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Technical Paper

The Study of NOx and PM Reduction Using Urea Selective Catalytic Reduction System for Heavy Duty Diesel Engine

2007-04-16
2007-01-1576
To reduce NOx and Particulate Matter (PM) emissions from a heavy-duty diesel engine, the effects of urea selective catalytic reduction (SCR) systems were studied. Proto type urea SCR system was composed of NO oxidation catalyst, SCR catalyst and ammonia (NH3) reduction catalyst. The NOx reduction performance of urea SCR system was improved by a new zeolite type catalyst and mixer for urea distribution at the steady state operating conditions. NOx and PM reduction performance of the urea SCR system with DPF was evaluated over JE05 mode of Japan. The NOx reduction efficiency of the urea SCR catalyst system was 72% at JE05 mode. The PM reduction efficiency of the urea SCR catalyst system with DPF was 93% at JE05 mode. Several kinds of un-regulated matters were detected including NH3 and N2O leak from the exhaust gas. It is necessary to have further study for detailed measurements for un-regulated emissions from urea solution.
Technical Paper

The Study of NOx Reduction Using Plasma-assisted SCR System for a Heavy Duty Diesel Engine

2011-04-12
2011-01-0310
To reduce NOx emissions from a heavy-duty engine at low exhaust temperature conditions, the plasma-assisted SCR (Selective Catalytic Reduction) system was evaluated. The plasma-assisted SCR system is mainly composed of an ammonia gas supply system and a plasma reactor including a pellet type SCR catalyst. The preliminary test with simulated gases of diesel exhaust showed an improvement in the NOx reduction performance by means of the plasma-assisted SCR system, even below 150°C conditions. Furthermore, NOx reduction ratio was improved up to 77% at 110°C with increase in the catalyst volume. Also NOx emissions from a heavy-duty diesel engine over the transient test mode in Japan (JE05) were reduced by the plasma-assisted SCR system. However, unregulated emissions, e.g., aldehydes, were increased with the plasma environment. This paper reports the advantages and disadvantages of the plasma-assisted SCR system for a heavy-duty diesel engine.
Technical Paper

Reaction Path Analysis and Modeling of NOx Reduction in a Cu-chabazite SCR Catalyst Considering Cu Redox Chemistry and Reversible Hydrolysis of Cu Sites

2020-09-15
2020-01-2181
In this study, reaction path analysis and modeling of NOx reduction phenomena by selective catalytic reduction (SCR) with NH3 over a Cu-chabazite catalyst were conducted considering changes in the valence state of Cu sites and local structure due to differences in ligands to the Cu sites. The analysis showed that in the Cu-chabazite catalyst, NOx was mainly reduced by adsorbed NH3 on divalent Cu sites accompanied by a change in valence state of Cu from divalent to monovalent. It is known that the activation energy of NOx reduction on a Cu-chabazite catalyst changes between low temperatures ≤ 200 °C and mid to high temperatures ≥ 300 °C. To express this phenomenon, a reversible hydrolysis reaction based on the difference in coordination state of hydroxyl groups (OH−) to Cu sites at low and high temperatures was introduced into the model.
Technical Paper

Reaction Analysis and Modeling of Fast SCR in a Cu-Chabazite SCR Catalyst Considering Generation and Decomposition of Ammonium Nitrate

2021-09-05
2021-24-0073
In this study, reaction path analysis and modeling of NOx reduction phenomena by fast SCR reaction on a Cu-chabazite catalyst were conducted, considering the formation and decomposition of ammonium nitrate (NH4NO3). White crystals of NH4NO3 decompose at temperatures < 200 °C. Thus, the reaction behavior changes at 200 °C under fast SCR reaction conditions. NH4NO3 formation can occur on both Cu sites and Brønsted acid sites, which are active sites for NOx reduction in the Cu-chabazite catalyst, but it is unclear where NH4NO3 accumulates on the catalyst. Analyses using catalyst test pieces with different active sites were performed to estimate this accumulation. The results suggested that NH4NO3 accumulation does not depend on the presence of either Cu sites or Brønsted acid sites. Therefore, it is assumed that NH4NO3 can be accumulated everywhere on the catalyst, including on the zeolite framework. This phenomenon was included in the model as formation/accumulation sites S'.
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

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

2019-01-15
2019-01-0024
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

Improvement of NOx Reduction Rate of Urea-SCR System by NH3 Adsorption Quantity Control

2008-10-06
2008-01-2498
A urea SCR system was combined with a DPF system to reduce NOx and PM in a four liters turbocharged with intercooler diesel engine. Significant reduction in NOx was observed at low exhaust gas temperatures by increasing NH3 adsorption quantity in the SCR catalyst. Control logic of the NH3 adsorption quantity for transient operation was developed based on the NH3 adsorption characteristics on the SCR catalyst. It has been shown that NOx can be reduced by 75% at the average SCR inlet gas temperature of 158 deg.C by adopting the NH3 adsorption quantity control in the JE05 Mode.
Technical Paper

Improvement of Low-Temperature Performance of The NOx Reduction Efficiency on the Urea-SCR Catalysts

2013-04-08
2013-01-1076
Diesel engine has a good fuel economy and high durability and used widely for power source such as heavy duty in the world. On the other hand, it is required to reduce NOx (Nitrogen Oxides) and PM (Particulate Matter) emissions further from diesel exhaust gases to preserve atmosphere. The urea-SCR (Selective Catalytic Reduction) system is the most promising measures to reduce NOx emissions. DPF (Diesel Particulate Filter) system is commercialized for PM reduction. However, in case that a vehicle has a slow speed as an urban area driving, a diesel exhaust temperature is too low to activate SCR catalyst for NOx reduction in diesel emissions. Moreover, the diesel exhaust temperature becomes lower as a future engine has less fuel consumption. The purpose of this study is reduction of NOx emission from a heavy-duty diesel engine using the Urea SCR system at the low temperature.
Technical Paper

Improvement of HC-SCR Performance by Fuel Reforming Using a Low Temperature Oxidation

2021-04-06
2021-01-0591
A fuel reforming technology using a low temperature oxidation was developed to improve a NOx reduction performance of HC-SCR (Hydrocarbons Selective Catalytic Reduction) system, which does not require urea. The low-temperature oxidization of a diesel fuel in gas phase produces NOx reduction agents with high NOx reduction ability such as aldehydes and ketones. A pre-evaporation-premixing-type reformer was adopted in order to generate a uniform temperature field and a uniform fuel/air premixed gas, and to promote the low temperature oxidation efficiently. As a fundamental study, elementary reaction analysis for n-hexadecane/air premixtures was carried out to investigate the suitable reformer temperature and fuel/air equivalence ratio for generation of oxygenated hydrocarbons. It was found that the reforming efficiency was highest at the reforming temperature around 623 to 673K, and aldehydes and ketones were produced.
Technical Paper

Impact Study of High Biodiesel Blends on Exhaust Emissions to Advanced Aftertreatment Systems

2010-04-12
2010-01-1292
In Biodiesel Fuel Research Working Group(WG) of Japan Auto-Oil Program(JATOP), some impacts of high biodiesel blends have been investigated from the viewpoints of fuel properties, stability, emissions, exhaust aftertreatment systems, cold driveability, mixing in engine oils, durability/reliability and so on. In the impact on exhaust emissions, the impact of high biodiesel blends into diesel fuel on diesel emissions was evaluated. The wide variety of biodiesel blendstock, which included not only some kinds of fatty acid methyl esters(FAME) but also hydrofined biodiesel(HBD) and Fischer-Tropsch diesel fuel(FTD), were selected to evaluate. The main blend level evaluated was 5, 10 and 20% and the higher blend level over 20% was also evaluated in some tests. The main advanced technologies for exhaust aftertreatment systems were diesel particulate filter(DPF), Urea selective catalytic reduction (Urea-SCR) and the combination of DPF and NOx storage reduction catalyst(NSR).
Technical Paper

Experimental and Numerical Analysis for a Urea-SCR Catalytic Converter

2016-04-05
2016-01-0973
Urea-SCR (Selective Catalytic Reduction) systems are getting a lot of attention as the most promising NOx reduction technology for heavy-duty diesel engine exhaust. In order to promote an effective development for an optimal urea-SCR after-treatment system, it is important to clarify the decomposition behavior of the injected urea and a detailed reaction chemistry of the reactants on the catalyst surface in exhaust gases. In this paper we discuss experimental and numerical studies for the development of a numerical simulation model for the urea-SCR catalyst converter. As a first step, in order to clarify the behavior of reductants in an urea-SCR converter, two types of diagnostic technique were developed; one is for measuring the amount of NH3, and the other is for measuring the amount of total reductants including unreacted urea and iso-cyanic acid. These techniques were applied to examine the behavior of reductants at the inlet and inside the SCR converter.
Technical Paper

Emission Characteristics from After-Treatment System of Medium and Light Duty Engines

2014-04-01
2014-01-1501
1 To meet the Japan Post New-Long-Term (Japan 2009) emissions regulation introduced in 2009, The Hydrocarbon Selective Catalytic Reduction (HC-SCR) system for the NOx emission with a diesel fuel was chosen among various deNOx after-treatment systems (the Urea-SCR, the NOx storage-Reduction Catalyst and so on). The HC-SCR was adopted, in addition to combustion modification of diesel engine (mainly cooled EGR) as the New DPR system. The New DPR system for medium and light duty vehicles was developed as a world's first technology by Hino Motors. Advantages of the New DPR are compact to easy-to-install catalyst converter and no urea solution (DEF) injection (regardless urea infrastructure) as compared the Urea-SCR system.
Technical Paper

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

2018-09-10
2018-01-1707
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

Development of the Burner Systems for EPA2010 Medium Duty Diesel Vehicles

2011-04-12
2011-01-0295
EPA 2010 emissions regulations - currently the strictest standards in the world - place particular emphasis on exhaust gas thermal control technology. The Burner System, a device developed to control exhaust gas temperatures, is the most effective means of raising exhaust gas temperature, as this system can function under any engine conditions, including low engine speed and torque. The Burner System begins operating immediately when the engine is started, activating the Diesel Exhaust Fluid (DEF) - Selective Catalytic Reduction (SCR) System immediately, because the Burner System is active, it enables the diesel particulate filter active regeneration under any engine operating conditions as well. This technical paper reports Burner System (ActiveClean™ Thermal Regenerator) development results.
Technical Paper

Development of High Accuracy and Quick Light-off NOx Sensor

2018-04-03
2018-01-0334
For the purpose of coping with the strengthening of NOx exhaust gas control and fuel consumption control, it is indispensable to improve the NOx purification capacity. In view of this, vehicle manufacturers are in the course of developing high performance SCR (Selective Catalytic Reduction) systems [1, 2]. For such SCR systems to be realized, high precision NOx sensors for carrying out urea injection quantity control and SCR degradation diagnosis are absolutely indispensable. Detection of NOx concentration by means of a NOx sensor is generally performed as follows: O2 is discharged by means of an O2 detection electrode; remaining NOx is decomposed by a NOx detection electrode; NOx concentration is then detected as electric current that flows when oxygen ions are conduct through solid electrolyte. In order to detect NOx of ppm-order, it is necessary to detect minute current of nA-order with high accuracy.
Technical Paper

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

2019-12-19
2019-01-2236
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

Acceleration of Fast-SCR Reactions by Eliminating “The Ammonia Blocking Effect”

2024-06-12
2024-37-0001
The recent and future trends of energy for heavy-duty vehicles are considered e-fuel, H2, and electricity, and the Selective Catalytic Reduction (SCR) system is necessary for achieving the goals of zero-emission internal combustion engines that use e-fuel and H2 as a fuel. The Japanese automotive industry uses a Cu-zeolite based SCR catalyst since Vanadium is designated as a specific chemical substance, which the Ministry of Environment prohibits its release into the atmosphere. This study attempted purification rate improvement by controlling the NH3 supply with a mini-reactor and by simulated exhaust gas. Specifically, the experiment was done by examining the effect of the pulse amplitude, frequency, and duty ratio on the purification rate by supplying the NH3 pulse injection to the test piece Cu-chabazite catalyst. Additionally, the results of the reactor experiment were validated by numerical simulation considering the detailed surface reaction processes on the catalyst.
Technical Paper

A Study on the Improvement of NOx Reduction Efficiency for a Urea SCR System

2015-09-01
2015-01-2014
Urea SCR (Selective Catalytic Reduction) exhaust after-treatment systems are one of the most promising measures to reduce NOx emissions from diesel engines. Both Cu-zeolite (Cu-SCR) and Fe-zeolite (Fe-SCR) urea SCR systems have been studied extensively but not many detailed studies have been conducted on the combination of both systems. Thus, we carried out studies on such Combined-SCR systems and their capability to reduce NOx under various engine operating conditions. We also conducted transient engine tests using different catalyst systems to compare their performance. The results show that combined-SCR systems can reduce NOx more effectively than Fe-SCR or Cu-SCR alone. The best NOx reduction performance was achieved at a Cu ratio of 0.667 (i.e. Fe: Cu =1: 2). Combined-SCR thus apparently benefits from the characteristics of both Cu-SCR and Fe-SCR, allowing it to reduce NOx over a wide range of operating conditions.
Technical Paper

A Study on N2O Formation Mechanism and Its Reduction in a Urea SCR System Employed in a DI Diesel Engine

2012-09-10
2012-01-1745
N₂O is known to have a significantly high global warming potential. We measured N₂O emissions in engine-bench tests by changing the NO/NH₃ ratio and exhaust gas temperature at the oxidation catalyst inlet in a heavy-duty diesel engine equipped with a urea SCR (selective catalytic reduction) system. The results showed that the peak N₂O production ratio occurred at an exhaust gas temperature of around 200°C and the maximum value was 84%. Moreover, the N₂O production ratio increased with increasing NO/NH₃. Thus, we concluded that N₂O is produced via the NO branching reaction. Based on our results, two methods were proposed to decrease N₂O formation. At low temperatures ~200°C, NO should be reduced by controlling diesel combustion to lower the contribution of NO to N₂O production. This is essential because the SCR system cannot reduce NOx at low temperatures.
Technical Paper

A Study of a New Aftertreatment System (1): A New Dosing Device for Enhancing Low Temperature Performance of Urea-SCR

2006-04-03
2006-01-0642
In order to reduce diesel NOx emissions, aftertreatment methods including LNT (Lean NOx Trap) and urea SCR (Selective Catalytic Reduction) have been researched. One of the shortcomings of urea SCR is its NOx reduction performance degradation at low exhaust gas temperatures and possible emission of unregulated byproducts. Here, a new type of a urea-dosing device to overcome these shortcomings is studied. This dosing device actively produces ammonia without depending upon the exhaust gas temperature, and designed for onboard application. The device incorporates an electrically heated bypass with a hydrolysis catalyst. An injector supplies urea solution into the bypass. The bypass is heated only when thermolysis is needed to produce ammonia (NH3). The hydrolysis catalyst further assists in the production of NH3. The ammonia gas obtained is then mixed with the main exhaust gas flow.
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