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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.

Laser-induced incandescence is used to measure time-resolved diesel particulate emissions for two lean NOx trap regeneration strategies that utilize intake throttling and in-cylinder fuel enrichment. The results show that when the main injection event is increased in duration and delayed 13 crank-angle degrees, particulate emissions are very high. For a repetitive pattern of 3 seconds of rich regeneration followed by 27 seconds of NOx-trap loading, we find a monotonic increase in particulate emissions during the loading intervals that approaches twice the initial baseline particulate level after 1000 seconds. In contrast, particulate emissions during the regeneration intervals are constant throughout the test sequence.

Ethanol is a very attractive fuel from an end-use perspective because it has a high chemical octane number and a high latent heat of vaporization. When an engine is optimized to take advantage of these fuel properties, both efficiency and power can be increased through higher compression ratio, direct fuel injection, higher levels of boost, and a reduced need for enrichment to mitigate knock or protect the engine and aftertreatment system from overheating. The ASTM D5798 specification for high level ethanol blends, commonly called “E85,” underwent a major revision in 2011. The minimum ethanol content was revised downward from 68 vol% to 51 vol%, which combined with the use of low octane blending streams such as natural gasoline introduces the possibility of a lower octane “E85” fuel.

This paper describes the simultaneous reduction of nitrogen oxides (NOx) and particulate matter (PM) in a modern light-duty diesel engine under high exhaust gas recirculation (EGR) levels. Simultaneous reduction of NOx and PM emissions was observed under lean conditions at several low to moderate load conditions using two different approaches. The first approach utilizes a throttle to increase EGR rate beyond the maximum rate possible with sole use of the EGR valve for a particular engine condition. The second approach does not use a throttle, but rather uses a combination of EGR and manipulation of injection parameters. A significant reduction in particulate matter size and concentration was observed corresponding to the reduction in particulate mass. This PM reduction was accompanied by a significant shift in the heat release profile. In addition, there were significant cylinder-to-cylinder variations in particulate matter characteristics, gaseous emissions, and heat release.

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.

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.

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.

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.

Gasoline direct injection (GDI) engines can offer improved fuel economy and higher performance over their port fuel-injected (PFI) counterparts, and are now appearing in increasingly more U.S. and European vehicles. Small displacement, turbocharged GDI engines are replacing large displacement engines, particularly in light-duty trucks and sport utility vehicles, in order for manufacturers to meet more stringent fuel economy standards. GDI engines typically emit the most particulate matter (PM) during periods of rich operation such as start-up and acceleration, and emissions of air toxics are also more likely during this condition. A 2.0 L GDI engine was operated at lambda of 0.91 at typical loads for acceleration (2600 rpm, 8 bar BMEP) on three different fuels; an 87 anti-knock index (AKI) gasoline (E0), 30% ethanol blended with the 87 AKI fuel (E30), and 48% isobutanol blended with the 87 AKI fuel.

Ethanol is a biofuel commonly used in gasoline blends to displace petroleum consumption; its utilization is on the rise in the United States, spurred by the biofuel utilization mandates put in place by the Energy Independence and Security Act of 2007 (EISA). The United States Environmental Protection Agency (EPA) has the statutory responsibility to implement the EISA mandates through the promulgation of the Renewable Fuel Standard. EPA has historically mandated an emissions certification fuel specification that calls for ethanol-free fuel, except for the certification of flex-fuel vehicles. However, since the U.S. gasoline marketplace is now virtually saturated with E10, some organizations have suggested that inclusion of ethanol in emissions certification fuels would be appropriate.

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 Energy Independence and Security Act of 2007 requires the U.S. to use 36 billion gallons of renewable fuel per year by 2022. Domestic ethanol production has increased steadily in recent years, growing from less than 5 billion gallons per year (bgpy) in 2006 to over 13 bgpy in 2010. While there is interest in developing non-oxygenated renewable fuels for use in conventional vehicles as well as interest in expanding flex-fuel vehicle (FFV) production for increased E85 use, there remains concern that EISA compliance will require further use of oxygenated biofuels in conventional vehicles. The Environmental Protection Agency (EPA) recently granted partial approval to a waiver allowing the use of E15 in 2001 and newer light-duty vehicles.

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.

Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.

Previously reported work with a full-scale ethanol-SCR system featuring a Ag-Al2O3 catalyst demonstrated that this particular system has potential to reduce NOx emissions 80-90% for engine operating conditions that allow catalyst temperatures above 340°C. A concept explored was utilization of a fuel-borne reductant, in this case ethanol “stripped” from an ethanol-diesel micro-emulsion fuel. Increased tailpipe-out emissions of hydrocarbons, acetaldehyde and ammonia were measured, but very little N2O was detected. In the current increment of work, a number of light alcohols and other hydrocarbons were used in experiments to map their performance with the same Ag-Al2O3 catalyst. These exploratory tests are aimed at identification of compounds or organic functional groups that could be candidates for fuel-borne reductants in a compression ignition fuel, or could be produced by some workable method of fuel reforming.

The CRC Fuels for Advanced Combustion Engines working group has worked to identify a matrix of research diesel fuels for use in advanced combustion research applications. Nine fuels were specified and formulated to investigate the effects of cetane number aromatic content and 90% distillation fraction. Standard ASTM analyses were performed on the fuels as well as GC/MS and1H/13C NMR analyses and thermodynamic characterizations. Details of the actual results of the fuel formulations compared with the design values are presented, as well as results from standard analyses, such as heating value, viscosity and density. Cetane number characterizations were accomplished by using both the engine method and the Ignition Quality Tester (IQT™) apparatus.