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Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.

Selective catalytic reduction (SCR) of nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.

Recent studies have shown that for a given RON, fuels with a higher sensitivity (RON-MON) tend to have better antiknock performance at most knock-limited conditions in modern engines. The underlying chemistry behind fuel sensitivity was therefore investigated to understand why this trend occurs. Chemical kinetic models were used to study fuels of varying sensitivities; in particular their autoignition delay times and chemical intermediates were compared. As is well known, non-sensitive fuels tend to be paraffins, while the higher sensitivity fuels tend to be olefins, aromatics, diolefins, napthenes, and alcohols. A more exact relationship between sensitivity and the fuel's chemical structure was not found to be apparent. High sensitivity fuels can have vastly different chemical structures. The results showed that the autoignition delay time (τ) behaved differently at different temperatures. At temperatures below 775 K and above 900 K, τ has a strong temperature dependence.

This paper reviews the relevant literature on the effects of sulfated ash, phosphorus, and sulfur on DPF, LNT, and SCR catalysts. Exhaust backpressure increase due to DPF ash accumulation, as well as the rate at which ash is consumed from the sump, were the most studied lubricant-derived DPF effects. Based on several studies, a doubling of backpressure can be estimated to occur within 270,000 to 490,000 km when using a 1.0% sulfated ash oil. Postmortem DPF analysis and exhaust gas measurements revealed that approximately 35% to 65% less ash was lost from the sump than was expected based on bulk oil consumption estimates. Despite significant effects from lubricant sulfur and phosphorus, loss of LNT NOX reduction efficiency is dominated by fuel sulfur effects. Phosphorus has been determined to have a mild poisoning effect on SCR catalysts. The extent of the effect that lubricant phosphorus and sulfur have on DOCs remains unclear, however, it appears to be minor.

The life of an automotive engine is often limited by the ability of its components to resist wear. Zinc dialkyldithiophosphate (ZDDP) is an engine oil additive that reduces wear in an engine by forming solid antiwear films at points of moving contact. The effects of this additive are fairly well understood, but there is little theory behind the kinetics of antiwear film formation and removal. This lack of dynamic modeling makes it difficult to predict the effects of wear at the design stage for an engine component or a lubricant formulation. The purpose of this discussion is to develop a framework for modeling the formation and evolution of ZDDP antiwear films based on the relevant chemical pathways and physical mechanisms at work.

Battery packs for Hybrids, Plug-in Hybrids, and Electric Vehicles are assembled from a system of modules (sheets) with a tight sheet metal casing around them. Each module consists of an array of individual cells which vary in the composition of electrodes and separator from one manufacturer to another. In this paper a general procedure is outlined on the development of a constitutive and computational model of a cylindrical cell. Particular emphasis is placed on correct prediction of initiation and propagation of a tearing fracture of the steel can. The computational model correctly predicts rupture of the steel can which could release aggressive chemicals, fumes, or spread the ignited fire to the neighboring cells. The initiation site of skin fracture depends on many factors such as the ductility of the casing material, constitutive behavior of the system of electrodes, and type of loading.

Diesel exhaust fluid, DEF, (32.5 wt.% urea aqueous solution) is widely used as the NH3 source for selective catalytic reduction (SCR) of NOx in diesel aftertreatment systems. The transformation of sprayed liquid phase DEF droplets to gas phase NH3 is a complex physical and chemical process. Briefly, it experiences water vaporization, urea thermolysis/decomposition and hydrolysis. Depending on the DEF doser, decomposition reaction tube (DRT) design and operating conditions, incomplete decomposition of injected urea could lead to solid urea deposit formation in the diesel aftertreatment system. The formed deposits could lead to engine back pressure increase and DeNOx performance deterioration etc. The formed urea deposits could be further transformed to chemically more stable substances upon exposure to hot exhaust gas, therefore it is critical to understand this transformation process.

The chemistry of unburned hydrocarbon oxidation in SI engine exhaust was modeled as a function of temperature and concentration of unburned gas for lean and rich mixtures. Detailed chemical kinetic mechanisms were used to model isothermal reactions of unburned fuel/air mixture in an environment of burned gases at atmospheric pressure. Simulations were performed using five pure fuels (methane, ethane, propane, n-butane and toluene) for which chemical kinetic mechanisms and steady state hydrocarbon (HC) emissions data were available. A correlation is seen between reaction rates and HC emissions for different fuels. Calculated relative amounts of intermediate oxidation products are shown to be consistent with experimental measurements.

The oxidation chemistry of paraffins, aromatics, olefins and MTBE were examined. Detailed chemical kinetics calculations were carried out for oxidation of these compounds in the engine cycle. The oxidation rates are very sensitive to temperature. At temperatures of over 1400 K (depending on the fuel), all the hydrocarbons are essentially oxidized for typical residence time in the engine. Based on the kinetics calculations, a threshold temperature is defined for the conversion of the fuel species to CO, CO2, H2O and partially oxidized products. The difference in the survival fraction between aromatics and non-aromatics is attributed to the higher threshold temperature of the aromatics.

THE autoignition characteristics of several fuels under various conditions of mixture strength, compression ratio, and temperature have been studied by means of a rapid-compression machine. The behaviors of a knock inhibitor, tetraethyl lead, and a knock inducer, ethyl nitrite, have also been studied. Simultaneous records of pressure, volume, and the inflammation have been obtained. These records show the diverse aspects of the autoignition phenomenon and indicate, among other things, according to the authors, that a comparison of the detonating tendencies of fuels must include not only a consideration of the length of the delay period but also an evaluation of the rate of pressure rise during autoignition. Physical interpretations of the data are presented but chemical interpretations have been avoided. The work was exploratory in nature. The authors hope that the results will stimulate activity in this important branch of combustion research.

The Cu-zeolite (CuZ) SCR catalyst enables higher NOx conversion efficiency in part because it can store a significant amount of NH3. “NH3 storage control”, where diesel exhaust fluid (DEF) is dosed in accord with a target NH3 loading, is widely used with CuZ catalysts to achieve very high efficiency. The NH3 loading actually achieved on the catalyst is currently estimated through a stoichiometric calculation. With future high-capacity CuZ catalyst designs, it is likely that the accuracy of this NH3 loading estimate will become limiting for NOx conversion efficiency. Therefore, a direct measurement of NH3 loading is needed; RF sensing enables this. Relative to RF sensing of soot in a DPF (which is in commercial production), RF sensing of NH3 adsorbed on CuZ is more challenging. Therefore, more attention must be paid to the “microwave resonance cavity” created within the SCR assembly. The objective of this study was to develop design guidelines to enable and enhance RF sensing.

Catalytic and non-catalytic engine aftertreatment components, such as the diesel oxidation catalyst (DOC), selective catalytic reduction on filter (SCRF), the gasoline particulate filter (GPF) and the diesel particulate filter (DPF) are complex, multifunctional emissions control technologies that are robustly designed for extended use in harsh automotive exhaust environments. Over the useful component lifetime, lubricant-derived inorganic and incombustible ash accumulates in and/or on the surface of the aforementioned aftertreatment components, resulting in degraded performance and other potential problems. In order to better understand effects of ash in such components, a multiscale analytical approach is necessary, requiring a variety of experimental tools.