In a set of five fuels, reducing sulfur from 450 to 50 ppm, reduced fleet average tailpipe emissions of HC, NMHC and CO each by about 18%, and reduced NOx 8%. The largest effect on HC and CO emissions was observed in FTP Bag 2. This and the absence of any significant effect on engine emissions indicate that sulfur affected the performance of the catalytic converters. The response of HC and NMHC to fuel sulfur content was non-linear and increased as sulfur level was reduced. In the second set of three fuels, reducing sulfur from 50 to 10 ppm reduced HC and NMHC by 6% and CO by 10%, but had no significant effect on NOx. The effects on HC, NMHC and NOx were not significantly different from predictions based on the prior fuel set. The reduction in CO was larger than predicted.
Technical Paper

Effects of Fuel Properties on Mass Exhaust Emissions During Various Modes of Vehicle Operation

1993-10-01
932726
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.
Technical Paper

How Heavy Hydrocarbons in the Fuel Affect Exhaust Mass Emissions: Modal Analysis — The Auto/Oil Air Quality Improvement Research Program

1993-10-01
932724
Modal analyses have been performed on engine-out and tailpipe hydrocarbon and carbon monoxide mass emissions to help understand why fuels with increasing amounts of heavy hydrocarbon constituents produce significantly higher tailpipe hydrocarbon emissions, yet do not produce significantly higher tailpipe carbon monoxide emissions. Mass emissions were acquired for a fleet of ten 1989 model year vehicles operating on twenty six fuels of differing heavy hydrocarbon composition. These fuels formed two statistically designed matrices: one examining the effects of medium, heavy, and tail reformate and medium and heavy catalytically cracked components; and the other examining the effects of heavy paraffinic versus heavy aromatic components and the effects of the 50% distillation temperature.
Technical Paper

Effects of Heavy Hydrocarbons in Gasoline on Exhaust Mass Emissions, Air Toxics, and Calculated Reactivity - Auto/Oil Air Quality Improvement Research Program

1993-10-01
932723
Emission effects of gasoline hydrocarbon components distilling above 300°F were investigated to determine whether the effect of 90% distillation temperature (T90) found in an earlier Auto/Oil Program study is due to fuel distillation properties or to hydrocarbon composition, and also to determine whether the T90 effect is linear. Twenty-six fuels were tested in two sets. In Matrix A, the independent variables were catalytically cracked (FCC) and reformate stocks with nominal distillation ranges of 300 to 350, 350 to 400 and 400+°F. In Matrix B, the independent variables were a reformate stock (320 to 370°F), a heavy alkylate (330 to 475°F), and a light alkylate distilling below 300°F, which was used to vary fuel T50 at fixed levels of T90. Exhaust mass and speciation were measured using ten 1989 vehicles of the Auto/Oil Current Fleet. Tailpipe hydrocarbon emissions were found to increase nonlinearly with progressive addition of the heavier components.
Technical Paper

Fuel Effects in Auto/Oil High Emitting Vehicles

1993-03-01
930137
Fuel effects on exhaust emissions of a sample of seven high emitting vehicles were studied. The vehicles had various mechanical problems and all ran fuel rich. The degree of enrichment varied between tests, and strongly affected mass emissions. Variable enrichment can cause incorrect apparent fuel effects to be calculated if not accounted for in data analysis. After variable enrichment was compensated for, the percentage effects of fuel oxygen, RVP, and olefins were largely in agreement with prior findings for normally emitting vehicles. Reducing fuel sulfur and T90 may have less benefit on hydrocarbon emissions in these high emitters than in normal emitters, and reducing sulfur may have less benefit on CO emissions. Reducing aromatics may be somewhat more helpful in reducing hydrocarbon and CO emissions in the high emitters.
Technical Paper

The Autoignition Chemistries of Primary Reference Fuels, Olefin/Paraffin Binary Mixtures, and Non-Linear Octane Blending

1992-10-01
922325
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.
Technical Paper

Effects of Gasoline Composition on Vehicle Engine-Out and Tailpipe Hydrocarbon Emissions - The Auto/Oil Air Quality Improvement Research Program

1992-02-01
920329
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.
Technical Paper

The Autoignition Chemistry of Paraffinic Fuels and Pro-Knock and Anti-Knock Additives: A Detailed Chemical Kinetic Study

1991-10-01
912314
A numerical model is used to examine the chemical kinetic processes leadING to knocking in spark-ignition internal combustion engines. The construction and validation of the model is described in detail, including low temperature reaction paths involving alkylperoxy radical isomerization. The numerical model is applied to C1 to C7 paraffinic hydrocarbon fuels, and a correlation is developed between the Research Octane Number (RON) and the computed time of ignition for each fuel. Octane number is shown to depend on the rates of OH radical production through isomerization reactions, and factors influencing the rate of isomerization such as fuel molecule size and structure are interpreted in terms of the kinetic model. knock behavior of fuel mixtures is examined, and the manner in which pro-knock and anti-knock additives influence ignition is studied numerically. The kinetics of methyl tert-butyl ether (MTBE) is discussed in particular detail.
Technical Paper

The Chemical Origin of Fuel Octane Sensitivity

1990-10-01
902137
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.
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