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Technical Paper

The Effect of Diesel Sulfur Content and Oxidation Catalysts on Transient Emissions at High Altitude from a 1995 Detroit Diesel Series 50 Urban Bus Engine

Regulated emissions (THC, CO, NOx, and PM) and particulate SOF and sulfate fractions were determined for a 1995 Detroit Diesel Series 50 urban bus engine at varying fuel sulfur levels, with and without catalytic converters. When tested on EPA certification fuel without an oxidation catalyst this engine does not appear to meet the 1994 emissions standards for heavy duty trucks, when operating at high altitude. An ultra-low (5 ppm) sulfur diesel base stock with 23% aromatics and 42.4 cetane number was used to examine the effect of fuel sulfur. Sulfur was adjusted above the 5 ppm level to 50, 100, 200, 315 and 500 ppm using tert-butyl disulfide. Current EPA regulations limit the sulfur content to 500 ppm for on highway fuel. A low Pt diesel oxidation catalyst (DOC) was tested with all fuels and a high Pt diesel oxidation catalyst was tested with the 5 and 50 ppm sulfur fuels.
Technical Paper

Spectroscopic Study of Biodiesel Degradation Pathways

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.
Journal Article

Selection Criteria and Screening of Potential Biomass-Derived Streams as Fuel Blendstocks for Advanced Spark-Ignition Engines

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.
Journal Article

Review: Fuel Volatility Standards and Spark-Ignition Vehicle Driveability

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.
Technical Paper

Regulated and Unregulated Exhaust Emissions Comparison for Three Tier II Non-Road Diesel Engines Operating on Ethanol-Diesel Blends

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).
Technical Paper

Regulated Emissions from Biodiesel Tested in Heavy-Duty Engines Meeting 2004 Emission Standards

Biodiesel produced from soybean oil, canola oil, yellow grease, and beef tallow was tested in two heavy-duty engines. The biodiesels were tested neat and as 20% by volume blends with a 15 ppm sulfur petroleum-derived diesel fuel. The test engines were a 2002 Cummins ISB and 2003 DDC Series 60. Both engines met the 2004 U.S. emission standard of 2.5 g/bhp-h NOx+HC (3.35 g/kW-h) and utilized exhaust gas recirculation (EGR). All emission tests employed the heavy-duty transient procedure as specified in the U.S. Code of Federal Regulations. Reduction in PM emissions and increase in NOx emissions were observed for all biodiesels in all engines, confirming observations made in older engines. On average PM was reduced by 25% and NOx increased by 3% for the two engines tested for a variety of B20 blends. These changes are slightly larger in magnitude, but in the same range as observed in older engines.
Technical Paper

Rapid Deactivation of Lean-Burn Natural Gas Engine Exhaust Oxidation Catalysts

Methane emissions from lean-burn natural gas engines can be relatively high. As natural gas fueled vehicles become more prevalent, future regulations may restrict these emissions. Preliminary reports indicated that conventional, precious metal oxidation catalysts rapidly deactivate (in less than 50 hours) in lean-burn natural gas engine exhaust. This investigation is directed at quantifying this catalyst deactivation and understanding its cause. The results may also be relevant to oxidation of lean-burn propane and gasoline engine exhaust. A platinum/palladium on alumina catalyst and a palladium on alumina catalyst were aged in the exhaust of a lean-burn natural gas engine (Cummins B5.9G). The engine was fueled with compressed natural gas. Catalyst aging was accomplished through a series of steady state cycles and heavy-duty transient tests (CFR 40 Part 86 Subpart N) lasting 10 hours. Hydrocarbons in the exhaust were speciated by gas chromatography.
Technical Paper

Quantification of Biodiesel Content in Fuels and Lubricants by FTIR and NMR Spectroscopy

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).
Technical Paper

Operating Experience and Teardown Analysis for Engines Operated on Biodiesel Blends (B20)

Biodiesel has been used to reduce petroleum consumption and pollutant emissions. B20, a 20% blend of biodiesel with 80% petroleum diesel, has become the most common blend used in the United States. Little quantitative information is available on the impact of biodiesel on engine operating costs and durability. In this study, eight engines and fuel systems were removed from trucks that had operated on B20 or diesel, including four 1993 Ford cargo vans and four 1996 Mack tractors (two of each running on B20 and two on diesel). The engines and fuel system components were disassembled, inspected, and evaluated to compare wear characteristics after 4 years of operation and more than 600,000 miles accumulated on B20. The vehicle case history-including mileage accumulation, fuel use, and maintenance costs-was also documented. The results indicate that there was little difference that could be attributed to fuel in operational and maintenance costs between the B20- and diesel-fueled groups.
Journal Article

Knock Resistance and Fine Particle Emissions for Several Biomass-Derived Oxygenates in a Direct-Injection Spark-Ignition Engine

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.
Technical Paper

In-Use Emissions from Natural Gas Fueled Heavy-Duty Vehicles

The objective of the work described here is to test the performance of closed-loop controlled, heavy-duty CNG engines in-use, on fuels of different methane content; and to compare their performance with similar diesel vehicles. Performance is measured in terms of pollutant emissions, fuel economy, and driveability. To achieve this objective, three buses powered by closed-loop controlled, dedicated natural gas engines were tested on the heavy-duty chassis dynamometer facility at the Colorado Institute for Fuels and High Altitude Engine Research (CIFER). Emissions of regulated pollutants (CO, NOx, PM, and THC or NMHC), as well as emissions of alde-hydes for some vehicles, are reported. Two fuels were employed: a high methane fuel (90%) and a low methane fuel (85%). It was found that the NOx, CO, and PM emissions for a given cycle and vehicle are essentially constant for different methane content fuels.
Journal Article

Impacts of Biodiesel Fuel Blends Oil Dilution on Light-Duty Diesel Engine Operation

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.
Journal Article

Impact of a Diesel High Pressure Common Rail Fuel System and Onboard Vehicle Storage on B20 Biodiesel Blend Stability

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.
Technical Paper

Impact of Fuel Metal Impurities on the Durability of a Light-Duty Diesel Aftertreatment System

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).
Technical Paper

Impact of Biodiesel Blends on Fuel System Component Durability

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.
Journal Article

Heat of Vaporization Measurements for Ethanol Blends Up To 50 Volume Percent in Several Hydrocarbon Blendstocks and Implications for Knock in SI Engines

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.
Technical Paper

Fuel Additive and Blending Approaches to Reducing NOx Emissions from Biodiesel

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.
Technical Paper

Fischer-Tropsch Diesel Fuels - Properties and Exhaust Emissions: A Literature Review

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.
Journal Article

Exploring the Relationship Between Octane Sensitivity and Heat-of-Vaporization

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.
Journal Article

Evaluation of Fuel-Borne Sodium Effects on a DOC-DPF-SCR Heavy-Duty Engine Emission Control System: Simulation of Full-Useful Life

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.