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Technical Paper

Screening of Potential Biomass-Derived Streams as Fuel Blendstocks for Mixing Controlled Compression Ignition Combustion

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.
Technical Paper

Heat of Vaporization and Species Evolution during Gasoline Evaporation Measured by DSC/TGA/MS for Blends of C1 to C4 Alcohols in Commercial Gasoline Blendstocks

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.
Technical Paper

Determining Off-cycle Fuel Economy Benefits of 2-Layer HVAC Technology

This work presents a methodology to determine the off-cycle fuel economy benefit of a 2-Layer HVAC system which reduces ventilation and heat rejection losses of the heater core versus a vehicle using a standard system. Experimental dynamometer tests using EPA drive cycles over a broad range of ambient temperatures were conducted on a highly instrumented 2016 Lexus RX350 (3.5L, 8 speed automatic). These tests were conducted to measure differences in engine efficiency caused by changes in engine warmup due to the 2-Layer HVAC technology in use versus the technology being disabled (disabled equals fresh air-considered as the standard technology baseline). These experimental datasets were used to develop simplified response surface and lumped capacitance vehicle thermal models predictive of vehicle efficiency as a function of thermal state.
Technical Paper

Measured and Predicted Vapor Liquid Equilibrium of Ethanol-Gasoline Fuels with Insight on the Influence of Azeotrope Interactions on Aromatic Species Enrichment and Particulate Matter Formation in Spark Ignition Engines

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.
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

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.
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

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.
Journal Article

Simulated Real-World Energy Impacts of a Thermally Sensitive Powertrain Considering Viscous Losses and Enrichment

It is widely understood that cold ambient temperatures increase vehicle fuel consumption due to heat transfer losses, increased friction (increased viscosity lubricants), and enrichment strategies (accelerated catalyst heating). However, relatively little effort has been dedicated to thoroughly quantifying these impacts across a large set of real world drive cycle data and ambient conditions. This work leverages experimental dynamometer vehicle data collected under various drive cycles and ambient conditions to develop a simplified modeling framework for quantifying thermal effects on vehicle energy consumption. These models are applied over a wide array of real-world usage profiles and typical meteorological data to develop estimates of in-use fuel economy. The paper concludes with a discussion of how this integrated testing/modeling approach may be applied to quantify real-world, off-cycle fuel economy benefits of various technologies.
Journal Article

Effect of Accelerated Aging Rate on the Capture of Fuel-Borne Metal Impurities by Emissions Control Devices

Small impurities in the fuel can have a significant impact on the emissions control system performance over the lifetime of the vehicle. Of particular interest in recent studies has been the impact of sodium, potassium, and calcium that can be introduced either through fuel constituents, such as biodiesel, or as lubricant additives. In a collaboration between the National Renewable Energy Laboratory and the Oak Ridge National Laboratory, a series of accelerated aging studies have been performed to understand the potential impact of these metals on the emissions control system. This paper explores the effect of the rate of accelerated aging on the capture of fuel-borne metal impurities in the emission control devices and the subsequent impact on performance. Aging was accelerated by doping the fuel with high levels of the metals of interest. Three separate evaluations were performed, each with a different rate of accelerated aging.
Journal Article

Overcoming the Range Limitation of Medium-Duty Battery Electric Vehicles through the use of Hydrogen Fuel-Cells

Battery electric vehicles possess great potential for decreasing lifecycle costs in medium-duty applications, a market segment currently dominated by internal combustion technology. Characterized by frequent repetition of similar routes and daily return to a central depot, medium-duty vocations are well positioned to leverage the low operating costs of battery electric vehicles. Unfortunately, the range limitation of commercially available battery electric vehicles acts as a barrier to widespread adoption. This paper describes the National Renewable Energy Laboratory's collaboration with the U.S. Department of Energy and industry partners to analyze the use of small hydrogen fuel-cell stacks to extend the range of battery electric vehicles as a means of improving utility, and presumably, increasing market adoption.
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).
Journal Article

Impact of Biodiesel Impurities on the Performance and Durability of DOC, DPF and SCR Technologies

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.
Technical Paper

The Impacts of Mid-level Biofuel Content in Gasoline on SIDI Engine-out and Tailpipe Particulate Matter Emissions

In this work, the influences of ethanol and iso-butanol blended with gasoline on engine-out and post three-way catalyst (TWC) particle size distribution and number concentration were studied using a General Motors (GM) 2.0L turbocharged spark ignition direct injection (SIDI) engine. The engine was operated using the production engine control unit (ECU) with a dynamometer controlling the engine speed and the accelerator pedal position controlling the engine load. A TSI Fast Mobility Particle Sizer (FMPS) spectrometer was used to measure the particle size distribution in the range from 5.6 to 560 nm with a sampling rate of 1 Hz. U.S. federal certification gasoline (E0), two ethanol-blended fuels (E10 and E20), and 11.7% iso-butanol blended fuel (BU12) were tested. Measurements were conducted at 10 selected steady-state engine operation conditions. Bi-modal particle size distributions were observed for all operating conditions with peak values at particle sizes of 10 nm and 70 nm.
Journal Article

Expanding the Experimental Capabilities of the Ignition Quality Tester for Autoigniting Fuels

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.
Journal Article

Fuels for Advanced Combustion Engines Research Diesel Fuels: Analysis of Physical and Chemical Properties

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.
Journal Article

Effect of Unburned Methyl Esters on the NOx Conversion of Fe-Zeolite SCR Catalyst

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.
Journal Article

1000-Hour Durability Evaluation of a Prototype 2007 Diesel Engine with Aftertreatment Using B20 Biodiesel Fuel

A prototype 2007 ISL Cummins diesel engine equipped with a diesel oxidation catalyst (DOC), diesel particle filter (DPF), variable geometry turbocharger (VGT), and cooled exhaust gas recirculation (EGR) was tested at Southwest Research Institute (SwRI) under a high-load accelerated durability cycle for 1000 hours with B20 soy-based biodiesel blends and ultra-low sulfur diesel (ULSD) fuel to determine the impact of B20 on engine durability, performance, emissions, and fuel consumption. At the completion of the 1000-hour test, a thorough engine teardown evaluation of the overhead, power transfer, cylinder, cooling, lube, air handling, gaskets, aftertreatment, and fuel system parts was performed. The engine operated successfully with no biodiesel-related failures. Results indicate that engine performance was essentially the same when tested at 125 and 1000 hours of accumulated durability operation.
Journal Article

Field Evaluation of Biodiesel (B20) Use by Transit Buses

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.
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.