Search Results

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.

We describe a study to identify potential biofuels that enable advanced spark ignition (SI) engine efficiency strategies to be pursued more aggressively. A list of potential biomass-derived blendstocks was developed. An online database of properties and characteristics of these bioblendstocks was created and populated. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a bioblendstock met the requirements for advanced SI engines. Criteria included melting point (or cloud point) < -10°C and boiling point (or T90) <165°C. Compounds insoluble or poorly soluble in hydrocarbon were eliminated from consideration, as were those known to cause corrosion (carboxylic acids or high acid number mixtures) and those with hazard classification as known or suspected carcinogens or reproductive toxins.

Spark-ignition engine fuel standards have been put in place to ensure acceptable hot and cold weather driveability (HWD and CWD). Vehicle manufacturers and fuel suppliers have developed systems that meet our driveability requirements so effectively that drivers overwhelmingly find that their vehicles reliably start up and operate smoothly and consistently throughout the year. For HWD, fuels that are too volatile perform more poorly than those that are less volatile. Vapor lock is the apparent cause of poor HWD, but there is conflicting evidence in the literature as to where in the fuel system it occurs. Most studies have found a correlation between degraded driveability and higher dry vapor pressure equivalent or lower TV/L = 20, and less consistently with a minimum T50. For CWD, fuels with inadequate volatility can cause difficulty in starting and rough operation during engine warmup.

Regulated and unregulated emissions (individual hydrocarbons, ethanol, aldehydes and ketones, polynuclear aromatic hydrocarbons (PAH), nitro-PAH, and soluble organic fraction of particulate matter) were characterized in engines utilizing duplicate ISO 8178-C1 eight-mode tests and FTP smoke tests. Certification No. 2 diesel (400 ppm sulfur) and three ethanol/diesel blends, containing 7.7 percent, 10 percent, and 15 percent ethanol, respectively, were used. The three, Tier II, off-road engines were 6.8-L, 8.1-L, and 12.5-L in displacement and each had differing fuel injection system designs. It was found that smoke and particulate matter emissions decreased with increasing ethanol content. Changes to the emissions of carbon monoxide and oxides of nitrogen varied with engine design, with some increases and some decreases. As expected, increasing ethanol concentration led to higher emissions of acetaldehyde (increases ranging from 27 to 139 percent).

The use of biodiesel requires the development of proper quantification procedures for biodiesel content in blends and in lubricants (fuel dilution in oil). Although the ester carbonyl stretch at 1746 wavenumbers (cm-1) is the most prominent band in the IR spectrum of biodiesel, it is difficult to use for quantification purposes due to a severe fluctuation of absorption strength from sample to sample, even at the same biodiesel content. We have demonstrated that the ester carbonyl fluctuation is not caused by variation in the ester alkyl chain length; but is most likely caused by the degree of hydrogen bonding of the ester functional group with water in the sample. Water molecules can form complexes with the ester compound affecting the strength of the ester carbonyl band. The impact of water on quantification of the biodiesel content of blends was significant, even for B100 samples that met the proposed ASTM D6751 water limit of 500 ppm by D6304 (Karl Fischer Methdod).

Several high octane number oxygenates that could be derived from biomass were blended with gasoline and examined for performance properties and their impact on knock resistance and fine particle emissions in a single cylinder direct-injection spark-ignition engine. The oxygenates included ethanol, isobutanol, anisole, 4-methylanisole, 2-phenylethanol, 2,5-dimethyl furan, and 2,4-xylenol. These were blended into a summertime blendstock for oxygenate blending at levels ranging from 10 to 50 percent by volume. The base gasoline, its blends with p-xylene and p-cymene, and high-octane racing gasoline were tested as controls. Relevant gasoline properties including research octane number (RON), motor octane number, distillation curve, and vapor pressure were measured. Detailed hydrocarbon analysis was used to estimate heat of vaporization and particulate matter index (PMI). Experiments were conducted to measure knock-limited spark advance and particulate matter (PM) emissions.

Chassis dynamometer testing of two 60 foot articulated transit busses, one conventional and one hybrid, was conducted at the National Renewable Energy Laboratory's, ReFUEL facility. Both test vehicles were 2004 New Flyer busses powered by Caterpillar C9 8.8L engines, with the hybrid vehicle incorporating a GM-Allison advanced hybrid electric drivetrain. Both vehicles also incorporated an oxidizing diesel particulate filter. The fuel economy and emissions benefits of the hybrid vehicle were evaluated over four driving cycles; Central Business District (CBD), Orange County (OCTA), Manhattan (MAN) and a custom test cycle developed from in-use data of the King County Metro (KCM) fleet operation. The hybrid vehicle demonstrated the highest improvement in fuel economy (mpg basis) over the low speed, heavy stop-and-go driving conditions of the Manhattan test cycle (74.6%) followed by the OCTA (50.6%), CBD (48.3%) and KCM (30.3%).

Increasing interest in biofuels—specifically, biodiesel as a pathway to energy diversity and security—have necessitated the need for research on the performance and utilization of these fuels and fuel blends in current and future vehicle fleets. One critical research area is related to achieving a full understanding of the impact of biodiesel fuel blends on advanced emission control systems. In addition, the use of biodiesel fuel blends can degrade diesel engine oil performance and impact the oil drain interval requirements. There is limited information related to the impact of biodiesel fuel blends on oil dilution. This paper assesses the oil dilution impacts on an engine operating in conjunction with a diesel particle filter (DPF), oxides of nitrogen (NOx) storage, a selective catalytic reduction (SCR) emission control system, and a 20% biodiesel (soy-derived) fuel blend.

Adoption of high-pressure common-rail (HPCR) fuel systems, which subject diesel fuels to higher temperatures and pressures, has brought into question the veracity of ASTM International specifications for biodiesel and biodiesel blend oxidation stability, as well as the lack of any stability parameter for diesel fuel. A controlled experiment was developed to investigate the impact of a light-duty diesel HPCR fuel system on the stability of 20% biodiesel (B20) blends under conditions of intermittent use and long-term storage in a relatively hot and dry climate. B20 samples with Rancimat induction periods (IPs) near the current 6.0-hour minimum specification (6.5 hr) and roughly double the ASTM specification (13.5 hr) were prepared from a conventional diesel and a highly unsaturated biodiesel. Four 2011 model year Volkswagen Passats equipped with HPCR fuel injection systems were utilized: one on B0, two on B20-6.5 hr, and one on B20-13.5 hr.

Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. Using an accelerated aging procedure, a set of production exhaust systems from a 2011 Ford F250 equipped with a 6.7L diesel engine have been aged to an equivalent of 150,000 miles of thermal aging and metal exposure. These exhaust systems included a diesel oxidation catalyst (DOC), selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ULSD containing no measureable metals, B20 containing sodium, B20 containing potassium and B20 containing calcium. Metals levels were selected to simulate the maximum allowable levels in B100 according to the ASTM D6751 standard. Analysis of the aged catalysts included Federal Test Procedure emissions testing with the systems installed on a Ford F250 pickup, bench flow reactor testing of catalyst cores, and electron probe microanalysis (EPMA).

An ultra-low sulfur diesel (ULSD) fuel was blended with three different biodiesel samples at 5 and 20 volume percent. The biodiesel fuels were derived from rapeseed and soybean oils, and in addition, a highly oxidized biodiesel was prepared from the soy biodiesel by oxidation under controlled conditions. A set of five elastomers commonly used in automotive fuel systems were examined before and after immersion in the six test blends and base fuel at 60°C for 1000 hours. The elastomers were evaluated for hardness, tensile strength, volume change and compression. Injector wear tests were also conducted on the base petrodiesel fuel and the biodiesel blends using a 500-hour test method developed for this study. Bosch VE (in-line) rotary pumps were evaluated for wear after testing for 500 hours on the base fuel, B5 and B20 test fuels. Additionally, a test procedure was developed to accelerate wear on common rail pumps over 500 hours.

The objective of this work was to measure knock resistance metrics for ethanol-hydrocarbon blends with a primary focus on development of methods to measure the heat of vaporization (HOV). Blends of ethanol at 10 to 50 volume percent were prepared with three gasoline blendstocks and a natural gasoline. Performance properties and composition of the blendstocks and blends were measured, including research octane number (RON), motor octane number (MON), net heating value, density, distillation curve, and vapor pressure. RON increases upon blending ethanol but with diminishing returns above about 30 vol%. Above 30% to 40% ethanol the curves flatten and converge at a RON of about 103 to 105, even for the much lower RON NG blendstock. Octane sensitivity (S = RON - MON) also increases upon ethanol blending. Gasoline blendstocks with nearly identical S can show significantly different sensitivities when blended with ethanol.

Conventional diesel engines will continue to hold a vital role in the heavy- and medium-duty markets for the transportation of goods along with many other uses. The ability to offset traditional diesel fuels with low-net-carbon biofuels could have a significant impact on reducing the carbon footprint of these vehicles. A prior study screened several hundred candidate biofuel blendstocks based on required diesel blendstock properties and identified 12 as the most promising. Eight representative biofuel blendstocks were blended at a 30% volumetric concentration with EPA certification ultra-low-sulfur diesel (ULSD) and were investigated for emissions and fuel efficiency performance. This study used a single cylinder engine (based on the Ford 6.7L engine) using Conventional Diesel Combustion (CDC), also known as Mixing Control Compression Ignition (MCCI). The density, cetane number, distillation curve and sooting tendency (using the yield sooting index method) of the fuels were measured.

Blending of 20% biodiesel with petroleum diesel is well known to cause a significant reduction in PM emissions but also can cause NOx emissions to increase by 1 to 3 percent. This study has examined a number of approaches for NOx reduction for 20% biodiesel/petroleum diesel blends (B20). These approaches included blending with a nominally 10% aromatic diesel, zero aromatic Fisher-Tropsch (FT) diesel, and use of fuel additives. Biodiesel produced from soybean oil and from yellow grease was examined. Testing was conducted in at 1991 DDC Series 60 truck engine using the U.S. heavy-duty FTP. Emissions of NOx, PM, CO, and THC are reported. Relative to certification diesel the B20 fuels exhibited 20% lower PM emissions but 3.3 and 1% higher NOx emissions for soy and yellow grease based blends, respectively. The 10% aromatic fuel exhibited 12% lower PM and 6% lower NOx. FT diesel had the lowest emissions with a 33% reduction in PM and 16% lower NOx.

Natural gas, coal, and biomass can be converted to diesel fuel through Fischer-Tropsch (F-T) processes. Variations of the F-T process and/or product work-up can be used to tailor the fuel properties to meet end-users needs. Regardless of feedstock or process, F-T diesel fuels typically have a number of very desirable properties. This review describes typical F-T diesel fuel properties, discusses how these fuel properties impact pollutant emissions, and draws together data from known engine and chassis dynamometer studies of emissions. The comparison of fuel properties reveals that F-T diesel fuel is typically one of two types - a very high cetane number (>74), zero aromatic product or a moderate cetane (∼60), low aromatic (≤15%) product. The very high cetane fuels typically have less desirable low temperature properties while the moderate cetane fuels have cold flow properties more typical of conventional diesel fuels.

The latent heat-of-vaporization (HoV) of blends of biofuel and hydrocarbon components into gasolines has recently experienced expanded interest because of the potential for increased HoV to increase fuel knock resistance in direct-injection (DI) engines. Several studies have been conducted, with some studies identifying an additional anti-knock benefit from HoV and others failing to arrive at the same conclusion. Consideration of these studies holistically shows that they can be grouped according to the level of fuel octane sensitivity variation within their fuel matrices. When comparing fuels of different octane sensitivity significant additional anti-knock benefits associated with HoV are sometimes observed. Studies that fix the octane sensitivity find that HoV does not produce additional anti-knock benefit. New studies were performed at ORNL and NREL to further investigate the relationship between HoV and octane sensitivity.

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 exhaust emissions from a single-cylinder version of a heavy-duty diesel engine with exhaust gas recirculation (EGR) were studied using 12 diesel fuels derived from oil sands and conventional sources. The test fuels were blended from 22 refinery streams to produce four fuels (two from each source) at three different total aromatic levels (10, 20, and 30% by mass). The cetane numbers were held constant at 43. Exhaust emissions were measured using the AVL eight-mode steady-state test procedure. PM emissions were accurately modeled by a single regression equation with two predictors, total aromatics and sulphur content. Sulphate emissions were found to be independent of the type of sulphur compound in the fuel. NOx emissions were accurately modeled by a single regression equation with total aromatics and density as predictor variables. PM and NOx emissions were significantly significantly affected by fuel properties, but crude oil source did not play a role.

Knock-limited loads for a set of surrogate gasolines all having nominal 100 research octane number (RON), approximately 11 octane sensitivity (S), and a heat of vaporization (HOV) range of 390 to 595 kJ/kg at 25°C were investigated. A single-cylinder spark-ignition engine derived from a General Motors Ecotec direct injection (DI) engine was used to perform load sweeps at a fixed intake air temperature (IAT) of 50 °C, as well as knock-limited load measurements across a range of IATs up to 90 °C. Both DI and pre-vaporized fuel (supplied by a fuel injector mounted far upstream of the intake valves and heated intake runner walls) experiments were performed to separate the chemical and thermal effects of the fuels’ knock resistance. The DI load sweeps at 50°C intake air temperature showed no effect of HOV on the knock-limited performance. The data suggest that HOV acts as a thermal contributor to S under the conditions studied.

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.