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Technical Paper

Countering the Effects of Media Interferences and Background Contamination in Collection of Low Concentration Aldehydes and Ketones in Engine Exhaust with Dinitrophenylhydrazine (DNPH) Derivatization

2011-08-30
2011-01-2060
This paper discusses a method developed to counter the variability of media interferences for the measurement of aldehydes and ketones in automotive exhaust. Dinitrophenylhydrazine (DNPH) Derivatization Methodology for the collection of aldehyde and ketone compounds in vehicle exhaust has been in use for over thirty years. These carbonyl compounds are captured by passing diluted exhaust gas through a sample medium containing DNPH. The sampling medium can take the form of DNPH dispersed on a solid sorbent or as a DNPH solution in a solvent such as acetonitrile. Carbonyl compounds react readily to form DNPH derivatives which are stable and which absorb ultra-violet (UV) light, facilitating quantitative measurement. However, when the procedure was developed, emissions rates from vehicles were much higher than the current (2010) emissions levels.
Journal Article

Catalytic Formulation for NO2 Suppression and Control

2008-06-23
2008-01-1548
To counter the adverse impact on the formation of harmful unregulated emissions such as nitro-polycyclic aromatic hydrocarbons (NPAH), catalyst companies and researchers have been developing catalytic coatings that have the capability of suppressing the formation of NO2. NO2 is formed at low exhaust temperatures with potentially greater concentrations at part load engine operation. Haldor Topsoe, a catalyst company from Denmark, developed such a catalytic coating for DPFs. A sample was provided to Southwest Research Institute (SwRI) to conduct this research with a view of potentially improving NO2-suppressing formulations in the future. The Haldor Topsoe diesel particulate filter (DPF) with its novel coating was tested together with three other DPFs and the results confirmed the capability of this DPF to suppress the formation of NO2. This characteristic was apparent in all five engine test modes selected to cover the full engine operating range.
Journal Article

Development of a Synthetic Diesel Exhaust

2008-04-14
2008-01-0067
A two-phase study was performed to establish a standard diesel exhaust composition which could be used in the future development of light-duty diesel exhaust aftertreatment. In the first phase, a literature review created a database of diesel engine-out emissions. The database consisted chiefly of data from heavy-duty diesel engines; therefore, the need for an emission testing program for light- and medium-duty engines was identified. A second phase was conducted to provide additional light-duty vehicle emissions data from current technology vehicles. Engine-out diesel exhaust from four 2004 model light-duty vehicles with a variety of engine displacements was collected and analyzed. Each vehicle was evaluated using five steady-state engine operating conditions and two transient test cycles (the Federal Test Procedure and the US06). Regulated emissions were measured along with speciation of both volatile and semi-volatile components of the hydrocarbons.
Technical Paper

Developmental Fuels Emissions Evaluation

2005-10-24
2005-01-3704
Emissions characterization of three, small off-road engines of less than 19 kW power rating operating on two developmental fuels and one reference fuel was performed. The two fuels were formulated to remove benzene completely, curtail sulfur, and in one blend, include a substantial proportion of ethyl tert-butyl ether (ETBE). The engines selected included one side-valve four-stroke engine, one overhead valve four-stroke engine and one handheld two-stroke engine. The engines were maintained in stock condition. Exhaust emissions from operation with the two developmental fuels were compared to those from operation with light-duty certification-grade gasoline. California Air Resources Board (CARB) Small Off-Road Engine (SORE) emissions test methods and test cycles were used to test the engines. Duplicate tests were performed on each engine using dilute sampling procedures. Hydrocarbon speciation was performed on one replicate with each fuel.
Technical Paper

Regulated and Unregulated Exhaust Emissions Comparison for Three Tier II Non-Road Diesel Engines Operating on Ethanol-Diesel Blends

2005-05-11
2005-01-2193
Regulated and unregulated emissions (individual hydrocarbons, ethanol, aldehydes and ketones, polynuclear aromatic hydrocarbons (PAH), nitro-PAH, and soluble organic fraction of particulate matter) were characterized in engines utilizing duplicate ISO 8178-C1 eight-mode tests and FTP smoke tests. Certification No. 2 diesel (400 ppm sulfur) and three ethanol/diesel blends, containing 7.7 percent, 10 percent, and 15 percent ethanol, respectively, were used. The three, Tier II, off-road engines were 6.8-L, 8.1-L, and 12.5-L in displacement and each had differing fuel injection system designs. It was found that smoke and particulate matter emissions decreased with increasing ethanol content. Changes to the emissions of carbon monoxide and oxides of nitrogen varied with engine design, with some increases and some decreases. As expected, increasing ethanol concentration led to higher emissions of acetaldehyde (increases ranging from 27 to 139 percent).
Technical Paper

Development of an Ethanol-Fueled Ultra-Low Emissions Vehicle

1998-05-04
981358
A 1993 Ford Taurus Flexible Fuel Vehicle (FFV) designed to operate on gasoline or methanol has been modified to run on Ed85 (85 vol.% denatured ethanol, 15 vol.% gasoline) and has demonstrated the ability to meet California's Ultra-Low Emissions Vehicle (ULEV) standards. The vehicle maintains the excellent driveability with potentially increased performance and similar efficiency to the baseline vehicle. Using standard twin OEM catalysts, FTP-75 emissions were 0.085 g/mi NOx, 0.88 g/mi CO, and 0.039 g/mi reactivity-adjusted NMOG. Using close-coupled catalysts upstream of the OEM catalysts, FTP-75 emissions were 0.031 g/mi NOx, 0.297 g/mi CO, and 0.015 g/mi reactivity-adjusted NMOG. The catalysts were aged to about 4,000 miles of equivalent use. These emissions compare with ULEV standards of 0.2 g/mi NOx, 1.7 g/mi CO, and 0.04 g/mi NMOG at 50,000 miles of use.
Technical Paper

Reactivity and Exhaust Emissions from an EHC-Equipped LPG Conversion Vehicle Operating on Butane/Propane Fuel Blends

1996-10-01
961991
This paper describes experiments conducted to determine Federal Test Procedure (FTP) exhaust emissions, ozone-forming potentials, specific reactivities, and reactivity adjustment factors for several butane/propane alternative fuel blends run on a light-duty EHC-equipped gasoline vehicle converted to operate on liquefied petroleum gas (LPG). Duplicate emission tests were conducted on the light-duty vehicle at each test condition using appropriate EPA FTP test protocol. Hydrocarbon speciation was utilized to determine reactivity-adjusted non-methane organic gas (NMOG) emissions for one test on each fuel.
Technical Paper

Reactivity Comparison of Exhaust Emissions from Heavy-Duty Engines Operating on Gasoline, Diesel, and Alternative Fuels

1995-10-01
952442
This paper describes experiments conducted to determine the ozone-forming potentials, specific reactivities, and reactivity adjustment factors for various heavy-duty engines operating on “industry average” (RF-A) gasoline, California Phase 2 gasoline, compressed natural gas (CNG), liquefied petroleum gas (LPG), and diesel fuel. Each engine/fuel combination was tested in triplicate using the EPA heavy-duty transient cold- and hot-start test protocol. Hydrocarbon speciation was conducted for all tests to allow for the determination of ozone-forming potentials, using California Air Resources Board maximum incremental reactivity factors as well as determination of the Clean Air Act “toxic” emissions.
Technical Paper

Use of Butane as an Alternative Fuel-Emissions from a Conversion Vehicle Using Various Blends

1995-10-01
952496
This paper describes experiments conducted to determine the regulated emissions, ozone-forming potentials, specific reactivities, and reactivity adjustment factors for eight butane and propane alternative fuel blends run on a light-duty vehicle, emission certified to be a California transitional low emission vehicle (TLEV) and converted to operate on liquefied petroleum gas (LPG). Duplicate EPA FTP emission tests were conducted with each fuel. Hydrocarbon speciation was utilized to determine reactivity-adjusted non-methane organic gases (NMOG) emissions for one test on each fuel. Results showed that all eight fuels could allow the converted vehicle to pass California ultra-low emission vehicle (ULEV) NMOG and oxides of nitrogen (NOx) standards. Six of the eight fuels could allow the vehicle to pass ULEV carbon monoxide (CO) standards. BUTANE has been an important gasoline blending component for many years.
Technical Paper

Heavy-Duty Diesel Hydrocarbon Speciation:Key Issues and Technological Challenges

1993-10-01
932853
Development of methodology for diesel hydrocarbon speciation of C12-C22 compounds and the application of that methodology to determine total ozone forming potential of diesel exhaust emissions is an extremely complicated task. Methodology has already been developed for speciating C1-C12 exhaust emissions from engines and vehicles fueled with gasoline, diesel, and alternate fuels. However, very little or no information is available for exhaust speciation of C12-C22 compounds as sampling and analytical constraints make the collection and analysis of the higher molecular weight compounds extremely challenging. Key issues related to the definition of “hydrocarbons” also need to be addressed prior to promulgation of future reactivity-based legislation for diesels (e.g., Which exhaust hydrocarbon compounds actually exist in gas-phase and participate in atmospheric ozone formation?).
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