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Technical Paper

Detection of Polar Compounds Condensed on Particulate Matter Using Capillary Electrophoresis-Mass Spectrometry

2020-04-14
2020-01-0395
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.
Journal Article

Compatibility of Elastomers with Polyoxymethylene Dimethyl Ethers and Blends with Diesel

2020-04-14
2020-01-0620
Polyoxymethylene dimethyl ethers (PODEs) have shown promise as candidates for diesel fuel blendstocks due to their low sooting tendency, high cetane number, and diesel-comparable boiling point range. However, there is a lack of literature regarding compatibility of PODEs with common automotive elastomers, which would be a prerequisite to their adoption into the marketplace. To address this need, an exposure study and complementary solubility analysis were undertaken. A commercially available blend of PODEs with polymerization degree ranging from 3 to 6 was blended with diesel certification fuel at 0, 33, 50, 67, at 100% by mass. Elastomer coupons were exposed to the various blends for a period of 4 weeks and evaluated for volume swell.
Journal Article

Characterization of Hydrocarbon Emissions from Gasoline Direct-Injection Compression Ignition Engine Operating on a Higher Reactivity Gasoline Fuel

2017-03-28
2017-01-0747
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.
Journal Article

Compatibility Assessment of Elastomeric Infrastructure Materials with Neat Diesel and a Diesel Blend Containing 20 Percent Fast Pyrolysis Bio-oil

2015-04-14
2015-01-0888
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.
Journal Article

Compatibility Assessment of Plastic Infrastructure Materials with Off-Highway Diesel and a Diesel Blend Containing 20 Percent Fast Pyrolysis Bio-Oil

2015-04-14
2015-01-0893
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.
Technical Paper

Effectiveness Stabilization and Plugging in EGR Cooler Fouling

2014-04-01
2014-01-0640
Fouling in EGR coolers occurs because of the presence of soot and condensable species (such as hydrocarbons) in the gas stream. Fouling leads to one of two possible outcomes: stabilization of effectiveness and plugging of the gas passages within the cooler. Deposit formation in the cooler under high-temperature conditions results in a fractal deposit that has a characteristic thermal conductivity of ∼0.033 W/m*K and a density of 0.0224 g/cm3. Effectiveness becomes much less sensitive to changes in thermal resistance as fouling proceeds, creating the appearance of “stabilization” even in the presence of ongoing, albeit slow, deposit growth. Plugging occurs when the deposit thermal resistance is several times lower because of the presence of large amounts of condensed species. The deposition mechanism in this case appears to be soot deposition into a liquid film, which results in increased packing efficiency and decreased void space in the deposit relative to high-temperature deposits.
Technical Paper

Analysis of Lacquer Deposits and Plugging Found in Field-Tested EGR Coolers

2014-04-01
2014-01-0629
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.
Technical Paper

Neutron Tomography of Exhaust Gas Recirculation Cooler Deposits

2014-04-01
2014-01-0628
Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOx emissions standards. Exhaust gas laden with particulate matter flows through the EGR cooler which causes deposits to form through thermophoresis and condensation. The low thermal conductivity of the resulting deposit reduces the effectiveness of the EGR system. In order to better understand this phenomenon, industry-provided coolers were characterized using neutron tomography. Neutrons are strongly attenuated by hydrogen but only weakly by metals which allows for non-destructive imaging of the deposit through the metal heat exchanger. Multiple 2-D projections of cooler sections were acquired by rotating the sample around the axis of symmetry with the spatial resolution of each image equal to ∼70 μm. A 3-D tomographic set was then reconstructed, from which slices through the cooler sections were extracted across different planes.
Journal Article

Removal of EGR Cooler Deposit Material by Flow-Induced Shear

2013-04-08
2013-01-1292
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.
Technical Paper

Lubricating Oil Consumption on the Standard Road Cycle

2013-04-08
2013-01-0884
Automobile manufacturers strive to minimize oil consumption from their engines due to the need to maintain emissions compliance over the vehicle life. Engine oil can contribute directly to organic gas and particle emissions as well as accelerate emissions degradation due to catalyst poisoning. During the Department of Energy Intermediate Ethanol Blends Catalyst Durability program, vehicles were aged using the Standard Road Cycle (SRC). In this program, matched sets of three or four vehicles were acquired; each vehicle of a set was aged on ethanol-free retail gasoline, or the same base gasoline blended with 10, 15, or 20% ethanol (E0, E10, E15, E20). The primary purpose of the program was to assess any changes in tailpipe emissions due to the use of increased levels of ethanol. Oil consumption was tracked during the program so that any measured emissions degradation could be appropriately attributed to fuel use or to excessive oil consumption.
Technical Paper

Microstructural Analysis of Deposits on Heavy-Duty EGR Coolers

2013-04-08
2013-01-1288
Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOX emissions standards and has negative impacts on cooler sizing and engine performance. In order to improve our knowledge of cooler fouling as a function of engine operating parameters and to predict and enhance performance, 19 tube-in-shell EGR coolers were fouled using a 5-factor, 3-level design of experiments with the following variables: (1) EGR flow rate, (2) EGR inlet gas temperature, (3) coolant temperature, (4) soot level, and (5) hydrocarbon concentration. A 9-liter engine and ULSD fuel were used to form the cooler deposits. Coolers were run until the effectiveness stabilized, and then were cooled down to room temperature and run for an additional few hours in order to measure the change in effectiveness due to shut down. The coolers were cut open and the mass per unit area of the deposit was measured as a function of distance down the tube.
Journal Article

Combustion Studies with FACE Diesel Fuels: A Literature Review

2012-09-10
2012-01-1688
The CRC Fuels for Advanced Combustion Engines (FACE) Working Group has provided a matrix of experimental diesel fuels for use in studies on the effects of three parameters, Cetane number (CN), aromatics content, and 90 vol% distillation temperature (T90), on combustion and emissions characteristics of advanced combustion strategies. Various types of fuel analyses and engine experiments were performed in well-known research institutes. This paper reviews a collection of research findings obtained with these nine fuels. An extensive collection of analyses were performed by members of the FACE working group on the FACE diesel fuels as a means of aiding in understanding the linkage between fuel properties and combustion and emissions performance. These analyses included non-traditional chemical techniques as well as established ASTM tests. In a few cases, both ASTM tests and advanced analyses agreed that some design variables differed from their target values when the fuels were produced.
Journal Article

Carbonyl Formation during High Efficiency Clean Combustion of FACE Fuels

2010-10-25
2010-01-2212
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.
Technical Paper

In-Cylinder Fuel Blending of Gasoline/Diesel for Improved Efficiency and Lowest Possible Emissions on a Multi-Cylinder Light-Duty Diesel Engine

2010-10-25
2010-01-2206
In-cylinder fuel blending of gasoline with diesel fuel is investigated on a multi-cylinder light-duty diesel engine as a strategy to control in-cylinder fuel reactivity for improved efficiency and lowest possible emissions. This approach was developed and demonstrated at the University of Wisconsin through modeling and single-cylinder engine experiments. The objective of this study is to better understand the potential and challenges of this method on a multi-cylinder engine. More specifically, the effect of cylinder-to-cylinder imbalances and in-cylinder charge motion as well as the potential limitations imposed by real-world turbo-machinery were investigated on a 1.9-liter four-cylinder engine. This investigation focused on one engine condition, 2300 rpm, 5.5 bar net mean effective pressure (NMEP). Gasoline was introduced with a port-fuel-injection system.
Journal Article

Characterization of Field-Aged EGR Cooler Deposits

2010-10-25
2010-01-2091
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.
Journal Article

Fuels for Advanced Combustion Engines Research Diesel Fuels: Analysis of Physical and Chemical Properties

2009-11-02
2009-01-2769
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.
Technical Paper

ULSD and B20 Hydrocarbon Impacts on EGR Cooler Performance and Degradation

2009-11-02
2009-01-2802
Exhaust gas recirculation (EGR) cooler fouling has emerged as an important issue in diesel engine development. Uncertainty about the level of impact that fuel chemistry may have upon this issue has resulted in a need to investigate the cooler fouling process with emerging non-traditional fuel sources to gage their impact on the process. This study reports experiments using both ultra-low sulfur diesel (ULSD) and 20% biodiesel (B20) at elevated exhaust hydrocarbon conditions to investigate the EGR cooler fouling process. The results show that there is little difference between the degradation in cooler effectiveness for ULSD and B20 at identical conditions. At lower coolant temperatures, B20 exhibits elevated organic fractions in the deposits compared with ULSD, but this does not appear to lead to incremental performance degradation under the conditions studied.
Technical Paper

Experimental Investigation of the Effects of Fuel Characteristics on High Efficiency Clean Combustion in a Light-Duty Diesel Engine

2009-11-02
2009-01-2669
An experimental study was performed to understand fuel property effects on low temperature combustion (LTC) processes in a light-duty diesel engine. These types of combustion modes are often collectively referred to as high efficiency clean combustion (HECC). A statistically designed set of research fuels, the Fuels for Advanced Combustion Engines (FACE), were used for this study. Engine conditions of 1500rpm, 2.6bar BMEP was chosen for investigating fuel property effects on HECC operation in a GM 1.9-L common rail diesel engine. The FACE fuel matrix includes nine combinations of fuel properties including cetane number (30 to 55), aromatic content (20 to 45%), and 90% distillation temperature (270 to 340°C). HECC operation was achieved with high levels of exhaust gas recirculation (EGR) and adjusting injection parameters, such as higher fuel rail pressure and single injection event, which is also known as premixed charge compression ignition (PCCI) combustion.
Journal Article

Modeling of Thermophoretic Soot Deposition and Hydrocarbon Condensation in EGR Coolers

2009-06-15
2009-01-1939
EGR coolers are effective to reduce NOx emissions from diesel engines due to lower intake charge temperature. EGR cooler fouling reduces heat transfer capacity of the cooler significantly and increases pressure drop across the cooler. Engine coolant provided at 40–90 C is used to cool EGR coolers. The presence of a cold surface in the cooler causes particulate soot deposition and hydrocarbon condensation. The experimental data also indicates that the fouling is mainly caused by soot and hydrocarbons. In this study, a 1-D model is extended to simulate particulate soot and hydrocarbon deposition on a concentric tube EGR cooler with a constant wall temperature. The soot deposition caused by thermophoresis phenomena is taken into account the model. Condensation of a wide range of hydrocarbon molecules are also modeled but the results show condensation of only heavy molecules at coolant temperature.
Technical Paper

Direct Measurement of EGR Cooler Deposit Thermal Properties for Improved Understanding of Cooler Fouling

2009-04-20
2009-01-1461
Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOx emissions standards. This paper reports results of a study of fundamental aspects of EGR cooler fouling. An apparatus and procedure were developed to allow surrogate EGR cooler tubes to be exposed to diesel engine exhaust under controlled conditions. The resulting fouled tubes were removed and analyzed. Volatile and non-volatile deposit mass was measured for each tube. Thermal diffusivity of the deposited soot cake was measured by milling a window into the tube and using the Xenon flash lamp method. The heat capacity of the deposit was measured at temperatures up to 430°C and was slightly higher than graphite, presumably due to the presence of hydrocarbons. These measurements were combined to allow calculation of the deposit thermal conductivity, which was determined to be 0.041 W/mK, only ∼1.5 times that of air and much lower than the 304 stainless steel tube (14.7 W/mK).
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