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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.

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.

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.

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.

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.

High-efficiency clean combustion (HECC) modes provide simultaneous reductions in diesel particulate matter and nitrogen-oxides emissions while retaining efficiencies characteristic of normal diesel engines. Fuel parameters may have significant impacts on the ability to operate in HECC modes and on the emissions produced in HECC modes. In this study, 3 diesel-range fuels and 2 oxygenated blends are burned in both normal and HECC modes at 3 different engine conditions. The results show that fuel effects play an important role in the emissions of hydrocarbons, particulate matter, and carbon monoxide but do not significantly impact NOx emissions in HECC modes. HECC modes are achievable with 5% biodiesel blends in addition to petroleum-based and oil-sands derived fuels. Soot precursor and oxygenated compound concentrations in the exhaust were observed to generally increase with the sooting tendency of the fuel in HECC modes.

Saab Automobile recently released the BioPower engines, advertised to use increased turbocharger boost and spark advance on ethanol fuel to enhance performance. Specifications for the 2.0 liter turbocharged engine in the Saab 9-5 Biopower 2.0t report 150 hp (112 kW) on gasoline and a 20% increase to 180 hp (134 kW) on E85 (nominally 85% ethanol, 15% gasoline). While FFVs sold in the U.S. must be emissions certified on Federal Certification Gasoline as well as on E85, the European regulations only require certification on gasoline. Owing to renewed and growing interest in increased ethanol utilization in the U.S., a European-specification 2007 Saab 9-5 Biopower 2.0t was acquired by the Department of Energy and Oak Ridge National Laboratory (ORNL) for benchmark evaluations. Results show that the vehicle's gasoline equivalent fuel economy on the Federal Test Procedure (FTP) and the Highway Fuel Economy Test (HFET) are on par with similar U.S.-legal flex-fuel vehicles.

New regulations requiring increases in vehicle fuel economy are challenging automotive manufacturers to identify fuel-efficient engines for future vehicles. Lean gasoline direct injection (GDI) engines offer significant increases in fuel efficiency over the more common stoichiometric GDI engines already in the marketplace. However, particulate matter (PM) emissions from lean GDI engines, particularly during stratified combustion modes, are problematic for lean GDI technology to meet U.S. Environmental Protection Agency Tier 3 and other future emission regulations. As such, the control of lean GDI PM with wall-flow filters, referred to as gasoline particulate filter (GPF) technology, is of interest. Since lean GDI PM chemistry and morphology differ from diesel PM (where more filtration experience exists), the functionality of GPFs needs to be studied to determine the operating conditions suitable for efficient PM removal.

The exhaust chemistry of combustion regimes characterized by simultaneous low-NOX and low-PM emissions were investigated on a Mercedes 1.7-L diesel engine. Two approaches for entering low-NOX low-PM regimes were explored using a California specification low aromatic certification diesel fuel. Detailed characterizations of gas-phase hydrocarbons, particulate soluble organics, and aldehydes are presented for both approaches. Results indicate significant formation of partially oxygenated hydrocarbons and fuel reformation products during periods of low-NOX, low-PM combustion.

The Office of Heavy Vehicle Technologies supports research to enable high-efficiency diesel engines to meet future emissions regulations, thus clearing the way for their use in light trucks as well as continuing as the most efficient powerplant for freight-haulers. Compliance with Tier 2 emission regulations for light-duty vehicles will require effective exhaust emission controls (aftertreatment) for diesels in these applications. Diesel-powered heavy trucks face a similar situation for the 2007 regulations announced by EPA in December 2000. DOE laboratories are working with industry to improve emission control technologies in projects ranging from application of new diagnostics for elucidating key mechanisms, to development and evaluation of prototype devices. This paper provides an overview of these R&D efforts, with examples of key findings and developments.

Advanced combustion regimes such as homogeneous charge compression ignition (HCCI) and premixed charge compression ignition (PCCI) offer benefits of reduced nitrogen oxides (NOX) and particulate matter (PM) emissions. However, these combustion strategies often generate higher carbon monoxide (CO) and hydrocarbon (HC) emissions. In addition, aldehydes and ketone emissions can increase in these modes. In this study, the engine-out emissions of a compression-ignition engine operating in a fuel reactivity-controlled PCCI combustion mode using in-cylinder blending of gasoline and diesel fuel have been characterized. The work was performed on a 1.9-liter, 4-cylinder diesel engine outfitted with a port fuel injection system to deliver gasoline to the engine. The engine was operated at 2300 rpm and 4.2 bar brake mean effective pressure (BMEP) with the ratio of gasoline-to-diesel fuel that gave the highest engine efficiency and lowest emissions.

In this investigation, oil shale crude obtained from the Green River Formation in Colorado using Paraho Direct retorting was mildly hydrotreated and distilled to produce 7 narrow boiling point fuels of equal volumes. The resulting derived cetane numbers ranged between 38.3 and 43.9. Fuel chemistry and bulk properties strongly correlated with boiling point. The fuels were run in a simple HCCI engine to evaluate combustion performance. Each cut exhibited elevated NOx emissions, from 150 to 300ppm higher than conventional ULSD under similar conditions. Engine performance and operating range were additionally dictated by distillation temperatures which are a useful predictor variable for this fuel set. In general, cuts with low boiling point achieved optimal HCCI combustion phasing while higher boiling point cuts suffered a 25% fuel economy decrease, compared to conventional diesel under similar HCCI conditions, and incurred heavy engine deposits.

The low temperature conditions that occur during high efficiency clean combustion (HECC) often lead to the formation of partially oxidized HC species such as aldehydes, ketones and carboxylic acids. Using the diesel fuels specified by the Fuels for Advanced Combustion Engines (FACE) working group, carbonyl species were collected from the exhaust of a light duty diesel engine operating under HECC conditions. High pressure liquid chromatography - mass spectrometry (LC-MS) was used to speciate carbonyls as large as C 9 . A relationship between carbonyl species formed in the exhaust and fuel composition and properties was determined. Data were collected at the optimum fuel efficiency point for a typical road load condition. Results of the carbonyl analysis showed changes in formaldehyde and acetaldehyde formation, formation of higher molecular weight carbonyls and the formation of aromatic carbonyls.