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Significant A/F ratio excursion may occur during some engine transient operations, especially for transient periods of throttle tip in or tip out. A/F ratio excursion results in excessive emissions, extra fuel consumption, driveability deterioration and three-way-catalyst (TWC) efficiency drop. Simple two-parameter (X, τ) wall wetting models have traditionally been used to describe this transient A/F ratio excursion phenomenon. The transient fuel control techniques are utilized for this model to be applicable across vehicles, engines, fuel types and ambient conditions, so as to compensate for the A/F ratio excursion with the extra compensation fuel. More complicated model structures must be further expanded and model dependence on various environment conditions must be established to achieve a precise model. In this paper, a simple linear approach is proposed for transient fuel control, using least squares estimation.

An experimental and modeling study was conducted to study the passive regeneration of a catalyzed particulate filter (CPF) by the oxidation of particulate matter (PM) via thermal and Nitrogen dioxide/temperature-assisted means. Emissions data in the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR and a diesel oxidation catalyst (DOC) - catalyzed particulate filter (CPF) in the exhaust system was measured and used for this study. A series of experiments was conducted to evaluate the performance of the DOC, CPF and DOC+CPF configurations at various engine speeds and loads.

Model-based control strategies are important for meeting the dual objective of maximizing NOx reduction and minimizing NH3 slip in urea-SCR catalysts. To be implementable on the vehicle, the models should capture the essential behavior of the system, while not being computationally intensive. This paper discusses the adequacy of two different reduced order SCR catalyst models and compares their performance with a higher order model. The higher order model assumes that the catalyst has both diffusion and reaction kinetics, whereas the reduced order models contain only reaction kinetics. After describing each model, its parameter identification and model validation based on experiments on a Navistar I6 7.6L engine are presented. The adequacy of reduced order models is demonstrated by comparing the NO, NO2 and NH3 concentrations predicted by the models to their concentrations from the test data.

The operation of NOx Adsorber catalysts (NAC), also often referred to as Lean NOx Trap catalysts or NOx Storage-reduction catalysts, entails frequent periodic NOx regeneration events. These are accomplished by creating a net reducing, fuel-rich environment in the exhaust. The reduction of hydrocarbon emissions which occur during such fuel-rich events is challenging, due to the oxygen-deficient environment. In order to overcome this limitation, two possibilities exist: (i) oxygen can be stored during lean phase, to be used for hydrocarbon slip oxidation in the subsequent rich phase, or (ii) unreacted hydrocarbons can be trapped during the rich phase and oxidized during the following lean phase. In this work, two groups of catalytic solutions were developed and evaluated for hydrocarbon emission control based on these approaches: an Oxygen Storage Compound (OSC) based catalyst and zeolite-based hydrocarbon trap catalyst.

A one-dimensional model simulating the oxidation of CO, HC, and NO was developed to predict the gaseous emissions downstream of a diesel oxidation catalyst (DOC). The model is based on the conservation of mass, species, and energy inside the DOC and draws on past research literature. Steady-state experiments covering a wide range of operating conditions (exhaust temperatures, flow rates and gaseous emissions) were performed, and the data were used to calibrate and validate the model. NO conversion efficiencies of 50% or higher were obtained at temperatures between 300°C and 350°C. CO conversion efficiencies of 85% or higher and HC conversion efficiencies of 75% or higher were found at every steady state condition above 200°C. The model agrees well with the experimental results at temperatures from 200°C to 500°C, and volumetric flow rates from 8 to 42 actual m3/min.

In this work, an alternative method is proposed and validated for quantifying the axial performance of a state-of-the-art Cu zeolite SCR catalyst. Catalyst cores of a standard length, with varying lengths of wash-coated regions were used to axially resolve the functional performance of the SCR catalyst. This proposed method was validated by quantifying the catalyst entrance and exit effects, as well as the effect of non-uniform wash-coat loading densities. This method is less susceptible to some of the complications highlighted in the previous studies, such as flow uniformity between channels, as well as radiative heating effects, since the product gases are sampled across the entire monolith cross-section rather than through a single catalyst channel. The specific catalyst functions quantified include: NO and NH₃ oxidation, NH₃ storage capacity, as well as NOx conversion efficiency.

Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.

Gasoline is a complex fuel. Many of the constituents of gasoline that are beneficial for the internal combustion engine (ICE) are expected to be challenging for on-board reformers in fuel-cell vehicles. To address these issues, the autothermal reforming of gasoline and individual components of gasoline has been investigated. The results indicate that aromatic components require higher temperatures and longer contact times to reform than paraffinic components. Napthenic components require higher temperatures to reform, but can be reformed at higher space velocities than paraffinic components. The effects of sulfur are dependent on the catalyst. These results suggest that further evolution of gasoline could reduce the demands on the reformer and provide a better fuel for a fuel-cell vehicle.

The primary goal of this project was to design and implement an oxidation catalyst specific to a high-performance spark ignited two stroke engines to reduce vehicle-out emissions. The primary challenges of two stroke catalysis at high loads include controlling the catalytic reaction temperature as well as minimizing the increase in exhaust back pressure due to the addition of a catalyst. Reaction temperature is difficult to control due to high HC and CO concentrations paired with an excess of oxygen in the exhaust stream. By limiting catalyst conversion efficiency, the reaction temperatures were controlled. Two stroke engines are also inherently sensitive to changes in exhaust back pressure and therefore location and sizing of the catalyst are key design considerations. Because of these challenges significant effort was directed toward developing the two-stroke specific catalyst design process.

The detailed morphological properties of diesel particulate matter were analyzed along the exhaust system at various engine operating conditions (in a range of 1000 - 2500 rpm and 10 - 75 % loads of maximum torques). A 1.7-L turbocharged light-duty diesel engine was powered with California low-sulfur diesel fuel injected by a common-rail injection system, of which particulate emissions were controlled by an exhaust gas recirculation (EGR) system and two oxidation catalysts. A unique thermophoretic sampling system first developed for internal combustion engine research, a high-resolution transmission electron microscope (TEM), and a customized image processing/data acquisition system were key instruments that were used for the collection of particulate matter, subsequent imaging of particle morphology, and detailed analysis of particle dimensions and fractal geometry, respectively.

A 1998 Toyota Corona passenger car with a direct injection spark ignition (DISI) engine was tested at constant engine speed (2000 rpm) over a range of loads. Engine-out and tailpipe emissions of gas phase species were measured each second. This allowed examination of the engine-out emissions for late and early injection. Regeneration of the lean NOx trap/catalyst was also examined, as was the efficiency of NOx reduction. NOx stored in the trap/catalyst is released at the leading edge of regenerations, such that the tailpipe NOx is higher than the engine-out NOx for a brief period. The efficiency of NOx reduction was <50% for the lowest loads examined. As the load increased, the efficiency of NOx reduction decreased to near 0% due to excessive catalyst temperatures. Loads sufficiently high to require a rich mixture produce high NOx reduction efficiencies, but in this case the NOx reduction occurs via the three-way catalysts on this vehicle.

In order to determine any synergistic effects from reforming multicomponent fuels and to determine the effects of fuel additives and impurities we have investigated the autothermal reforming of fuel blends, including paraffin-aromatic, paraffin-naphthene, paraffin-oxygenate, and paraffin-detergent binary mixtures. The results indicate that aromatic, naphthenic, and detergent components adversely effect the reforming of paraffinic species. The results suggest that competitive adsorption at the catalyst sites decreases conversion rates of the paraffinic species. The paraffinic species are displaced by more strongly adsorbing species, leading to decreased kinetics for paraffin conversion.

A novel laboratory methodology has been developed and applied to evaluate performance of NOx Adsorber catalysts, based on the detailed analysis of micro-core samples obtained from various locations in a full-size catalyst. The technique includes a protocol for evaluating various aspects of NOx performance, as well as direct measurements of the amount of sulfur on the catalyst. This method was used to determine the NOx performance and distribution of sulfur loading on several engine aged catalysts. It showed the ability to differentiate poor NOx performance due to insufficient desulfation from that due to thermal degradation. This method further quantifies different forms of sulfur that are present on the catalyst. These forms of sulfur are distinguished by the temperature at which they are removed. In addition, the aspects of sulfur behavior that are important to this technique are discussed.

The physical and morphological properties of the particulate matter emitted from a 1.7-liter light-duty diesel engine were characterized by observing its evolution in size and fractal geometry along the exhaust system. A common-rail direct-injection diesel engine, the exhaust system of which was equipped with a turbocharger, EGR, and two oxidation catalysts, was powered with a California low-sulfur diesel fuel at various engine-operating conditions. A unique thermophoretic sampling system, a high-resolution transmission electron microscope (TEM), and customized image processing/data acquisition systems were key instruments that were used for the collection of particulate matter, subsequent imaging of particle morphology, and detailed analysis of particle dimensions and fractal geometry, respectively. The measurements were carried out at four different positions along the exhaust pipe.

Steady-state particulate loading experiments were conducted on an advanced production catalyzed particulate filter (CPF), both with and without a diesel oxidation catalyst (DOC). A heavy-duty diesel engine was used for this study with the experiments conducted at 20, 40, 60 and 75 % of full load (1120 Nm) at rated speed (2100 rpm). The data obtained from these experiments were used and are necessary for calibrating the MTU 1-D 2-Layer CPF model. These experimental and modeling results were compared to previous research conducted at MTU that used the same engine but an earlier development version of the combination of DOC and CPF. The motivation for the comparison of the two systems was to determine whether the reformulated production catalysts performed as good or better than the early development catalysts. The results were compared to understand the filtration and oxidation differences between the two DOC+CPF and the CPF-only aftertreatment systems.

In this study, a DOC catalyst was experimentally studied in an engine test cell with a2010 Cummins 6.7L ISB diesel and a production aftertreatment system. The test matrix consisted of steady state, active regeneration with in-cylinder fuel dosing and transient conditions. Conversion efficiencies of total hydrocarbon (THC), CO, and NO were quantified under each condition. A previously developed high-fidelity DOC model capable of predicting both steady state and transient active regeneration gaseous emissions was calibrated to the experimental data. The model consists of a single 1D channel where mass and energy balance equations were solved for both surface and bulk gas regions. The steady-state data were used to identify the activation energies and pre-exponential factors for CO, NO and HC oxidation, while the steady-state active regeneration data were used to identify the inhibition factors. The transient data were used to simulate the thermal response of the DOC.

The prediction accuracy of a three-way catalyst (TWC) model is highly associated with the ability of the model to incorporate the reaction kinetics of the emission process as a lambda function. In this study, we investigated the O2 and H2 concentration profiles of TWC reactions and used them as critical inputs for the development of a global TWC model. We presented the experimental data and global kinetic model showing the impact of thermal degradation on the performance of the TWC. The performance metrics investigated in this study included CH4, NOx, and CO conversions under lean, rich, and dithering light-off conditions to determine the kinetics of oxidation reactions and reduction/reforming/water-gas shift reactions as a function of thermal aging. The O2 and H2 concentrations were measured using mass spectrometry to track the change in the oxidation state of the catalyst and to determine the mechanism of the reactions under these light-off conditions.

Particulate and gaseous emissions from a Mitsubishi Legnum GDI™ wagon were measured for FTP-75, HWFET, SC03, and US06 cycles. The vehicle has a 1.8-L spark-ignition direct-injection engine. Such an engine is considered a potential alternative to the compression-ignition direct-injection engine for the PNGV program. Both engine-out and tailpipe emissions were measured. The fuels used were Phase-2 reformulated gasoline and Indolene. In addition to the emissions, exhaust oxygen content and exhaust-gas temperature at the converter inlet were measured. Results show that the particulate emissions are measurable and are significantly affected by the type of fuel used and the presence of an oxidation catalyst. Whether the vehicle can meet the PNGV goal of 0.01 g/mi for particulates depends on the type of fuel used. Both NMHC and NOx emissions exceed the PNGV goals of 0.125 g/mi and 0.2 g/mi, respectively. Meeting the NOx goal will be especially challenging.

Different blends of gasoline range hydrocarbons were investigated to determine the effect of aromatic, naphthenic, and paraffinic content on performance in an autothermal reformer. In addition, we investigated the effects of detergent, antioxidant, and oxygenate additives. These tests indicate that composition effects are minimal at temperatures of 800°C and above, but at lower temperatures or at high gas hourly space velocities (GHSV approaching 100,000 h-1) composition can have a large effect on catalyst performance. Fuels high in aromatic and naphthenic components were more difficult to reform. In addition, additives, such as detergents and oxygenates were shown to decrease reformer performance at lower temperatures.

The effects of propylene (C₃H₆) and dodecane (n-C₁₂H₂₆) exposure on the NH₃-based selective catalytic reduction (SCR) performance of two Cu-exchanged zeolite catalysts were investigated. The first sample was a model Cu/beta zeolite sample and the second a state-of-the-art Cu/zeolite sample, with the zeolite material characterized by relatively small pores. Overall, the state-of-the-art sample performed better than the model sample, in terms of hydrocarbon inhibition (which was reduced) and N₂O formation (less formed). The state-of-the-art sample was completely unaffected by dodecane at temperatures lower than 300°C, and only slightly inhibited (less than 5% conversion loss), for standard SCR, by C₃H₆. There was no evidence of coke formation on this catalyst with C₃H₆ exposure. The model sample was more significantly affected by hydrocarbon exposure. With C₃H₆, inhibition is associated with its partial oxidation intermediates adsorbed on the catalyst surface.