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Regulated and unregulated exhaust emissions (individual hydrocarbons, aldehydes and ketones, polynuclear aromatic hydrocarbons (PAH), and nitro-polynuclear aromatic hydrocarbons (NPAH)) were characterized for the following alternate diesel combustion modes: premixed charge compression ignition (PCCI), and low-temperature combustion (LTC). PCCI and LTC were studied on a PSA light-duty high-speed diesel engine. Engine-out emissions of carbonyl compounds were significantly increased for all LTC modes and for PCCI-Lean conditions as compared to diesel operation; however, PCCI-Rich produced much lower carbonyl emissions than diesel operations. For PAH compounds, emissions were found to be substantially increased over baseline diesel operation for LTC-Lean, LTC-Rich, and PCCI-Lean conditions. PCCI-Rich operation, however, gave PAH emission rates comparable to baseline diesel operation.

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.

Results from work focusing on the development of an ultra low emissions, high efficiency, natural gas-fueled heavy- duty engine are discussed in this paper. The engine under development was based on a John Deere 8.1L engine; this engine was significantly modified from its production configuration during the course of an engine optimization program funded by the National Renewable Energy Laboratory. Previous steady-state testing indicated that the modified engine would provide simultaneous reductions in nonmethane hydrocarbon emissions and fuel consumption while maintaining equivalent or lower NOx levels. Federal Test Procedure transient tests confirmed these expectations. Very low NOx emissions, averaging 1.0 g/bhp-hr over hot-start cycles, were attained; at these conditions, reductions in engine-out nonmethane hydro-carbons emissions (NMHC) were approximately 30 percent, and fuel consumption over the cycle was also reduced relative to the baseline.

The use of compressed natural gas as an alternative to conventional fuels has received a great deal of attention as a strategy for reducing air pollution from motor vehicles. In many cases, regulatory action has been taken to displace diesel fuel with natural gas in truck and bus applications. Emissions results of heavy-duty transient FTP testing of two Cummins L10-240G natural gas engines are presented. Regulated emissions of non-methane hydrocarbons, total hydrocarbons, CO, NOx, and particulate were characterized, along with emissions of formaldehyde. The effects of air/fuel ratio adjustments on these emissions were explored, as well as the effectiveness of catalytic aftertreatment in reducing exhaust emissions. Compared to typical heavy-duty diesel engine emissions, CNG-fueled engines using exhaust aftertreatment have great potential for meeting future exhaust emission standards, although in-use durability is unproven.

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.

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.

The use of biodiesel fuels derived from vegetable oils or animal fats as a substitute for conventional petroleum fuel in diesel engines has received increased attention. This interest is based on a number of properties of biodiesel including the fact that it is produced from a renewable resource, its biodegradability, and its potential beneficial effects on exhaust emissions. As part of Tier 1 compliance requirements for EPA's Fuel Registration Program, a detailed chemical characterization of the transient exhaust emissions from three modern diesel engines was performed, both with and without an oxidation catalyst. This characterization included several forms of hydrocarbon speciation, as well as measurement of aldehydes, ketones, and alcohols. In addition, both particle-phase and semivolatile-phase PAH and nitro-PAH compounds were measured. Unregulated emissions were characterized with neat biodiesel and with a blend of biodiesel and conventional diesel fuel.

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 a research program on exhaust emissions from snowmobile engines, including both emissions characterization and estimation of national emissions impact. Tests were conducted on three popular 2-stroke twins and on one rotary (Wankel) engine. Emissions that were measured included total hydrocarbons, (paraffinic) hydrocarbons by NDIR, CO, CO2, NO (by two methods), NOx, O2, aldehydes, light hydrocarbons, particulate, and smoke. Emissions of SOx were estimated on the basis of fuel consumed, and evaporative hydrocarbons were projected to be negligible for actual snowmobile operation. During emissions tests, intake air temperature was controlled to approximately -7°C (20°F), and room air at approximately 24°C (75°F) was used for engine cooling. Based on test results and the best snowmobile population and usage data available, impact of snowmobile emissions on a national scale was computed to be minimal.

In an attempt to characterize emissions from small air-cooled utility engines, five gasoline-fueled models were operated over a variety of speeds and loads, and important exhaust constituents were measured. These emissions included hydrocarbons, CO, CO2, NO, O2, aldehydes, light hydrocarbons, particulates, and smoke. Emissions of SOx were estimated on the basis of the fuel consumed; evaporative losses of hydrocarbons were also estimated. The impact of small engine emissions was calculated on the basis of the test results and information on national engine populations and usage. From these data, it appears that the 50 million or more small engines currently being used account for only a small part of pollutants from all sources.

Gasoline direct injection (GDI) has changed the exhaust composition in comparison with the older port fuel injection (PFI) systems. More recently, light-duty vehicle engine manufactures have combined these two technologies to take advantage of the knock benefits and fuel economy of GDI with the low particulate emission of PFI. These dual injection strategy engines have made a change in the combustion emission composition produced by these engines. Understanding the impact of these changes is essential for automotive companies and aftertreatment developers. A novel sampling system was designed to sample the exhaust generated by a dual injection strategy gasoline vehicle using the United States Federal Test Procedure (FTP). This sampling system was capable of measuring the regulated emissions as well as collecting the entire exhaust from the vehicle for measuring unregulated emissions.

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).

Improved designs of extruded metal electrically heated catalysts (EHC) in combination with a traditional converter achieved the California ultra-low emission vehicle (ULEV) standard utilizing 50% less electrical energy than previous prototypes. This energy reduction is largely achieved by reducing the mass of the EHC. In addition to energy reduction, the battery voltage is reduced from 24 volts to 12 volts, and the power is reduced from 12 kilowatts to 3 kilowatts. Also discussed is the impact EHC mass, EHC catalytic activity, and no EHC preheating has on non-methane hydrocarbon emissions, energy requirements, and power requirements.

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.

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.

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.

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.

Since the conception of the internal combustion engine, smoky and ill-smelling exhaust was prevalent. Over the last century, significant improvements have been made in improving combustion and in treating the exhaust to reduce these effects. One group of compounds typically found in exhaust, polycyclic aromatic hydrocarbons (PAH), usually occurs at very low concentrations in diesel engine exhaust. Some of these compounds are considered carcinogenic, and most are considered hazardous air pollutants (HAP). Many methods have been developed for sampling, handling, and analyzing PAH. For this study, an improved method for dilute exhaust sampling was selected for sampling the PAH in diesel engine exhaust. This sampling method was used during transient engine operation both with and without aftertreatment to show the effect of aftertreatment.

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.

NOx reduction efficiency in simulated lean exhaust conditions has been examined for three proprietary catalyst materials using a non-thermal plasma discharge as a pretreatment stage to the catalyst. Using propene as the reducing agent for selective catalytic reduction, 74% reduction of NOx has been observed in the presence of 20 ppm SO2. For sulfur-free simulated exhaust, 84% NOx reduction has been obtained. Results show that the impact of sulfur on the samples examined can vary widely from virtually no effect (< 5%) to more than 20% loss in activity depending on the catalyst. Any loss due to sulfur poisoning appears to be irreversible according to limited measurements on poisoned catalysts exposed to sulfur-free exhaust streams. Catalysts were tested over a temperature range of 473-773K, with the highest activity observed at 773K. Examination of this large temperature window has shown that the optimum C1:NOx ratio changes with temperature.