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For diesel emission control systems containing a Diesel Oxidation Catalyst (DOC) and a Catalyzed Soot Filter (CSF) the DOC is used to oxidize the additional fuel injected into the cylinder and/or the exhaust pipe for the purpose of increasing the CSF inlet temperature during the soot regeneration. Hydrocarbon (HC) oxidation performance of the DOC is affected by HC species as well as a catalyst design, i.e., precious metal species, support materials and additives. How engine-out HC species vary as a function of fuel supply conditions is not well understood. In addition, the relationship between catalyst design and oxidation activity of different hydrocarbon species requires further study. In this study, diesel fuel was supplied by in-cylinder, post injection and exhaust HC species were measured by a gas chromatograph-mass spectrometry (GC-MS) and a gas analyzer. The post injection timing was set to either 73°, 88° or 98° ATDC(after top dead center).

Palladium catalysts are known to show higher methane oxidation performance than platinum and/or rhodium catalysts. In this paper, the higher oxidative dehydrogenation activity on palladium is proposed as a reason for the superior methane oxidation. When other oxidation reactions are considered, higher affinity of palladium to oxygen has also been suggested[1]. In this study, oxygen chemical potential on platinum and palladium catalyst surfaces under oxidation conditions was measured using a specially designed electrochemical sensor. The oxygen chemical potential was calculated from the sensor potential by the Nernst equation. As a result, oxygen potential on palladium during the methane oxidation reaction was found to be much higher than that of platinum, correlating with affinity to oxygen and higher methane oxidation performance. The rate of oxygen adsorption and desorption on platinum and palladium was evaluated in an engine experiment using a dual lambda-sensor procedure.

Precious metal catalysts, such as Pt/Al2O3, are the primary active ingredient in diesel oxidation catalysts (DOC) used to control CO, HC and SOF emissions. Sintering of precious metal is one of the main deterioration factors of catalytic performance. In hot applications sintering of the alumina support material has also been suggested to accelerate precious metal sintering. Investigation of sintering rates may allow estimation of the catalyst life and provide information important for catalyst durability improvement. In this study, Pt/Al2O3 was used as a model catalyst and a sintering model for thermal aging was constructed. Pt sintering could be expressed by a differential equation which includes both Pt and support material sintering, but better fit to experimental data resulted from inclusion of a factor that includes an Al2O3 phase change.

Three way catalysts (TWC) contain Oxygen Storage Component (OSC) materials to enhance HC, CO oxidation and NOx reduction performance under standard operating conditions where there is rapid perturbation of the air-to-fuel ratio (A/F). The OSC function is required to storage and to release oxygen, however the optimum storage capacity and release rate to maximize HC, CO and NOx conversion varies as a function of engine operating conditions, such as A/F perturbation frequency, amplitude and temperature. At the same time, it is necessary for the vehicle on board diagnostics (OBD) systems to monitor that the catalyst OSC is functioning correctly. Detailed understanding of how OSC characteristics can simultaneously match gas performance and OBD functionality are not well known. In this study, modeling of the OSC function was attempted by considering chemical functions to be analogous to that in an equivalent electrical circuit, having components of resistance and capacitance.

Pre-filter diesel oxidation catalyst (DOC) development for a DOC-CSF system has been conducted. The pre-filter DOC is required to efficiently oxidize fuel and generate heat to regenerate accumulated soot within the catalyzed soot filter (CSF). Therefore, high thermal durability is required. In addition, good transient hydrocarbon (HC) activity is required for the DOC to reduce tailpipe HC emissions. The required performance is dependent on the OEM's system control strategy. A DOC catalyst designed to have well dispersed Pt showed high fuel combustion performance. Such high Pt dispersion was obtained by using high specific surface area Al2O3. Zeolite included into the catalyst formulation showed higher transient HC performance compared to a catalyst without zeolite. The effective catalyst layer depth with respect to transient HC activity was studied by computer simulation.

Sulfate generation by diesel oxidation catalysts (DOC) is still a problem although sulfur concentration in the diesel fuel will be reduced in future. Two approaches were attempted to reduce the sulfate generation without inhibiting the HC and CO oxidation performance. One was to use an optimized support material that adsorbs less SO2 and has sufficient specific surface area for HC/CO oxidation. Another approach was to apply a layer on the catalyst, which prevents SO2 adsorption. Sulfate generation was successfully reduced while maintaining high HC/CO oxidation performance.

Three Way Catalysts (TWC) contain oxygen storage components (OSC) to enhance HC, CO oxidation and NOx reduction performance under standard operating conditions where there is rapid perturbation of the air-to-fuel ratio (A/F). The OSC function is required to storage and to release oxygen, however the optimum storage capacity and release rate to maximize HC, CO and NOx conversion varies as a function of engine operating conditions, such as A/F perturbation frequency, amplitude and temperature. At the same time it is necessary for the vehicle on board diagnostics (OBD) systems to monitor that the catalyst OSC is functioning correctly. Detailed understanding of how OSC characteristics can simultaneously match gas performance and OBD functionality are not well known. In this study, several TWC catalysts were prepared with different types of OSC materials such that oxygen storage capacity and activation energy for oxygen release could be varied over a wide range.

Performance improvements resulting from the adoption of a new type CeO2-ZrO2-based material were found using a two-brick three way catalyst (TWC) system. Compared to a conventional CeO2-ZrO2-based material, this new type CeO2-ZrO2 has both a larger oxygen storage capacity and a slower oxygen release rate. Such characteristics were confirmed by fundamental studies. Vehicle evaluations showed this material was most effective for hot NOx control when used in the rear catalyst, especially after fuel cuts. The improvement in NOx was thought to be caused by the increased oxygen storage capacity (OSC), which effectively stored excess oxygen during fuel cuts. As a result, the air-to-fuel ratio (A/F) surrounding the active sites could be kept at stoichiometry even if the engine control shifted to a lean setting.

Combustion behavior of the SOF (Soluble organic fraction) fraction of diesel particulate by flow-thru type diesel oxidation catalysts (DOC) was studied. A two brick DOC system with an air gap showed higher SOF performance than a single brick DOC of the same total volume. Collision frequency of the TPM (total particulate matter) to the catalyst layer was studied by calculation of the turbulence energy in the gas flow channel. No large difference in collision frequency was observed between one brick and two bricks. The front face effect was calculated from the geometric surface and it was confirmed that such an effect was small in the two brick DOC case. The SOF performance advantage for the two brick DOC system separated by an air gap was due to a thermo-mass effect created by reducing the DOC volume.

The transient HC performance of diesel oxidation catalysts is known to be greatly improved by addition of Zeolite material. The authors already reported how to estimate the effective washcoat thickness in our previous study [1]. To understand in more detail the effective catalyst layer thickness, a precise gas diffusion model and parameters of HC adsorption and desorption rate were determined in this study. The random pore model was used for a gas diffusion calculation to simulate the macro porosity of the catalyst layer and micro porosity of the Zeolite material. HC adsorption capacity as a function of temperature and HC concentration was measured by Temperature Programmed Desorption (TPD). HC desorption rate was evaluated by changing the TPD ramping rate. HC reaction rate was evaluated by using a model gas reactor. Calculated catalyst performance correlated to the experimental results, thus validating the model.

Palladium is well known to catalyze methane (CH4) oxidation more efficiently than platinum (Pt) and/or rhodium (Rh) catalysts. The mechanism for methane oxidation on palladium is hypothesized to proceed via a radical intermediate. Direct identification of a radical species was not detected by Electron Spin Resonance Spectroscopy (ESR). However, indirect evidence for a radical intermediate was found by identification of ethane (C2H6), the methyl radical(CH3 ˙ ) coupling product, by Mass spectroscopy analysis under CH4/O2 conditions.

In a Diesel Oxidation Catalyst (DOC) and Catalyzed Soot Filter (CSF) system, the DOC is used to oxidize additional fuel injected into the cylinder and/or exhaust pipe in order to increase the CSF's inlet temperature during soot regeneration. The catalyst's hydrocarbon (HC) oxidation performance is known to be strongly affected by the HC species present and the catalyst design. However, the engine operating conditions and additive fuel supply parameters also affect the oxidation performance of DOCs, but the effects of these variables have been insufficiently examined. Therefore, in this study, the oxidation performance of a DOC was examined in experiments in which both exhaust gas recirculation (EGR) levels and exhaust pipe injection parameters were varied. The results were then analyzed and optimal conditions were identified using modeFRONTIER.