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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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

A prototype three-way catalyst (TWC) with NOX storage component was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly-rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. Adding a NOX storage component to a TWC provides two benefits in the context of a passive SCR system: (1) enabling longer lean operation by storing NOX upstream and preserving NH3 inventory on the downstream SCR catalyst; and (2) increasing the quantity and rate of NH3 production during rich operation.

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 effect of diesel cetane number, total aromatic content T90, and fuel nitrogen content on regulated emissions (HC, CO, NOx, and PM) from a 1991 DDC Series 60 engine were measured Emissions tests were conducted using the EPA heavy-duty transient test (CFR 40 Part 86 Subpart N) at a laboratory located 5,280 feet (1609 m) above sea level. The objective of this work was to determine if the effect of fuel chemistry at high altitude is similar to what is observed at sea level and to examine the effect of specific fuel chemistry variables on emissions. An initial tea series was conducted to examine the effect of cetane number and aromatics. Transient emissions for this test series indicated much higher (50 to 75%) particulate emissions at high altitude than observed on the same model engine and similar fuels at sea level.

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.

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).

Phosphorous in diesel exhaust is derived via engine oil consumption from the zinc dialkyldithiophosphate (ZDDP) oil additive used for engine wear control. Phosphorous present in the engine exhaust can react with an exhaust catalyst and cause loss of performance through masking or chemical reaction. The primary effect is loss of light-off or low temperature performance. Although the amount of ZDDP used in lube oil is being reduced, it appears that there may is a minimum level of ZDDP needed for engine durability. One of the ways of reducing the effects of the resulting phosphorous on catalysts might be to alter the chemical state of the phosphorous to a less damaging form or to develop catalysts which are more resistant to phosphorous poisoning. In this study, lube oil containing ZDDP was added at an accelerated rate through a variety of engine pathways to simulate various types of engine wear or oil disposal practices.

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.

Emissions of six 32 passenger transit buses were characterized using one of the West Virginia University (WVU) Transportable Heavy Duty Emissions Testing Laboratories, and the fixed base chassis dynamometer at the Colorado Institute for Fuels and High Altitude Engine Research (CIFER). Three of the buses were powered with 1997 ISB 5.9 liter Cummins diesel engines, and three were powered with the 1997 5.9 liter Cummins natural gas (NG) counterpart. The NG engines were LEV certified. Objectives were to contrast the emissions performance of the diesel and NG units, and to compare results from the two laboratories. Both laboratories found that oxides of nitrogen and particulate matter (PM) emissions were substantially lower for the natural gas buses than for the diesel buses. It was observed that by varying the rapidity of pedal movement during accelerations in the Central Business District cycle (CBD), CO and PM emissions from the diesel buses could be varied by a factor of three or more.

The U.S. Department of Energy’s Co-Optimization of Fuels and Engines initiative (Co-Optima) aims to simultaneously transform both transportation fuels and engines to maximize performance and energy efficiency. Researchers from across the DOE national laboratories are working within Co-Optima to develop merit functions for evaluating the impact of fuel formulations on the performance of advanced engines. The merit functions relate overall engine efficiency to specific measurable fuel properties and will serve as key tools in the fuel/engine co-optimization process. This work focused on developing a term for the Co-Optima light-duty boosted spark ignition (SI) engine merit function that captures the effects of fuel composition on emissions control system performance. For stoichiometric light-duty SI engines, the majority of NOx, NMOG, and CO emissions occur during cold start, before the three-way catalyst (TWC) has reached its “light-off” temperature.