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Ethanol is a very effective reductant for nitrogen oxides (NOX) over silver/alumina (Ag/Al2O3) catalysts in lean exhaust environments. With the widespread availability of ethanol/gasoline-blended fuel in the U.S., lean gasoline engines equipped with Ag/Al2O3 catalysts have the potential to deliver higher fuel economy than stoichiometric gasoline engines and to increase biofuel utilization while meeting exhaust emissions regulations. In this work a pre-commercial 2 wt% Ag/Al2O3 catalyst was evaluated on a 2.0-liter BMW lean burn gasoline direct injection engine for the selective catalytic reduction (SCR) of NOX with ethanol/gasoline blends. The ethanol/gasoline blends were delivered via in-pipe injection upstream of the Ag/Al2O3 catalyst with the engine operating under lean conditions. A number of engine conditions were chosen to provide a range of temperatures and space velocities for evaluation of catalyst performance.

NOx emissions from a heavy-duty diesel engine were reduced by more than 90% and 80% utilizing a full-scale ethanol-SCR system for space velocities of 21000/h and 57000/h respectively. These results were achieved for catalyst temperatures between 360 and 400°C and for C1:NOx ratios of 4-6. The SCR process appears to rapidly convert ethanol to acetaldehyde, which subsequently slipped past the catalyst at appreciable levels at a space velocity of 57000/h. Ammonia and N2O were produced during conversion; the concentrations of each were higher for the low space velocity condition. However, the concentration of N2O did not exceed 10 ppm. In contrast to other catalyst technologies, NOx reduction appeared to be enhanced by initial catalyst aging, with the presumed mechanism being sulfate accumulation within the catalyst. A concept for utilizing ethanol (distilled from an E-diesel fuel) as the SCR reductant was demonstrated.

We describe a study to identify potential biofuels that enable advanced spark ignition (SI) engine efficiency strategies to be pursued more aggressively. A list of potential biomass-derived blendstocks was developed. An online database of properties and characteristics of these bioblendstocks was created and populated. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a bioblendstock met the requirements for advanced SI engines. Criteria included melting point (or cloud point) < -10°C and boiling point (or T90) <165°C. Compounds insoluble or poorly soluble in hydrocarbon were eliminated from consideration, as were those known to cause corrosion (carboxylic acids or high acid number mixtures) and those with hazard classification as known or suspected carcinogens or reproductive toxins.

The DOE Office of Heavy Vehicle Technologies (OHVT) and its predecessor organizations have maintained aggressive projects in diesel exhaust aftertreatment since 1993. The Energy Policy Act of 1992, Section 2027, specifically authorized DOE to help accelerate the ability of U. S. diesel engine manufacturers to meet emissions regulations while maintaining the compression ignition engines inherently high efficiency. A variety of concepts and devices have been evaluated for NOx and Particulate matter (PM) control. Additionally, supporting technology in diagnostics for catalysis, PM measurement, and catalyst/reductant systems are being developed. This paper provides a summary of technologies that have been investigated and provides recent results from ongoing DOE-sponsored R&D. NOx control has been explored via active NOx catalysis, several plasma-assisted systems, electrochemical cells, and fuel additives.

A minimally invasive spatially resolved capillary inlet mass spectrometer has been used to quantify EGR/air mixing in a Cummins V-8 medium-duty diesel engine. Two EGR-system hardware designs were evaluated in terms of EGR-air mixing at the intake manifold inlet and port-to-port EGR charge uniformity. Performance was assessed at four modalized-FTP engine conditions. One design is found to be considerably better, particularly at three of the four engine conditions. Specific questions such as the effect of maximizing mass air flow on EGR mixing, and if particular cylinders are EGR starved are investigated. The detailed performance characteristics suggest areas to focus improvement efforts, and serve as a foundation for identifying the non-uniformity EGR barriers and origins.

The development of an optimized heat treatment schedule, with the aim of maximizing strength and relieving tensile residual stress, is important to prevent in-service cylinder distortion in Al alloy engine blocks containing cast-in gray iron liners. However, to effectively optimize the engine block heat treatment schedule, the current solutionizing parameters must be analyzed and compared to the as-cast condition to establish a baseline for residual stress relief. In this study, neutron diffraction was carried out to measure the residual stress along the aluminum cylinder bridge following solution heat treatment. The stresses were measured in the hoop, radial and axial orientations and compared to a previous measured as-cast (TSR) engine block. The results suggest that solution heat treatment using the current production parameters partially relieved tensile residual stress in the Al cylinder bridge, with stress relief being more effective near the bottom of the cylinder.

A number of studies have identified a tendency for exhaust gas recirculation (EGR) coolers to foul to a steady-state level and subsequently not degrade further. One possible explanation for this behavior is that the shear force imposed by the gas velocity increases as the deposit thickens. If the shear force reaches a critical level, it achieves a removal of the deposit material that can balance the rate of deposition of new material, creating a stabilized condition. This study reports efforts to observe removal of deposit material in-situ during fouling studies as well as an ex-situ removal through the use of controlled air flows. The critical gas velocity and shear stress necessary to cause removal of deposit material is identified and reported. In-situ observations failed to show convincing evidence of a removal of deposit material. The results show that removal of deposit material requires a relatively high velocity of 40 m/s or higher to cause removal.

Radio frequency (RF)-based sensors provide a direct measure of the particulate filter loading state. In contrast to particulate matter (PM) sensors, which monitor the concentration of PM in the exhaust gas stream for on-board diagnostics purposes, RF sensors have historically been applied to monitor and control the particulate filter regeneration process. This work developed an RF-based particulate filter control system utilizing both conventional and fast response RF sensors, and evaluated the feasibility of applying fast-response RF sensors to provide a real-time measurement of engine-out PM emissions. Testing with a light-duty diesel engine equipped with fast response RF sensors investigated the potential to utilize the particulate filter itself as an engine-out soot sensor.

In the present study, a bench-flow reactor is used to perform lean/rich thermal cycling on model “Ba+K” LNT catalysts at temperatures of 700, 800, 900 and 1000°C using simulated diesel exhaust gases. Deterioration of NOx performance is measured and the deactivation mechanisms of thermally-aged “Ba+K” LNTs are identified using characterization techniques such as TEM, XRD and EPMA. Results indicate that the deterioration is minimal at 700 and 800°C, however, at aging temperatures exceeding 800°C the severity of thermal aging depends on aging temperature as well as number of aging cycles.

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.

Phosphorous in diesel exhaust is derived via engine oil consumption from the zinc dialkyldithiophosphate (ZDDP) oil additive used for engine wear control. Phosphorous present in the engine exhaust can react with an exhaust catalyst and cause loss of performance through masking or chemical reaction. The primary effect is loss of light-off or low temperature performance. Although the amount of ZDDP used in lube oil is being reduced, it appears that there may is a minimum level of ZDDP needed for engine durability. One of the ways of reducing the effects of the resulting phosphorous on catalysts might be to alter the chemical state of the phosphorous to a less damaging form or to develop catalysts which are more resistant to phosphorous poisoning. In this study, lube oil containing ZDDP was added at an accelerated rate through a variety of engine pathways to simulate various types of engine wear or oil disposal practices.

A prototype emissions control system consisting of a close-coupled lightoff catalyst, catalyzed diesel particle filter (CDPF), and a NOX adsorber was evaluated on a Mercedes A170 CDI. This laboratory experiment aimed to determine whether the benefits of these technologies could be utilized simultaneously to allow a light-duty diesel vehicle to achieve levels called out by U.S. Tier 2 emissions legislation. This research was carried out by driving the A170 through the U.S. Federal Test Procedure (FTP), US06, and highway fuel economy test (HFET) dynamometer driving schedules. The vehicle was fueled with a 3-ppm ultra-low sulfur fuel. Regeneration of the NOX adsorber/CDPF system was accomplished by using a laboratory in-pipe synthesis gas injection system to simulate the capabilities of advanced engine controls to produce suitable exhaust conditions. The results show that these technologies can be combined to provide high pollutant reduction efficiencies in excess of 90% for NOX and PM.

The nine CRC fuels for advanced combustion engines (FACE fuels) have been evaluated in a simple, premixed HCCI engine under varying conditions of fuel rate, air-fuel ratio, and intake temperature. Engine performance was found to vary mainly as a function of combustion phasing as affected by fuel cetane and engine control variables. The data was modeled using statistical techniques involving eigenvector representation of the fuel properties and engine control variables, to define engine response and allow optimization across the fuels for best fuel efficiency. In general, the independent manipulation of intake temperature and air-fuel ratio provided some opportunity for improving combustion efficiency of a specific fuel beyond the direct effect of targeting the optimum combustion phasing of the engine (near 5 CAD ATDC).

As part of a multi-agency study concerning emissions and fuel consumption from heavy-duty diesel truck idling, Oak Ridge National Laboratory personnel measured CO, HC, NOx, CO2, O2, particulate matter (PM), aldehyde and ketone emissions from truck idle exhaust. Two methods of quantifying PM were employed: conventional filters and a Tapered Element Oscillating Microbalance (TEOM). A partial flow micro-dilution tunnel was used to dilute the sampled exhaust to make the PM and aldehyde measurements. The work was performed at the U.S. Army's Aberdeen Test Center's (ATC) climate controlled chamber. ATC performed 37 tests on five class-8 trucks (model years ranging from 1992 to 2001). One was equipped with an 11 hp diesel auxiliary power unit (APU), and another with a diesel direct-fired heater (DFH). The APU powers electrical accessories, heating, and air conditioning, whereas a DFH heats the cab in cold weather. Both devices offer an alternative to extended truck-engine idling.

More stringent emissions regulations are continually being proposed to mitigate adverse human health and environmental impacts of internal combustion engines. With that in mind, it has been proposed that vehicular particulate matter (PM) emissions should be regulated based on particle number in addition to particle mass. One aspect of this project is to study different sample handling methods for number-based aerosol measurements, specifically, two different methods for removing volatile organic compounds (VOCs). One method is a thermodenuder (TD) and the other is an evaporative chamber/diluter (EvCh). These sample-handling methods have been implemented in an engine test cell with a spark-ignited direct injection (SIDI) engine. The engine was designed for stoichiometric, homogeneous combustion.

Low temperature combustion (LTC) has been shown to yield higher brake thermal efficiencies with lower NOx and soot emissions, relative to conventional diesel combustion (CDC). However, while demonstrating low soot carbon emissions it has been shown that LTC operation does produce particulate matter whose composition appears to be much different than CDC. The particulate matter emissions from dual-fuel reactivity controlled compression ignition (RCCI) using gasoline and diesel fuel were investigated in this study. A four cylinder General Motors 1.9L ZDTH engine was modified with a port-fuel injection system while maintaining the stock direct injection fuel system. The pistons were modified for highly premixed operation and feature an open shallow bowl design. RCCI operation was carried out using a certification grade 97 research octane gasoline and a certification grade diesel fuel.

The objective of this research is a detailed investigation of particulate sizing and number count from a spark-ignited, direct-injection (SIDI) engine at different operating conditions. The engine is a 549 [cc] single-cylinder, four-valve engine with a flat-top piston, fueled by Tier II EEE. A baseline engine operating condition, with a low number of particulates, was established and repeatability at this condition was ascertained. This baseline condition is specified as 2000 rpm, 320 kPa IMEP, 280 [°bTDC] end of injection (EOI), and 25 [°bTDC] ignition timing. The particle size distributions were recorded for particle sizes between 7 and 289 [nm]. The baseline particle size distribution was relatively flat, around 1E6 [dN/dlogDp], for particle diameters between 7 and 100 [nm], before dropping off to decreasing numbers at larger diameters. Distributions resulting from a matrix of different engine conditions were recorded.

This work explores the effect of the particle matter index (PMI) and aromatic content on fuel wall impingement associated with stochastic pre-ignition (SPI). Statically significant measurements of SPI rates are directly coupled with laser induced florescence (LIF) measurements of fuel dilution from spray-linear impingement. Literature suggests that PMI is could be correlated with the number of SPI events, but the root cause(s) of PMI and SPI are directly causational or are a predicator of SPI. Three fuels have been used in this study with 3 different PMI and two different aromatic contents. The fuels are direct injected at two different injection timings, an earlier injection timing which initially targets the piston crown, 310°CA bTDC, and a later injection timing that the liner, 220°CA bTDC start of injection timings (SOI) respectively. The earlier 310 SOI injection increases soot, whereas the later 220°CA SOI targets the liner and increases wall-wetting.

A single cylinder engine was operated in HCCI mode with diesel-range fuels, spanning a range in cetane number (CN) from 34 to 62. In addition to measurements of standard gaseous emissions (CO, HC, and NOx), multiple sampling and analysis techniques were used to identify and measure the individual exhaust HC species including an array of oxygenated compounds. A new analytical method, using liquid chromatography (LC) with electrospray ionization-mass spectrometry (ESI-MS) in tandem with ultraviolet (UV) detection, was developed to analyze the longer chain aldehydes as well as carboxylic acids. Results showed an abundance of formic and butyric acid formation at or near the same concentration levels as formaldehyde and other aldehydes.