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Two methods of sampling exhaust emissions are typically used for characterizing emissions from diesel engines: total dilution which uses a constant volume sampling (CVS) system and partial flow dilution which relies on proportionally diluting a small part from the main exhaust stream. The CVS dilutes the entire exhaust flow to a constant volumetric flowrate which allows for proportional sampling of the exhaust species during transient engine operation. For partial dilution sampling during transient engine operation, obtaining a proportional sample is more rigorous and dilution of the extracted sample must be continuously changed throughout the cycle in order for the extracted sample flowrate to be proportional to the continuously changing exhaust flow. Typically, regulated emissions measured using both methods for an engine platform have shown good correlation. The focus for this work was on the experimental investigation of the two methods for the measurement of unregulated species.

Advanced combustion strategies used to improve efficiency, emissions, and performance in internal combustion engines (IC) alter the chemical composition of engine-out emissions. The characterization of exhaust chemistry from advanced IC engines requires an analytical system capable of measuring a wide range of compounds. For many years, the widely accepted Coordinating Research Council (CRC) Auto/Oil procedure[1,2] has been used to quantify hydrocarbon compounds between C1 and C12 from dilute engine exhaust in Tedlar polyvinyl fluoride (PVF) bags. Hydrocarbons greater than C12+ present the greatest challenge for identification in diesel exhaust. Above C12, PVF bags risk losing the higher molecular weight compounds due to adsorption to the walls of the bag or by condensation of the heavier compounds. This paper describes two specialized exhaust gas sampling and analytical systems capable of analyzing the mid-range (C10 - C24) and the high range (C24+) hydrocarbon in exhaust.

A series of tests were performed on a gasoline powered engine with a Dedicated EGR® (D-EGR®) system. The results showed that changes in engine performance, including improvements in burn rates and stability and changes in emissions levels could not be adequately accounted for solely due to the presence of reformate in the EGR stream. In an effort to adequately characterize the engine's behavior, a new parameter was developed, the Total Inert Dilution Ratio (TIDR), which accounts for the changes in the EGR quality as inert gases are replaced by reactive species such as CO and H2.

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.

A solid particle number measurement system (SPNMS) was developed using a catalytic stripper (CS) technology instead of an evaporation tube (ET). The ET is used in commercially available systems, compliant with the Particle Measurement Program (PMP) protocol developed for European Union (EU) solid particle number regulations. The catalytic stripper consists of a small core of a diesel exhaust oxidation catalyst. The SPNMS/CS met all performance requirements under the PMP protocol. It showed a much better performance in removing large volatile tetracontane particles down to a size well below the PMP lower cut-size of 23 nm, compared to a SPNMS equipped with an ET instead of a CS. The SPNMS/CS also showed a similar performance to a commercially available system when used on a gasoline direct injection (GDI) engine exhaust.

The spark ignition (SI) engine has been known to exhibit several different abnormal combustion phenomena, such as knock or pre-ignition, which have been addressed with improved engine design or control schemes. However, in highly boosted SI engines, Low-Speed Pre-Ignition (LSPI), a pre-ignition event typically followed by heavy knock, has developed into a topic of major interest due to its potential for engine damage. Previous experiments associated increases in hydrocarbon emissions with the blowdown event of an LSPI cycle [1]. Also, the same experiments showed that there was a dependency of the LSPI activity on fuel and/or lubricant compositions [1]. Based on these findings it was hypothesized that accumulated hydrocarbons play a role in LSPI and are consumed during LSPI events. A potential source for accumulated HC is the top land piston crevice.

This paper analyzes the aging of zeolite based hydrocarbon traps to guide development of diagnostic algorithms. Previous research has shown the water adsorption ability of zeolite ages along with the hydrocarbon adsorption ability, and this leads to a possible diagnostic algorithm: the water concentration in the exhaust can be measured and related to aging. In the present research, engine experiments demonstrate that temperature measurements are also related to aging. To examine the relationship between temperature-based and moisture-based diagnostic algorithms, a transient, nonlinear heat and mass transfer model of the exhaust during cold-start is developed. Despite some idealizations, the model replicates the qualitative behavior of the exhaust system. A series of parametric studies reveals the sensitivity of the system response to aging and various noise factors.

A new on-board portable emission measurement system (PEMS) for gaseous emissions has been designed and developed to meet CFR Part 1065 requirements. The new system consists of a heated flame ionization detector (HFID) for the measurement of total hydrocarbon, a heated chemiluminescence detector (HCLD) for the measurement of NOx, and a heated non-dispersive infra-red detector (HNDIR) for the measurement of CO and CO2. The oxygen interference and relative sensitivity of several hydrocarbon components have been optimized for the HFID. The CO2 and H2O quenching effect on the HCLD have been compensated using measured CO2 and H2O concentration. The spectral overlap and molecular interaction of H2O on the HNDIR measurement has also been compensated using an independent H2O concentration measurement. The basic performance of the new on-board emission measurement system has been verified accordingly with CFR part 1065 and all of the performances have met with CFR part 1065 requirement.

Two large, heavy light-duty gasoline vehicles (2004 model year Ford F-150 with a 5.4 liter V8 and GMC Yukon Denali with a 6.0 liter V8) were baselined for emission performance over the FTP driving cycle in their stock configurations. Advanced emission systems were designed for both vehicles employing advanced three-way catalysts, high cell density ceramic substrates, and advanced exhaust system components. These advanced emission systems were integrated on the test vehicles and characterized for low mileage emission performance on the FTP cycle using the vehicle's stock engine calibration and, in the case of the Denali, after modifying the vehicle's stock engine calibration for improved cold-start and hot-start emission performance.

Many studies suggest that lean-NOx SCR proceeds via oxidation of NO to NO2 by oxygen, followed by the reaction of the NO2 with hydrocarbons. On catalysts that are not very effective in catalyzing the equilibration of NO+O2 and NO2, the rate of N2 formation is substantially higher when the input NOx is NO2 instead of NO. The apparent bifunctional mechanism in the SCR of NOx has prompted the use of mechanically mixed catalyst components, in which one component is used to accelerate the oxidation of NO to NO2, and another component catalyzes the reaction between NO2 and the hydrocarbon. Catalysts that previously were regarded as inactive for NOx reduction could therefore become efficient when mixed with an oxidation catalyst. Preconverting NO to NO2 opens the opportunity for a wider range of SCR catalysts and perhaps improves the durability of these catalysts. This paper describes the use of a non-thermal plasma as an efficient means for selective partial oxidation of NO to NO2.

Lower explosion limits (LEL) and the chemical compositions of JP-8, Jet A and JP-5 fuel vapors were determined in a sealed combustion vessel equipped with a spark igniter, a gas-sampling probe, and sensors to measure pressure rise and fuel temperature. Ignition was detected by pressure rise in the vessel. Pressure rises up to 60 psig were observed near the flash points of the test fuels. The fuel vapors in the vessel ignited from as much as 11°F below flash-point measurements. Detailed hydrocarbon speciation of the fuel vapors was performed using high-resolution gas chromatography. Over 300 hydrocarbons were detected in the vapors phase. The average molecular weight, hydrogen to carbon ratio, and LEL of the fuel vapors were determined from the concentration measurements. The jet fuel vapors had molecular weights ranging from 114 to 132, hydrogen to carbon ratios of approximately 1.93, and LELs comparable to pure hydrocarbons of similar molecular weight.

Newly designed Teflon® O-rings along with XAD-2 resin, stainless steel screens, lock rings, and glass cartridges were used to construct a new semi-volatile organic compounds (SVOC's) sampling device. This new sampling device allows direct and repeated sampling, extraction, and cleaning without ever having to be disassembled or reassembled. This new XAD-2 glass cartridge (X2) was compared with three other sampling methods namely Empore® membrane (EM), hexane impinger (HI), and “Cold Trap” (CT) for SVOC sampling efficiency on diesel engine exhaust emissions. The X2 method showed the highest overall SVOC collection efficiency, followed by the EM and HI methods. The X2 method has higher trapping efficiency for the oxygenates, polycyclic aromatic hydrocarbons (PAH's), alkyl cyclohexanes, and the alkyl aromatics than the other three SVOC sampling methods. The HI method has the highest trapping efficiency for the normal alkanes.

A novel urea evaporation and mixing device has been developed to improve the overall performance of a urea-SCR system. The device was tested with a MY2007 Cummins ISB 6.7L diesel engine equipped with an SCR aftertreatment system. Test results show that the device effectively improved the overall NO conversion efficiency of the SCR catalyst over both steady-state and transient engine operating conditions, while NH₃ slip from the catalyst decreased.

The equipment for collecting dilute exhaust samples involves the use of bag materials (i.e., Tedlar®) that emit hydrocarbons that contaminate samples. This study identifies a list of materials and treatments to produce bags that reduce contamination. Based on the average emission rates, baked Tedlar®, Capran® treated with alumina deposition, supercritical CO2 extracted Kynar® and supercritical CO2 extracted Teflon NXT are capable of achieving the target hydrocarbon emission rate of less than 15 ppbC per 30 minutes. CO2 permeation tests were also performed. Tedlar, Capran, Kynar and Teflon NXT showed comparable average permeation rates. Based on the criteria of HC emission performance, changes in measured CO2 concentration, ease of sealing, and ease of surface treatment, none of the four materials could be distinguished from one another.

This study compared diesel exhaust emission from four different diesel fuels: a conventional low sulfur D2 diesel (0.03% sulfur, 28% aromatics), California Air Resources Board (CARB) diesel (0.015% sulfur, 8% aromatics), “Swedish” diesel (<0.001% sulfur, 4% aromatics), and a Fischer-Tropsch (F-T) diesel (<0.0001% sulfur, <0.1% aromatics) fuel. The comparison included regulated emissions, hydrocarbon speciation, air toxics, aldehydes and ketones, particle size distribution, and greenhouse gas emissions. Testing was conducted using a Cummins B-Series engine installed both in a heavy light-duty truck operating on a chassis dynamometer and on an engine dynamometer. The chassis driving cycles included city, highway, and aggressive driving operation. Engine dynamometer tests included the U.S. transient cycle.

A recently completed program was developed to evaluate ultra-low sulfur diesel fuels and passive diesel particle filters (DPF) in several different truck and bus fleets operating in Southern California. The primary test fuels, ECD and ECD-1, are produced by ARCO, a BP company, and have less than 15 ppm sulfur content. A test fleet comprised of heavy-duty trucks and buses were retrofitted with one of two types of catalyzed diesel particle filters, and operated for one year. As part of this program, a chemical characterization study was performed in the spring of 2001 to compare the exhaust emissions using the test fuels with and without aftertreatment. A detailed speciation of volatile organic hydrocarbons (VOC), polycyclic aromatic hydrocarbons (PAH), nitro-PAH, carbonyls, polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzo-p-furans (PCDF), inorganic ions, elements, PM10, and PM2.5 in diesel exhaust was performed for a select set of vehicles.

A study was performed in the spring of 2001 to chemically characterize exhaust emissions from trucks and buses fueled by various test fuels and operated with and without diesel particle filters. This study was part of a multi-year technology validation program designed to evaluate the emissions impact of ultra-low sulfur diesel fuels and passive diesel particle filters (DPF) in several different heavy-duty vehicle fleets operating in Southern California. The overall study of exhaust chemical composition included organic compounds, inorganic ions, individual elements, and particulate matter in various size-cuts. Detailed descriptions of the overall technology validation program and chemical speciation methodology have been provided in previous SAE publications (2002-01-0432 and 2002-01-0433).

Diesel engines are far more efficient than gasoline engines of comparable size, and emit less greenhouse gases that have been implicated in global warming. In 2000, the US EPA proposed very stringent emissions standards to be introduced in 2007 along with low sulfur (< 15 ppm) diesel fuel. The California Air Resource Board (CARB) has also established the principle that future diesel fueled vehicles should meet the same low emissions standards as gasoline fueled vehicles and the EPA followed suit with its Tier II emissions regulation. Achieving such low emissions cannot be done through engine development and fuel reformulation alone, and requires application of NOx and particulate matter (PM) aftertreatment control devices. There is a widespread consensus that NOx adsorbers and particulate filter are required in order for diesel engines to meet the 2007 emissions regulations for NOx and PM. In this paper, the key exhaust characteristics from an advanced diesel engine are reviewed.

The emission capability of an exhaust system tuned for improved engine performance from an in-line four-cylinder engine has been investigated. The exhaust system comprises two close-coupled catalysts; each located in separate exhaust streams and has been termed the 4-2 close-coupled catalysts (CCC) -1 system. It has been shown that, given equivalent total catalyst volume, this system configuration results in compromised high exhaust flow rate emissions performance compared with a single catalyst (4-1semi-CCC) system. This emissions performance deficit has been attributed to the effect of engine frequency flow pulsations, which result in relatively high peak space velocities in the 4-2CCC-1 system despite the mean space velocity being consistent. Engine-based AFR Bias Sweep tests suggest that hydrocarbon emissions are most strongly affected by this phenomenon. At lower exhaust flow rates, the difference in performance between the two systems is negligible.

In the effort to design reliable diesel engines which meet the strict US Federal Regulations for emissions, considerable progress has been made by engine manufacturers. Particulate emissions are now below 0.25 g/BHPh and after 1994 will be below 0.1 g/BHPh. Diesel fuel has a revised specification limit of 0.05% sulfur as a means to assist diesel engine manufacturers in complying with the 1994 standard. Diesel oxidation catalysts (DOC) have been chosen as another means. A DOC can efficiently oxidize soluble organic particulate matter (SOF) and gaseous hydrocarbons while easily oxidizing SO2 to SO3-the latter being a particulate and undesirable. Selective DOCs have been developed which maintain the activity for SOF and minimize the undesirable SO2 oxidation step. However, performance for gaseous hydrocarbons may be negatively affected.