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Technical Paper

Modeling Three-Way Catalyst Converters During Cold Starts And Potential Improvements

Three-way catalyst (TWC) converters are often used to purify toxic substances contained in exhaust emissions from gasoline engines. However, a large amount of CO, NOx and THC may be emitted before the TWC reaches its light-off temperature during a cold start. In this work, a numerical model was developed for studying the purification performance of a close-coupled TWC converter during the cold start period. The TWC model was built using axisuite, commercial software by Exothermia S.A. Model gas experiments were designed for calibrating the chemical reaction scheme and corresponding reaction rate parameters in the TWC model. The TWC model was able to simulate the purification performance of CO, NOx and THC under both lean and rich air-fuel equivalence ratios (λ) for different conditions. The light-off temperature and oxygen storage capacity (OSC) behavior were also successfully validated in the model. Vehicle tests were conducted on a chassis dynamometer to verify the TWC model.
Technical Paper

Analysis of NH3 Diffusion Phenomena in a Selective Catalytic Reduction Coated Diesel Particulate Filter Catalyst Using a Simple One-Dimensional Core Model

This paper describes a method for estimating constants related to NH3 gas diffusion phenomena to the active sites in a selective catalytic reduction diesel particulate filter (SCR/DPF) catalyst. A simple one-dimensional NH3 gas diffusion model based on the pore structure inside the catalyst was developed and used to estimate the intracrystalline diffusion coefficient. It was shown that the estimated value agreed well with experimental data.
Technical Paper

A Fundamental Study on Combustion Characteristics in a Pre-Chamber Type Lean Burn Natural Gas Engine

Pre-chamber spark ignition technology can stabilize combustion and improve thermal efficiency of lean burn natural gas engines. During compression stroke, a homogeneous lean mixture is introduced into pre-chamber, which separates spark plug electrodes from turbulent flow field. After the pre-chamber mixture is ignited, the burnt jet gas is discharged through multi-hole nozzles which promotes combustion of the lean mixture in the main chamber due to turbulence caused by high speed jet and multi-points ignition. However, details mechanism in the process has not been elucidated. To design the pre-chamber geometry and to achieve stable combustion under the lean condition for such engines, it is important to understand the fundamental aspects of the combustion process. In this study, a high-speed video camera with a 306 nm band-pass filer and an image intensifier is used to visualize OH* self-luminosity in rapid compression-expansion machine experiment.
Technical Paper

Analysis and Modeling of NOx Reduction Based on the Reactivity of Cu Active Sites and Brønsted Acid Sites in a Cu-Chabazite SCR Catalyst

The NOx-reducing activity of a Cu-chabazite selective catalytic reduction (SCR) catalyst was analyzed over a wide temperature range. The analysis was based on the ammonia SCR (NH3-SCR) mechanism and accounted for Cu redox chemistry and reactions at Brønsted acid sites. The reduction of NOx to N2 (De-NOx) at Cu sites was found to proceed via different paths at low and high temperatures. Consequently, the rate-limiting step of the SCR reaction at Cu sites varied with the temperature. The rate of NOx reduction at Cu sites below 200°C was determined by the rate of Cu oxidation. Conversely, the rate of NOx reduction above 300°C was determined by the rate of NH3 adsorption on Cu sites. Moreover, the redox state of the active Cu sites differed at low and high temperatures. To clarify the role of the chabazite Brønsted acid sites, experiments were also performed using a H-chabazite catalyst that lacks Cu sites.
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

Kinetic Modeling of Ammonia-SCR and Experimental Studies over Monolithic Cu-ZSM-5 Catalyst

Ammonia-selective catalytic reduction (SCR) systems have been introduced commercially in diesel vehicles, however catalyst systems with higher conversion efficiency and better control characteristics are required to know the actual emissions during operation and the emissions in random test cycles. Computational fluid dynamics (CFD) is an effective approach when applied to SCR catalyst development, and many models have been proposed, but these models need experimental verification and are limited in the situations they apply to. Further, taking account of redox cycle is important to have better accuracy in transient operation, however there are few models considering the cycle. Model development considering the redox reactions in a zeolite catalyst, Cu-ZSM-5, is the object of the research here, and the effects of exhaust gas composition on the SCR reaction and NH3 oxidation at high temperatures are investigated.
Technical Paper

Effects of Soot Deposition on NOx Purification Reaction and Mass Transfer in a SCR/DPF Catalyst

Experimental studies were carried out to investigate the effect of soot deposition on NOx purification phenomena in an ammonia selective catalytic reduction coated diesel particulate filter (SCR/DPF) catalyst. To study soot deposition effects on the chemical reactions and mass transfer, two types of testing device were used. A synthetic gas bench enabling tests to be conducted with temperature and flow rate ranges relevant to real driving conditions was used to investigate the soot influence on reduction of NOx to N2 (DeNOx). A micro-reactor that removed the effect of soot deposition on mass transfer in the catalyst layer was used to analyze chemical reactions on a soot surface and their interaction with the SCR catalyst. A filter test brick of a Cu-zeolite SCR/DPF catalyst and a powder catalyst were used for the synthetic gas bench and micro-reactor tests, respectively. Engine soot was sampled in all the tests.
Technical Paper

A Quasi Two Dimensional Model of Transport Phenomena in Diesel Particulate Filters - The Effects of Particle Diameter on the Pressure Drop in DPF Regeneration Mode-

Experimental and numerical studies on the combustion of the particulate matter in the diesel particulate filter with the particulate matter loaded under different particulate matter loading condition were carried out. It was observed that the pressure losses through diesel particulate filter loaded with particulate matter having different mean aggregate particle diameters during both particulate matter loading and combustion periods. Diesel particulate filter regeneration mode was controlled with introducing a hot gas created in Diesel Oxidation Catalyst that oxidized hydrocarbon injected by a fuel injector placed on an exhaust gas pipe. The combustion amount was calculated with using a total diesel particulate filter weight measured by the weight meter both before and after the particulate matter regeneration event.
Journal Article

Detailed Diesel Combustion and Soot Formation Analysis with Improved Wall Model Using Large Eddy Simulation

A mixed time-scale subgrid large eddy simulation was used to simulate mixture formation, combustion and soot formation under the influence of turbulence during diesel engine combustion. To account for the effects of engine wall heat transfer on combustion, the KIVA code's standard wall model was replaced to accommodate more realistic boundary conditions. This were carried out by implementing the non-isothermal wall model of Angelberger et al. with modifications and incorporating the log law from Pope's method to account for the wall surface roughness. Soot and NOx emissions predicted with the new model are compared to experimental data acquired under various EGR conditions.
Technical Paper

A Quasi Two Dimensional Model of Transport Phenomena in Diesel Particulate Filters - The Effects of Particle and Wall Pore Diameter on the Pressure Drop -

Experimental and numerical studies were conducted on diesel particulate filters (DPFs) under different soot loading conditions and DPF configurations. Pressure drops across DPFs with various mean pore diameters loaded with soots having different mean particle diameters were measured by introducing exhaust gases from a 2.2 liter inline four-cylinder, TCI diesel engine designed for use in passenger cars. A mechanistic hypothesis was then proposed to explain the observed trends, accounting for the effects of the soot loading regime in the wall and the soot cake layer on the pressure drop. This hypothesis was used to guide the development and validation of a numerical model for predicting the pressure drop in the DPF. The relationship between the permeability and the porosity of the wall and soot cake layer was modeled under various soot loading conditions.
Technical Paper

Developments of the Reduced Chemical Reaction Scheme for Multi-Component Gasoline Fuel

The reduced chemical reaction scheme which can take the effect of major fuel components on auto ignition timing into account has been developed. This reaction scheme was based on the reduced reaction mechanism for the primary reference fuels (PRF) proposed by Tsurushima [1] with 33 species and 38 reactions. Some pre-exponential factors were modified by using Particle Swarm Optimization to match the ignition delay time versus reciprocal temperature which was calculated by the detailed scheme with 2,301 species and 11,116 elementary chemical reactions. The result using the present reaction scheme shows good agreements with that using the detailed scheme for the effects of EGR, fuel components, and radical species on the ignition timing under homogeneous charge compression ignition combustion (HCCI) conditions.
Technical Paper

Computational Study to Improve Thermal Efficiency of Spark Ignition Engine

The objective of this paper is to investigate the potential of lean burn combustion to improve the thermal efficiency of spark ignition engine. Experiments used a single cylinder gasoline spark ignition engine fueled with primary reference fuel of octane number 90, running at 4000 revolution per minute and at wide open throttle. Experiments were conducted at constant fueling rate and in order to lean the mixture, more air is introduced by boosted pressure from stoichiometric mixture to lean limit while maintaining the high output engine torque as possible. Experimental results show that the highest thermal efficiency is obtained at excess air ratio of 1.3 combined with absolute boosted pressure of 117 kPa. Three dimensional computational fluid dynamic simulation with detailed chemical reactions was conducted and compared with results obtained from experiments as based points.
Journal Article

A Numerical Study of the Effects of FAME Blends on Diesel Combustion and Emissions Characteristics Using a 3-D CFD Code Combined with Detailed Kinetics and Phenomenological Soot Formation Models

The objective of the present research is to analyze the effects of using oxygenated fuels (FAMEs) on diesel engine combustion and emission (NOx and soot). We studied methyl oleate (MO), which is an oxygenated fuel representative of major constituents of many types of biodiesels. Engine tests and numerical simulations were performed for 100% MO (MO100), 40% MO blended with JIS#2 diesel (MO40) and JIS#2 diesel (D100). The effects of MO on diesel combustion and emission characteristics were studied under engine operating conditions typically encountered in passenger car diesel engines, focusing on important parameters such as pilot injection, injection pressure and exhaust gas recirculation (EGR) rate. We used a diesel engine complying with the EURO4 emissions regulation, having a displacement of 2.2 L for passenger car applications. In engine tests comparing MO with diesel fuel, no effect on engine combustion pressure was observed for all conditions tested.
Technical Paper

Modeling of Diesel Engine Components for Model-Based Control (First Report): The construction and validation of a model of the Air Intake System

Model based control design is an important method for optimizing engine operating conditions so as to simultaneously improve engines' thermal efficiency and emission profiles. Modeling of intake system that includes an intake throttle valve, an EGR valve and a variable geometry turbocharger was constructed based on conservation laws combined with maps. Calculated results were examined the predictive accuracy of fresh charge mass flow, EGR rate and boost pressure.
Journal Article


We have constructed a quasi-2-dimensional NH₃-SCR model with detailed surface reactions to analyze the NOx conversion mechanism and reasons for its inhibition at low temperatures. The model consists of seven detailed surface reactions proposed by Grozzale et al., and calculates longitudinal gas flow, gas phase-catalyst phase mass transfer, and mass diffusion within the catalyst phase in the depth dimension. Using the model, we have analyzed the results of pulsed ammonia (NH₃) feed tests at various catalyst temperatures, and results show that ammonium nitrate (NH₄NO₃) is the inhibitor in NH₃-SCR reactions at low temperatures. In addition, we found that cutting the supply of NH₃ causes decomposition of NH₄NO₃, providing surface ammonia (NH₄+), which rapidly reacts with adjacent NOx, leading to an instantaneous rise in nitrogen (N₂) formation.
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

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

Control Strategy for Urea-SCR System in Single Step Load Transition

Urea-SCR system has a high NOx reduction potential in the steady-state diesel engine operation. In complicated transient operations, however, there are certain problems with the urea-SCR system in that NOx reduction performance degrades and adsorbed NH3 would be emitted. Here, optimum urea injection methods and exhaust bypass control to overcome these problems are studied. This exhaust bypass control enables NO/NOx ratio at the inlet of SCR catalyst to be decreased widely, which prevents over production of NO2 at the pre-oxidation catalyst. Steady-state and simple transient engine tests were conducted to clarify NOx reduction characteristics when optimum urea injection pattern and exhaust bypass control were applied. In simple transient test, only the engine load was rapidly changed for obtaining the fundamental knowledge concerning the effect of those techniques.
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

The Effect of Intake, Injection Parameters and Fuel Properties on Diesel Combustion and Emissions

To improve urban air pollution, stringent emissions regulations for heavy-duty diesel engines have been proposed and will become effective in Japan, the EU, and the United States in a few years. To comply with such future regulations, it is critical to investigate the effects of intake and injection parameters and fuel properties on engine performance, efficiency and emissions characteristics, associated with the use of aftertreatment systems. An experimental study was carried out to identify such effects. In addition, the KIVA-3 code was used to gain insight into cylinder events. The results showed improvements in NOx-Smoke and BSFC trade-offs at high-pressure injection in conjunction with EGR and supercharging.