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Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.

Advanced combustion strategies used to improve efficiency, emissions, and performance in internal combustion engines (IC) alter the chemical composition of engine-out emissions. The characterization of exhaust chemistry from advanced IC engines requires an analytical system capable of measuring a wide range of compounds. For many years, the widely accepted Coordinating Research Council (CRC) Auto/Oil procedure[1,2] has been used to quantify hydrocarbon compounds between C1 and C12 from dilute engine exhaust in Tedlar polyvinyl fluoride (PVF) bags. Hydrocarbons greater than C12+ present the greatest challenge for identification in diesel exhaust. Above C12, PVF bags risk losing the higher molecular weight compounds due to adsorption to the walls of the bag or by condensation of the heavier compounds. This paper describes two specialized exhaust gas sampling and analytical systems capable of analyzing the mid-range (C10 - C24) and the high range (C24+) hydrocarbon in exhaust.

Octane appetite of modern engines has changed as engine designs have evolved to meet performance, emissions, fuel economy and other demands. The octane appetite of seven modern vehicles was studied in accordance with the octane index equation OI=RON-KS, where K is an operating condition specific constant and S is the fuel sensitivity (RONMON). Engines with a displacement of 2.0L and below and different combinations of boosting, fuel injection, and compression ratios were tested using a decorrelated RONMON matrix of eight fuels. Power and acceleration performance were used to determine the K values for corresponding operating points. Previous studies have shown that vehicles manufactured up to 20 years ago mostly exhibited negative K values and the fuels with higher RON and higher sensitivity tended to perform better.

Over the last two decades, global emission regulations have become more stringent and have required the use of more advanced fuel injection systems. This includes the use of tighter tolerances, more rapid injections and internal components actuated by weaker injection forces. Unfortunately, these design features make the entire system more susceptible to fuel contaminants. Over the last six years, the composition of these contaminants has evolved from hard insoluble debris, such as dust and rocks, to soluble chemical contaminants. Recent research by the diesel engine manufacturers, fuel injection equipment suppliers and the fuel and fuel additive industry has discovered a major source of the soluble chemical contaminant that leads to injector deposits to be derived from cost effective and commonly used additives used to protect against pipeline corrosion.

In this study we investigated the interaction of short- and long-chain hydrocarbons (HCs), represented by propene (C₃H₆) and n-dodecane (n-C₁₂H₂₆), respectively, with a state-of-the-art small-pore Cu-Zeolite SCR catalyst. By varying HC adsorption conditions, we determined that physisorption was the primary mechanism for some minor HC storage at low temperatures (≺ 200°C), while chemical transformation was involved in more substantial HC storage at higher temperatures (200-400°C). The latter was evidenced by the oxygen-dependent and thermally activated nature of the storage process, and further confirmed by the carbon-rich composition of the deposits. The nature of HC-derived deposits of different origins and amounts was further probed using the standard SCR reaction at kinetically challenging conditions (at 200°C), as well by ammonia adsorption/desorption experiments.

The dual-fuel combustion process of ethanol and n-heptane was characterized experimentally in an optically accessible engine and numerically through a chemical kinetic 3D-CFD investigation. Previously reported formaldehyde PLIF distributions were used as a tracer of low-temperature oxidation of straight-chained hydrocarbons and the numerical results were observed to be in agreement with the experimental data. The numerical and experimental evidence suggests that a change in the speed of flame propagation is responsible for the observed behavior of the dual-fuel combustion, where the energy release duration is increased and the maximum rate of pressure rise is decreased. Further, an explanation is provided for the asymmetrical energy release profile reported in literature which has been previously attributed to an increase in the diffusion-controlled combustion phase.

Accurate estimation of catalyst bed temperatures is very crucial for effective control and diagnostics of aftertreatment systems. The architecture of most aftertreatment systems contains temperature sensors for measuring the exhaust gas temperatures at the inlet and outlet of the aftertreatment systems. However, the temperature that correctly reflects the temperature of the chemical reactions taking place on the catalyst surface is the catalyst bed temperature. From the Arrhenius relationship which governs the chemical reaction kinetics occurring in different aftertreatment systems, the rate of chemical reaction is very sensitive to the reaction temperature. Considerable changes in tailpipe emissions can result from small changes in the reaction temperature and robust emissions control systems should be able to compensate for these changes in reaction temperature to achieve the desired tailpipe emissions.

A technique was developed for measuring the Laminar Burning Velocity (LBV) of multi-component fuel blends for use in high-performance spark-ignition engines. This technique involves the use of a centrally-ignited spherical combustion chamber, and a complementary analysis code. The technique was validated by examining several single-component fuels, and the computational procedure was extended to handle multi-component fuels without requiring detailed knowledge of their chemical composition. Experiments performed on an instrumented high-speed engine showed good agreement between the observed heat-release rates of the fuels and their predicted ranking based on the measured LBV parameters.

The overall program objectives were three fold: assess the benefits and limitations of oxygenated diesel fuels on engine performance and emissions identify oxygenates most suitable for potential use in future diesel formulations based on physico-chemical properties (e.g. flash point), toxicity, biodegradability and estimated cost of production perform limited emissions and performance testing of the oxygenated diesel blends select at least two oxygenated compounds for advanced engine testing In Part 1 of this program which is described in this paper, an extensive literature review was conducted to identify potential oxygenates for blending into diesel fuels. As many as 71 oxygenates were identified for the initial screening process. Based on a set of physical and chemical properties, a screening methodology was developed to select the 8 oxygenates that will be eligible for engine testing.

Lower explosion limits (LEL) and the chemical compositions of JP-8, Jet A and JP-5 fuel vapors were determined in a sealed combustion vessel equipped with a spark igniter, a gas-sampling probe, and sensors to measure pressure rise and fuel temperature. Ignition was detected by pressure rise in the vessel. Pressure rises up to 60 psig were observed near the flash points of the test fuels. The fuel vapors in the vessel ignited from as much as 11°F below flash-point measurements. Detailed hydrocarbon speciation of the fuel vapors was performed using high-resolution gas chromatography. Over 300 hydrocarbons were detected in the vapors phase. The average molecular weight, hydrogen to carbon ratio, and LEL of the fuel vapors were determined from the concentration measurements. The jet fuel vapors had molecular weights ranging from 114 to 132, hydrogen to carbon ratios of approximately 1.93, and LELs comparable to pure hydrocarbons of similar molecular weight.