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Technical Paper

Development of Three-Way Catalysts Enhanced NOx Purifying Activity

Growing concerns about the depletion of raw materials as vehicle ownership continues to increase is prompting automakers to look for ways of decreasing the use of platinum-group metals (PGMs) in the exhaust systems. This research has developed a new catalyst with strong robustness against fluctuations in the exhaust gas and excellent nitrogen oxide (NOx) conversion performance. One of the key technologies is a new OSC material that has low surface area (SA) and high OSC performance. We enhanced the pyrochlore- ceria/zirconia (CZ) which has a very small SA. In order to enhance the heat resistance and promote the OSC reaction, we selected and optimized the additive element. This material showed high OSC performance especially in the temperature range of 400 degrees or less. Another key technology is washcoat structure that has high gas diffusivity by making connected pore in the washcoat (New pore forming technology).
Technical Paper

Development of Advanced Three-Way Catalyst with Improved NOx Conversion

Countries and regions around the world are tightening emissions regulations in reaction to the increasing awareness of environmental conservation. At the same time, growing concerns about the depletion of raw materials as vehicle ownership continues to increase is prompting automakers to look for ways of decreasing the use of platinum-group metals (PGMs) in the exhaust systems. This research has developed a new catalyst with strong robustness against fluctuations in the exhaust gas and excellent nitrogen oxide (NOx) conversion performance. This catalyst incorporates rhodium (Rh) clusters with a particle size of several nanometers, and stabilized CeO2-ZrO2 solid-solution (CZ) with a pyrochlore crystal structure as a high-volume oxygen storage capacity (OSC) material with a slow O2 storage rate.
Technical Paper

Universal Diesel Engine Simulator (UniDES) 2nd Report: Prediction of Engine Performance in Transient Driving Cycle Using One Dimensional Engine Model

The aim of this research is to develop the diesel combustion simulation (UniDES: Universal Diesel Engine Simulator) that incorporates multiple-injection strategies and in-cylinder composition changes due to exhaust gas recirculation (EGR), and that is capable of high speed calculation. The model is based on a zero-dimensional (0D) cycle simulation, and represents a multiple-injection strategy using a multi-zone model and inhomogeneity using a probability density function (PDF) model. Therefore, the 0D cycle simulation also enables both high accuracy and high speed. This research considers application to actual development. To expand the applicability of the simulation, a model that accurately estimates nozzle sac pressure with various injection quantities and common rail pressures, a model that accounts for the effects of adjacent spray interaction, and a model that considers the NOx reduction phenomenon under high load conditions were added.
Journal Article

Low Emissions and High-Efficiency Diesel Combustion Using Highly Dispersed Spray with Restricted In-Cylinder Swirl and Squish Flows

A new clean diesel combustion concept has been proposed and its excellent performance with respect to gas emissions and fuel economy were demonstrated using a single cylinder diesel engine. It features the following three items: (1) low-penetrating and highly dispersed spray using a specially designed injector with very small and numerous orifices, (2) a lower compression ratio, and (3) drastically restricted in-cylinder flow by means of very low swirl ports and a lip-less shallow dish type piston cavity. Item (1) creates a more homogeneous air-fuel mixture with early fuel injection timings, while preventing wall wetting, i.e., impingement of the spray onto the wall. In other words, this spray is suitable for premixed charge compression ignition (PCCI) operation, and can decrease both nitrogen oxides (NOx) and soot considerably when the utilization range of PCCI is maximized.
Journal Article

Numerical Simulation for Designing Next Generation TWC System with Detailed Chemistry

A one-dimensional (1-D) micro-kinetic reaction model with considering mass transport inside porous washcoat was developed to promote an effective development of multi-functional catalysts. The validation of this model has been done successfully through the comparison with a set of basic experiments. A numerical simulation study was conducted for the various catalyst configurations of three-way catalysts under Federal Test Procedure (FTP75) condition. It was found that a double layer type had a significant advantage in the total mass emissions, especially in NOx emissions. The reaction mechanisms in these catalysts were numerically clarified from the view point of detailed reaction dynamics. We concluded that the utilization of the numerical simulation with the detailed chemistry was effective for the optimization of catalyst design.
Technical Paper

Exhaust Gas Pressure Sensor

As the whole world has been getting more concerned about the environmental protection, the emission regulations are getting stricter. The requirement to diesel engine is to develop the high-level engine management system to reduce both PM(Particulate Matter)and NOx. For PM reduction, post-treatment technology using a pressure sensor and a diesel particulate filter (hereinafter referred to as DPF) is necessary. This system burns out the clogged PM at the filter that the pressure sensor detects. The pressure sensor used in the DPF system has to be at an affordable price and to be reliable against corrosion, freezing, moisture and clogged soot in the harsh environment of exhaust gas with high humidity where highly-acid condensation water and the produced soot can intrude. This paper describes our newly developed pressure sensor that is suitable for the DPF system. The main features are as follows: a. Semiconductor type sensor with a simple structure and being less costly. b.
Journal Article

Emissions Reduction Potential of Extremely High Boost and High EGR Rate for an HSDI Diesel Engine and the Reduction Mechanisms of Exhaust Emissions

The effects of an increasing boost pressure, a high EGR rate and a high injection pressure on exhaust emissions from an HSDI (High Speed Direct Injection) diesel engine were examined. The mechanisms were then investigated with both in-cylinder observations and 3DCFD coupled with ϕT-map analysis. Under a high-load condition, increasing the charging efficiency combined with a high injection pressure and a high EGR rate is an effective way to reduce NOx and soot simultaneously, which realized an ultra low NOx of 16ppm at 1.7MPa of IMEP (Indicated Mean Effective Pressure). The flame temperature with low NOx and low soot emissions is decreased by 260K from that with conventional emissions. Also, the distribution of the fuel-air mixture plot on a ϕT-map is moved away from the NOx and soot formation peninsula, compared to the conventional emissions case.
Technical Paper

A Study on Natural Gas Fueled Homogeneous Charge Compression Ignition Engine - Expanding the Operating Range and Combustion Mode Switching

Natural gas homogeneous charge compression ignition (HCCI) engines require high compression ratios and intake air heating because of the high auto-ignition temperature of natural gas. In the first study, the natural gas fueled HCCI combustion with internal exhaust gas recirculation (EGR) was achieved without an intake air heater. The effects of the combustion chamber configuration, turbocharging, and external EGR were investigated for expanding the operating range. As a result, it was cleared that the combination of internal / external EGR and turbocharging is effective for expanding the HCCI operational range toward high loads. Meanwhile, the HCCI combustion characteristics at high engine speeds were unstable because of an insufficient reaction time for auto-ignition. Although the engine operation with a richer air-fuel ratio was effective for improving the combustion stability, the combustion noise (CN) was at an unacceptable level.
Technical Paper

Improvement of NOx Storage-Reduction Catalyst

In order to enhance the catalytic performance of the NOx Storage-Reduction Catalyst (NSR Catalyst), the sulfur tolerance of the NSR catalyst was improved by developing new support and NOx storage materials. The support material was developed by nano-particle mixing of ZrO2-TiO2 and Al2O3 in order to increase the Al2O3-TiO2 interface and to prevent the ZrO2-TiO2 phase from sintering. A Ba-Ti oxide composite material was also developed as a new NOx storage material containing highly dispersed Ba. It was confirmed that the sulfur tolerance and activity of the developed NSR catalyst are superior to that of the conventional one.
Technical Paper

Dual-Fuel PCI Combustion Controlled by In-Cylinder Stratification of Ignitability

A concept of dual-fuel, Premixed Compression Ignition (PCI) combustion controlled by two fuels with different ignitability has been developed to achieve drastically low NOx and smoke emissions. In this system, isooctane, which was used to represent high-octane gasoline, was supplied from an intake port and diesel fuel was injected directly into an engine cylinder at early timing as ignition trigger. It was found that the ignition timing of this PCI combustion can be controlled by changing the ratio of amounts of injected two fuels and combustion proceeds very mildly by making spatial stratifications of ignitability in the cylinder even without EGR, as preventing the whole mixture from igniting simultaneously. The operable range of load, where NOx and smoke were less than 10ppm and 0.1 FSN, respectively, was extended up to 1.2MPa of IMEP using an intake air boosting system together with dual fueling.
Technical Paper

Development of High Performance Three-Way-Catalyst

In conventional gasoline engine vehicles, three-way catalysts are used to simultaneously remove HC, CO and NOx from the exhaust gas. The effectiveness of the catalyst to remove these harmful species depends strongly on the oxygen concentration in the exhaust gas. Deterioration of three-way catalyst results in a reduction in its purification activity and OSC (oxygen storage capacity). In this investigation, additive elements were used to enhance the durability and OSC of the catalyst support material. An optimized formulation of a CeO2-ZrO2 and a ZrO2 material was developed to have excellent durability, improved OSC, enhanced interaction between precious metals and support materials, and increase thermal stability. Using these newly developed support materials, catalysts with increased performance was designed.
Technical Paper

Total-NOx Sensor Based on Mixed-Potential for Detecting of Low NOx Concentrations

We have been developing the mixed-potential type NOx sensor which can detect the total-NOX concentration directly in exhausts for automobiles. It has been confirmed that the sensor is capable of detecting wide concentrations of total-NOx from 20 to 1000 ppm under the condition from rich-burn (A/F=12) to lean-burn without any interference from reducing gases, such as HC and CO. In addition, it has been confirmed that the sensor output is correlated fairly well to NOx concentrations from the analyzer in the engine test at any rotations. The results obtained here indicate that the present sensor has great possibility of being utilized as an on-board NOx sensor for practical use.
Technical Paper

A Concept of Plasma Assisted Catalyst System Using a DeNOx Catalyst for an Automobile Diesel Engine

Through the basic research of the plasma assisted catalyst system using DeNOx catalysts and the gas analysis of the system, its conceptual use for automobile diesel engine applications has been studied. This study has shown that the length between the plasma reactor and the catalyst reactor does not affect the NOx conversion. To obtain an efficient NOx conversion, the plasma should affect both the HC as the reductant and NOx at the same time. In the case of γ-Al2O3 and C3H6, the main component for NOx reduction was CH3CHO generated by the plasma. Under 250 deg. C, the temperature was too low for the γ-Al2O3 to become effective. Therefore, the NOx conversion became low. At 400 deg. C, the NOx conversion became high. However, at 600 deg. C, the CH3CHO for reducing NOx was not generated, and the NOx conversion decreased.
Technical Paper

NOx Reduction Behavior on Catalysts With Non-Thermal Plasma in Simulated Oxidizing Exhaust Gas

NOx reduction activity in an oxidizing exhaust gas was significantly improved by discharging non-thermal plasma and catalysts (plasma assisted catalysis). We investigated effective catalyst for plasma assisted catalysis in view of hydrocarbon-selective catalytic reduction(HC-SCR). Plasma assist was effective for γ-alumina and alkali or alkaline earth metals loaded zeolite and γ-alumina showed the highest NOx conversion among these catalysts. On the other hand, Plasma assist was not effective for Cu-ZSM-5 and Pt loaded catalyst. The NOx conversion for the plasma assisted γ-alumina decreased by formation of a deposit on the catalyst below 400°C. It is shown that indium loading on γ-alumina improved the NOx reduction activity and suppressed the degradation of the NOx reduction activity at 300°C with plasma assist.
Technical Paper

Analysis of Mixture Formation Process in a Stoichiometric Direct Injection Gasoline Engine

The stoichiometric direct injection gasoline engines have higher torque performance than the port injection engines, as the volumetric efficiency can be increased due to the cooling effects of charging air by the fuel evaporation in the cylinder. They need only 3-way catalyst, leading to the cost down. However there exists the injection timing (region) that increased volumetric efficiency does not lead to higher torque. In order to investigate the phenomena, the in-cylinder mixture formation process has been analyzed by the LIF and the CFD techniques. As the results, it has been revealed that the phenomena are caused by the inhomogeneous mixture distribution before the ignition timing.
Technical Paper

An Intelligent Catalyst

The catalyst of the crystalline ceramics known as a perovskite-type oxide was designed and controlled at the atomic level in order to create a new function for self-regeneration of precious metals in a usage ambience without auxiliary treatment. We have already reported that a catalyst with Pd supported on the perovskite-type oxide has higher activity than a catalyst with Pd supported on alumina. It was also found that Pd supported on the perovskite catalyst is finely dispersed [1, 2 and 3] The object of this study was to investigate the mechanism of self-regeneration by using hyper-analytical facilities. XAFS analysis, at SPring-8 (8 GeV), revealed that Pd is in six-fold coordinations with oxygen in a perovskite crystal, which indicating that Pd occupies the B site of the unit formula of ABO3 in the perovskite crystal structure under oxidation atmosphere.
Technical Paper

Research and Development of a New Direct Injection Gasoline Engine

A new stratified charge combustion system has been developed for direct injection gasoline engines. The special feature of this system is employment of a thin fan-shaped fuel spray formed by a slit nozzle. The stratified mixture is produced by the combination of this fan-spray and a shell-shaped piston cavity. Both under-mixing and over-mixing of fuel in the stratified mixture is reduced by this system. This combustion system does not require distinct charge motion such as tumble or swirl, which enables intake port geometry to be simplified to improve full load performance. The effects of the new system on engine performance at part load are improved fuel consumption and reduced smoke, CO and HC emissions, obviously at medium load and medium engine speed. HC emissions at light load are also improved even with high EGR conditions.
Technical Paper

Effect of Hydrocarbon Molecular Structure on Diesel Exhaust Emissions Part 2: Effect of Branched and Ring Structures of Paraffins on Benzene and Soot Formation

The effect of the chemical reactivity of diesel fuel on PM formation was investigated using a flow reactor and a shock tube. Reaction products from the flow-reactor pyrolysis of the three diesel fuels used for the engine tests in Part 1(1) (“Base”, “Improved” and Swedish “Class-1”) were analyzed by gas chromatography. At 850C, Swedish “Class-1” fuel was found to produce the most PM precursors such as benzene and toluene among the three fuels, even though it contains very low amounts of aromatics. The chemical analyses described in Part 1 revealed that “Class-1” contains a large amount of branched and cyclic structures in the saturated hydrocarbon portion of the fuel. These results suggest that the presence of such branched and ring structures can increase exhaust PM emissions.