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.

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 technology path has been identified for development of a high efficiency, durable, gasoline engine, targeted at achieving performance and emissions levels necessary to meet heavy-duty, on-road standards of the foreseeable future. Initial experimental and numerical results for the proposed technology concept are presented. This work summarizes internal research efforts conducted at Southwest Research Institute. An alternative combustion system has been numerically and experimentally examined. The engine utilizes gasoline as the fuel, with a combination of enabling technologies to provide high efficiency operation at ultra-low emissions levels. The concept is based upon very highly-dilute combustion of gasoline at high compression ratio and boost levels. Results from the experimental program have demonstrated engine-out NOx emissions of 0.06 g/hp/hr, at single-cylinder brake thermal efficiencies (BTE) above thirty-four percent.

The engine selected for this work was a Caterpillar 3176 engine. Engine exhaust emissions, performance, and heat release rates were measured as functions of engine configuration, engine speed and load. Two engine configurations were used, a standard 1994 design and a 1994 configuration with EGR designed to achieve a NOx emissions level of 2.5 gm/hp-hr. Measurements were performed at 7 different steady-state, speed-load conditions on thirteen different test fuels. The fuel matrix was statistically designed to independently examine the effects of the targeted fuel properties. Cetane number was varied from 40 to 55, using both natural cetane number and cetane percent improver additives. Aromatic content ranged from 10 to 30 percent in two different forms, one in which the aromatics were predominantly mono-aromatic species and the other, where a significant fraction of the aromatics were either di- or tri-aromatics.

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.

A zero-dimensional cycle simulation model coupled with a chemical equilibrium model and a two-zone combustion model has been extended to predict nitric oxide formation and emissions from spark-ignited, lean-burn natural gas engines. It is demonstrated that using the extended Zeldovich mechanism alone, the NOx emissions from an 8.1-liter, 6-cylinder, natural gas engine were significantly under predicted. However, by combining the predicted NOx formation from both the extended Zeldovich thermal NO and the Fenimore prompt NO mechanisms, the NOx emissions were predicted with fair accuracy over a range of engine powers and lean-burn equivalence ratios. The effect of injection timing on NOx emissions was under predicted. Humidity effects on NOx formation were slightly under predicted in another engine, a 6.8-liter, 6-cylinder, natural gas engine. Engine power was well predicted in both engines, which is a prerequisite to accurate NOx predictions.

An emissions reduction strategy was developed and demonstrated to significantly reduce cold-start hydrocarbon (HC) and CO emissions from a spark ignition (SI), gasoline-fueled engine. This strategy involved cold-starting the engine with an ultra-fuel rich calibration, while metering near-stoichiometric fractions of air directly into the exhaust ports. Using this approach, exhaust constituents spontaneously ignited at the exhaust ports and burned into the exhaust manifold and exhaust pipe leading to the catalytic converter. The resulting exotherm accelerated catalyst heating and significantly decreased light-off time following a cold-start on the FTP-75 with a Ford Escort equipped with a 1.9L engine. Mass emissions measurements acquired during the first 70 seconds of the FTP-75 revealed total-HC and CO reductions of 68 and 50 percent, respectively, when compared to baseline measurements.

A menu-driven, PC-based model, ALAMO_ENGINE, has been developed to predict the nitrogen oxides (NOx) reductions in direct-injected, diesel engines due to exhaust gas recirculation (EGR), emulsified fuels, manifold or in-cylinder water injection, fuel injection timing changes, humidity effects, and intake air temperature changes. The approach was to use a diesel engine cycle simulation with detailed gas composition calculations for the intake and exhaust gases (including EGR, water concentration, fuel-type effects, etc.), coupled with a code to calculate stoichiometric, adiabatic flame temperatures and expressions that correlate measured NOx emissions with the flame temperature. Execution times are less than 10 seconds on a 486-66 MHz PC.

High-speed movie films, and laser-diffraction drop sizing were used to evaluate the structure, penetration rate, cone angle, and drop size distribution of diesel sprays in a constant volume pressure vessel. As further means of evaluating the data, comparisons are made between the film measurements, and calculations from a dense gas jet model. In addition to the high-speed film data that describes the overall structure of the spray as a function of time, a laser diffraction instrument was used to measure drop size distribution through a cross-section of the spray. In terms of the growth of the total spray volume (a rough measure of the amount of air entrained in the spray), spray impingement causes an initial delay, but generally the same overall growth rate as an equivalent unimpeded spray. Agreement between measurements and calculations is excellent for a diesel spray with a 0.15 mm D orifice and relatively high injection pressures.

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?).

Twelve different hole shapes for diesel injector tips were characterized with DF-2 diesel fuel for spray cone angle over a range of injection pressures from 21 MPa (3 kpsi) to 69 MPa (10 kpsi). A baseline and two of the most radical designs were also tested for drop-size distribution and liquid volume fraction (liquid fuel-air ratio) over a range of pressures from 41 MPa (6 kpsi) to 103 MPa (15 kpsi). All hole shapes were circular in cross-section with minimum diameters of 0.4 mm (0.016 in.), and included converging and diverging hole shapes. Overall hole lengths were constant at 2.5 mm (0.098 in.), for an L/d of 6.2. However, the effective L/d may have been less for some of the convergent and divergent shapes.