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Technical Paper

Exhaust Purification Performance Enhancement by Early Activation of Three Way Catalysts for Gasoline Engines Used in Hybrid Electric Vehicles

Three-way catalyst (TWC) converters are used to remove harmful substances (e.g., carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons (HC)) emitted from gasoline engines. However, a large amount of emissions could be emitted before the TWC reaches its light-off temperature during a cold start. For hybrid electric vehicles (HEVs) powered by gasoline engines, the emission purification performance by TWC converters unfortunately deteriorates because of mode switching from engine to battery and vice versa, which can repeatedly generate cold start conditions for the TWCs. In this study, aiming to reduce emissions from series HEVs by early activation of TWCs, numerical simulations and experiments are carried out. An HEV is tested on a chassis dynamometer in the Worldwide Light-duty Test Cycle (WLTC) mode. The upstream and downstream gas conditions of the close-coupled catalyst converter are measured.
Technical Paper

Optimization of TWC Design for Various Engine Operation Conditions

Three-way catalysts (TWCs) for gasoline-powered vehicles commonly contain Pt group metals (Pt, Pd, and Rh) as active components and Al2O3 or OSC as supports, with Pd and Rh being most frequently employed in view of their high thermal durability. Hybrid electric vehicles (HEVs) have been recently developed to meet strict fuel efficiency regulations, by using feature engines that are much more energy-efficient than those of conventional gasoline vehicles and lend themselves to fixed-point operation control. Therefore, the engine exhaust-induced stress experienced by TWCs in HEVs and the corresponding aging conditions are expected to differ from those in conventional vehicles, which, in turn, should be reflected by a change in the optimal catalyst design. Herein, to facilitate the design of optimum next-generation TWCs, we investigate the deterioration of these catalysts (Pt, Pd, Rh supported on Al2O3 or OSC) under various conditions reflecting different engine operation modes.
Technical Paper

Improvement of CO Oxidation Performance by Controlling Pd State in DOC

Diesel oxidation catalysts (DOCs) combining the functions of Pd and Pt-Pd alloys have been used in practice to satisfy the strict exhaust emission regulations that have been specified for passenger cars in recent years. Pd is an indispensable component in DOCs because it exhibits superior oxidation activity for CO and HC. To reduce the amount of precious metal used and to improve robustness, it is important to control the electronic state and gas adsorption characteristics of Pd and PdOx during catalytic reactions.In this study, by investigating the CO adsorption behavior of Pd, it was observed that Pd supported on a CeO2/ZrO2 mixed-oxide material (CZ) showed a preferable CO adsorption state and better CO light-off performance. Pd in Pd/CZ became metallic with increasing reaction time, and the CO oxidation performance of Pd/CZ decreased. This change in activity was correlated with CO adsorption on Pd changing from linear-type to bridge-type adsorption.
Technical Paper

Detailed Mechanism of S Poisoning and De-Sulfation Treatment of Cu-SCR Catalyst

Modern diesel emission control systems often use Urea Selective Catalytic Reduction (Urea-SCR) for NOx control. One of the most active SCR catalysts is based on Cu-zeolite, specifically Cu-Chabazite (Cu-CHA), also known as Cu-SSZ-13. The Cu-SCR catalyst exhibits high NOx control performance and has a high thermal durability. However, its catalytic performance deteriorates upon long-term exposure to sulfur. This work describes our efforts to investigate the detailed mechanism of poisoning of the catalyst by sulfur, the optimum conditions required for de-sulfation, and the recovery of catalytic activity. Density functional theory (DFT) calculations were performed to locate the sulfur adsorption site within the Cu-zeolite structure. Analytical characterization of the sulfur-poisoned catalyst was performed using Extreme Ultraviolet Photoelectron Spectroscopy (EUPS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS).
Technical Paper

Effect of Ba and La Additives to the Pd Layer of a Pd:Rh TWC

A new Pd-Rh three-way catalyst (TWC) for close-coupled (CC) applications was developed to improve low temperature gas activity. In this study the TWC has a layered structure with Pd in the top layer and Rh in the bottom layer. The specific objectives of this study was to compare Ba and La additives to Pd in the top layer. Alumina was used for the Pd support and La or Ba were co-impregnated with Pd. The catalysts were engine aged at 950°C for 200 h and evaluated on a vehicle using the European NEDC test, for CO, HC and NOx performance. After this aging, the Pd-La catalyst showed higher gas performance than the Pd-Ba catalyst, especially in the cold start region. This improvement was correlated to the Pd particle size and the sintering suppression observed upon addition of La. Sintering suppression was also observed upon addition of Ba; however, the mechanism appears to be different from that of La addition.
Technical Paper

New Concept of Fuel Combustion DOC

Diesel exhaust emission control systems often contain DOC (Diesel Oxidation Catalyst) + CSF (Catalyzed Soot Filter) components. In this system PM (particulate matter) is filtered and accumulated in the CSF and such filtered PM is periodically combusted by supplying heat to the CSF. The heat to CSF is generated within the DOC by an exothermic reaction with extra fuel supplied to the DOC. Here the exothermic performance of DOC depends on not only the active catalytic site (such as Pt and/or Pd) but also on the characteristics of the porous material supporting the precious metals. Various properties of Al2O3, i.e. pore diameter, pore volume, BET surface area, acidity, basicity and the Ea (activation energy) of fuel combustion, used in DOCs and PGM particle size of each DOC were measured. The fuel combustion performance of each DOC was evaluated by diesel engine bench.
Journal Article

Development of TWC and PGM Free Catalyst Combination as Gasoline Exhaust Aftertreatment

Reduction of the amount of platinum group metals (PGM: Pt, Pd, Rh) utilized in three-way catalysts (TWC) has been required from a point of resource shortage and cost effectiveness. A conventional TWC system is composed of a close-coupled (CC) catalyst and an underfloor (UF) catalyst, both PGM-based. The CC-TWC promotes HC/CO oxidation and NOx reduction by CO. The UF-TWC mainly facilitates further NOx reduction by CO. In this study, a TWC system comprising a CC catalyst with PGM and an UF catalyst without PGM has been described. The newly developed system, performing reasonably well with a conventional stoichiometric gasoline combustion engine, offers an opportunity to reduce PGM usage. In this system, the UF-non-PGM catalyst is composed of a Ni/CeO2 bottom layer which functions as a deNOx catalyst with CO-NO reaction and a zeolite based top layer which works as a deNOx catalyst with passive NH3-SCR reaction.
Journal Article

Surface Conductivity Measurement of Catalyst Materials by EUPS and Its Correlation to Catalyst Performance

Commercial three way catalysts (TWC) are designed to eliminate HC, CO and NOx pollutants emitted from gasoline powered internal combustion engines. TWC have been optimized over many years to meet ever more stringent emission regulations. It has long been speculated that surface electrical conductivity may be a key parameter in controlling catalytic activity, however until now it has not been possible to reliably measure this physical parameter on a catalytic surface. In this study, the surface electrical conductivity of catalyst powders, such as Rh/ CeO1-x-ZrxO2, Rh/ZrO2 and Rh/Al2O3, were measured by EUPS (Extreme Ultraviolet excited Photoelectron Spectroscopy). Then the measured electrical conductivity was compared with catalyst performance from CO-NO and water gas shift reactions which are important for controlling automobile exhaust emissions from gasoline vehicles.
Technical Paper

Development of Highly Efficient Lean NOx Catalyst System in Low Exhaust Gas Temperature

The reduction of NOx in exhaust gas has been a major challenge in diesel engine development. For the NOx reduction issues, a new Lean NOx Catalyst (LNC) aftertreatment system has been developed by Honda. A feature of the LNC system is the method that is used to reduce NOx through an NH₃-Selective Catalytic Reduction (NH₃-SCR). In an LNC system NOx is adsorbed at lean conditions, then converted to NH₃ at rich conditions and subsequently reduced in the next lean phase. In recent years, as the efficiency of the diesel engine has improved, the exhaust gas temperatures have been reduced gradually. Therefore, the aftertreatment system needs to be able to purify NOx at lower temperatures. The development of a new LNC which has a high activity at low temperature has been carried out. For the improvement of the LNC three material improvements were developed. The first of these was the development of a NOx adsorbent which is matching the targeted exhaust gas temperatures.
Technical Paper

Modeling of Phosphorus Poisoning Phenomena over Diesel Oxidation Catalysts

To predict how DOC performance deteriorates with a lifetime of use, it is important to understand the mechanisms of catalyst aging. In off-road applications, due to the continuous high load usage and relatively high oil consumption rate, poisoning of the Diesel Oxidation Catalyst (DOC) with Phosphorus may become an important durability issue. In this study, 3D modeling has been performed to study the P poisoning mechanism and 1D modeling has been performed to investigate P poisoning parameters that effect DOC performance deterioration. From postmortem analysis on engine aged DOCs there is a general trend that P deposits tend to collect at the outermost catalyst surface. Two types of 3D modeling were performed in this study to understand how P migrates into the bulk of the catalyst. In one case, P migrates into catalyst layer by gas phase diffusion and in the other case P first adsorbs on the catalyst surface and then migrates by solid diffusion into the bulk.
Technical Paper

Detailed Analysis of Particulate Matter Emitted from Biofueled Diesel Combustion with High EGR

Difference of engine combustion characteristics, species and amount of exhaust gas and PM (particulate matter consisted of SOF and Soot and Ash), and especially PM oxidation characteristics were studied when diesel fuel or bio-fuel, here PME (palm oil methyl ester) as an example, was used as a fuel. The fueling rate was adjusted to obtain the same torque for both fuels and engine was operated under several range of EGR (Exhaust Gas Recirculation) ratio. Under such conditions, PME showed shorter ignition delay time and lower R.H.R (rate of heat release) under 0-40% EGR ratio. With respect to engine exhaust gas species, CO, NO, THC and HCHO, CH3CHO concentration was almost the same when the EGR ratio is higher than 35% (Intake-Air/Fuel: A/F=20). However, PME also showed lower exhaust gas emission when the EGR ratio is higher than 30%.
Technical Paper

Modeling of OSC Function over Three-way Catalyst

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.
Journal Article

Multiple Regression Analysis of OSC Characteristics under Transient TWC Conditions

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.
Technical Paper

Optimization of Exhaust Pipe Injection Conditions for Diesel Oxidation

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.
Technical Paper

Modeling of Catalyst Sintering and Study of Accelerated Aging Based on Pt/Al2o3 as a Model Catalyst

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.
Technical Paper

Oxygen Partial Pressure over Precious Metals and Its Effect on HC Oxidation Performance

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.
Technical Paper

Influence of Diesel Post Injection Timing on HC Emissions and Catalytic Oxidation Performance

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).
Technical Paper

Effective Catalyst Layer Study by Computer Calculation

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.
Technical Paper

Development of Methane Oxidation Catalyst and Its Mechanism

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.
Technical Paper

SOF Combustion Behavior in Flow-thru Diesel Oxidation Catalysts

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.