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The quality of neat biodiesel (B100) is critical for ensuring biodiesel blends used in diesel-powered vehicles do not adversely impact engine performance. In the United States, B100 is required to meet ASTM International’s purity and fuel property requirements in D6751, “Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels.” Here we review the development of this standard for the different grades of B100. The BQ-9000 program, which currently covers over 90% of U.S. and Canadian production volumes, is also described. Engine and original equipment manufacturers have expressed a desire for credible, third-party data on values of various ASTM B100 properties in the commercial market to inform their efforts to address future emissions and durability requirements.

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.

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).

A biodiesel / petroleum fuel blend and practical low-cost methods of emission control were sought to obtain reductions in emissions from diesel generators. Little direct testing of biodiesel in diesel-powered electric generators has been done. Laboratory and field evaluations were conducted to determine the influence of using biodiesel on diesel exhaust emissions. B20 (20% biodiesel / 80% petroleum diesel) was chosen because of previously successful studies with this blend level, and there is evidence that the NOx emissions increase that result from using B20 can be controlled using existing technology. B85 was selected because it is a “high blend,” which promised to give a large decrease in PM at the expense of a larger increase in NOx than B20, but still within the range of control with existing technology. Charge-air cooling and a fuel additive were tested as NOx controls. For PM, CO, and HC reduction, a diesel oxidation catalyst (DOC) was evaluated.

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.

It is estimated that operating continuously on a B20 fuel containing the current allowable ASTM specification limits for metal impurities in biodiesel could result in a doubling of ash exposure relative to lube-oil-derived ash. The purpose of this study was to determine if a fuel containing metals at the ASTM limits could cause adverse impacts on the performance and durability of diesel emission control systems. An accelerated durability test method was developed to determine the potential impact of these biodiesel impurities. The test program included engine testing with multiple DPF substrate types as well as DOC and SCR catalysts. The results showed no significant degradation in the thermo-mechanical properties of cordierite, aluminum titanate, or silicon carbide DPFs after exposure to 150,000 mile equivalent biodiesel ash and thermal aging. However, exposure of a cordierite DPF to 435,000 mile equivalent aging resulted in a 69% decrease in the thermal shock resistance parameter.

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.

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.

The objective of this research project was to compare B20 (20% biodiesel fuel) and ultra-low-sulfur (ULSD) diesel-fueled buses in terms of fuel economy, vehicle maintenance, engine performance, component wear, and lube oil performance. We examined 15 model year (MY) 2002 Gillig 40-foot transit buses equipped with MY 2002 Cummins ISM engines. The engines met 2004 U.S. emission standards and employed exhaust gas recirculation (EGR). For 18 months, eight of these buses operated exclusively on B20 and seven operated exclusively on ULSD. The B20 and ULSD study groups operated from different depots of the St. Louis (Missouri) Metro, with bus routes matched for duty cycle parity. The B20- and ULSD-fueled buses exhibited comparable fuel economy, reliability (as measured by miles between road calls), and total maintenance costs. Engine and fuel system maintenance costs were also the same for the two groups after correcting for the higher average mileage of the B20 group.

This paper reports the development of new fuel ignition quality and combustion experiments performed using the Ignition Quality Tester (IQT). Prior SAE papers (961182, 971636, 1999-01-3591, and 2001-01-3527) documented the development of the IQT constant volume combustion chamber experimental apparatus to measure ignition qualities of diesel-type fuels. The ASTM International test method D6890 was developed around the IQT device to allow the rapid determination of derived cetane number (DCN). Interest in chemical kinetic models for the ignition of diesel and biodiesel model compounds is increasing to support the development of advanced engines and fuels. However, rigorous experimental validation of these kinetic models has been limited for a variety of reasons. Shock tubes and rapid compression machines are typically limited to premixed gas-phase studies, for example.

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.

A 1.9 liter Volkswagen TDI engine has been modified to accomodate the addition of hydrogen into the intake manifold via timed port fuel injection. Engine out particulate matter and the emissions of oxides of nitrogen were investigated. Two fuels,low sulfur diesel fuel (BP50) and soy methyl ester (SME) biodiesel (B99), were tested with supplemental hydrogen fueling. Three test conditions were selected to represent a range of engine operating modes. The tests were executed at 20, 40, and 60 % rated load with a constant engine speed o 1700 RPM. At each test condition the percentage of power from hydrogen energy was varied from 0 to 40 %. This corresponds to hydrogen flow rates ranging from 7 to 85 liters per minute. Particulate matter (PM) emissions were measured using a scaning mobility particle sizer (SMPS) and a two stage micro dilution system. Oxides of nitrogen were also monitored.

Due to raising interest in diesel powered passenger cars in the U.S. in combination with a desire to reduce dependency on imported petroleum, there has been increased attention to the operation of diesel vehicles on fuels blended with biodiesel. One of several factors to be considered when operating a vehicle on biodiesel blends is understanding the impact and performance of the fuel on the emission control system. This paper documents the impact of the biodiesel blends on engine-out emissions as well as the overall system performance in terms of emission control system calibration and the overall system efficiency. The testing platform is a light-duty HSDI diesel engine with a Euro 4 base calibration in a 1700 kg sedan vehicle. It employs 2nd generation common-rail injection system with peak pressure of 1600 bar as well as cooled high-pressure EGR. The study includes 3 different fuels (U.S.

Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300°C. These stored HCs inhibit or block NOx-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NOx conversion begins at between 100° and 200°C. When exposure to unburned fuel occurs at higher temperatures (250°-400°C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NOx conversion is inhibited until it is heated to 400°C.

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.

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.

The objective of this research project was to compare the emissions of oxides of nitrogen (NOx) from transit buses on as many as five different fuels and three standard transit duty cycles to establish if there is a real-world biodiesel NOx increase for transit bus duty cycles and engine calibrations. Prior studies have shown that B20 can cause a small but significant increase in NOx emissions for some engines and duty cycles. Six buses spanning engine build years 1998 to 2011 were tested on the National Renewable Energy Laboratory's Renewable Fuels and Lubricants research laboratory's heavy-duty chassis dynamometer with certification diesel, certification B20 blend, low aromatic [California Air Resources Board (CARB)] diesel, low aromatic B20 blend, and B100 fuels over the Manhattan, Orange County and UDDS test cycles.

This project’s objective was to generate experimental data to evaluate the impact of metals doped B20 on diesel particle filter (DPF) ash loading and performance compared to that of conventional petrodiesel. The effect of metals doped B20 vs. conventional diesel on a DPF was quantified in a laboratory controlled accelerated ash loading study. The ash loading was conducted on two DPFs – one using ULSD fuel and the other on B20 containing metals dopants equivalent to 4 ppm B100 total metals. Engine oil consumption and B20 metals levels were accelerated by a factor of 5, with DPFs loaded to 30 g/L of ash. Details of the ash loading experiment and on-engine DPF performance evaluations are presented in the companion paper (Part I). The DPFs were cleaned, and ash samples were taken from the cleaned material. X-ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD) were conducted on the ash samples.

The project objective was to generate experimental data to evaluate the impact of metals doped B20 on DPF ash loading and performance compared to that of conventional petrodiesel. Accelerated ash loading was conducted on two DPFs – one exposed to regular diesel fuel and the other to B20 containing metal dopants equivalent to 4 ppm B100 total metals (currently total metals are limited to 10 ppm in ASTM D6751, the standard for B100). Periodic performance evaluations were conducted on the DPFs at 10 g/L ash loading intervals. After the evaluations at 30 g/L, the DPF was cleaned with a commercial DPF cleaning machine and another round of DPF evaluations were conducted. A comparison of the effect of ash loading with the two fuels and DPF cleaning is presented. The metals doped B20 fuel resulted in ash that was similar to that deposited when exposed to ULSD (lube oil ash) and exhibited similar ash cleaning removal efficiency.