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Technical Paper

Statistical Treatise on Critical Biodiesel (B100) Quality Properties in the United States from 2004-2022

2023-08-28
2023-24-0097
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.
Journal Article

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

2019-04-02
2019-01-0570
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

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

2018-04-03
2018-01-0361
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.
Technical Paper

Investigation of the Impact of Fuel Properties on Particulate Number Emission of a Modern Gasoline Direct Injection Engine

2018-04-03
2018-01-0358
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.
Technical Paper

Impacts of Biofuel Blending on MCCI Ignition Delay with Review of Methods for Defining Cycle-by-Cycle Ignition Points from Noisy Cylinder Pressure Data

2021-04-06
2021-01-0497
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.
Journal Article

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

2011-04-12
2011-01-1136
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

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

2019-01-15
2019-01-0014
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.
Journal Article

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

2009-11-02
2009-01-2777
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

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

2014-04-01
2014-01-1500
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

Distillation-based Droplet Modeling of Non-Ideal Oxygenated Gasoline Blends: Investigating the Role of Droplet Evaporation on PM Emissions

2017-03-28
2017-01-0581
In some studies, a relationship has been observed between increasing ethanol content in gasoline and increased particulate matter (PM) emissions from vehicles equipped with spark ignition engines. The fundamental cause of the PM increase seen for moderate ethanol concentrations is not well understood. Ethanol features a greater heat of vaporization (HOV) than gasoline and also influences vaporization by altering the liquid and vapor composition throughout the distillation process. A droplet vaporization model was developed to explore ethanol’s effect on the evaporation of aromatic compounds known to be PM precursors. The evolving droplet composition is modeled as a distillation process, with non-ideal interactions between oxygenates and hydrocarbons accounted for using UNIFAC group contribution theory. Predicted composition and distillation curves were validated by experiments.
Technical Paper

Diesel Oxidation Catalyst Performance with Biodiesel Formulations

2024-04-09
2024-01-2711
Biodiesel (i.e., mono-alkyl esters of long chain fatty acids derived from vegetable oils and animal fats) is a renewable diesel fuel providing life-cycle greenhouse gas emission reductions relative to petroleum-derived diesel. With the expectation that there would be widespread use of biodiesel as a substitute for ultra-low sulfur diesel (ULSD), there have been many studies looking into the effects of biodiesel on engine and aftertreatment, particularly its compatibility to the current aftertreatment technologies. The objective of this study was to generate experimental data to measure the effectiveness of a current technology diesel oxidation catalysts (DOC) to oxidize soy-based biodiesel at various blend levels with ULSD. Biodiesel blends from 0 to 100% were evaluated on an engine using a conventional DOC.
Journal Article

Biodiesel Impact on Engine Lubricant Dilution During Active Regeneration of Aftertreatment Systems

2011-12-06
2011-01-2396
Experiments were conducted with ultra low sulfur diesel (ULSD) and 20% biodiesel blends (B20) to compare lube oil dilution levels and lubricant properties for systems using late in-cylinder fuel injection for aftertreatment regeneration. Lube oil dilution was measured by gas chromatography (GC) following ASTM method D3524 to measure diesel content, by Fourier transform infrared (FTIR) spectrometry following a modified ASTM method D7371 to measure biodiesel content, and by a newly developed back-flush GC method that simultaneously measures both diesel and biodiesel. Heavy-duty (HD) engine testing was conducted on a 2008 6.7L Cummins ISB equipped with a diesel oxidation catalyst (DOC) and diesel particle filter (DPF). Stage one of engine testing consisted of 10 consecutive repeats of a forced DPF regeneration event. This continuous operation with late in-cylinder fuel injection served as a method to accelerate lube-oil dilution.
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