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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

2019-04-02
2019-01-1140
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 (12:1 and 10:1). 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)

2007-10-29
2007-01-4082
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

2008-04-14
2008-01-0843
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

2013-04-08
2013-01-0881
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

2017-03-28
2017-01-1179
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

2009-04-20
2009-01-1071
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

2005-10-24
2005-01-3884
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

2008-04-14
2008-01-1265
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

2002-03-04
2002-01-0957
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

2016-04-05
2016-01-0694
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.
Journal Article

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

2012-09-10
2012-01-1744
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

2002-10-21
2002-01-2824
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.
Technical Paper

New Exhaust Emission Control System with Two A/F Sensors

2017-03-28
2017-01-0917
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

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

2016-04-05
2016-01-0960
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

1999-10-25
1999-01-3501
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

2016-04-05
2016-01-1192
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

2008-04-14
2008-01-1266
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.
Technical Paper

Improvements in Low Temperature Diesel Combustion with Blending ETBE to Diesel Fuel

2007-07-23
2007-01-1866
The effects of blending ETBE to diesel fuel on the characteristics of low temperature diesel combustion and exhaust emissions were investigated in a naturally-aspirated DI diesel engine with large rates of cooled EGR. Low temperature smokeless diesel combustion in a wide EGR range was established with ETBE blended diesel fuel as mixture homogeneity is promoted with increased premixed duration due to decreases in ignitability as well as with improvement in fuel vaporization due to the lower boiling point of ETBE. Increasing the ETBE content in the fuel helps to suppress smoke emissions and maintain efficient smokeless operation when increasing EGR, however a too high ETBE content causes misfiring at larger rates of EGR. While the NOx emissions increase with increases in ETBE content at high intake oxygen concentrations, NOx almost completely disappears when reducing the intake oxygen content below 14 % with cooled EGR.
Technical Paper

Improvement of NOx Storage-Reduction Catalyst

2007-04-16
2007-01-1056
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

Hexagonal Cell Ceramic Substrates for Lower Emission and Backpressure

2008-04-14
2008-01-0805
Stringent emission regulations call for advanced catalyst substrates with thinner walls and higher cell density. However, substrates with higher cell density increase backpressure, thinner cell wall substrates have lower mechanical characteristics. Therefore we will focus on cell configurations that will show a positive effect on backpressure and emission performance. We found that hexagonal cells have a greater effect on emission and backpressure performance versus square or round cell configurations. This paper will describe in detail the advantage of hexagonal cell configuration versus round or square configurations with respect to the following features: 1 High Oxygen Storage Capacity (OSC) performance due to uniformity of the catalyst coating layer 2 Low backpressure due to the large hydraulic diameter of the catalyst cell 3 Quick light off characteristics due to efficient heat transfer and low thermal mass
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