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Technical Paper

Using Chemical Kinetics to Understand Effects of Fuel Type and Compression Ratio on Knock-Mitigation Effectiveness of Various EGR Constituents

Exhaust gas recirculation (EGR) can be used to mitigate knock in SI engines. However, experiments have shown that the effectiveness of various EGR constituents to suppress knock varies with fuel type and compression ratio (CR). To understand some of the underlying mechanisms by which fuel composition, octane sensitivity (S), and CR affect the knock-mitigation effectiveness of EGR constituents, the current paper presents results from a chemical-kinetics modeling study. The numerical study was conducted with CHEMKIN, imposing experimentally acquired pressure traces on a closed reactor model. Simulated conditions include combinations of three RON-98 (Research Octane Number) fuels with two octane sensitivities and distinctive compositions, three EGR diluents, and two CRs. The experimental results point to the important role of thermal stratification in the end-gas to smooth peak heat-release rate (HRR) and prevent acoustic noise.
Technical Paper

Unregulated Emissions Evaluation of Gasoline Combustion Systems (Lean Burn / Stoichiometric DISI and MPI), State of the Art Diesel Aftertreatment Technologies (DPF, urea-SCR and DOC), and Fuel Qualities Effects (EtOH, ETBE, Aromatics and FAME)

In order to clarify future automobile technologies and fuel qualities to improve air quality, second phase of Japan Clean Air Program (JCAPII) had been conducted from 2002 to 2007. Predicting improvement in air quality that might be attained by introducing new emission control technologies and determining fuel qualities required for the technologies is one of the main issues of this program. Unregulated material WG of JCAPII had studied unregulated emissions from gasoline and diesel engines. Eight gaseous hydrocarbons (HC), four Aldehydes and three polycyclic aromatic hydrocarbons (PAHs) were evaluated as unregulated emissions. Specifically, emissions of the following components were measured: 1,3-Butadiene, Benzene, Toluene, Xylene, Ethylbenzene, 1,3,5-Trimethyl-benzene, n-Hexane, Styrene as gaseous HCs, Formaldehyde, Acetaldehyde, Acrolein, Benzaldehyde as Aldehydes, and Benzo(a)pyrene, Benzo(b)fluoranthene, Benzo(k)fluoranthene as PAHs.
Technical Paper

Universal Diesel Engine Simulator (UniDES): 1st Report: Phenomenological Multi-Zone PDF Model for Predicting the Transient Behavior of Diesel Engine Combustion

We have developed a novel engine cycle simulation program (UniDES: universal diesel engine simulator) to reproduce the diesel combustion process over a wide range of engine operating parameters, such as the amount of injected fuel, the injection timing, and the EGR ratio. The approach described in this paper employs a zoning model, where the in-cylinder region is divided into up to five zones. We also applied a probability density function (PDF) concept to each zone to consider the effect of spatial non-homogeneities, such as local equivalence ratios and temperature, on the combustion characteristics. We linked this program to the commonly used commercial GT-Power® software (UniDES+GT). As a result, we were able to reproduce transient engine behavior very accurately.
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

Study of Oxide Supports for PEFC Catalyst

Polymer electrolyte membrane fuel cell (PEFC) systems for fuel cell vehicles (FCVs) require both performance and durability. Carbon is the typical support material used for PEFC catalysts. However, hydrogen starvation at the anode causes high electrode potential states (e.g., 1.3 V with respect to the reversible hydrogen electrode) that result in severe carbon support corrosion. Serious damage to the carbon support due to hydrogen starvation can lead to irreversible performance loss in PEFC systems. To avoid such high electrode potentials, FCV PEFC systems often utilize cell voltage monitor systems (CVMs) that are expensive to use and install. Simplifying PEFC systems by removing these CVMs would help reduce costs, which is a vital part of popularizing FCVs. However, one precondition for removing CVMs is the adoption of a durable support material to replace carbon.
Technical Paper

Study of Large OSC Materials (Ln2O2SO4) on the Basis of Sulfur Redox Reaction

Three-way catalyst shows high performance under stoichiometric atmosphere. The CeO2-ZrO2 based materials (CZ) are added as a buffer of O2 concentration. To improve the catalyst performance the larger O2 storage capacity (OSC) are needed. Theoretically, the sulfur oxidation-reduction reaction moves oxygen 8 times larger than cerium. We focused on this phenomenon and synthesized Ln2O2SO4 as a new OSC material. The experimental result under model gas shows that the OSC of Ln2O2SO4 is 5 times lager than CZ.
Technical Paper

Study of Improvements in NOx Reduction Performance on Simultaneous Reduction System of PM and NOx

Performance improvements were studied for the diesel particulate and NOx reduction system (DPNR), a system that simultaneously reduces NOx and Particulate Matter (PM) from diesel engine exhaust gas. The experimental system (hereinafter called the “dual DPNR”) consists of two DPNR catalysts arranged in parallel, each provided with an exhaust throttle valve downstream to control the exhaust gas flow to the catalyst, plus a fuel injector that precisely controls the air-fuel ratio and the catalyst bed temperature. The fuel injector is used to supply a rich mixture to the DPNR catalyst, and the flow of exhaust gas is switched between the two catalysts by operating the exhaust throttle valves alternately. Tests were conducted with the engine running at steady state. The results indicated that the NOx reduction performance dramatically improved and the loss of fuel economy from the NOx reduction reduced.
Journal Article

Study of Alternative Oxygen Reduction Electrocatalyst for Pt Based on Transition Metal Chalcogenides

The development of an alternative oxygen reduction electrocatalyst to platinum based electrocatalysts is critical for practical use of the polymer electrolyte membrane fuel cell (PEMFC). Transition metal sulfide chalcogenides have recently been reported as a possible candidate for Pt replacement. Our work focused on chalcogenides composed of ruthenium, molybdenum, and sulfur (RuMoS). We elucidate the factors affecting electrocatalytic activity of carbon supported RuXMoY SZ catalyst. This was demonstrated through a correlation of oxygen reduction reaction (ORR) activity of the catalysts with structural changes resulting from designed changes in sulfur composition in the catalysts.
Technical Paper

Simultaneous PM and NOx Reduction System for Diesel Engines

A new after-treatment system called DPNR (Diesel Particulate-NOx Reduction System) has been developed for simultaneous and continuous reduction of particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust gas. This system consists of both a new catalytic technology and a new diesel combustion technology which enables rich operating conditions in diesel engines. The catalytic converter for the DPNR has a newly developed porous ceramic structure coated with a NOx storage reduction catalyst. A fresh DPNR catalyst reduced more than 80 % of both PM and NOx. This paper describes the concept and performance of the system in detail. Especially, the details of the PM oxidation mechanism in DPNR are described.
Technical Paper

Research on the Measures for Improving Cycle-to-Cycle Variations under High Tumble Combustion

Improving vehicle fuel economy is a central part of efforts toward achieving a sustainable society. An effective way for accomplishing this aim is to enhance the engine thermal efficiency. Measures to mitigate knocking and reduce engine cooling heat loss are important aspects of enhancing the engine thermal efficiency. Cooled exhaust gas recirculation (EGR) is regarded as a key technology because it is capable of achieving both of these objectives. For this reason, it has been adopted in a wide range of both hybrid and conventional vehicles in recent years. Toyota has been introducing these technologies as ESTEC (Economy with Superior Thermal Efficient Combustion). Improving cycle-to-cycle variations in combustion, in addition to fast combustion is essential for achieving high engine thermal efficiency.
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.
Journal Article

Reaction Mechanism Analysis of Di-Air-Contributions of Hydrocarbons and Intermediates

The details of Di-Air, a new NOx reduction system using continuous short pulse injections of hydrocarbons (HC) in front of a NOx storage and reduction (NSR) catalyst, have already been reported. This paper describes further studies into the deNOx mechanism, mainly from the standpoint of the contribution of HC and intermediates. In the process of a preliminary survey regarding HC oxidation behavior at the moment of injection, it was found that HC have unique advantages as a reductant. The addition of HC lead to the reduction or metallization of platinum group metals (PGM) while keeping the overall gas atmosphere in a lean state due to adsorbed HC. This causes local O₂ inhibition and generates reductive intermediate species such as R-NCO. Therefore, the specific benefits of HC were analyzed from the viewpoints of 1) the impact on the PGM state, 2) the characterization of intermediate species, and 3) Di-Air performance compared to other reductants.
Technical Paper

Parametric Study and Clarification of Determination Factors of Diesel Exhaust Emission Using a Single Cylinder Engine and Model Fuels - JCAP Combustion Analysis Working Group Report Part I

Single cylinder engine testing was carried out to clearly understand the test results of multi-cylinder engines reported by the Diesel WG in JCAP (Japan Clean Air Program) (1), (2), (3) and (4). In this tests, engine specifications such as fuel injection pressure, nozzle hole diameter, turbo-charging pressure, EGR rate, and fuel properties such as 1-, 2-, 3-ring aromatics content, n-,i-paraffins content, and T90 were parametrically changed and their influence on the emissions were studied. PM emission generally increased in each engine condition with increased aromatic contents and T90. In particular, multi ring aromatics brought about large increases in PM regardless of the engine conditions. The influence of fuel properties on NOx emission is smaller than the influence on PM emission. Some other fuels that have various side chain structures of 1-ring aromatics, normal paraffins only and various naphthene contents were also investigated.
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

New Exhaust Emission Control System with Two A/F Sensors

Exhaust systems must satisfy a wide range of requirements, including lowering emissions to comply with future fuel economy and emissions regulations. To help meet these requirements, new emissions control systems have been developed today. In addition, since air-fuel ratio (hereafter, A/F) control has a major impact on emissions, a new two-A/F sensor system with A/F sensors provided both upstream and downstream of the catalyst was developed, incorporating an A/F control capable of further lowering emissions with greater robustness. This development identified the hysteresis characteristics of the O2 sensor downstream of the catalyst as an important factor affecting emissions during conventional A/F control. Subsequently, reaction analysis was carried out using sensor reaction models and by evaluating sensors under real-world operating conditions.
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

Model-Based OBD Logic Utilizing Adsorption and Desorption Model of NH3 in SCR Catalyst

Urea selective catalytic reduction (SCR) systems are a promising technology for helping to lower NOx emissions from diesel engines. These systems also require on-board diagnostic (OBD) systems to detect malfunctioning catalysts. Conventional OBD methodology for a SCR catalyst involves the measurement of NOx concentration downstream of the catalyst. However, considering future OBD regulations, erroneous diagnostics may occur due to variations in the actual environment. Therefore, to enhance OBD accuracy, a new methodology was examined that utilizes NH3 slip as a new diagnostic parameter in addition to NOx. NH3 slip increases as the NOx reduction performance degrades, because both phenomena are based on deterioration in the capability of the SCR catalyst to adsorb NH3. Furthermore, NH3 can be measured by existing NOx sensors because NH3 is oxidized to NO internally. To make use of NH3 slip, an estimation model was developed.
Technical Paper

Influence of Sulfur Concentration in Gasoline on NOx Storage - Reduction Catalyst

Influence of sulfur poisoning on NOx storage - reduction catalysts (NSR catalysts) was examined using both model gas and an actual vehicle. Deterioration of NSR catalysts is explained as the balance of sulfate formation in lean operating conditions and the amount of sulfate decomposed under rich operating conditions. This study focused on sulfate decomposition characteristics of NSR catalysts. First, sulfate decomposition characteristics of an NSR catalyst were examined in a model gas test. It was found that the initial temperature of SOx release was higher than the sulfur poisoning temperature. Crystal growth of sulfate by increasing temperature was assumed, and hence suppressed SOx release. Second, various sulfur concentrations (8 - 500 ppm) in gasoline were used for vehicle durability. The duration of one durability cycle was 1,260 seconds, including a 60 second regeneration of sulfur poisoning (AFR 14.2, 700 °C).
Journal Article

In-Situ Liquid TEM Study on the Degradation Mechanism of Fuel Cell Catalysts

Electrode catalyst (platinum) degradation represents a major challenge to the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) in Fuel Cell Vehicles (FCVs). While various mechanisms have been proposed and investigated previously, there is still a need to develop in situ imaging techniques that can characterize and provide direct evidence to confirm the degradation process. In the present study, we report an in situ transmission electron microscopy (TEM) method that enables real time, high-resolution observation of carbon-supported platinum nanoparticles in liquid electrolyte under working conditions. By improving the design of the Micro Electro Mechanical Systems (MEMS) sample holder, the migration and aggregation of neighboring platinum nanoparticles could be visualized consistently and correlated to applied electrode potentials during aging process (i.e., cyclic voltammetry cycles).
Technical Paper

In Situ Observation of Catalysis Reactions Using Transmission Electron Microscope

Transmission electron microscope (TEM) is a powerful tool for studying catalyst materials at nano-size and/or atomic level. Conventional TEM usually needs to be observed at room temperature in high vacuum conditions. A gaseous atmosphere and high temperature condition may change the properties of catalyst materials. Recently we developed an in situ observation system in TEM for observing the oxidation and reduction under a gas atmosphere at high temperature. Using the new in situ observation system in TEM, the morphological changes of the nano particle and support were observed in the heated gaseous atmosphere at atomic level in real time.