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A novel non-phosphorus antiwear additive, NP-1, was evaluated as a partial substitute for zinc dialkyldithiophosphate (ZDTP). ZDTP, an antiwear/antioxidant engine oil additive may under certain conditions cause three way catalyst (TWC) deactivation due to formation of an amorphous zinc pyrophosphate, Zn2P2O7, glaze. Antiwear and antioxidant properties of NP-1 alone and in combination with ZDTP were compared with ZDTP only containing formulations. The effects of NP-1 on TWC activity during pulsator modulation and steady-state conditions showed that the TWC maintained good overall activity during 24,000 simulated miles.

The objective of this study is to investigate the removal of methane (CH4), nitric oxide (NO), and carbon monoxide (CO) from simulated natural gas vehicle (NGV) exhaust over a palladium catalyst. The effects of changes in space velocity and natural gas sulfur (S) content were studied. The study suggests that the NGV has to be operated slightly rich of stoichiometry to achieve simultaneous removal of the three constituents. The CH4 conversion decreases with an increase in the space velocity. The CO and NO conversions remain unaffected over the space velocity range (10,000 hr-1 to 100,000 hr-1) investigated. The presence of sulfur dioxide in the exhaust lowers the CH4 conversion and increases the CO conversion in the rich region. The NO conversion remains unaffected. Studies were conducted over model catalysts to investigate the modes of CH4 removal from the simulated NGV exhaust.

A new estimator for IC engine A/F ratio is described. A/F ratio is important for engine operation since it determines the quantities of engine emissions, such as HC, CO, NOx, the conversion efficiency of catalyst systems, and the engine combustion stability. The A/F ratio estimator described in this paper is based on a fundamental metric that relies on inducing and detecting crankshaft speed fluctuations caused by modulating the engine's fuel injection pulse widths. Fuel pulse width modulation varies the instantaneous combustion A/F ratio crankshaft velocity. Synchronous measurement of crankshaft velocity provides a metric that, when used with other engine state variables as inputs to a conventional neural network, can accurately estimate A/F ratio. The estimator provides A/F information when a physical sensor is not available.

Aftertreatment system design involves multiple tradeoffs between engine performance, fuel economy, regulatory emission levels, packaging, and cost. Selection of the best design solution (or “architecture”) is often based on an assumption that inherent catalyst activity is unaffected by location within the system. However, this study acknowledges that catalyst activity can be significantly impacted by location in the system as a result of varying thermal exposure, and this in turn can impact the selection of an optimum system architecture. Vehicle experiments with catalysts aged over a range of mild to moderate to severe thermal conditions that accurately reflect select locations on a vehicle were conducted on a chassis dynamometer. The vehicle test data indicated CO and NOx could be minimized with a catalyst placed in an intermediate location.

Speciated HC emissions from the exhaust system of a production engine without an active catalyst have been obtained with 3 sec time resolution during a 70°F cold start using two control strategies. For the conventional cold start, the emissions were initially enriched in light fuel alkanes and depleted in heavy aromatic species. The light alkanes fell rapidly while the lower vapor pressure aromatics increased over a period of 50 sec. These results indicate early retention of low vapor pressure fuel components in the intake manifold and exhaust system. Loss of higher molecular weight HC species does occur in the exhaust system as shown by experiments in which the exhaust system was preheated to 100° C. The atmospheric reactivity of the exhaust HC emissions for photochemical smog formation increases as the engine warms.

A simplified method was developed to obtain three-way catalyst performance data to be used for predicting vehicle CVS-H emissions. This method involves engine dynamometer aging of catalysts and characterization of their performance as a function of four variables, namely, redox potential, temperature, space velocity and a modulation parameter. In the process of reducing the number of variables, several simplifications were made. The simplifications, their limitations and the characteristic trends in the performance of a 11 Pt/Rh catalyst are discussed.

Measurements of oxygen storage capacity (OSC) and HC conversion efficiency for 17 catalysts were carried out in the laboratory. All catalysts with steady state HC efficiency below 90% were found to have roughly equivalent and very low capacities to store oxygen. However, catalyst oxygen storage capacity was seen to rise sharply with HC conversion efficiency in excess of 90 percent. These results parallel the trends which are observed between rear HEGO/EGO indexes for OBD-II catalyst monitoring and HC conversion efficiency. In addition, temperature programed reduction (TPR) was found to lend insight into the relationship between catalyst OSC and HC conversion efficiency by providing a qualitative understanding of the mechanisms by which OSC deteriorates. TPR profiles showed that most of the usable oxygen storage is derived from surface ceria which is interacted with precious metals.

The pulse flame combustor was adapted by researchers at Ford Motor Company in the early 1970s in order to produce exhaust gas simulating the combustion products of the internal combustion engine for the evaluation of automotive catalysts. Over the years, the pulse flame combustor has found application in a wide variety of research oriented tasks associated with automotive catalysts and emissions. More recent research and development efforts which have resulted due to elevated demands toward lower vehicle emission levels have prompted continuing refinements of the apparatus and effected innovative approaches to the study of emerging automotive catalyst and emission control issues with the pulse flame combustor. This report provides an overview of the operation and design evolution of the pulse flame combustor. In addition, recent applications of this laboratory device for studying automotive catalysts, alternative fuels, and other automotive emission control topics are reviewed.

The microcomputer based ignition timing, EGR and fuel injection control system for the IIEC-2 concept vehicle is described. The techniques used to compensate the fuel delivery for EGR, to minimize response time and to compensate for engine and injector non-uniformity are emphasized. These measures, in conjunction with limit cycle air/fuel ratio control utilizing feedback from an exhaust gas oxygen sensor, are examined with respect to the effect on three-way catalyst performance.

A laboratory study was performed to assess the effects of sulfur poisoning and desulfation temperature on the NO conversion of a LNT+(Cu/SCR) in-situ system. Four LNT+(Cu/SCR) systems were aged for 4.5 hours without sulfur at 600, 700, 750, and 800°C using A/F ratio modulations to represent 23K miles of desulfations at different temperatures. NO conversion tests were performed on the LNT alone and on the LNT+SCR system using a 60 s lean/5 s rich cycle. The catalysts were then sulfur-poisoned at 400°C and desulfated four times and re-evaluated on the 60/5 tests. This test sequence was repeated 3 more times to represent 100K miles of desulfations. After simulating 23K miles of desulfations, the Cu-based SCR catalysts improved the NO conversion of the LNT at low temperatures (e.g., 300°C), although the benefit decreased as the desulfation temperature increased from 600°C to 800°C.

Sound attenuation and flow loss reduction are often two competing demands in vehicle breathing systems. The present study considers a full vehicle exhaust system and investigates both the sound attenuation and the flow performance of production configurations including the catalyst, the resonator, and the muffler. Dynamometer experiments have been conducted with a firing Ford 3.0L, V-6 engine at wide-open throttle with speeds ranging from 1000 to 5000 rpm. Measurements including the flow rates, the temperatures and the absolute dynamic pressures of the hot exhaust gases at key locations (upstream and downstream of every component) with fast-response, water-cooled piezo-resistive pressure transducers facilitate the calculation of acoustic performance of each component, as well as the determination of flow losses caused by these elements and their influence on the engine performance.

The effect of MMT on the OBD-II catalyst efficiency monitor has been investigated. The results conclusively show that manganese which is deposited onto the catalyst during the combustion of MMT- containing fuel provides for an increased level of catalyst oxygen storage capacity. This added oxygen storage was found to result in a reduced rear EGO sensor response and caused malfunctioning catalysts to be incorrectly diagnosed by the OBD-II catalyst efficiency monitor.

The effect of fuel sulfur on the dual HEGO sensor OBD-II catalyst monitor has been investigated. Laboratory studies revealed two competing effects of the fuel sulfur on the operation of the catalyst monitor: 1. the loss of catalyst oxygen storage capacity, and 2. the degradation in the response rate of the rear HEGO sensor. The magnitude of the loss in catalyst OSC relative to the increase in rear HEGO sensor response time determined whether the rear HEGO sensor index increased, decreased, or remained constant as the fuel sulfur level was increased. The effect of fuel sulfur on tailpipe emissions and the catalyst monitor was also measured for two LEVs equipped with Pd-only catalyst technology (a 1997MY Escort and a 1998MY Crown Victoria). For both vehicles, the effect of the fuel sulfur on the rear HEGO sensor response characteristics dominated; as the fuel sulfur level was increased, tailpipe emissions increased, but the rear HEGO sensor index decreased.

Automotive three-way catalysts (TWC) were characterized using temperature-programmed reduction (TPR), x-ray diffraction (XRD), Raman spectroscopy, chemisorption measurements and laboratory activity measurements. Capabilities and limitations of these standard analytical techniques for the characterization of production-type automotive catalysts are pointed out. With the exception of chemisorption techniques, all appear to have general utility for analyzing exhaust catalysts. The techniques were used to show that the noble metals and ceria in fresh Pt/Rh and Pd/Rh catalysts are initially highly dispersed and contain a mixture of interacting and non-interacting species. Thermal aging of these catalysts (in the reactor or vehicle) caused both precious metal and ceria particles to sinter, thereby decreasing the interaction between the two.

With the use of a simulated exhaust system, the sulfuric acid and sulfur dioxide emission from a monolith noble-metal oxidation catalyst (Engelhard IIB) is measured. It was found that the storage rate of sulfur onto an initially sulfur-free catalyst decreases to a few percent of the sulfur rejection rate within 3-4 h. The amount of sulfur on the catalyst when the catalyst is in equilibrium with 20 ppm sulfur in the gas phase varies between 0.3 weight percent of the catalyst at about 400°C to 0.1 weight percent at 600°C. The sulfur can readily desorb from the catalyst if the gas phase sulfur content is lowered or if the catalyst temperature is increased. It was found that the conversion of sulfur dioxide to sulfuric acid reaches thermodynamic equilibrium at temperatures of 400-500°C and space velocities of 30,000 h-1. These conditions correspond approximately to a small V8 engine at 20 mph cruise.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

Current demands for high fuel efficiency and low emissions in automotive powerplants have drawn attention to the two-stroke engine configuration. The present study measured trapping and scavenging efficiencies of a firing two-stroke spark-ignition engine by in-cylinder gas composition analysis. Intermediate results of the procedure included the trapped air-fuel ratio and residual exhaust gas fraction. Samples, acquired with a fast-acting electromagnetic valve installed in the cylinder head, were taken of the unburned mixture without fuel injection and of the burned gases prior to exhaust port opening, at engine speeds of 1000 to 3000 rpm and at 10 to 100% of full load. A semi-empirical, zero-dimensional scavenging model was developed based on modification of the non-isothermal, perfect-mixing model. Comparison to the experimental data shows good agreement.

Robust on-board diagnosis of emission catalyst performance requires the development of artificially damaged "threshold" catalysts that accurately mimic the performance of damaged catalysts in customer use. The threshold catalysts are used by emissions calibrators to determine fore-aft exhaust oxygen sensor responses that indicate catalyst failure. Rather than rely on traditional trial-and-error processes to generate threshold catalysts, we have used a DFSS (Design For Six-Sigma) approach that explores, at a research level, the relationship between oxygen storage capacity (OSC) of the catalyst (i.e., the fundamental property dictating the response of the aft oxygen sensor) and key process input variables: high-temperature exposure, phosphorus poisoning, and catalyst "recovery."

A simulated diesel exhaust is treated with a nonthermal plasma discharge under steady state conditions. The plasma effluent is then passed through a sodium zeolite-Y (NaY) catalyst followed by a platinum oxidation catalyst. Detailed FTIR measurements of gas composition are taken before, between, and after the treatment stages. The plasma discharge causes oxidation of NO primarily to NO2, with methyl nitrate and nitric acid byproducts. At the same time, HC is partially oxidized, creating species such as formaldehyde, acetaldehyde, CO and other partial oxidation products. When this mixture passes over the NaY catalyst, part of the NOx is reduced to N2, with the remainder primarily in the form of NO. Methyl nitrate decomposes to form methanol and NOx, and nitric acid is consumed. There is little HC conversion on this catalyst. Small quantities of HCN and N2O are formed. When the mixture then passes over the platinum catalyst, further NOx conversion occurs.

A model of Ford's current FTP based OBD-II catalyst monitor has been developed and used in determining the optimal monitored catalyst volume for several LEV applications. The model predictions were found to agree reasonably well with the available experimental data. Furthermore, the results of this study indicate that the optimal monitored catalyst volume for meeting LEV requirements is vehicle application specific. As a result, it is concluded that a general guideline for sizing of the monitored catalyst volume for LEVs will most likely be inadequate and could result in grossly suboptimal catalyst monitor function for some applications. The model which is described in this paper offers a potentially more effective means of determining the best monitored catalyst volume for a given vehicle application. It should be possible to utilize this model during the early phase of a vehicle program in order to provide for the optimal packaging of the catalyst monitor sensor (CMS).