Improved Emissions Speciation Methodology for Phase II of the Auto/Oil Air Quality Improvement Research Program - Hydrocarbons and Oxygenates

Siegl, Walter O.; Richert, Joel F. O.; Jensen, Trescott E.; Schuetzle, Dennis; Swarin, Stephen J.; Loo, Jeffrey F.; Prostak, Arnold; Nagy, Don; Schlenker, Ann M.

doi:10.4271/930142

Cited by 121 publications

(46 citation statements)

References 9 publications

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“…All elutions were completed within 2 h of sample collection. At the end of each year's sampling program, the extracted samples were analyzed by high-performance Liquid chromatography (HPLC) using a procedure nearly identical that developed for the Auto/Oil Air Quality Improvement Besearch Pro:gain (14). Carbonyl samples were analyzed Hoeklnan and co-workers (15)(16)(17) ylpentane which increased from 0.92 and 0.43 wt % in 1995 to 3.6 and 1.7 wt % of gasoline in 1996, respectively.…”

Section: Resultsmentioning

confidence: 99%

Impact of California Reformulated Gasoline on Motor Vehicle Emissions. 2. Volatile Organic Compound Speciation and Reactivity

Kirchstetter¹,

Singer²,

Harley³

et al. 1998

Environ. Sci. Technol.

109

122

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This paper addresses the impact of California phase 2 reformulated gasoline (RFG) on the composition and reactivity of motor vehicle exhaust and evaporative emissions. Significant changes to gasoline properties that occurred in the first half of 1996 included an increase in oxygen content; decreases in alkene, aromatic, benzene, and sulfur contents; and modified distillation properties. Vehicle emissions were measured in a San Francisco Bay Area roadway tunnel in summers 1994-1997; gasoline samples were collected from local service stations in summers 1995 and 1996. Equilibrium gasoline headspace vapor composition was calculated from measured liquid gasoline composition. Addition of methyl tert-butyl ether (MTBE) and reduction of alkenes and aromatics in gasoline between summers 1995 and 1996 led to corresponding changes in the composition of gasoline headspace vapors. Normalized reactivity of liquid gasoline and headspace vapors decreased by 23 and 19%, respectively. Ozone formation should be reduced because of both lower gasoline vapor pressure, which leads to lower mass emissions, and reduced reactivity of gasoline vapors. The reactivity of onroad emissions measured in the tunnel decreased by 8% or less. The reduction in reactivity of on-road emissions was less than that of evaporative emissions because of increased weight fractions of highly-reactive isobutene and formaldehyde in vehicle exhaust, which resulted from the increased use of MTBE in gasoline. On-road vehicle emissions of volatile organic compounds in the tunnel appear to be dominated by vehicles that have reduced catalytic converter activity.

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Section: Resultsmentioning

confidence: 99%

Impact of California Reformulated Gasoline on Motor Vehicle Emissions. 2. Volatile Organic Compound Speciation and Reactivity

Kirchstetter¹,

Singer²,

Harley³

et al. 1998

Environ. Sci. Technol.

109

122

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] The addition of oxygenated compounds such as alcohols or ethers (e.g., MTBE) to a fuel can change its exhausted pollutants. Many qualitative, but few quantitative, correlations have been established.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Gasoline Formulation on Specific Pollutant Emissions

Zervas

Montagne

Lahaye

1999

Journal of the Air & Waste Management Association

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Many recent works have dealt with the influence of fuel composition on regulated and specific pollutant emissions from spark ignition engines. While many qualitative correlations have been already proposed, only a few quantitative ones are known (benzene remains an exception).This paper describes qualitative and quantitative correlations between fuel composition and specific pollutant emissions (individual hydrocarbons, aldehydes, ketones, alcohols, and organic acids) of a spark ignition engine. The aim of this work was to find the precursors of the main specific pollutants. Then, for each of them, a multilinear equation has been calculated, illustrating the correlation between its concentration in exhaust gases and its content in the fuel. The results of these calculations point out which initial compound favors the formation of a determined pollutant. As lean conditions are probably going to be used in future commercial engines, the fuel effect has been studied for a broad range of equivalence ratios (from 0.8 to 1.2).Two fuel matrixes were designed. The first one was obtained by introducing eight pure hydrocarbons (nC 6 , nC 8 , isoC 8 , 1-hexene, cyclohexane, toluene, o-xylene, and IMPLICATIONSThe topic of this paper strongly interests both refiners and car manufacturers. Besides being of scientific interest, knowing precisely which compound induces which pollutant, could enable refiners to determine which gasoline formulations provide better control of pollutant emissions, especially toxic compounds and ozone precursors. Car manufacturers could use this information to optimize engine tunings and catalyst use to reduce those emissions. Further, these works are of scientific interest, helping to improve understanding of the possible impact of regulation changes on pollutant emissions, helping refiners to improve fuel formulations, and helping all parties concerned by helping to improve air quality. ethylbenzene) in an alkylate base. The second one was formulated to test the behavior of four oxygenated compounds (methanol, ethanol, isopropanol, and methyl tertio-butyl ether [MTBE]).Individual unburned hydrocarbons, aldehydes, alcohols, and organic acids were analyzed according to accurate methods developed in our laboratory.Results show that benzene exhaust is mainly emitted from benzene fuel, the substituted aromatics, and, to a lesser degree, from cyclohexane; 1,3-butadiene is produced from 1-hexene or cyclohexane; and isobutene is a product of isooctane and MTBE. Exhaust toluene comes mainly from toluene fuel, but also from o-xylene and ethylbenzene fuels. Isopropylbenzene exhaust seems to be produced only from ethylbenzene fuel. Exhaust concentrations of acetaldehyde and acetone showed a strong correlation with, respectively, ethanol and isopropanol fuel contents. Methacroleine exhaust concentration was strongly correlated with the fuel's isooctane content. Benzaldehyde was produced by the aromatic fuels. Methanol was found in the exhaust gases of all the oxygenated fuels. High quantities of hexane...

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“…Airborne Toxic Emissions. Specific emission rates for all HC species from C1 to C12 were determined for all catalyst and fuel combinations (13). While not reported here, these data are available upon request from the authors [JMN].…”

Section: Resultsmentioning

confidence: 99%

“…Compounds were identified by a retention time comparison with a 23-component standard supplied by Scotts Specialty. Carbonyl emissions species were collected using dinitrophenyl-hydrazine (DNPH) coated silica gel cartridges and were analyzed by high-pressure liquid chromatography (HPLC) according to the procedure specified by the Auto/Oil Air Quality Improvement Research Program (13). Carbonyl standards were supplied by Supelco.…”

Section: Program Design and Experimental Detailsmentioning

confidence: 99%

A Systems Evaluation on the Effectiveness of a Catalyst Retrofit Program in China

Jones¹,

Wilson²,

Norbeck³

et al. 2001

Environ. Sci. Technol.

Self Cite

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A low-cost, rare-earth oxide (REO) catalyst has been recommended as part of China's retrofit program for Chinese carbureted vehicles. This study evaluated: (1) the emission reduction efficiency of the REO catalyst during chassis dynamometer testing on the FTP cycle; (2) the effect that fuel properties had on tailpipe emissions and catalyst efficiency; (3) the importance of vehicle premaintenance as part of a retrofit protocol; and (4) the emission reductions obtained following implementation of the program.Results also show that current in-use Chinese noncatalyst, carbureted vehicles operate excessively rich, resulting in extremely high emissions of CO, gaseous toxic compounds, and other non-methane hydrocarbon species (NMHC). Preretrofit maintenance alone has the potential to reduce these emissions by ∼50%. Dynamometer emission tests showed emissions reductions of >95% for hydrocarbons, CO, and gaseous toxics after retrofit of the REO catalyst. In particular, the relative unit health risk associated with the decrease in emissions of airborne toxic compounds using unleaded Chinese fuel was reduced from 6.33 to 0.30. (Use of low-sulfur California Phase II gasoline rather than current in-use Chinese fuel reduced emissions further.) Following implementation of the program, a followup study showed that in-use emissions benefits were considerably less than anticipated, primarily because of poor quality control at the retrofit service centers, a less aggressive preretrofit maintenance procedure, and unauthorized modification to the recommended retrofit control system. Overall results indicate that a carefully controlled retrofit program using REO catalyst technology can reduce emissions significantly. However, welldefined implementation guidelines, and strict adherence to these guidelines are needed to achieve maximum benefits.

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Improved Emissions Speciation Methodology for Phase II of the Auto/Oil Air Quality Improvement Research Program - Hydrocarbons and Oxygenates

Cited by 121 publications

References 9 publications

Impact of California Reformulated Gasoline on Motor Vehicle Emissions. 2. Volatile Organic Compound Speciation and Reactivity

Impact of California Reformulated Gasoline on Motor Vehicle Emissions. 2. Volatile Organic Compound Speciation and Reactivity

The Influence of Gasoline Formulation on Specific Pollutant Emissions

A Systems Evaluation on the Effectiveness of a Catalyst Retrofit Program in China

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