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In the present study a reduced chemical reaction mechanism for biodiesel surrogate fuel was developed and validated for multi-dimensional engine combustion simulations. An existing detailed methyl butanoate mechanism that contained 264 species and 1219 reactions was chosen to represent the oxygenated portion of the fuel. The reduction process included flux analysis, ignition sensitivity analysis, and optimization of reaction rate constants under constant volume conditions. The current reduced mechanism consists of 41 species and 150 reactions and gives predictions in excellent agreement with those of the comprehensive mechanism. In order to validate the mechanism under biodiesel-fueled engine conditions, it was combined with another skeletal mechanism for n-heptane oxidation. This combined reaction mechanism can be used to adjust the energy content of the fuel, and account for diesel/biodiesel blend engine simulations.

Premixed low temperature combustion (LTC) in diesel engines simultaneously reduces soot and NOx at the expense of increased hydrocarbon (HC) and CO emissions. The use of biodiesel in the LTC regime has been shown to produce lower HC emissions than petroleum diesel; however, unburned methyl esters from biodiesel are more susceptible to particulate matter (PM) formation following atmospheric dilution due to their low volatility. In this study, the efficacy of a production-type diesel oxidation catalyst (DOC) for the conversion of light hydrocarbons species and heavier, semi-volatile species like those in unburned fuel is examined. Experimental data were taken from a high speed direct-injection diesel engine operating in a mid-load, late injection partially premixed LTC mode on ultra-low sulfur diesel (ULSD) and neat soy-based biodiesel (B100). Gaseous emissions were recorded using a conventional suite of analyzers and individual light HCs were measured using an FT-IR analyzer.

For renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement.

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.

Pure biodiesel fuel (B100) is typically made of fatty acid methyl esters (FAME). FAME has different physical properties as compared to mineral diesel such as higher surface tension, lower volatility and higher specific gravity. These differences lead to a larger droplet size and thus more wall impingement of the fuel during injection in the combustion chamber. This results in higher levels of fuel dilution as the oil is scraped down into the crankcase by the scraper ring. The lower volatility also makes biodiesel more difficult to evaporate once it enters the crankcase. For these reasons, levels of fuel dilution in biodiesel fueled engines are likely to be higher compared to mineral diesel fueled engines. When in-cylinder dosing is applied to raise the exhaust temperature required for the regeneration of Diesel Particulate Filters (DPF's), biodiesel dilution in the engine oil may be elevated to high levels.

In this study we identify components of a typical biodiesel fuel and estimate both their individual and mixed thermo-physical and transport properties. We then use the estimated mixture properties in computational simulations to gauge the extent to which combustion is modified when biodiesel is substituted for conventional diesel fuel. Our simulation studies included both conventional diesel combustion (DI) and premixed charge compression ignition (PCCI). Preliminary results indicate that biodiesel ignition is significantly delayed due to slower liquid evaporation, with the effects being more pronounced for DI than PCCI. The lower vapor pressure and higher liquid heat capacity of biodiesel are two key contributors to this slower rate of evaporation. Other physical properties are more similar between the two fuels, and their impacts are not clearly evident in the present study.

The effect of biodiesel content on homogeneous charge compression ignition (HCCI) engine performance has been investigated both experimentally and by computer simulation. Combustion experiments were performed in a single cylinder HCCI engine using blends of soy biodiesel in ultra low sulfur diesel, with concentrations ranging from 0 to 50 vol% and equivalence ratios (Φ) from 0.38 to 0.48. Data from the engine tests included combustion analysis and exhaust composition analysis with standard gaseous emissions equipment. The engine utilized a custom port fuel injection strategy to provide highly premixed charges of fuel and air, making it possible to compare the results with single zone chemical kinetics simulations that were performed using CHEMKIN III, with a reaction set including 670 species and over 3000 reactions.

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.

This study investigated the effects of soybean- and coconut-derived biodiesel fuels on combustion characteristics in a 1.7-liter direct injection, common rail diesel engine. Five sets of fuels were studied: 2007 ultra low sulfur diesel (ULSD), 5% and 20% volumetric blends of soybean biodiesel with ULSD (soybean B5 and B20), and 5% and 20% volumetric blends of coconut biodiesel with ULSD (coconut B5 and B20). In conventional diesel combustion mode, particulate matter (PM) and nitrogen oxides (NOx) emissions were similar for all fuels studied except soybean B20. Soybean B20 produced the lowest PM but the highest NOx emissions. Compared with conventional diesel combustion mode, high efficiency clean combustion (HECC) mode, achieved by increased EGR and combustion phasing, significantly reduced both PM and NOx emissions for all fuels studied at the expense of higher hydrocarbon (HC) and carbon monoxide (CO) emissions and an increase in fuel consumption (less than 4%).

Exhaust gas recirculation (EGR) coolers experience degradation of performance as a result of the buildup of material in the gas-side flow paths of the cooler. This material forms a deposit layer that is less thermally conductive than the stainless steel of the tube enclosing the gas, resulting in lower heat exchanger effectiveness. Biodiesel fuel has a fuel chemistry that is much more susceptible to polymerization than that of typical diesel fuels and may exacerbate deposit formation in EGR coolers. A study was undertaken to examine the fundamentals of EGR cooler deposit formation by using surrogate tubes to represent the EGR cooler. These tubes were exposed to engine exhaust in a controlled manner to assess their effectiveness, deposit mass, and deposit hydrocarbon content. The tubes were exposed to exhaust for varying lengths of time and for varying coolant temperatures. The results show that measurable differences in the response variables occur within a few hours.

Testing to investigate biodiesel's impact on the performance of a zeolite-based selective catalytic reduction (SCR) system was conducted. The tests employed a 2004 compliant Cummins ISB with common rail fuel injection, EGR, and variable geometry turbo. This 5.9L, 300HP engine was retrofitted with a Johnson-Matthey DPF + SCR (SCRT™) system. Testing was conducted over eight steady-state engine operating modes which provided a wide range of exhaust temperature and exhaust chemistry conditions. Fuels tested were a 2007 certification quality ultra-low sulfur diesel (ULSD), as well as a soy derived biodiesel in a B20 blend. B20 produced slightly lower catalyst temperatures and higher NO2:NOx ratios relative to ULSD, but no measureable difference in the overall NOx conversion over the SCR system. The dominant variable influencing SCR performance is the catalyst space velocity, which is unchanged with the use of B20.

Diesel particulate samples were collected from a light duty engine operated at a single speed-load point with a range of biodiesel and conventional fuel blends. The oxidation reactivity of the samples was characterized in a laboratory reactor, and BET surface area measurements were made at several points during oxidation of the fixed carbon component of both types of particulate. The fixed carbon component of biodiesel particulate has a significantly higher surface area for the initial stages of oxidation, but the surface areas for the two particulates become similar as fixed carbon oxidation proceeds beyond 40%. When fixed carbon oxidation rates are normalized to total surface area, it is possible to describe the oxidation rates of the fixed carbon portion of both types of particulates with a single set of Arrhenius parameters. The measured surface area evolution during particle oxidation was found to be inconsistent with shrinking sphere oxidation.

Because of the great interest in biodiesel fuels around the world, the International Energy Agency's Committee on Advanced Motor Fuels sponsored this project to determine emissions and performance of a number of biodiesel fuels with a special emphasis on unregulated emissions. Oak Ridge National Laboratory (ORNL) and Technical Research Centre in Finland (VTT) carried out the project with complementary work plans. Several different engines were used between the two sites, and in some cases emissions control catalysts were used, both at ORNL and at VTT. ORNL concentrated on light and medium duty engines, while VTT emphasized a heavy-duty engine and also used a light duty car as a test bed. Common fuels between the two sites for these tests were rape methyl ester in 30% blend and neat, soy methyl ester in 30% blend and neat, used vegetable oil methyl ester (UVOME) in 30% blend, and the Swedish environmental class 1 reformulated diesel (RFD).

Nine identical 40-ft. transit buses were operated on B20 and diesel for a period of two years - five of the buses operated exclusively on B20 (20% biodiesel blend) and the other four on petroleum diesel. The buses were model year 2000 Orion V equipped with Cummins ISM engines, and all operated on the same bus route. Each bus accumulated about 100,000 miles over the course of the study. B20 buses were compared to the petroleum diesel buses in terms of fuel economy, vehicle maintenance cost, road calls, and emissions. There was no difference between the on-road average fuel economy of the two groups (4.41 mpg) based on the in-use data, however laboratory testing revealed a nearly 2% reduction in fuel economy for the B20 vehicles. Engine and fuel system related maintenance costs were nearly identical for the two groups until the final month of the study.

Oxidative degradation of biodiesel under accelerated conditions has been examined by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and gravimetric measurement of deposit formation. The formation of gums and deposits caused by oxidation in storage or in an engine fuel system is a significant issue because of the potential for fuel pump and injector fouling. The results of this study indicate several important pathways for degradation and two pathways leading to formation of oligomers and, ultimately, deposits. Peroxides formed in the initial stage of oxidation can decompose to form aldehydes, ketones, and acids. These can react further in aldol condensation to form oligomers. Additionally, peroxides can react with fatty acid chains to form dimers and higher oligomers. Deposits form when the polarity and molecular weight of these oligomers is high enough.

It is advantageous to increase the specific power output of diesel engines and to operate them at higher load for a greater portion of a driving cycle to achieve better thermal efficiency and thus reduce vehicle fuel consumption. Such operation is limited by excessive smoke formation at retarded injection timing and high rates of cylinder pressure rise at more advanced timing. Given this window of operation, it is desired to understand the influence of fuel properties such that optimum combustion performance and emissions can be retained over the range of fuels commonly available in the marketplace. Data are examined from a direct-injection single-cylinder research engine for eight common diesel fuels including soy-based biodiesel blends at two high load operating points with no exhaust gas recirculation (EGR) and at a moderate load with four levels of EGR.

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.

In this study the volume and hardness were measured for thermoplastics and thermosetting resins with diesel containing up to 30% of the following blend stocks: biodiesel, renewable diesel, n-undecane, dibutoxymethane, 1-octanol, hexyl hexanoate, and 2-nonanone. Thermoplastics included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), polybutylene terephthalate (PBT), polypropylene (PP), high density polyethylene (HDPE), nylons, acetals, polyetherimide (PEI), polyetheretherketone (PEEK), a PET co-polymer, polyphthalamides (PPAs), polyarylamide (PARA) and ethylene tetrafluoroethylene (ETFE). Three thermosetting resins were also evaluated. The material specimens were exposed to the test fuels under ambient conditions for 16 weeks.

Tests of ultra-low sulfur diesel blended with soy-biodiesel at 5% and 20% were conducted using a 2002 model year Cummins ISB engine (with exhaust gas recirculation) that had been retrofitted with a passively regenerated catalyzed diesel particulate filter (DPF). Results show that on average, the DPF balance point temperature (BPT) is 45°C and 112°C lower for B20 blends and neat biodiesel, respectively, than for 2007 certification diesel fuel. Biodiesel causes a measurable increase in regeneration rate at a fixed steady-state condition, even at the 5% blending level. The data show no significant differences in NOx emissions for these fuels at the steady-state regeneration conditions, suggesting that differences in soot reactivity are responsible for the observed differences in BPT and regeneration rate.