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An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

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.

In February 2004 NASA released “The Vision for Space Exploration.” The important goals outlined in this document include extending human presence in the solar system culminating in the exploration of Mars. Unprocessed waste poses a biological hazard to crew health and morale. The waste processing methods currently under consideration include incineration, microbial oxidation, pyrolysis and compaction. Although each has advantages, no single method has yet been developed that is safe, recovers valuable resources including oxygen and water, and has low energy and space requirements. Thus, the objective of this project is to develop a low temperature oxidation process to convert waste cleanly and rapidly to carbon dioxide and water. In the Phase I project, TDA Research, Inc. demonstrated the potential of a low temperature oxidation process using ozone. In the current Phase II project, TDA and NASA Ames Research Center are developing a pilot scale low temperature ozone oxidation system.

Direct osmotic concentration (DOC) is an integrated membrane treatment process designed for the reclamation of spacecraft wastewater. The system includes forward osmosis (FO), membrane evaporation, reverse osmosis (RO) and an aqueous phase catalytic oxidation (APCO) post-treatment unit. This document describes progress in the third year of a four year project to advance hardware maturity of this technology to a level appropriate for human rated testing. The current status of construction and testing of the final deliverable is covered and preliminary calculations of equivalent system mass are funished.

Designers of future space vehicles envision simplifying the Atmosphere Revitalization (AR) system by combining the functions of trace contaminant (TC) control and carbon dioxide removal into one swing-bed system. Flow rates and bed sizes of the TC and CO2 systems have historically been very different. There is uncertainty about the ability of trace contaminant sorbents to adsorb adequately in a high-flow or short bed length configurations, and to desorb adequately during short vacuum exposures. This paper describes preliminary results of a comparative experimental investigation into adsorbents for trace contaminant control. Ammonia sorbents and low temperature catalysts for CO oxidation are the foci. The data will be useful to designers of AR systems for Constellation. Plans for extended and repeated vacuum exposure of ammonia sorbents are also presented.

In February 2004 NASA released “The Vision for Space Exploration.” The goals outlined in this document include extending the human presence in the solar system, culminating in the exploration of Mars. A key requirement for this effort is to identify a safe and effective method to process waste. Methods currently under consideration include incineration, microbial oxidation, pyrolysis, drying, and compaction. Although each has advantages, no single method has yet been developed that is safe, recovers valuable resources including oxygen and water, and has low energy and space requirements. Thus, the objective of this work was to develop a low temperature oxidation process to convert waste cleanly and rapidly to carbon dioxide and water. TDA and NASA Ames Research Center have developed a pilot scale low temperature ozone oxidation system to convert organic waste to CO2 and H2O.

Of the many competing technologies for resource recovery from solid wastes for long duration manned missions such as a lunar or Mars base, incineration technology is one of the most promising and certainly the most well developed in a terrestrial sense. Various factors are involved in the design of an optimum fluidized bed incinerator for inedible biomass. The factors include variability of moisture in the biomass, the ash content, and the amount of fuel nitrogen in the biomass. The crop mixture in the waste will vary; consequently the nature of the waste, the nitrogen content, and the biomass heating values will vary as well. Variation in feed will result in variation in the amount of contaminants such as nitrogen oxides that are produced in the combustion part of the incinerator. The incinerator must be robust enough to handle this variability. Research at NASA Ames Research Center using the fluidized bed incinerator has yielded valuable data on system parameters and variables.

Long-haul and other heavy-duty trucks, presently almost entirely powered by diesel fuel, face challenges meeting worldwide needs for greatly reducing nitrogen oxide (NOx) emissions. Dual-fuel gasoline-alcohol engines could potentially provide a means to cost-effectively meet this need at large scale in the relatively near term. They could also provide reductions in greenhouse gas emissions. These spark ignition (SI) flexible fuel engines can provide operation over a wide fuel range from mainly gasoline use to 100% alcohol use. The alcohol can be ethanol or methanol. Use of stoichiometric operation and a three-way catalytic converter can reduce NOx by around 90% relative to emissions from diesel engines with state of the art exhaust treatment.

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 effect of engine operating parameters (speed, spark timing, and fuel-air equivalence ratio [Φ]) on hydrocarbon (HC) oxidation within the cylinder and exhaust system is examined using propane or isooctane fuel. Quench gas (CO2) is introduced at two locations in the exhaust system (exhaust valve or port exit) to stop the oxidation process. Increasing the speed from 1500 to 2500 RPM at MBT spark timing decreases the total, cylinder-exit HC emissions by ∼50% while oxidation in the exhaust system remains at 40% for both fuels. For propane fuel at 1500 rpm, increasing Φ from 0.9 (fuel lean) to 1.1 (fuel rich) reduces oxidation in the exhaust system from 42% to 26%; at 2500 RPM, exhaust system oxidation decreases from 40% to approximately 0% for Φ = 0.9 and 1.1, respectively. Retarded spark increases oxidation in the cylinder and exhaust system for both fuels. Decreases in total HC emissions are accompanied by increased olefinic content and atmospheric reactivity.

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke.

Pyrolysis is a very versatile waste processing technology which can be tailored to produce a variety of solid liquid and/or gaseous products. The main disadvantages of pyrolysis processing are: (1) the product stream is more complex than for many of the alternative treatments; (2) the product gases cannot be vented directly into the cabin without further treatment because of the high CO concentrations. One possible solution is to combine a pyrolysis step with catalytic oxidation (combustion) of the effluent gases. This integration takes advantage of the best features of each process, which is insensitivity to product mix, no O2 consumption, and batch processing, in the case of pyrolysis, and simplicity of the product effluent stream in the case of oxidation. In addition, this hybrid process has the potential to result in a significant reduction in Equivalent System Mass (ESM) and system complexity.

Pyrolysis is a very versatile waste processing technology which can be tailored to produce a variety of solid, liquid, and/or gaseous products. The main disadvantages of pyrolysis processing are: (1) the product stream is more complex than for many of the alternative treatments; (2) the product gases cannot be vented directly into the cabin without further treatment because of the high CO concentrations. One possible solution is to combine a pyrolysis step with catalytic oxidation (combustion) of the effluent gases. This integration takes advantage of the best features of each process. The advantages of pyrolysis are: insensitivity to feedstock composition, no oxygen consumption, and batch operation. The main advantage of oxidation is the simplicity and consistency of the product stream. In addition, this hybrid process has the potential to result in a significant reduction in Equivalent System Mass (estimated at 10-40%) and system complexity.

The development of a cycle simulation model for the jet ignition prechamber stratified charge engine is described. Given the engine geometry, load, speed, air-fuel ratios and pressures and temperatures in the two intakes, flow ratio and a suitable combustion model, the cycle simulation predicts engine indicated efficiency and NO emissions. The relative importance of the parameters required to define the combustion model are then determined, and values for ignition delay and burn angle are obtained by matching predicted and measured pressure-time curves. The variation in combustion parameters with engine operating variables is then examined. Predicted and measured NO emissions are compared, and found to be in reasonable agreement over a wide range of engine operation. The relative contribution of the prechamber NO to total exhaust NO is then examined, and in the absence of EGR, found to be the major source of NO for overall air-fuel ratios leaner than 22:1.

The use of hydrogen as a fuel supplement for lean-burn engines at higher compression ratios has been studied extensively in recent years, with good promise of performance and efficiency gains. With the advances in reformer technology, the use of a gaseous fuel stock, comprising of substantially higher fractions of hydrogen and other flammable reformate species, could provide additional improvements. This paper presents the performance and emission characteristics of a gas mixture of equal volumes of hydrogen, CO, and methane. It has recently been reported that this gas mixture can be produced by reforming of ethanol at comparatively low temperature, around 300C. Experiments were performed on a 1.8-liter passenger-car Nissan engine modified for single-cylinder operation. Special pistons were made so that compression ratios ranging from CR= 9.5 to 17 could be used. The lean limit was extended beyond twice stoichiometric (up to lambda=2.2).

A one-dimensional model has been developed for the species and energy transfer over a thin (0.1-0.5 mm) layer of liquid fuel present on the wall of a spark-ignition engine. Time-varying boundary conditions during compression and flame passage were used to determine the rate of methanol vaporization and oxidation over a mid-speed, mid-load cycle, as a function of wall temperature. The heat of vaporization and the boiling point of the fuel were varied about a baseline to determine the effect of these characteristics, at a fixed operating point and lean conditions (ϕ = 0.9). The calculations show that the evaporation of fuels from layers on cold walls starts during flame passage, peaking a few milliseconds later, and continuing through the exhaust phase.

A one-dimensional model for crevice HC post-flame oxidation is used to calculate and understand the effect of operating parameters and fuel type (propane and isooctane) on the extent of crevice hydrocarbon and the product distribution in the post flame environment. The calculations show that the main parameters controlling oxidation are: bulk burned gas temperatures, wall temperatures, turbulent diffusivity, and fuel oxidation rates. Calculated extents of oxidation agree well with experimental values, and the sensitivities to operating conditions (wall temperatures, equivalence ratio, fuel type) are reasonably well captured. Whereas the bulk gas temperatures largely determine the extent of oxidation, the hydrocarbon product distribution is not very much affected by the burned gas temperatures, but mostly by diffusion rates. Uncertainties in both turbulent diffusion rates as well as in mechanisms are an important factor limiting the predictive capabilities of the model.

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.