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Thermal conductivity detection has long been used in gas chromatography to detect hydrogen and other diatomic gases in a gas sample. Thermal conductivity instruments that are not coupled to gas chromatographs are useful for detecting hydrogen in binary gas mixtures, but suffer from significant cross-interference from other gas species that are separated when the detector is used with a gas chromatograph. This study reports a method for using a commercially-available thermal conductivity instrument to detect and quantify hydrogen in a diesel exhaust stream. The instrument time response of approximately 40 seconds is sufficient for steady-state applications. Cross-interference from relevant gas species are quantified and discussed. Measurement uncertainty associated with the corrections for the various species is estimated and practical implications for use of the instrument and method are discussed.

All high-pressure exhaust gas recirculation (EGR) coolers become fouled during operation due to thermophoresis of particulate matter and condensation of hydrocarbons present in diesel exhaust. In some EGR coolers, fouling is so severe that deposits form plugs strong enough to occlude the gas passages thereby causing a complete failure of the EGR system. In order to better understand plugging and means of reducing its undesirable performance degradation, EGR coolers exhibiting plugging were requested from and provided by industry EGR engineers. Two of these coolers contained glassy, brittle, lacquer-like deposits which were analyzed using gas chromatography-mass spectrometry (GC-MS) which identified large amounts of oxygenated polycyclic aromatic hydrocarbons (PAHs). Another cooler exhibited similar species to the lacquer but at a lower concentration with more soot.

As interest has grown in diesel emissions and diesel engine aftertreatment, so has the importance of analyzing all components of the exhaust. One of the more costly and difficult measurements to make is the collection and analysis of semivolatile organic compounds (SOCs) in the exhaust. These compounds include alkane and alkenes from C12-C24, and the 2-5 ring polycyclic aromatic hydrocarbons (PAH). These compounds can be present in both the particulate (i.e. on the filter) and gaseous phase, and cannot be collected with bag samples. Typically, a sorbent is used downstream of the particulate collection filters to collect these compounds. Sorbent phases include polyurethane foam (PUF), Tenax™, XAD-type resins, and activated carbon. The SOCs are removed from the sorbent either by solvent extraction (PUF and XAD) or thermal desorption (Tenax™ and activated carbon). Each of these methods have advantages and disadvantages.

Lean NOx Trap (LNT) catalysts are capable of reducing NOx in lean exhaust from diesel engines. NOx is stored on the catalyst during lean operation; then, under rich exhaust conditions, the NOx is released from and reduced by the catalyst. The process of NOx release and reduction is called regeneration. One method of obtaining the rich conditions for regeneration is to inject additional fuel into the engine cylinders while throttling the engine intake air flow to effectively run the engine at rich air:fuel ratios; this method is called “in-cylinder” regeneration. In-cylinder regeneration of LNT catalysts has been demonstrated and is a candidate emission control technique for commercialization of light-duty diesel vehicles to meet future emission regulations. In the study presented here, a 1.7-liter diesel engine with a LNT catalyst system was used to evaluate in-cylinder regeneration techniques.

A high-resolution corrosion probe was placed within the airhorn section of the exhaust gas recirculation (EGR) loop of a heavy-duty diesel engine. The corrosion rate of the mild-steel probe elements was evaluated as a function of fuel sulfur level, EGR fraction, dewpoint margin, and humidity. No significant corrosion was observed while running the engine using a No. 2 grade, < 15ppm sulfur diesel fuel; however, high corrosion rates were observed with No. 2 diesel fuel (∼350 ppm sulfur) while condensing water in the EGR loop. The rate of corrosion on the mild steel elements increased with increasing levels of sulfate in the condensate. However, the engine conditions influencing the sulfate level were not clearly identified in this study.

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.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with nitrogen oxides (NOx) emissions standards. In order to better understand fouling mechanisms, eleven field-aged EGR coolers provided by seven different engine manufacturers were characterized using a suite of techniques. Microstructures were characterized using scanning electron microscopy (SEM) and optical microscopy following mounting the samples in epoxy and polishing. Optical microscopy was able to discern the location of hydrocarbons in the polished cross-sections. Chemical compositions were measured using thermal gravimetric analysis (TGA), differential thermal analysis (DTA), gas chromatography-mass spectrometry (GC-MS), x-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS) and x-ray diffraction (XRD). Mass per unit area along the length of the coolers was also measured.

Low temperature combustion engine technologies are being investigated for high efficiency and low emissions. However, such engine technologies often produce higher engine-out hydrocarbon (HC) and carbon monoxide (CO) emissions, and their operating range is limited by the fuel properties. In this study, two different fuels, a US market gasoline containing 10% ethanol (RON 92 E10) and a higher reactivity gasoline (RON 80 E0), were compared on Delphi’s second generation Gasoline Direct-Injection Compression Ignition (Gen 2.0 GDCI) multi-cylinder engine. The engine was evaluated at three operating points ranging from a light load condition (800 rpm/2 bar IMEPg) to medium load conditions (1500 rpm/6 bar and 2000 rpm/10 bar IMEPg). The engine was equipped with two oxidation catalysts, between which was located the exhaust gas recirculation (EGR) inlet. Samples were taken at engine-out, between the catalysts, and at tailpipe locations.

In this study, the compression ratio of a commercial 15L heavy-duty diesel engine was lowered and a split injection strategy was developed to promote partially premixed compression ignition (PPCI) combustion. Various low reactivity gasoline-range fuels were compared with ultra-low-sulfur diesel fuel (ULSD) for steady-state engine performance and emissions. Specially, particulate matter (PM) emissions were examined for their mass, size and number concentrations, and further characterized by organic/elemental carbon analysis, chemical speciation and thermogravimetric analysis. As more fuel-efficient PPCI combustion was promoted, a slight reduction in fuel consumption was observed for all gasoline-range fuels, which also had higher heating values than ULSD. Since mixing-controlled combustion dominated the latter part of the combustion process, hydrocarbon (HC) and carbon monoxide (CO) emissions were only slightly increased with the gasoline-range fuels.

The compatibility of elastomer materials used in fuel storage and dispensing applications was determined for an off-highway diesel fuel and a blend containing 20% bio-oil (Bio20) derived from a fast pyrolysis process. (This fuel blend is not to be confused with B20, which is a blend of diesel fuel with 20% biodiesel.) The elastomer types evaluated in this study included fluorocarbon, fluorosilicone, acrylonitrile rubber (NBR), styrene butadiene rubber (SBR), polyurethane, neoprene, and silicone. All of these elastomer types are used in sealing applications, but some, like the nitrile rubbers are also common hose materials. The elastomer specimens were exposed to the two fuel types for 4 weeks at 60°C. After measuring the wetted volume and hardness, the specimens were dried for 65 hours at 60°C and then remeasured. A solubility analysis was performed to better understand the performance of plastic materials in fuel blends composed of bio-oil and diesel.

The compatibility of plastic materials used in fuel storage and dispensing applications was determined for an off-highway diesel fuel and a blend containing 20% bio-oil (Bio20) derived from a fast pyrolysis process. Bio20 is not to be confused with B20, which is a diesel blend containing 20% biodiesel. The feedstock, processing, and chemistry of biodiesel are markedly different from bio-oil. Plastic materials included those identified for use as seals, coatings, piping and fiberglass resins, but many are also used in vehicle fueling systems. The plastic specimens were exposed to the two fuel types for 16 weeks at 60°C. After measuring the wetted volume and hardness, the specimens were dried for 65 hours at 60°C and then remeasured to determine extent of property change. A solubility analysis was performed to better understand the performance of plastic materials in fuel blends composed of bio-oil and diesel.

A new analytical method to aid in the understanding of the organic carbon (OC) phase of particulate matter (PM) from advanced compression ignition (ACI) operating modes, is presented. The presence of NO2 and unburned fuel aromatics in ACI emissions, and the low exhaust temperatures that result from this low temperature combustion strategy, provide the right conditions for the formation of carboxylic acids and nitroaromatic compounds. These polar compounds contribute to OC in the PM and are not typically measured using nonpolar solvent extraction methods such as the soluble organic fraction (SOF) method. The new extraction and detection method employs capillary electrophoresis with electrospray ionization mass spectrometry (CE-ESI MS) and was specifically developed to determine polar organic compounds in the ACI PM emissions. The new method identified both nitrophenols and aromatic carboxylic acids in the ACI PM.

The present manuscript consists of proof of concept experiments involving direct measurements and detailed chemical speciation from the top ring zone of a running engine. The work uses a naturally aspirated single cylinder utility engine that has been modified to allow direct liquid sample acquisition from behind the top ring. Samples were analyzed and speciated using gas chromatographic techniques. Results show that the liquid mixture in the top ring zone is neither neat lubricant nor fuel but a combination of the two with unique chemical properties. At the tested steady state no-load operating condition, the chemical species of the top ring zone liquid were found to be highly dependent on boiling point, where both low reactivity higher boiling point fuel species and lubricant are observed to be the dominant constituents.

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 recirculation of gases from the crankcase and valvetrain can potentially lead to the entrainment of lubricant in the form of aerosols or mists. As boost pressures increase, the blow-by flow through both the crankcase and the valve cover increases. The resulting lubricant can then become part of the intake charge, potentially leading to fouling of intake components such as the intercooler and the turbocharger. The entrained aerosol which can contain the lubricant and soot may or may not have the same composition as the bulk lubricant. The complex aerodynamic processes that lead to entrainment can strip out heavy components or volatilize light components. Similarly, the physical size and numbers of aerosol particles can be dependent upon the lubricant formulation and engine speed and load. For instance, high rpm and load may increase not only the flow of gases but the amount of lubricant aerosol.

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.

Direct injection spark-ignition (DISI) gasoline engines can offer better fuel economy and higher performance over their port fuel-injected counterparts, and are now appearing increasingly in more U.S. vehicles. Small displacement, turbocharged DISI engines are likely to be used in lieu of large displacement engines, particularly in light-duty trucks and sport utility vehicles, to meet fuel economy standards for 2016. In addition to changes in gasoline engine technology, fuel composition may increase in ethanol content beyond the 10% allowed by current law due to the Renewable Fuels Standard passed as part of the 2007 Energy Independence and Security Act (EISA). In this study, we present the results of an emissions analysis of a U.S.-legal stoichiometric, turbocharged DISI vehicle, operating on ethanol blends, with an emphasis on detailed particulate matter (PM) characterization.

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.

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.

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.