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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.

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.

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.

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.

Knock-limited loads for a set of surrogate gasolines all having nominal 100 research octane number (RON), approximately 11 octane sensitivity (S), and a heat of vaporization (HOV) range of 390 to 595 kJ/kg at 25°C were investigated. A single-cylinder spark-ignition engine derived from a General Motors Ecotec direct injection (DI) engine was used to perform load sweeps at a fixed intake air temperature (IAT) of 50 °C, as well as knock-limited load measurements across a range of IATs up to 90 °C. Both DI and pre-vaporized fuel (supplied by a fuel injector mounted far upstream of the intake valves and heated intake runner walls) experiments were performed to separate the chemical and thermal effects of the fuels’ knock resistance. The DI load sweeps at 50°C intake air temperature showed no effect of HOV on the knock-limited performance. The data suggest that HOV acts as a thermal contributor to S under the conditions studied.

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.

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).

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.

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.