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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.

Mixing controlled compression ignition, i.e., diesel engines are efficient and are likely to continue to be the primary means for movement of goods for many years. Low-net-carbon biofuels have the potential to significantly reduce the carbon footprint of diesel combustion and could have advantageous properties for combustion, such as high cetane number and reduced engine-out particle and NOx emissions. We developed a list of over 400 potential biomass-derived diesel blendstocks and populated a database with the properties and characteristics of these materials. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a blendstock met the basic requirements for handling in the diesel distribution system and use as a blend with conventional diesel. Criteria included cetane number ≥40, flashpoint ≥52°C, and boiling point or T90 ≤338°C.

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).

A relationship has been observed between increasing ethanol content in gasoline and increased particulate matter (PM) emissions from direct injection spark ignition (DISI) vehicles. The fundamental cause of this observation is not well understood. One potential explanation is that increased evaporative cooling as a result of ethanol’s high HOV may slow evaporation and prevent sufficient reactant mixing resulting in the combustion of localized fuel rich regions within the cylinder. In addition, it is well known that ethanol when blended in gasoline forms positive azeotropes which can alter the liquid/vapor composition during the vaporization process. In fact, it was shown recently through a numerical study that these interactions can retain the aromatic species within the liquid phase impeding the in-cylinder mixing of these compounds, which would accentuate PM formation upon combustion.

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.

Gasoline Direct Injection (GDI) has become the preferred technology for spark-ignition engines resulting in greater specific power output and lower fuel consumption, and consequently reduction in CO2 emission. However, GDI engines face a substantial challenge in meeting new and future emission limits, especially the stringent particle number (PN) emissions recently introduced in Europe and China. Studies have shown that the fuel used by a vehicle has a significant impact on engine out emissions. In this study, nine fuels with varying chemical composition and physical properties were tested on a modern turbo-charged side-mounted GDI engine with design changes to reduce particulate emissions. The fuels tested included four fuels meeting US certification requirements; two fuels meeting European certification requirements; and one fuel meeting China 6 certification requirements being proposed at the time of this work.

Conventional diesel combustion, also known as Mixing-Controlled Compression Ignition (MCCI), is expected to be the primary power source for medium- and heavy-duty vehicles for decades to come. Displacing petroleum-based ultra-low-sulfur diesel (ULSD) as much as possible with low-net-carbon biofuels will become necessary to help mitigate effects on climate change. Neat biofuels may have difficulty meeting current diesel fuel standards but blends of 30% biofuel in ULSD show potential as ‘drop-in’ fuels. These blends must not make significant changes to the combustion phasing of the MCCI process if they are to be used interchangeably with neat ULSD. An important aspect of MCCI phasing is the ignition delay (ID), i.e. the time between the start of fuel injection and the initial premixed autoignition that initiates the MCCI process.

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.

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).

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.

Evaporative cooling of the fuel-air charge by fuel evaporation is an important feature of direct-injection spark-ignition engines that improves fuel knock resistance and reduces pumping losses at intermediate load, but in some cases, may increase fine particle emissions. We have reported on experimental approaches for measuring both total heat of vaporization and examination of the evaporative heat effect as a function of fraction evaporated for gasolines and ethanol blends. In this paper, we extend this work to include other low-molecular-weight alcohols and present results on species evolution during fuel evaporation by coupling a mass spectrometer to our differential scanning calorimetry/thermogravimetric analysis instrument. The alcohols examined were methanol, ethanol, 1-propanol, isopropanol, 2-butanol, and isobutanol at 10 volume percent, 20 volume percent, and 30 volume percent.

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.

The CRC Fuels for Advanced Combustion Engines working group has worked to identify a matrix of research diesel fuels for use in advanced combustion research applications. Nine fuels were specified and formulated to investigate the effects of cetane number aromatic content and 90% distillation fraction. Standard ASTM analyses were performed on the fuels as well as GC/MS and1H/13C NMR analyses and thermodynamic characterizations. Details of the actual results of the fuel formulations compared with the design values are presented, as well as results from standard analyses, such as heating value, viscosity and density. Cetane number characterizations were accomplished by using both the engine method and the Ignition Quality Tester (IQT™) apparatus.

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.