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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.
Technical Paper

Comparison of the Particulate Matter Index and Particulate Evaluation Index Numbers Calculated by Detailed Hydrocarbon Analysis by Gas Chromatography (Enhanced ASTM D6730) and Vacuum Ultraviolet Paraffin, Isoparaffin, Olefin, Naphthene, and Aromatic Analysis (ASTM D8071)

2021-08-16
2021-01-5070
The Particulate Matter Index (PMI) is a tool that provides an indication of a fuel’s tendency to produce Particulate Matter (PM) emissions. Currently, the index is being used by various fuel laboratories and the Automotive OEMs as a tool to understand the gasoline fuel’s impact on both PM from engine hardware and vehicle-out emissions. In addition, a newer index that could be used to give an indication of the PM tendency of the gasoline range fuels, called the Particulate Evaluation Index (PEI), is shown to have a good correlation to PMI. The data used in those indices are collected from chemical analytical methods. This paper will compare gas chromatography (GC) methods used by three laboratories and discuss how the different techniques may affect the PMI and PEI calculation.
Technical Paper

Global Market Gasoline Quality Review: Five Year Trends in Particulate Emission Indices

2021-04-06
2021-01-0623
A gasoline’s chemical composition impacts a vehicle’s sooting tendency and therefore has been the subject of numerous emissions studies. From these studies, several mathematical correlation equations have been developed to predict a gasoline’s sooting tendency in modern spark-ignited internal combustion engine vehicles. This paper reviews the recently developed predictive tool methods and summarizes five years of global market fuel survey data to characterize gasoline sooting tendency trends around the world. Additionally, the paper will evaluate and suggest changes to the predictive methods to improve emissions correlations.
Journal Article

Fuel Effects on the Propensity to Establish Propagating Flames at SPI-Relevant Engine Conditions

2021-04-06
2021-01-0488
In order to further understand the sequence of events leading to stochastic preignition in a spark-ignition engine, a methodology previously developed by the authors was used to evaluate the propensity of a wide range of fuels to establishing propagating flames under conditions representative of those at which stochastic preignition (SPI) occurs. The fuel matrix included single component hydrocarbons, binary mixtures, and real fuel blends. The propensity of each fuel to establish a flame was correlated to multiple fuel properties and shown to exhibit consistent blending behaviors. No single parameter strongly predicted a fuel’s propensity to establish a flame, while multiple reactivity-based parameters exhibited moderate correlation. A two-stage model of the flame establishment process was developed to interpret and explain these results.
Technical Paper

Development of an Alternative Predictive Model for Gasoline Vehicle Particulate Matter and Particulate Number

2019-04-02
2019-01-1184
The Particulate Matter Index (PMI) is a helpful tool which provides an indication of a fuel’s sooting tendency. Currently, the index is being used by various laboratories and OEMs as a metric to understand the gasoline fuels impact on both sooting found on engine hardware and vehicle out emissions. This paper will explore a new method that could be used to give indication of the sooting tendency of the gasoline range fuels, called the Particulate Evaluation Index (PEI), and provide the detailed equation in its initial form. In addition, the PEI will be shown to have a good correlation agreement to PMI. The paper will then give a detailed explanation of the data used to develop it. Initial vehicle PM/PN data will also be presented that shows correlations of the indices to the vehicle response.
Technical Paper

Fast Gas Analyzer Observations of Stochastic Preignition Events

2019-04-02
2019-01-0254
The goal of this study was to generate exhaust fast gas data that could be used to identify phenomena that occur before, during, and after stochastic preignition (SPI), also called low-speed preignition (LSPI), events. Crank angle resolved measurement of exhaust hydrocarbons, NO, CO, and CO2 was performed under engine conditions prone to these events. Fuels and engine operating strategies were varied in an attempt to understand similarities and differences in SPI-related behavior that may occur between them. Several different uncommon (typically occurring in less than 1% of engine cycles) features of the fast gas data were identified, and the correlations between them and SPI events were explored. Although the thresholds used to define and identify these observations were arbitrary, they provided a practical means of identifying behavior in the fast gas data and correlating it to SPI occurrence.
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

Fuel & Lubricant Effects on Stochastic Preignition

2019-01-15
2019-01-0038
In this multi-phase study, fuel and lubricant effects on stochastic preignition (SPI) were examined. First, the behavior of fuels for which SPI data had previously been collected were characterized in terms of their combustion and emissions behavior, and correlations between these characteristics and their SPI behavior were examined. Second, new SPI data was collected for a matrix of fuels that was constructed to test and confirm hypotheses that resulted from interpretation of the earlier data in the study and from data in open literature. Specifically, the extent to which the presence of heavy components in the fuel affected SPI propensity, and the extent to which flame initiation propensity affected SPI propensity, were examined. Finally, the interaction of fuels with lubricants expected to exhibit a range of SPI propensities was examined.
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

China Market Gasoline Review Using Fuel Particulate Emission Correlation Indices

2017-10-08
2017-01-2401
The impact of gasoline composition on vehicle particulate emissions response has been widely investigated and documented. Correlation equations between fuel composition and particulate emissions have also been documented, e.g. Particulate Matter Index (PMI) and Particulate Evaluation Index (PEI). Vehicle PM/PN emissions correlate very well with these indices. In a previous paper, global assessment with PEI on fuel sooting tendency was presented [1]. This paper will continue the previous theme by the authors, and cover China gasoline in more detail. With air pollution an increasing concern, along with more stringent emission requirements in China, both OEMs and oil industries are facing new challenges. Emissions controls require a systematic approach on both fuels and vehicles. Chinese production vehicle particulate emissions for a range of PEI fuels are also presented.
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

Global Market Gasoline Range Fuel Review using Fuel Particulate Emission Correlation Indices

2016-10-17
2016-01-2251
The Particulate Matter Index (PMI) is a helpful tool which provides an indication of a fuel’s sooting tendency. Currently, the index is being used by various laboratories and OEMs as a metric to understand the gasoline range fuels impact on both sooting found on engine hardware and vehicle out emissions. This paper will explore a new method that could be used to give indication of the sooting tendency of the gasoline range fuels, with good correlation agreement to PMI. In addition, the paper will cover a global assessment of a gasoline range fuel’s sooting tendency based on the PMI number and the proposed method. Areas around the globe where market gasoline range fuels are of concern will be highlighted, in coordination with the new emissions regulations. Vehicle PM/PN data will also be presented that shows correlations of the indices to the vehicle response.
Technical Paper

Alternative Fuel Property Correlations to the Honda Particulate Matter Index (PMI)

2016-10-17
2016-01-2250
The Honda Particulate Matter Index (PMI) is a very helpful tool which provides an indication of a fuel’s sooting tendency. Currently, the index is being used by various laboratories and vehicle OEMs as a metric to understand a fuels impact on automotive engine sooting, in preparation for new global emissions regulations. The calculation of the index involves generating detailed hydrocarbon analysis (hydrocarbon molecular speciation) using gas chromatography laboratory equipment and the PMI calculation requires the exact list of compounds and correct naming conventions to work properly. The analytical methodology can be cumbersome, when the gas chromatography methodology has to be adjusted for new compounds that are not in the method, or if the compounds are not matching the list for quantification. Also, the method itself is relatively expensive, and not easily transferrable between labs.
Technical Paper

Impact of Fuel Octane Rating and Aromatic Content on Stochastic Pre-Ignition

2016-04-05
2016-01-0721
The effects of aromatic content and octane rating of gasoline fuels on stochastic pre-ignition (SPI) behaviors were investigated at typical operating conditions using a modern 2.0 L turbocharged engine. In-cylinder pressure time history measurements made during a speed-load test sequence designed to stimulate SPI were used to determine both the frequency of SPI occurrence and the in-cylinder peak pressure during such events. Six fuels were tested with varying levels of aromatic content (15 - 35% by vol.) and two octane rating levels (∼88 & 94 anti-knock index). The engine was operated using a production-intent calibration with equivalence ratio near one. Pressure and temperature in the intake manifold were held constant near two bar and 35°C respectively. Significant SPI activity was observed, with abnormal event frequencies up to ∼1 SPI event per 1,000 engine cycles and in-cylinder peak pressures up to ∼200 bar.
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

Fuel Octane and Volatility Effects on the Stochastic Pre-Ignition Behavior of a 2.0L Gasoline Turbocharged DI Engine

2014-04-01
2014-01-1226
Classic, hot-spot induced pre-ignition is a phenomenon that has been observed in gasoline spark ignited engines over the past 60-70 years. With the development of turbocharged, direct-injected (DI) gasoline engines, a new pre-ignition phenomenon occurring at low engine speeds and high loads has been encountered. Termed Stochastic Pre-ignition (SPI), it has become a significant issue to address in allowing for the full potential of gasoline turbo DI technology to improve powertrain efficiency. Many researchers are studying all aspects of the causes of Stochastic Pre-ignition, including causes by oil, fuel and engine hardware systems. The focus of this specific research was to study the relationship of fuel octane and volatility to Stochastic Pre-ignition behavior utilizing a GM 2.0L Gasoline Turbocharged DI engine (LHU).
Journal Article

Effects of Gasoline and Ethanol Fuel Corrosion Inhibitors on Powertrain Intake Valve Deposits

2013-04-08
2013-01-0893
Corrosion inhibitors (CIs) have been used for years to protect the supply and distribution hardware used for transportation of fuel from refineries and to buffer the potential organic acids present in an ethanol blended fuel to enhance storage stability. The impact of these inhibitors on spark-ignition engine fuel systems, specifically intake valve deposits, is known and presented in open literature. However, the relationship of the corrosion inhibitors to the powertrain intake valve deposit performance is not understood. This paper has two purposes: to present and discuss a second market place survey of corrosion inhibitors and how they vary in concentration in the final blended fuel, specifically E85 (Ethanol Fuel Blends); and, to show how the variation in the concentrations of the components of the CIs impacts the operation and performance of vehicles, specifically, the effects on intake valve deposit formation.
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.
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.
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