Search Results

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.

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.

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.

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.

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).

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.

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?).