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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

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

Assessing the Windage Tray Blockage Effect on Aeration in the Oil Sump

2007-10-29
2007-01-4109
The windage tray effect on aeration in the engine sump was assessed by replacing much of the windage tray materials with wire meshes of various blockages. The mesh was to prevent direct impact of the oil drops spinning off the crank shaft onto the sump oil, and simultaneously, to provide sufficient drainage so that there was no significant build up of windage tray oil film that would interact with these droplets. Aeration at the oil pump inlet was measured by X-ray absorption in a production V-6 SI engine motoring at 2000 to 6000 rpm. Within experimental uncertainty, these windage tray changes had no effect on aeration. Thus activities in the sump such as the interaction of the oil drops spun from the crank shaft with the sump oil or with the windage tray, and the agitation of the sump oil by the crank case gas, were not major contributors to aeration at the pump inlet.
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

The Mars Gravity Biosatellite: Atmospheric Reconditioning Strategies for Extended-Duration Rodent Life Support

2007-07-09
2007-01-3224
We present results which verify the design parameters and suggest performance capabilities/limitations of the Mars Gravity Biosatellite's proposed atmospherics control subassembly. Using a combination of benchtop prototype testing and analytic techniques, we derive control requirements for ammonia. Further, we demonstrate the dehumidification performance of our proposed partial gravity condensing heat exchanger. Ammonia production is of particular concern in rodent habitats. The contaminant is released following chemical degradation of liquid waste products. The rate of production is linked to humidity levels and to the design of habitat modules in terms of bedding substrate, air flow rates, choice of structural materials, and other complex factors. Ammonia buildup can rapidly lead to rodent health concerns and can negatively impact scientific return.
Technical Paper

Modeling Costs and Fuel Economy Benefits of Lightweighting Vehicle Closure Panels

2008-04-14
2008-01-0370
This paper illustrates a methodology in which complete material-manufacturing process cases for closure panels, reinforcements, and assembly are modeled and compared in order to identify the preferred option for a lightweight closure design. First, process-based cost models are used to predict the cost of lightweighting the closure set of a sample midsized sports utility vehicle (SUV) via material and process substitution. Weight savings are then analyzed using a powertrain simulation to understand the impact of lightweighting on fuel economy. The results are evaluated in the context of production volume and total mass change.
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

The Use of Semi-Solid Rheocasting (SSR) for Aluminum Automotive Castings

2003-03-03
2003-01-0433
Semi-solid metal (SSM) casting has long been identified as a high-volume process for producing safety-critical and structural automotive castings, but cost and complexity issues have limited its widespread commercial acceptance. Rheocasting, an SSM process that creates semi-solid slurry directly from liquid metal, eliminates the cost disadvantages of the process. However, the majority of rheocasting processes are complex and difficult to operate in the foundry environment. Recent work at MIT has led to the fundamental discovery that application of heat removal and convection as a molten alloy cools through the liquidus creates a non-dendritic, semi-solid slurry. A new process based on this understanding, S.S.R.™ (Semi-Solid Rheocasting), simplifies the rheocasting process by controlling heat removal and convection of an alloy during cooling using an external device. Solution heat treatable castings have been produced in a horizontal die casting machine with the S.S.R.™ process.
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

A Methodology for Evaluating Body Architecture Concepts Using Technical Cost Modeling

2011-04-12
2011-01-0767
The ability to make accurate decisions concerning early body-in-white architectures is critical to an automaker since these decisions often have long term cost and weight impacts. We address this need with a methodology which can be used to assist in body architecture decisions using process-based technical cost modeling (TCM) as a filter to evaluate alternate designs. Despite the data limitations of early design concepts, TCM can be used to identify key trends for cost-effectiveness between design variants. A compact body-in-white architecture will be used as a case study to illustrate this technique. The baseline steel structure will be compared to several alternate aluminum intensive structures in the context of production volume.
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.
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