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Technical Paper

Development of a Desulfurization Strategy for a NOx Adsorber Catalyst System

2001-03-05
2001-01-0510
The aggressive reduction of future diesel engine NOx emission limits forces the heavy- and light-duty diesel engine manufacturers to develop means to comply with stringent legislation. As a result, different exhaust emission control technologies applicable to NOx have been the subject of many investigations. One of these systems is the NOx adsorber catalyst, which has shown high NOx conversion rates during previous investigations with acceptable fuel consumption penalties. In addition, the NOx adsorber catalyst does not require a secondary on-board reductant. However, the NOx adsorber catalyst also represents the most sulfur sensitive emissions control device currently under investigation for advanced NOx control. To remove the sulfur introduced into the system through the diesel fuel and stored on the catalyst sites during operation, specific regeneration strategies and boundary conditions were investigated and developed.
Technical Paper

Effect of Fuel Sulfur on Emissions in California Low Emission Vehicles

1998-10-19
982726
The Coordinating Research Council conducted a program to measure the effect of fuel sulfur on emissions from California Low Emission Vehicles (LEVs). Twelve vehicles, two each from six production LEV models, were tested using low mileage as-received catalysts and catalysts aged to 100k by each vehicle manufacturer using “rapid-aging” procedures. There were seven test fuels: five conventional fuels with sulfur ranging from 30 to 630 ppm, and two California reformulated gasoline (RFG) with sulfur of 30 and 150 ppm. Reducing fuel sulfur produced statistically significant reductions in LEV fleet emissions of NMHC, NOx and CO. Comparing conventional fuel and California RFG at the same sulfur level: California RFG had lower NMHC and NOx emissions and higher CO emissions, but only some NMHC and NOx differences and none of the CO differences between conventional and California RFG were statistically significant.
Technical Paper

Sources of Vehicles Emissions in Three Day Diurnal SHED Tests - Auto/Oil Air Quality Improvement Research Program

1994-10-01
941965
Three-day diurnal SHED evaporative emissions were measured in a fleet of ten Auto/Oil current (1989) and 2 older (1984) vehicles using Auto/Oil Industry Average fuel. SHED temperature cycled each 24-hour period from 72 to 96 F (22.2 to 35.5C). Measurements included speciation of individual hydrocarbons in the SHED as well as total mass emissions at the end of each of the three 24-hour test periods. Previous evaporative emission studies provided evidence that permeation and/or fuel seepage could contribute significantly to the mass of diurnal and hot soak emissions. Data from this investigation were used to quantify the contribution of liquid fuel to total SHED emissions during diurnal testing. A calculation method, based on the concentration of 29 select hydrocarbons in the SHED, is presented to apportion SHED emissions between those associated with liquid fuel losses and those associated with fuel tank head space vapor losses.
Technical Paper

Emissions with Reformulated Gasoline and Methanol Blends in 1992 and 1993 Model Year Vehicles

1994-10-01
941969
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.
Technical Paper

A Dynamometer Study of Off-Cycle Exhaust Emissions - The Auto/Oil Air Quality Improvement Research Program

1997-05-01
971655
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.
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 Effects of Methanol/Gasoline Blends on Automobile Emissions

1992-02-01
920327
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.
Technical Paper

The Effect of Aromatics, MTBE, Olefins and T90 on Mass Exhaust Emissions from Current and Older Vehicles - The Auto/Oil Air Quality Improvement Research Program

1991-10-01
912322
Exhaust emissions were measured as a function of gasoline composition in two fleets of vehicles - 20 1989 vehicles and 14 1983-1985 vehicles. Eighteen different gasolines were tested which varied in aromatic, olefin, and MTBE content and in the 90 percent distillation temperature (T90). Subject to the cautions and qualifications described in the body of this paper, mass exhaust emissions in both fleets of vehicles were affected by changes in fuel composition. Responses to changes in MTBE and olefins were similar in both fleets: adding MTBE reduced emissions of HC and CO, and reducing olefins lowered emissions of NOx while raising emissions of HC. In the current fleet, reducing aromatics lowered HC and CO, while in the older fleet, reducing aromatics raised HC and lowered NOx. In the current fleet, lowering T90 reduced HC over 20%, while raising NOx slightly. In the older fleet, lowering T90 reduced HC by only 6%.
Technical Paper

Toxic Air Pollutant Vehicle Exhaust Emissions with Reformulated Gasolines

1991-10-01
912324
This paper presents results derived from Phase I of the Auto/Oil Air Quality Improvement Research Program. The Clean Air Act-defined mobile source toxic air pollutants benzene, 1,3-butadiene, formaldehyde and acetaldehyde have been measured in exhaust from twenty current model vehicles and fourteen older model vehicles during testing with 18 gasolines of varying composition. The gasoline fuel compositional variables evaluated included aromatic content, methyl tertiary-butyl ether (MTBE) content, olefin content, and the 90% distillation temperature (T90). The four fuel parameters were varied at target values of 45 and 20 vol % total aromatics, 0 and 15 vol % MTBE, 20 and 5 vol % total olefins and 360 and 280 °F 90% distillation temperature. An industry average fuel and an emissions certification test fuel were tested as reference fuels. In the current fleet, benzene levels were lowered when either fuel aromatics or T90 were reduced.
Technical Paper

Effects of Gasoline Sulfur Level on Mass Exhaust Emissions - Auto/Oil Air Quality Improvement Research Program

1991-10-01
912323
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.
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

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: Correlation of Fuel, Engine-Out, and Tailpipe Speciation — The Auto/Oil Air Quality Improvement Research Program

1993-10-01
932725
Species analyses have been performed on engine-out and tailpipe hydrocarbon mass emissions to help understand why fuels with increasing amounts of heavy hydrocarbon constituents produce significantly higher tailpipe hydrocarbon emissions. Mass and speciated hydrocarbon 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. In this paper the fates of fuel species were traced across the engine and across the catalyst, and correlations were developed between engine-out and tailpipe hydrocarbon species emissions and fuel composition.
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

Effects of Oxygenated Fuels and RVP on Automotive Emissions - Auto/Oil Air Quality Improvement Program

1992-02-01
920326
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.
Technical Paper

Running Loss Test Procedure Development

1992-02-01
920322
A running loss test procedure has been developed which integrates a point-source collection method to measure fuel evaporative running loss from vehicles during their operation on the chassis dynamometer. The point-source method is part of a complete running loss test procedure which employs the combination of site-specific collection devices on the vehicle, and a sampling pump with sampling lines. Fugitive fuel vapor is drawn into these collectors which have been matched to characteristics of the vehicle and the test cell. The composite vapor sample is routed to a collection bag through an adaptation of the ordinary constant volume dilution system typically used for vehicle exhaust gas sampling. Analysis of the contents of such bags provides an accurate measure of the mass and species of running loss collected during each of three LA-4* driving cycles. Other running loss sampling methods were considered by the Auto-Oil Air Quality Improvement Research Program (AQIRP or Program).
Technical Paper

Effects of Diesel Fuel Sulfur Level on Performance of a Continuously Regenerating Diesel Particulate Filter and a Catalyzed Particulate Filter

2000-06-19
2000-01-1876
This paper reports the test results from the DPF (diesel particulate filter) portion of the DECSE (Diesel Emission Control - Sulfur Effects) Phase 1 test program. The DECSE program is a joint government and industry program to study the impact of diesel fuel sulfur level on aftertreatment devices. A systematic investigation was conducted to study the effects of diesel fuel sulfur level on (1) the emissions performance and (2) the regeneration behavior of a continuously regenerating diesel particulate filter and a catalyzed diesel particulate filter. The tests were conducted on a Caterpillar 3126 engine with nominal fuel sulfur levels of 3 parts per million (ppm), 30 ppm, 150 ppm and 350 ppm.
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