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Journal Article

Study of On-Board Ammonia (NH3) Generation for SCR Operation

2010-04-12
2010-01-1071
Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.
Journal Article

Impact of Hydrocarbons on the Dual (Oxidation and SCR) Functions of Ammonia Oxidation Catalysts

2014-04-01
2014-01-1536
Ammonia oxidation (AMOX) catalysts are critical parts of most diesel aftertreatment systems around the world. These catalysts are positioned downstream of selective catalytic reduction (SCR) catalysts and remove unreacted NH3 that passes through the SCR catalyst. In many configurations, the AMOX catalyst is situated after a diesel oxidation catalyst and catalyzed diesel particulate filter that oxidize CO and hydrocarbons. However, in Euro V and proposed Tier 4 final aftertreatment architectures there is no upstream oxidation catalyst. In this study, the impact of hydrocarbons is evaluated on two different types of AMOX catalysts. One has dual washcoat layers-SCR washcoat on top of PGM washcoat-and the other has only a PGM washcoat layer. Results are presented for NH3 and hydrocarbon oxidation, NOx and N2O selectivity, and hydrocarbon storage. The AMOX findings are rationalized in terms of their impact on the individual oxidation and SCR functions.
Journal Article

Experimental and Modeling Study of Ash Impact on DPF Backpressure and Regeneration Behaviors

2015-04-14
2015-01-1063
One field-returned DPF loaded with a high amount of ash is examined using experimental and modeling approaches. The ash-related design factors are collected by coupling the inspection results from terahertz spectroscopy with a calibrated DPF model. The obtained ash packing density, ash layer permeability and ash distribution profile are then used in the simulation to assess the ash impact on DPF backpressure and regeneration behaviors. The following features have been observed during the simulation: 1 The ash packing density, ash layer permeability and ash distribution profile should be collected at the same time to ensure the accurate prediction of ash impact on DPF backpressure. Missing one ash property could mislead the measurement of the other two parameters and thus affects the DPF backpressure estimation. 2 The ash buildup would gradually increase the frequency for the backpressure-based active soot regeneration.
Journal Article

Conversion of Short-Chain Alkanes by Vanadium-Based and Cu/Zeolite SCR Catalysts

2016-04-05
2016-01-0913
The oxidation of short-chain alkanes, such as methane, ethane, and propane, from the exhaust of lean-burn natural gas and lean-burn dual-fuel (natural gas and diesel) engines poses a unique challenge to the exhaust aftertreatment community. Emissions of these species are currently regulated by the US Environmental Protection Agency (EPA) as either methane (Greenhouse Gas Emissions Standards) or non-methane hydrocarbon (NMHC). However, the complete catalytic oxidation of short-chain alkanes is challenging due to their thermodynamic stability. The present study focuses on the oxidation of short-chain alkanes by vanadium-based and Cu/zeolite selective catalytic reduction (SCR) catalysts, generally utilized to control NOx emissions from lean-burn engines. Results reveal that these catalysts are active for short-chain alkane oxidation, albeit, at conversions lower than those generally reported in the literature for Pd-based catalysts, typically used for short-chain alkane conversion.
Journal Article

Impact of Hydrothermal Aging on the Formation and Decomposition of Ammonium Nitrate on a Cu/zeolite SCR Catalyst

2017-03-28
2017-01-0946
Low-temperature (T ≤ 200°C) NOx conversion is receiving increasing research attention due to continued potential reductions in regulated NOx emissions from diesel engines. At these temperatures, ammonium salts (e.g., ammonium nitrate, ammonium (bi)sulfate, etc.) can form as a result of interactions between NH3 and NOx or SOx, respectively. The formation of these salts can reduce the availability of NH3 for NOx conversion, block active catalyst sites, and result in the formation of N2O, a regulated Greenhouse Gas (GHG). In this study, we investigate the effect of hydrothermal aging on the formation and decomposition of ammonium nitrate on a state-of-the-art Cu/zeolite selective catalytic reduction (SCR) catalyst. Reactor-based constant-temperature ammonium nitrate formation, temperature programmed oxidation (TPO), and NO titration experiments are used to characterize the effect of hydrothermal aging from 600 to 950°C.
Journal Article

Understanding System- and Component-Level N2O Emissions from a Vanadium-Based Nonroad Diesel Aftertreatment System

2017-03-28
2017-01-0987
Nitrous oxide (N2O), with a global warming potential (GWP) of 297 and an average atmospheric residence time of over 100 years, is an important greenhouse gas (GHG). In recognition of this, N2O emissions from on-highway medium- and heavy-duty diesel engines were recently regulated by the US Environmental Protection Agency (EPA) and National Highway Traffic Safety Administration’s (NHTSA) GHG Emission Standards. Unlike NO and NO2, collectively referred to as NOx, N2O is not a major byproduct of diesel combustion. However, N2O can be formed as a result of unselective catalytic reactions in diesel aftertreatment systems, and the mitigation of this unintended N2O formation is a topic of active research. In this study, a nonroad Tier 4 Final/Stage IV engine was equipped with a vanadium-based selective catalytic reduction (SCR) aftertreatment system. Experiments were conducted over nonroad steady and both cold and hot transient cycles (NRSC and NRTC, respectively).
Journal Article

Methods for Quantifying the Release of Vanadium from Engine Exhaust Aftertreatment Catalysts

2012-04-16
2012-01-0887
Titanium dioxide supported vanadium oxide catalysts have been successfully utilized for the selective catalytic reduction (SCR) of nitrogen oxides emitted from both stationary and mobile sources. Because of their cost and performance advantages in certain applications, vanadium-based SCR catalysts are now also being considered for integration into some U.S. Tier IV off-highway aftertreatment systems. However, concern exists that toxic vanadium compounds, such as vanadium pentoxide, could be released from these catalysts as a result of mechanical attrition or high temperature volatility. An experimental study has been conducted to compare various techniques for measuring the release of particle and vapor-phase vanadium from SCR catalysts. Previous research has utilized a powder reactor-based method to measure the vapor-phase release of vanadium, but there are inherent limitations to this technique.
Journal Article

NOx Reduction Using a Dual-Stage Catalyst System with Intercooling in Vehicle Gasoline Engines under Real Driving Conditions

2018-04-03
2018-01-0335
Selective catalytic reduction (SCR) of nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.
Technical Paper

The Effects of Sulfated Ash, Phosphorus and Sulfur on Diesel Aftertreatment Systems - A Review

2007-07-23
2007-01-1922
This paper reviews the relevant literature on the effects of sulfated ash, phosphorus, and sulfur on DPF, LNT, and SCR catalysts. Exhaust backpressure increase due to DPF ash accumulation, as well as the rate at which ash is consumed from the sump, were the most studied lubricant-derived DPF effects. Based on several studies, a doubling of backpressure can be estimated to occur within 270,000 to 490,000 km when using a 1.0% sulfated ash oil. Postmortem DPF analysis and exhaust gas measurements revealed that approximately 35% to 65% less ash was lost from the sump than was expected based on bulk oil consumption estimates. Despite significant effects from lubricant sulfur and phosphorus, loss of LNT NOX reduction efficiency is dominated by fuel sulfur effects. Phosphorus has been determined to have a mild poisoning effect on SCR catalysts. The extent of the effect that lubricant phosphorus and sulfur have on DOCs remains unclear, however, it appears to be minor.
Technical Paper

Development and Validation of a Predictive Model for DEF Injection and Urea Decomposition in Mobile SCR DeNOx Systems

2010-04-12
2010-01-0889
Selective catalytic reduction (SCR) of oxides of nitrogen with ammonia gas is a key technology that is being favored to meet stringent NOx emission standards across the world. Typically, in this technology, a liquid mixture of urea and water - known as Diesel Exhaust Fluid (DEF) - is injected into the hot exhaust gases leading to atomization and subsequent spray processes. The water content vaporizes, while the urea content undergoes thermolysis and forms ammonia and isocyanic acid, that can form additional ammonia through hydrolysis. Due to the increasing interest in SCR technology, it is desirable to have capabilities to model these processes with reasonable accuracy to both improve the understanding of processes important to the aftertreatment and to aid in system optimization. In the present study, a multi-dimensional model is developed to simulate DEF spray processes and the conversion of urea to ammonia. The model is then implemented into a commercial CFD code.
Technical Paper

Development, Validation and ECM Embedment of a Physics-Based SCR on Filter Model

2016-09-27
2016-01-8075
SCR on Filter (SCRoF) is an efficient and compact NOX and PM reduction technology already used in series production for light-duty applications. The technology is now finding its way into the medium duty and heavy duty market. One of the key challenges for successful application is the robustness to real world variations. The solution to this challenge can be found by using model-based control algorithms, utilizing state estimation by physics-based catalyst models. This paper focuses on the development, validation and real time implementation of a physics-based control oriented SCRoF model. An overview of the developed model will be presented, together with a brief description of the model parameter identification and validation process using engine test bench measurement data. The model parameters are identified following a streamlined approach, focusing on decoupling the effects of deNOx and soot phenomena.
Technical Paper

Lab Study of Urea Deposit Formation and Chemical Transformation Process of Diesel Aftertreatment System

2017-03-28
2017-01-0915
Diesel exhaust fluid, DEF, (32.5 wt.% urea aqueous solution) is widely used as the NH3 source for selective catalytic reduction (SCR) of NOx in diesel aftertreatment systems. The transformation of sprayed liquid phase DEF droplets to gas phase NH3 is a complex physical and chemical process. Briefly, it experiences water vaporization, urea thermolysis/decomposition and hydrolysis. Depending on the DEF doser, decomposition reaction tube (DRT) design and operating conditions, incomplete decomposition of injected urea could lead to solid urea deposit formation in the diesel aftertreatment system. The formed deposits could lead to engine back pressure increase and DeNOx performance deterioration etc. The formed urea deposits could be further transformed to chemically more stable substances upon exposure to hot exhaust gas, therefore it is critical to understand this transformation process.
Technical Paper

Thermal and Fluid Dynamic Considerations in Aftertreatment System Design for SCR Solid Deposit Mitigation

2012-04-16
2012-01-1287
Selective Catalytic Reduction (SCR) of oxides of nitrogen (NOx) with ammonia gas has established itself as an effective diesel aftertreatment technology to meet stringent emission standards enforced by worldwide regulatory bodies. Typically, in this technology, aqueous urea solution of eutectic composition - known as Diesel Exhaust Fluid (DEF) - is injected into hot exhaust gases leading to a series of thermal, fluid dynamic and reactive processes that eventually produces the ammonia necessary for NOx reduction reactions within monolithic catalytic substrates. Incomplete decomposition of the injected urea can lead to formation of solid deposits that adversely affect system performance by increasing the engine back pressure, reducing de-NOx efficiency, and lowering the overall fuel economy.
Technical Paper

NO2 Formation and Mitigation in an Advanced Diesel Aftertreatment System

2018-04-03
2018-01-0651
Nitrogen dioxide (NO2) is known to pose a risk to human health and contributes to the formation of ground level ozone. In recognition of its human health implications, the American Conference of Governmental Industrial Hygienists (ACGIH) set a Threshold Limit Value (TLV) of 0.2 ppmv NO2 in 2012. For mobile sources, NO2 is regulated as a component of NOx (NO + NO2). In addition, the European Commission has indicated it is considering separate Euro 6 light-duty diesel and Euro VI heavy-duty diesel NO2 emissions limits likely to mitigate the formation of ground level ozone in urban areas. In this study, we conduct component-level reactor-based experiments to understand the effects that various aftertreatment catalyst technologies including diesel oxidation catalyst (DOC), diesel particulate filter (DPF), selective catalytic reduction (SCR) catalyst and ammonia oxidation (AMOX) catalyst have on the formation and mitigation of NO2 emissions.
Technical Paper

Effect of Hydrothermal Aging on the Catalytic Performance and Morphology of a Vanadia SCR Catalyst

2013-04-08
2013-01-1079
Titania supported vanadia catalysts have been widely used for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) in diesel exhaust aftertreatment systems. Vanadia SCR (V-SCR) catalysts are preferred for many applications because they have demonstrated advantages of catalytic activity for NOx removal and tolerance to sulfur poisoning. The primary shortcoming of V-SCR catalysts is their thermal durability. Degradation in NOx conversion is also related to aging conditions such as at high temperatures. In this study, the impact that short duration hydrothermal aging has on a state-of-the-art V-SCR catalyst was investigated by aging for 2 hr intervals with progressively increased temperatures from 525 to 700°C. The catalytic performance of this V-SCR catalyst upon aging was evaluated by three different reactions of NH₃ SCR, NH₃ oxidation, and NO oxidation under simulated diesel exhaust conditions from 170 to 500°C.
Technical Paper

Sustained Low Temperature NOx Reduction

2018-04-03
2018-01-0341
Sustained NOx reduction at low temperatures, especially in the 150-200 °C range, shares some similarities with the more commonly discussed cold-start challenge, however, poses a number of additional and distinct technical problems. In this project, we set a bold target of achieving and maintaining 90% NOx conversion at the SCR catalyst inlet temperature of 150 °C. This project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015 and completed in 2017.
Technical Paper

A Numerical Model of Piston Secondary Motion and Piston Slap in Partially Flooded Elastohydrodynamic Skirt Lubrication

1994-03-01
940696
This paper presents a numerical model of the rotational and lateral dynamics of the piston (secondary motion) and piston slap in mixed lubrication. Piston dynamic behavior, frictional and impact forces are predicted as functions of crank angle. The model considers piston skirt surface waviness, roughness, skirt profile, thermal and mechanical deformations. The model considers partially-flooded skirt and calculates the pressure distributions and friction in the piston skirt region for both hydrodynamic and boundary lubrication. Model predictions are compared with measurements of piston position using gap sensors in a single-cylinder engine and the comparison between theory and measurement shows remarkable agreement.
Technical Paper

Air-Fuel Ratio Measurement Diagnostics During Cranking and Startup in a Port-Fuel-Injected Spark-Ignition Engine

2004-06-08
2004-01-1915
Cranking and startup fuel control has become increasingly important due to ever tightening emission requirements. Additionally, engine-off strategies during idle will require substantially more engine startup events with the associated need for very clean starts. Thus, knowledge of an engine's Air-Fuel Ratio (AFR) during its early cycles is necessary in order to optimize cranking and startup fueling. This paper examines and compares two methods of measuring an engine's AFR during engine startup (approximately the first second of operation); an in-cylinder technique using a Fast Flame Ionization Detector (FFID) and the conventional exhaust based Universal Exhaust Gas Oxygen (UEGO) sensor method. Engine starts using a Ford Zetec engine were performed at three different temperatures (0, 20 and 90 C) as well as different initial engine starting positions.
Technical Paper

Continuous Particulate Filter State of Health Monitoring Using Radio Frequency Sensing

2018-04-03
2018-01-1260
Reliable means for on-board detection of particulate filter failures or malfunctions are needed to meet diagnostics (OBD) requirements. Detecting these failures, which result in tailpipe particulate matter (PM) emissions exceeding the OBD limit, over all operating conditions is challenging. Current approaches employ differential pressure sensors and downstream PM sensors, in combination with particulate filter and engine-out soot models. These conventional monitors typically operate over narrowly-defined time windows and do not provide a direct measure of the filter’s state of health. In contrast, radio frequency (RF) sensors, which transmit a wireless signal through the filter substrate provide a direct means for interrogating the condition of the filter itself.
Technical Paper

Developing Design Guidelines for an SCR Assembly Equipped for RF Sensing of NH3 Loading

2018-04-03
2018-01-1266
The Cu-zeolite (CuZ) SCR catalyst enables higher NOx conversion efficiency in part because it can store a significant amount of NH3. “NH3 storage control”, where diesel exhaust fluid (DEF) is dosed in accord with a target NH3 loading, is widely used with CuZ catalysts to achieve very high efficiency. The NH3 loading actually achieved on the catalyst is currently estimated through a stoichiometric calculation. With future high-capacity CuZ catalyst designs, it is likely that the accuracy of this NH3 loading estimate will become limiting for NOx conversion efficiency. Therefore, a direct measurement of NH3 loading is needed; RF sensing enables this. Relative to RF sensing of soot in a DPF (which is in commercial production), RF sensing of NH3 adsorbed on CuZ is more challenging. Therefore, more attention must be paid to the “microwave resonance cavity” created within the SCR assembly. The objective of this study was to develop design guidelines to enable and enhance RF sensing.
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