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High-speed diagnostics capable of accurately resolving emission transients are required to provide the most detailed understanding and optimization of active exhaust-emissions-treatment processes, such as NOX adsorbers. A portable, mass-spectrometry-based instrument with high temporal resolution, linear response and broad dynamic range is described. This instrument provides transient-concentration measurement capability for many relevant exhaust species including total NOX. In applications for evaluation of NOX-adsorber systems using heavy-duty diesel engines, the instrument revealed relevant emission transients not previously resolved with conventional analyzers. Specifically, the instrument resolved transient emissions associated with the competition between desorption and reduction rates. The temporal resolution of the instruments is sufficient to resolve kinetic rates of the NOX-adsorber system.

In this research, small, single cylinder engines have been used to simulate larger engines in the areas of aftertreatment, combustion, and fuel formulation effects. The use of small engines reduces overall research cost and allows more rapid experiments to be run. Because component costs are lower, it is also possible to investigate more variations and to sacrifice components for materials characterization and for subsequent experiments. Using small engines in this way is very successful in some cases. In other cases, limitations of the engines influence the results and need to be accounted for in the experimental design and data analysis. Some of the results achieved or limitations found may be of interest to the small engine market, and this paper is offered as a summary of the authors' research in these areas. Research is being conducted in two areas. First, small engines are being used to study the rapid aging and poisoning of exhaust aftertreatment catalysts.

On a gasoline engine platform, homogeneous charge compression ignition (HCCI) holds the promise of improved fuel economy and greatly reduced engine-out NOx emissions, without an increase in particulate matter emissions. In this investigation, a variable compression ratio (CR) engine equipped with a throttle and intake air heating was used to test the robustness of these control parameters to accommodate a series of fuels blended from reference gasoline, straight run refinery naphtha, and ethanol. Higher compression ratios allowed for operation with higher octane fuels, but operation could not be achieved with the reference gasoline, even at the highest compression ratio. Compression ratio and intake heat could be used separately or together to modulate combustion. A lambda of 2 provided optimum fuel efficiency, even though some throttling was necessary to achieve this condition. Ethanol did not appear to assist combustion, although only two ethanol-containing fuels were evaluated.

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/γ-AI2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation.

In order to meet common fuel specifications such as cetane number and volatility, a refinery must blend a number of refinery stocks derived from various process units in the refinery. Fuel chemistry can be significantly altered in meeting fuel specifications. Additionally, fuel specifications are seldom changed in isolation, and the drive to meet one specification may alter other specifications. Homogeneous charge compression ignition (HCCI) engines depend on the kinetic behavior of a fuel to achieve reliable ignition and are expected to be more dependent on fuel specifications and chemistry than today's conventional engines. Regression analysis can help in determining the underlying relationships between fuel specifications, chemistry, and engine performance. Principal Component Analysis (PCA) is used as an adjunct to regression analysis in this work, because of its ability to deal with co-linear variables and potential to uncover ‘hidden’ relationships between the variables.

The effects of variable compression ratio (CR) and fuel composition on thermal efficiency were investigated in a homogeneous charge compression ignition (HCCI) engine using blends of n-heptane and toluene with research octane numbers (RON) of 0 to 90. Experiments were conducted by performing CR sweeps at multiple intake temperatures using both unthrottled operation, and constant Φ conditions by throttling to compensate for varying air density. It was found that CR is effective at changing and controlling the HCCI combustion phasing midpoint, denoted here as CA 50. Thermal efficiency was a strong function of CA 50, with overly advanced CA 50 leading to efficiency decreases. Increases in CR at a constant CA 50 for a given fuel composition did, in most cases, increase efficiency, but the relationship was weaker than the dependence of efficiency on CA 50.

Diesel fuels derived from different types of crude oil can exhibit different chemistry while still meeting market requirements and specifications. Oil sands derived fuels typically contain a larger proportion of cycloparaffinic compounds, which result from the cracking and hydrotreating of bitumens in the crude. In the current study, 17 refinery streams consisting of finished fuels and process streams were obtained from a refinery using 100% oil sands derived crude oil. All samples except one met the ULSD standard of 15 ppm sulfur. The samples were characterized for properties and chemistry and run in a simple premixed HCCI engine using intake heating for combustion phasing control. Results indicate that the streams could be equally well characterized by chemistry or properties, and some simple correlations are presented. Cetane number was found to relate mainly to mono-aromatic content and the cycloparaffins did not appear to possess any unique diesel related chemical effects.

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.

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.

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.

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.

As the world market develops for biodiesel fuels, it is likely that a wider variety of biodiesels will become available, both locally and globally, and require engines to operate on a wider variety of fuels than experienced today. At the same time, tighter emissions regulations and a drive for improved fuel economy have focused interest on advanced combustion modes such as HCCI or PCCI, which are known to be more sensitive to fuel properties. This research covers two series of biodiesel fuels. In the first, B20 blends of natural methyl esters derived from palm, coconut, rape, soy, and mustard were evaluated at light load in an HCCI research engine to determine combustion and performance characteristics. These fuels showed performance differences between the biodiesels and the base #2 ULSD fuel, but did not allow separation of chemical effects due to the small number of fuels and correlation of various properties.

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.

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.

We report experimental observations of cyclic combustion variability during the transition between propagating flame combustion and homogeneous charge compression ignition (HCCI) in a single-cylinder, stoichiometrically fueled, spark-assisted gasoline engine. The level of internal EGR was controlled with variable valve actuation (VVA), and HCCI combustion was achieved at high levels of internal EGR using the VVA system. Spark-ignition was used for conventional combustion and was optionally available during HCCI. The transition region between purely propagating combustion and HCCI was mapped at multiple engine speeds and loads by incrementally adjusting the internal EGR level and capturing data for 2800 sequential cycles. These measurements revealed a complex sequence of high COV, cyclic combustion variations when operating between the propagating flame and HCCI limits.

High Efficiency Clean Combustion (HECC) strategies such as homogenous charge compression ignition (HCCI) and pre-mixed charge compression ignition (PCCI) offer much promise for the reduction of NOx and PM from diesel engines. While delivering low PM and low NOx, these combustion modes often produce much higher levels of CO and HC than conventional diesel combustion modes. In addition, partially oxygenated species such as formaldehyde (an MSAT) and other aldehydes increase with HECC modes. The higher levels of CO and HCs have the potential to compromise the performance of the catalytic aftertreatment, specifically at low load operating points. As HECC strategies become incorporated into vehicle calibrations, manufacturers need to avoid producing MSATs in higher quantities than found in conventional combustion modes. This paper describes research on two different HECC strategies, HCCI and PCCI.

Urea-SCR systems are potentially a highly-effective means of NOX reduction for light-duty diesel vehicles. However, use of urea-SCR technologies at low temperatures presents unique technical challenges. This study was undertaken to provide more knowledge about low temperature urea decomposition and the resulting effects on SCR performance. Data are presented for experiments using two SCR catalysts of differing size with a light-duty diesel engine. Analyses of the NOX reduction efficiency, NH3 storage phenomena, and unregulated emissions are shown. Over production of NO2 by the oxidation catalyst is demonstrated to be problematic at 25,000 hr-1 space velocity for a range of temperatures. This leads to production of N2O by both SCR catalysts that is higher when urea is injected than when NH3 is injected.

The influence of fuel rail pressure (FRP) and urea-selective catalytic reduction (SCR) on particulate matter (PM) formation is investigated in this paper along with notes regarding the NOx and other emissions. Increasing FRP was shown to reduce the overall soot and total PM mass for four operating conditions. These conditions included two high speed conditions (2400 rpm at 540 and 270 Nm of torque) and two moderated speed conditions (1400 rpm at 488 and 325 Nm). The concentrations of CO2 and NOx increased with fuel rail pressure and this is attributed to improved fuel-air mixing. Interestingly, the level of unburned hydrocarbons remained constant (or increased slightly) with increased FRP. PM concentration was measured using an AVL smoke meter and scanning mobility particle sizer (SMPS); and total PM was collected using standard gravimetric techniques. These results showed that the smoke number and particulate concentrations decrease with increasing FRP.

Advanced diesel combustion modes offer the promise of reduced engine-out particulate and nitrogen oxide emissions, thereby reducing the demand on post-combustion emission control devices. In this activity, a light-duty diesel engine was operated in conventional and advanced combustion modes. The advanced combustion modes investigated correspond to both clean (i.e., low PM and low NOX) and clean efficient combustion. The low-NOX, low-PM mode is considered an intermediate condition and the low-NOX, low-PM efficient mode is referred to as high efficiency clean combustion (HECC). Particulate and gaseous emissions were analyzed during all of these experiments. The detailed exhaust chemistry analysis provided significant new information to improving our understanding of these modes as well as identifying potentially important unregulated emissions.