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Technical Paper

Understanding Catalyst Overheating Protection (COP) as a Source of Post-TWC Ammonia Emissions from Petrol Vehicle

2022-08-30
2022-01-1032
TWC exposure to extreme temperature could result in irreversible damage or thermal failure. Thus, a strategy embedded in the engine control unit (ECU) called catalyst overheating protection (COP) will be activated to prevent TWC overheating. When COP is activated, the command air-fuel ratio will be enriched to cool the catalyst monolith down. Fuel enrichment has been proven a main prerequisite for ammonia formation in hot TWCs as a by-product of NOx reduction. Hence, COP events could theoretically be a source of post-catalyst ammonia from petrol vehicles, but this theory is yet to be confirmed in published literature. This paper validated this hypothesis using a self-programmed chassis-level test. The speed of the test vehicle was set to constant while the TWC temperature was raised stepwise until a COP event was activated.
Technical Paper

Kinetic Measurements of HNCO Hydrolysis over SCR Catalyst

2018-09-10
2018-01-1764
To meet the strict emission regulations for diesel engines, an advanced processing device such as a Urea-SCR (selective catalytic reduction) system is used to reduce NOx emissions. The Real Driving Emissions (RDE) test, which is implemented in the European Union, will expand the range of conditions under which the engine has to operate [1], which will lead to the construction of a Urea-SCR system capable of reducing NOx emissions at lower and higher temperature conditions, and at higher space velocity conditions than existing systems. Simulations are useful in improving the performance of the urea-SCR system. However, it is necessary to construct a reliable NOx reduction model to use for system design, which covers the expanded engine operation conditions. In the urea-SCR system, the mechanism of ammonia (NH3) formation from injected aqueous urea solution is not clear. Thus, it is important to clarify this mechanism to improve the NOx reduction model.
Journal Article

Prediction of Spray Behavior in Injected by Urea SCR Injector and the Reaction Products

2017-10-08
2017-01-2375
In the urea SCR system, urea solution is injected by injector installed in the front stage of the SCR catalyst, and NOx can be purified on the SCR catalyst by using NH3 generated by the chemical reaction of urea. NH3 is produced by thermolysis of urea and hydrolysis of isocyanic acid after evaporation of water in the urea solution. But, biuret and cyanuric acid which may cause deposit are sometimes generated by the chemical reactions without generating NH3. Spray behavior and chemical reaction of urea solution injected into the tail-pipe are complicated. The purpose of this study is to reveal the spray behavior and NH3 generation process in the tail-pipe, and to construct the model capable of predicting those accurately. In this report, the impingement spray behavior is clarified by scattered light method in high temperature flow field. Liquid film adhering to the wall and deposit generated after evaporation of water from the liquid film are photographed by the digital camera.
Technical Paper

Degradation of DeNOx Performance of a Urea-SCR System in In-Use Heavy-Duty Vehicles Complying with the New Long-Term Regulation in Japan and Estimation of its Mechanism

2016-04-05
2016-01-0958
Degradation of the deNOx performance has been found in in-use heavy-duty vehicles with a urea-SCR system in Japan. The causes of the degradation were studied, and two major reasons are suggested here: HC poisoning and deactivation of pre-oxidation catalysts. Hydrocarbons that accumulated on the catalysts inhibited the catalysis. Although they were easily removed by a simple heat treatment, the treatment could only partially recover the original catalytic performance for the deNOx reaction. The unrecovered catalytic activity was found to result from the decrease in conversion of NO to NO2 on the pre-oxidation catalyst. The pre-oxidation catalyst was thus studied in detail by various techniques to reveal the causes of the degradation: Exhaust emission tests for in-use vehicles, effect of heat treatment on the urea-SCR systems, structural changes and chemical changes in active components during the deactivation were systematically investigated.
Technical Paper

A Study of Hydrogen Internal Combustion Engine EGR System

2014-04-01
2014-01-1071
NOx are the only harmful emissions of hydrogen internal combustion engine. EGR is one of the effective methods to reduce NOx. The traditional EGR is not suitable for hydrogen internal combustion engine. Therefore, the study of influence of hot EGR on hydrogen internal combustion engine is important. A 2.0L hydrogen internal combustion engine with hot EGR system model is employed to optimize the diameter and position of hot EGR based on a simulation analysis. The result shows that both of the combustion temperature and NOx increase as EGR increases due to the rise of intake temperature for low load condition, for heavy load, with the increase of EGR rate, NOx emissions decreases slightly before the mixture equivalence ratio comes to 1and then dropped significantly after the mixture equivalence ratio greater than 1. Unburned hydrogen in TWC has the effect of reducing NOx after catalysts decrease largely.
Technical Paper

Effects of Electrically Heated Catalyst on the Low Temperature Performance of Vanadium-Based SCR Catalyst on Diesel Engine

2014-04-01
2014-01-1527
The NOx conversion efficiency of vanadium-based SCR catalyst is lower under low temperature. Utilizing an exhaust analyzer, the effects of electrically heated catalyst on the performance of vanadium-based SCR catalyst under low temperature was studied on the engine test bench. The inlet temperature of SCR catalyst without the electrically heated catalyst were in the range of 150°C∼270°C under various steady engine modes, and the NSR (Normalized Stoichiometric Ratio) was set as 0.4,0.6,0.8,1.0. The results showed that under the space velocity of 20000h−1, with the application of the electrically heated catalyst, the inlet temperature of SCR increased about 19.9°C on average and the NOx conversion efficiency improved about 8.0%. The NOx conversion efficiency increased 1.7%∼8.6% at the temperatures of 150°C∼174°C, and 1.0%∼15.9% at the temperatures of 186°C∼270°C.
Technical Paper

A Study of the Adaptability of Three Way Catalytic Converter under Hydrogen-Gasoline Dual-Fuel Alternate Working Mode

2014-04-01
2014-01-1342
Nowadays, the world is facing severe energy crisis and environment problems. Development of hydrogen fuel vehicles is one of the best ways to solve these problems. Due to the difficulties of infrastructures, such as the hydrogen transport and storage, hydrogen fuel vehicles have not been widely used yet. As a result, Hydrogen-gasoline dual-fuel vehicle is a solution as a compromise. In this paper, three way catalytic converter (TWC) was used to reduce emissions of hydrogen-gasoline dual-fuel vehicles. On wide open throttle and load characteristics, the conversion efficiency of TWC in gasoline engine was measured. Then the TWC was connected to a hydrogen internal combustion engine. After switching the hydrogen and gasoline working mode, emission data was measured. Experiment results show that the efficiency of a traditional TWC can be maintained above 85%., while it works in a hydrogen-gasoline dual-fuel alternative working mode.
Technical Paper

Impact of Fuel Metal Impurities on the Durability of a Light-Duty Diesel Aftertreatment System

2013-04-08
2013-01-0513
Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. Using an accelerated aging procedure, a set of production exhaust systems from a 2011 Ford F250 equipped with a 6.7L diesel engine have been aged to an equivalent of 150,000 miles of thermal aging and metal exposure. These exhaust systems included a diesel oxidation catalyst (DOC), selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ULSD containing no measureable metals, B20 containing sodium, B20 containing potassium and B20 containing calcium. Metals levels were selected to simulate the maximum allowable levels in B100 according to the ASTM D6751 standard. Analysis of the aged catalysts included Federal Test Procedure emissions testing with the systems installed on a Ford F250 pickup, bench flow reactor testing of catalyst cores, and electron probe microanalysis (EPMA).
Journal Article

HC Traps for Gasoline and Ethanol Applications

2013-04-08
2013-01-1297
In-line hydrocarbon (HC) traps are not widely used to reduce HC emissions due to their limited durability, high platinum group metal (PGM) concentrations, complicated processing, and insufficient hydrocarbon (HC) retention temperatures required for efficient conversion by the three-way catalyst component. New trapping materials and system architectures were developed utilizing an engine dynamometer test equipped with dual Fourier Transform Infrared (FTIR) spectrometers for tracking the adsorption and desorption of various HC species during the light-off period. Parallel laboratory reactor studies were conducted which show that the new HC trap formulations extend the traditional adsorption processes (i.e., based on physic-sorption and/or adsorption at acid sites) to chemical reaction mechanisms resulting in oligomerized, dehydro-cyclization, and partial coke formation.
Technical Paper

Advanced Urea SCR System Study with a Light Duty Diesel Vehicle

2012-04-16
2012-01-0371
U.S. federal vehicle emission standards effective in 2007 require tight control of NOx and hydrocarbon emissions. For light-duty vehicles, the current standard of Tier 2 Bin 5 is about 0.07 g/mi NOx and 0.09 g/mi NMOG (non-methane organic gases) at 120,000 mi. However, the proposed future standard is 0.03 g/mi for NMOG + NOx (~SULEV30) at 150,000 mi. There is a significant improvement needed in catalyst system efficiencies for diesel vehicles to achieve the future standard, mainly during cold start. In this study, a less than 6000 lbs diesel truck equipped with an advanced urea Selective Catalytic Reduction (SCR) system was used to pursue lower tailpipe emissions with an emphasis on vehicle calibration and catalyst package. The calibration was tuned by optimizing exhaust gas recirculation (EGR) fuel injection and cold start strategy to generate desirable engine-out emissions balanced with reasonable temperatures.
Technical Paper

Real-time Analysis of Benzene in Exhaust Gas from Driving Automobiles Using Jet-REMPI Method

2009-11-02
2009-01-2740
Real-time analysis of benzene in automobile exhaust gas was performed using the Jet-REMPI (supersonic jet / resonance enhanced multi-photon ionization) method. Real-time benzene concentration of two diesel trucks and one gasoline vehicle driving in Japanese driving modes were observed under ppm level at 1 s intervals. As a result, it became obvious that there were many differences in their emission tendencies, because of their car types, driving conditions, and catalyst conditions. In two diesel vehicle, benzene emission tendencies were opposite. And, in a gasoline vehicle, emission pattern were different between hot and cold conditions due to the catalyst conditions.
Technical Paper

Detection of Deteriorated Catalyst on Vehicle under Actual Operation Conditions: Application of FFT Analysis to Signal Wave by the Dual Oxygen Sensors Method

2007-07-23
2007-01-1927
The object of this study is to investigate an on-board diagnostic method to detect the deterioration of a three-way catalyst (TWC) under actual vehicle operating conditions, including the acceleration state. The signal data of two oxygen sensors were processed by the fast Fourier transformation (FFT) method. As a result, we found that the power spectrum of the signal waves can be the index of catalyst deterioration degree. Furthermore, it was confirmed that the difference between the power spectrum of the upstream oxygen sensor signal and one of the downstream oxygen sensor signal named ΔPower is effective index for detection of deteriorated catalyst under acceleration conditions.
Technical Paper

Optimization of Engine System for Application of Biodiesel Fuel

2007-07-23
2007-01-2028
Application of biodiesel fuel (BDF) to diesel engine is very effective to reduce CO2 emission, because biodiesel is carbon neutral in principle. However, biodiesels yield an increase in NOx emission from conventional diesel engine, compared with diesel fuel case. Therefore, some strategies are needed for meeting the future emission regulations when using biodiesel. In this study, rapeseed oil methyl ester (RME) was applied to diesel engine equipped with exhaust gas recirculation (EGR) system and NOx storage reduction (NSR) catalyst. NOx reduction rate of NSR catalyst was drastically decreased by using RME, even if injection quantity of RME for rich spike was enhanced. However, an increase in EGR rate could reduce NOx emission without the deterioration in smoke and PM emissions.
Technical Paper

SOF Component of Lubricant Oil on Diesel PM in a High Boosted and Cooled EGR Engine

2007-04-16
2007-01-0123
The engine in the research is a single cylinder DI diesel using the emission reduction techniques such as high boost, high injection pressure and broad range and high quantity of exhaust gas recirculation (EGR). The study especially focuses on the reduction of particulate matter (PM) under the engine operating conditions. In the experiment the authors measured engine performance, exhaust gases and mass of PM by low sulfur fuel such as 3 ppm and low sulfur lubricant oil such as 0.26%. Then the PM components were divided into soluble organic fraction (SOF) and insoluble organic fraction (ISOF) and they were measured at each engine condition. The mass of SOF was measured from the fuel fraction and lubricant oil fraction by gas chromatography. Also each mass of soot fraction and sulfate fraction was measured as components of ISOF. The experiment was conducted at BMEP = 2.0 MPa as full load condition of the engine and changing EGR rate from 0% to 40 %.
Technical Paper

Effects of Fuel Properties on the Performance of Advanced Diesel NOx Aftertreatment Devices

2006-10-16
2006-01-3443
In the Japan Clean Air Program II (JCAP II) Diesel WG, effects of fuel properties on the performance of two types of diesel NOx emission aftertreatment devices, a Urea-SCR system and a NOx storage reduction (NSR) catalyst system, were examined. For a Urea-SCR system, the NOx emission reduction performance with and without an oxidation catalyst installed in front of the SCR catalyst at low exhaust gas temperature operation was compared. For an NSR catalyst system, the effect of fuel sulfur on both emissions and fuel economy during 50,000 km driving was examined. Furthermore, effects of other fuel properties such as distillation on exhaust emissions were investigated. The results show that sulfur is the influential factor for both devices. Namely, high NOx emission reduction performance of the Urea-SCR system with the oxidation catalyst at low exhaust gas temperature operation is influenced by sulfur.
Technical Paper

Impact of Oil-derived Sulfur and Phosphorus on Diesel NOx Storage Reduction Catalyst - JCAP II Oil WG Report

2006-10-16
2006-01-3312
Emission regulations for diesel-powered vehicles have been gradually tightening. Installation of after-treatment devices such as diesel particulate filters (DPF), NOx storage reduction (NSR) catalysts, and so on is indispensable to satisfy rigorous limits of particulate matter (PM) and nitrogen oxides (NOx). Japan Clean Air Program II Oil Working Group (JCAPII Oil WG) has been investigating the effect of engine oil on advanced diesel after-treatment devices. First of all, we researched the impact of oil-derived ash on continuous regeneration-type diesel particulate filter (CR-DPF), and already reported that the less sulfated ash in oil gave rise to lower pressure drop across CR-DPF [1]. In this paper, impact of oil-derived sulfur and phosphorus on NSR catalyst was investigated using a 4L direct injection common-rail diesel engine with turbo-intercooler. This engine equipped with NSR catalyst meets the Japanese new short-term emission regulations.
Technical Paper

Development of DME Engine for Heavy-duty Truck

2006-04-03
2006-01-0052
In recent years, attention has focused on smokeless, sulfur-free dimethyl ethyl (DME) as a clean fuel for heavy-duty diesel vehicles [1]. In this development, the DME engine applied for 20-ton GVW truck was developed under the auspices of the Ministry of Land, Infrastructure and Transport of Japan, the first known instance worldwide. With careful design of the fuel system considering DME's unique fuel characteristics and suitable combustion improvement, higher torque was obtained with DME, compared to diesel fueling. and also use of the proper EGR and catalyst, exhaust emissions levels were generally less than one-fourth of new long-term regulation value promulgated in 2005 Japan.
Technical Paper

Emission Characteristics of a Urea SCR System under Catalysts Activated and De-Activated Conditions

2006-04-03
2006-01-0639
Urea SCR (Selective Catalytic Reduction) system has high potential of reducing NOx. But such as system durability and safety under deteriorated catalysts conditions have not been well enough clarified because it is new technology for vehicles. In this paper, current NOx emission level of an engine equipped with urea SCR system is discussed and then exhaust emission characteristics were analyzed when the SCR catalyst and/or oxidation catalyst lose their functions. When both SCR and oxidation catalyst were de-activated, not only NOx but also PM increased remarkably, which were much more than the engine-out emissions. Oxidation catalyst downstream of SCR catalyst was effective to suppress such deteriorations.
Technical Paper

Feasibility Study of Urea SCR Systems on Heavy Duty Commercial Vehicles

2004-06-08
2004-01-1944
Four urea SCR systems were developed and evaluated on a C/D and on the road to investigate their potential for Japanese emission regulations in 2005 and beyond. Test results showed that NOx conversion ratios were 50 to 70% during the Japanese D13 mode cycle, and the ratios under the transient driving cycle were lower than those tested during a steady state. Unregulated emissions, such as benzene, aldehyde and benzo[a]pyrene, existed either at a trace level using the oxidation catalyst, or lower than a base diesel engine, when no oxidation catalyst was used. The health effects of particulate matter emitted from the SCR system were almost the same as those from conventional diesel engines, as evaluated by the Ames test and in vitro micronucleus test. Thermal degradation products, such as cyanuric acid and melamine, were two to four figures lower compared with the toxicological information of Safety Information Resources Inc. (SIRI).
Technical Paper

77 Basic Investigation of Particulate Matters (O-PM)) and Polycyclic Aromatic Hydrocarbons Emitted by Two-stroke Motorcycles

2002-10-29
2002-32-1846
Characteristics of mass emission of unburned Oil-Particulate Matter and polycyclic aromatic hydrocarbons from two-stroke scooter were investigated. The tests were carried out under with and without oxidation catalyst and various air-fuel ratio ranging from 12 to 16 at 50:1 of fuel-oil mixing ratio for easy sampling. Unburned Oil-Particulate Matter and 4- to 7-rings polycyclic aromatic hydrocarbons were trapped on filter. These compounds were analyzed by high performance liquid chromatography with fluorescence detector. Mass emission of polycyclic aromatic hydrocarbons and unburned Oil-Particulate Matter tends to decrease as air-fuel ratio which increased up to stoichiometric ratio. The highest conversion ratio of unburned Oil-Particulate Matter on the oxidation catalyst was 64%. Conversion ratio of polycyclic aromatic hydrocarbons increased as rings are smaller.
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