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Presented in this paper is an on-line method for estimating the oxygen storage capacity contained within a catalyst. The oxygen storage capacity of a catalyst changes over time due to catalyst brick temperatures, poisoned catalyst sites, and thermal aging. Information regarding the current oxygen storage capacity of a catalyst is advantageous in the development of robust emission control strategies and on-board diagnostics. The method of collecting the oxygen storage capacity information is extremely important for measurement accuracy and repeatability. Furthermore, the information must be obtained in such a way that it is transparent to the operator and may be implemented on-line during normal drive cycles. This on-line method for estimation of oxygen storage capacity of a catalyst has been demonstrated on a Ford F150 platform with an underbody catalyst.

Particulate and manganese mass emissions have been measured as a function of mileage for four Escort and four Explorer vehicles using 1) MMT (Methylcyclopentadienyl Manganese Tricarbonyl) added to the gasoline at 1/32 g Mn/gal and 2) gasoline without MMT. The MMT was used in half of the fleet starting at 5,000 miles. The vehicles were driven on public roads at an average speed of 54 mph to accumulate mileage. This report describes the particulate and manganese emissions, plus emissions of four air toxics at 5,000, 20,000, 55,000, 85,000 and 105,000 miles. Four non-regulated emissions were measured and their average values for vehicles without MMT were 0.6 mg/mi for formaldehyde, 0.7 mg/mi for 1,3-butadiene, 9 mg/mi for benzene and 12 mg/mi for toluene. Corresponding values for MMT-fueled vehicles were between 1.5 and 2.4 times higher.

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.

Lean-burn SIDI engine technology offers improved fuel economy; however, the reduction of NOx during lean-operation continues to be a major technical hurdle in the implementation of energy efficient technology. There are several aftertreatment technologies, including the lean NOx trap and active urea SCR, which have been widely considered, but they all suffer from high material cost and require customer intervention to fill the urea solution. Recently reported passive NH₃-SCR system - a simple, low-cost, and urea-free system - has the potential to enable the implementation of lean-burn gasoline engines. Key components in the passive NH₃-SCR aftertreatment system include a close-coupled TWC and underfloor SCR technology. NH₃ is formed on the TWC with short pulses of rich engine operation and the NH₃ is then stored on the underfloor SCR catalysts.

With a tighter regulatory environment, reduction of hydrocarbon (HC) and NOx emissions during cold-start has emerged as a major challenge for diesel engines. In the complex diesel aftertreatment system, more than 90% of engine-out NOx is removed in the underfloor SCR. However, the combination of low temperature exhaust and heat sink over DOC delays the SCR light-off during the cold start. In fact, the first 350 seconds during the cold light-duty FTP75 cycle contribute more than 50% of the total NOx tailpipe emission due to the low SCR temperature. For a fast SCR light-off, electrically heated catalyst (EHC) technology has been suggested to be an effective solution as a rapid warm-up strategy. In this work, the EHC, placed in front of DOC, utilizes both electrical power and hydrocarbon fuel. The smart energy management during the cold-start was crucial to optimize the EHC integrated aftertreatment system.

Diesel engines have the potential to significantly increase vehicle fuel economy and decrease CO₂ emissions; however, efficient removal of NOx and particulate matter from the engine exhaust is required to meet stringent emission standards. A conventional diesel aftertreatment system consists of a Diesel Oxidation Catalyst (DOC), a urea-based Selective Catalyst Reduction (SCR) catalyst and a diesel particulate filter (DPF), and is widely used to meet the most recent NOx (nitrogen oxides comprising NO and NO₂) and particulate matter (PM) emission standards for medium- and heavy-duty sport utility and truck vehicles. The increasingly stringent emission targets have recently pushed this system layout towards an increase in size of the components and consequently higher system cost. An emerging technology developed recently involves placing the SCR catalyst onto the conventional wall-flow filter.

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.

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.

Recent Federal and California legislation have mandated major improvements in emission control. Tailpipe HC emission must be decreased an order of magnitude for the California Ultra Low Emission Vehicle (ULEV) standard. Present feedback A/F* control systems employ a Heated Exhaust Gas Oxygen sensor (HEGO sensor) upstream of the catalyst to perform A/F feedback control. Limitations on the ultimate accuracy of these switching sensors are well known. To overcome these limitations a linear Universal Exhaust Gas Oxygen sensor (UEGO sensor) placed downstream from the minicatalyst is employed to attain improved A/F control and therefore, higher three-way catalyst (TWC) conversion efficiency. This configuration was granted a patent in 1992 (1**). This study compares performance differences between the two feedback control systems on a Ford Mustang. In initial studies both the UEGO and HEGO sensors were compared at the midposition location downstream of a minicatalyst.

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.

Bench reactor experiments were carried out to investigate the effects of operating temperature, precious metal loading, space velocity, and air-fuel (A/F) ratio on the performance of palladium (Pd) catalysts under simulated natural gas vehicle (NGV) exhaust conditions. The performance of these catalysts under simulated gasoline vehicle (GV) conditions was also investigated. In the case of simulated NGV exhaust, where methane was used as the prototypical hydrocarbon (HC) species, peak three-way conversion was obtained under richer conditions than required with simulated GV exhaust (propane and propene HC species). Moreover, the hydrocarbon efficiency of the catalyst under simulated NGV exhaust conditions was more sensitive to both A/F ratio and perturbations in A/F ratio than the HC efficiency under GV exhaust conditions.

Afterburning of a rich exhaust/air mixture ahead of the catalyst has been shown in earlier papers to offer an effective means of achieving catalyst light-off in very short times. Protection of the catalyst from overheating is an important aspect of systems using EGI, and on board diagnostics will be required to check for proper function of EGI. In this paper, some options for these requirements are discussed, using a high temperature linear thermistor.

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.

In joint partnership with its catalyst suppliers, Ford has made significant advances in the performance of Pd-only three way catalyst (TWC) technology through improvements in catalyst oxygen storage. The following manuscript describes in detail the performance advancement of Ford's Pd-only washcoat technology through the use of laboratory, engine dynamometer, and vehicle emission data.

Effectiveness of flow through catalytic diesel particulate aftertreatment devices in reducing particulate emissions is investigated on Ford's 1360 kg (3000 lb.) Sierra 1.8L Turbo-Diesel passenger car. Flow-through monolith type EAO reference catalyst and AC Rochester diesel catalyst are evaluated using Phillip's Control No. 2 diesel fuel, low sulfur (0.05% S) and ultra-low sulfur (0.001% S) diesel fuels. Comparisons are made with baseline exhaust emissions for FTP75 and Highway chassis dynamometer test procedures. Effects of catalyst aging of 320, 1610 and 6450 km (200, 1000 and 4000 miles) are examined. Results, based on 6450 km (4000 mile) limited durability, show that a ceramic monolith substrate of 400 cells per square inch (cpsi) with AC Rochester catalyst is capable of reducing particulate as well as HC and CO emissions to well below the 1994 Government mandated emission requirements with low (0.05% S) and ultra low (0.001% S) sulfur fuel.

This paper describes a study which was carried out to assess the potential for using a gasoline burner to heat the catalytic convertor during cold start. The results showed the catalyst/burner concept to be a promising LEV/ULEV capable technology. On a 1993 Ford Grand Marquis equipped with a catalyst burner system, catalyst light-off was achieved in less than 15 seconds while cold start HC emissions during the first 60 seconds of the FTP test were reduced by 60%. In addition, data are presented which compare the performance of the catalyst/burner to an electrically heated catalyst. In the tests performed, the catalyst/burner system out performed the EHC. Practical considerations, however, such as safety, durability, system integration, and packaging still need to be addressed.

A new laboratory test for measuring catalyst oxygen storage capacity has been developed. The test accurately predicts catalyst performance on the vehicle during transient A/F excursions and correlates well with vehicle CO and Nox tailpipe emissions. The test was subsequently used to facilitate improved oxygen storage capacity for new Pd-only washcoat formulations.

For several years, a single-cylinder, spark-ignited engine without catalyst has been operated at Ford on single-component fuels that are constituents of gasoline as well as on simple fuel mixtures. This paper presents a review of these experiments as well as others pertinent to understanding hydrocarbon emissions. The engine was run at four steady-state conditions which are typical of normal operation. The fuel structure and the engine operating conditions affected both the total HC emissions and the reactivity of these emissions for forming photochemical smog in the atmosphere. These experiments identified major precursor species of the toxic HC emissions benzene and 1,3-butadiene to be alkylated benzenes and either straight chain terminal olefins or cyclic alkanes, respectively. In new data presented, the primary exhaust hydrocarbon species from MTBE combustion is identified as isobutene.

This paper provides an overview of the dual EGO sensor method for OBD-II catalyst efficiency monitoring. The processes governing the relationship between catalyst oxygen storage, HC conversion efficiency, and rear EGO sensor response are reviewed in detail. A simple physical model relating catalyst oxygen storage capacity and rear EGO sensor response is constructed and used in conjunction with experimental data to provide additional insight into the operation of the catalyst monitor. The effect that the catalyst washcoat formulation has in determining the relationship between catalyst oxygen storage capacity and HC conversion efficiency and its impact on the catalyst monitor is also investigated. Lastly, the effects of catalyst failure mode, fuel sulfur, and the fuel additive MMT on the catalyst monitor's ability to properly diagnose catalyst function are discussed.

The regulated and non-regulated emissions of a current diesel passenger car and two light-duty diesel trucks with catalysts and particulate traps were measured to better understand the effects of aftertreatment devises on the environment. The passenger car, a 1.8 L IDI TC Sierra, was tested both with and without three different diesel oxidation catalysts (DOC) and with two fuel sulfur levels, 0 and 0.05 wt%. One light-duty truck, a 2.5 L DI NA Transit, was tested on one fuel, 0.05 wt% sulfur, with and without three different particulate trap/regeneration systems and with and without a urea lean NOx catalyst (LNC) system. A second similar Transit was tested on the 0.05 wt% sulfur fuel with an electrically regenerated trap system. The results are compared to each other, regulated emission standards, and to emissions from gasoline vehicles.