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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.

Fundamental understanding of the sources of fuel-derived Unburned Hydrocarbon (UHC) emissions in heavy duty diesel engines is a key piece of knowledge that impacts engine combustion system development. Current emissions regulations for hydrocarbons can be difficult to meet in-cylinder and thus after treatment technologies such as oxidation catalysts are typically used, which can be costly. In this work, Computational Fluid Dynamics (CFD) simulations are combined with engine experiments in an effort to build an understanding of hydrocarbon sources. In the experiments, the combustion system design was varied through injector style, injector rate shape, combustion chamber geometry, and calibration, to study the impact on UHC emissions from mixing-controlled diesel combustion.

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 number of oxidation catalysts have been prepared using different types of advanced support materials such as ceria-zirconia, silica-titania, spinels and perovskites. Active metals such as Pd and Au-Pd were loaded by conventional impregnation techniques and/or deposition-precipitation methods. A liquid hydrocarbon delivery system was designed and implemented for the catalyst test benches in order to simulate the diesel engine exhaust environment. The activity of fresh (no degreening) catalysts was evaluated with traditional CO and light hydrocarbons (C2H4, C3H6) as well as with heavy hydrocarbons such as C10 H22.

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.

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.

Various gold catalysts were prepared using commercial and in-house fabricated advanced catalyst supports that included mesoporous silica, mesoporous alumina, sol-gel alumina, and transition metal oxides. Gold nanoparticles were loaded on the supports by co-precipitation, deposition-precipitation, ion exchange and surface functionalization techniques. The average gold particle size was ∼20nm or less. The oxidation activity of the prepared catalysts was studied using carbon monoxide and light hydrocarbons (ethylene, propylene and propane) in presence of water and CO2 and the results are presented.

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.

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 paper describes two independent studies on γ-alumina as a plasma-activated catalyst. γ-alumina (2.5 - 4.3 wt%) was coated onto the surface of mesoporous silica to determine the importance of aluminum surface coordination on NOx conversion in conjunction with nonthermal plasma. Results indicate that the presence of 5- and 6- fold aluminum coordination sites in γ-alumina could be a significant factor in the NOx reduction process. A second study examined the effect of changing the reducing agent on NOx conversion. Several hydrocarbons were examined including propene, propane, isooctane, methanol, and acetaldehyde. It is demonstrated that methanol was the most effective reducing agent of those tested for a plasma-facilitated reaction over γ-alumina.

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.

Natural gas quality, in terms of the volume fraction of higher hydrocarbons, strongly affects the auto-ignition characteristics of the air-fuel mixture, the engine performance and its controllability. The influence of natural gas composition on engine operation has been investigated both experimentally and through chemical kinetic based cycle simulation. A range of two component gas mixtures has been tested with methane as the base fuel. The equivalence ratio (0.3), the compression ratio (19.8), and the engine speed (1000 rpm) were held constant in order to isolate the impact of fuel autoignition chemistry. For each fuel mixture, the start of combustion was phased near top dead center (TDC) and then the inlet mixture temperature was reduced. These experimental results have been utilized as a source of data for the validation of a chemical kinetic based full-cycle simulation.

A slipstream of exhaust from a Caterpillar 3126B engine was diverted into a plasma-catalytic NOx control system in the space velocity range of 7,000 to 100,000 hr-1. The stream was first fed through a non-thermal plasma that was formed in a coaxial cylinder dielectric barrier discharge reactor. Plasma treated gas was then passed over a catalyst bed held at constant temperature in the range of 573 to 773 K. Catalysts examined consisted of γ-alumina, indium-doped γ-alumina, and silver-doped γ-alumina. Road and rated load conditions resulted in engine out NOx levels of 250 - 600 ppm. The effects of hydrocarbon level, catalyst temperature, and space velocity are discussed where propene and in one case ultra-low sulfur diesel fuel (late cycle injection) were the reducing agents used for NOx reduction. Results showed NOx reduction in the range of 25 - 97% depending on engine operating conditions and management of the catalyst and slipstream conditions.

This paper describes the findings of a laboratory effort to demonstrate improved automotive exhaust emission control with a cold-start hydrocarbon collection system. The emission control strategy developed in this study incorporated a zeolite molecular sieve in the exhaust system to collect cold-start hydrocarbons for subsequent release to an active catalytic converter. A prototype emission control system was designed and tested on a gasoline-fueled vehicle. Continuous raw exhaust emission measurements upstream and downstream of the zeolite molecular sieve revealed collection, storage, and release of cold-start hydrocarbons. Federal Test Procedure (FTP) emission results show a 35 percent reduction in hydrocarbons emitted during the cold-transient segment (Bag 1) due to adsorption by the zeolite.