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Journal Article

Spatially-Resolved Thermal Degradation Induced Temperature Pattern Changes along a Commercial Lean NOX Trap Catalyst

2010-04-12
2010-01-1214
The low-temperature performance characteristics of a commercial lean NOX trap catalyst were evaluated using infra-red thermography (IRT) before and after a high-temperature aging step. Reaction tests included propylene oxidation, oxygen storage capacity measurements, and simulated cycling conditions for NOX reduction, using H₂ as the reductant during the regeneration step of the cycle. Testing with and without NO in the lean phase showed thermal differences between the reductant used in reducing the stored oxygen and that for nitrate decomposition and reduction. IRT clearly demonstrated where NOX trapping and regeneration were occurring spatially as a function of regeneration conditions, with variables including hydrogen content of the regeneration phase and lean- and rich-phase cycle times.
Journal Article

Why Cu- and Fe-Zeolite SCR Catalysts Behave Differently At Low Temperatures

2010-04-12
2010-01-1182
Cu- and Fe-zeolite SCR catalysts emerged in recent years as the primary candidates for meeting the increasingly stringent lean exhaust emission regulations, due to their outstanding activity and durability characteristics. It is commonly known that Cu-zeolite catalysts possess superior activity to Fe-zeolites, in particular at low temperatures and sub-optimal NO₂/NOx ratios. In this work, we elucidate some underlying mechanistic differences between these two classes of catalysts, first based on their NO oxidation abilities, and then based on the relative properties of the two types of exchanged metal sites. Finally, by using the ammonia coverage-dependent NOx performance, we illustrate that state-of-the-art Fe-zeolites can perform better under certain transient conditions than in steady-state.
Journal Article

Simulation of Organic Rankine Cycle Power Generation with Exhaust Heat Recovery from a 15 liter Diesel Engine

2015-04-14
2015-01-0339
The performance of an organic Rankine cycle (ORC) that recovers heat from the exhaust of a heavy-duty diesel engine was simulated. The work was an extension of a prior study that simulated the performance of an experimental ORC system developed and tested at Oak Ridge National laboratory (ORNL). The experimental data were used to set model parameters and validate the results of that simulation. For the current study the model was adapted to consider a 15 liter turbocharged engine versus the original 1.9 liter light-duty automotive turbodiesel studied by ORNL. Exhaust flow rate and temperature data for the heavy-duty engine were obtained from Southwest Research Institute (SwRI) for a range of steady-state engine speeds and loads without EGR. Because of the considerably higher exhaust gas flow rates of the heavy-duty engine, relative to the engine tested by ORNL, a different heat exchanger type was considered in order to keep exhaust pressure drop within practical bounds.
Journal Article

Impact of Carbonaceous Compounds Present in Real-World Diesel Exhaust on NOx Conversion over Vanadia-SCR Catalyst

2016-04-05
2016-01-0921
Exposure of hydrocarbons (HCs) and particulate matter (PM) under certain real-world operating conditions leads to carbonaceous deposit formation on V-SCR catalysts and causes reversible degradation of its NOx conversion. In addition, uncontrolled oxidation of such carbonaceous deposits can also cause the exotherm that can irreversibly degrade V-SCR catalyst performance. Therefore carbonaceous deposit mitigation strategies, based on their characterization, are needed to minimize their impact on performance. The nature and the amount of the deposits, formed upon exposure to real-world conditions, were primarily carried out by the controlled oxidation of the deposits to classify these carbonaceous deposits into three major classes of species: i) HCs, ii) coke, and iii) soot. The reversible NOx conversion degradation can be largely correlated to coke, a major constituent of the deposit, and to soot which causes face-plugging that leads to decreased catalyst accessibility.
Journal Article

Impact of Rh Oxidation State on NOx Reduction Performance of Multi-Component Lean NOx Trap (LNT) Catalyst

2016-04-05
2016-01-0947
Typical Lean NOx Trap (LNT) catalyst composition includes precious metal components (Pt, Pd, and/or Rh), responsible for NO oxidation during lean operation and NOx reduction during rich operation. It was found that redox history of commercial LNT catalyst plays a significant role on deciding its NOx conversion under Lean/Rich cyclic condition. Further test had shown that fully formulated LNT catalyst being pre-reduced had shown much better NO reduction activity during the temperature-programmed reduction (TPRx) of NO than the same LNT catalyst being oxidized. The following study with Rh-only and Pt-only catalyst had demonstrated that Rh plays a key role on the large variation of the NO reduction function due to oxidation state change over LNT catalyst.
Journal Article

Aftertreatment Architecture and Control Methodologies for Future Light Duty Diesel Emission Regulations

2017-03-28
2017-01-0911
Future light duty vehicles in the United States are required to be certified on the FTP-75 cycle to meet Tier 3 or LEV III emission standards [1, 2]. The cold phase of this cycle is heavily weighted and mitigation of emissions during this phase is crucial to meet the low tail pipe emission targets [3, 4]. In this work, a novel aftertreatment architecture and controls to improve Nitrogen Oxides (NOx) and Hydrocarbon (HC) or Non Methane Organic gases (NMOG) conversion efficiencies at low temperatures is proposed. This includes a passive NOx & HC adsorber, termed the diesel Cold Start Concept (dCSC™) catalyst, followed by a Selective Catalytic Reduction catalyst on Filter (SCRF®) and an under-floor Selective Catalytic Reduction catalyst (SCR). The system utilizes a gaseous ammonia delivery system capable of dosing at two locations to maximize NOx conversion and minimize parasitic ammonia oxidation and ammonia slip.
Journal Article

Effect of Transition Metal Ion Properties on the Catalytic Functions and Sulfation Behavior of Zeolite-Based SCR Catalysts

2017-03-28
2017-01-0939
Copper- and Iron- based metal-zeolite SCR catalysts are widely used in US and European diesel aftertreatment systems to achieve drastic reduction in NOx emission. These catalysts are highly selective to N2 under wide range of operating conditions. Nevertheless, the type of transition metal has a significant impact on the key performance and durability parameters such as NOx conversion, selectivity towards N2O, hydrothermal stability, and sensitivity to fuel sulfur content. In this study, we explained the differences in the performance characteristics of these catalysts based on their relative acidic-basic nature of transition metal present in these catalysts using practically relevant gas species present in diesel exhaust such as NO2, SOx, and NH3. These experiments show that Fe-zeolite has relatively acidic nature as compared to Cu-zeolite that causes NH3 inhibition and hence explains low NOx conversion on Fe-zeolite at low temperature under standard SCR conditions.
Journal Article

Investigation of the Impact of Real-World Aging on Diesel Oxidation Catalysts

2012-04-16
2012-01-1094
Real-world operation of diesel oxidation catalysts (DOCs), used in a variety of aftertreatment systems, subjects these catalysts to a large number of permanent and temporary deactivation mechanisms. These include thermal damage, induced by generating exotherm on the catalyst; exposure to various inorganic species contained in engine fluids; and the effects of soot and hydrocarbons, which can mask the catalyst in certain operating modes. While some of these deactivation mechanisms can be accurately simulated in the lab, others are specific to particular engine operation regimes. In this work, a set of DOCs, removed from prolonged service in the field, has been subjected to a detailed laboratory study. Samples obtained from various locations in these catalysts were used to characterize the extent and distribution of deactivation.
Journal Article

N2O Formation and Mitigation in Diesel Aftertreatment Systems

2012-04-16
2012-01-1085
The high global warming potential of nitrous oxide (N₂O) led to its recent inclusion in the list of regulated pollutants under the emerging greenhouse gas regulations. While N₂O can be present in small quantities among the combustion products, it can also be generated as a minor byproduct in various types of aftertreatment systems. In this work, a systematic review of sources of N₂O is presented, along with the potential mechanisms of formation in a typical selective-catalytic-reduction-based diesel exhaust aftertreatment system. It is demonstrated that diesel oxidation catalysts (DOC), selective catalytic reduction (SCR) catalyst, and ammonia slip catalyst (ASC) can all potentially contribute to N₂O formation, depending on the catalyst material and exhaust gas conditions, as well as aftertreatment operation strategies. Furthermore, catalysts used in SCR aftertreatment system are also shown to decompose and/or reduce N₂O to N₂ under select conditions.
Journal Article

New Insights into Reaction Mechanism of Selective Catalytic Ammonia Oxidation Technology for Diesel Aftertreatment Applications

2011-04-12
2011-01-1314
Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.
Journal Article

The Impact of Ammonium Nitrate Species on Low Temperature NOx Conversion Over Cu/CHA SCR Catalyst

2017-03-28
2017-01-0953
Cu/CHA catalysts have been widely used in the industry, due to their desirable performance characteristics including the unmatched hydrothermal stability. While broadly recognized for their outstanding activity at or above 200°C, these catalysts may not show desired levels of NOx conversion at lower temperatures. To achieve high NOx conversions it is desirable to have NO2/NOx close to 0.5 for fast SCR. However even under such optimal gas feed conditions, sustained use of Cu/CHA below 200°C leads to ammonium nitrate formation and accumulation, resulting in the inhibition of NOx conversion. In this contribution, the formation and decomposition of NH4NO3 on a commercial Cu/CHA catalyst have been investigated systematically. First, the impact of NH4NO3 self-inhibition on SCR activity as a function of temperature and NO2/NOx ratios was investigated through reactor testing.
Technical Paper

Development of a New 13L Heavy-Duty Diesel Engine Using Analysis-Led Design

2008-06-23
2008-01-1515
The paper covers the design and development of a new 13L heavy-duty diesel engine intended primarily for heavy truck applications in China. It provides information on the specific characteristics of the engine that make it particularly suitable for operation in China, and describes in detail some of the design techniques that were used. To meet these exacting requirements, extensive use was made of Analysis-Led Design, which allows components, sub-systems and the entire engine, aftertreatment and vehicle system to be modeled before designs are taken to prototype hardware. This enables a level of system and sub-system optimization not previously available. The paper describes the emissions strategy for China, and the physical design strategy for the new engine, and provides some engine performance robustness details. The engine architecture is discussed and the paper details the analysis of the major components - cylinder block, head, head seal, power cylinder and bearings.
Technical Paper

The Effects of Thermal Degradation on the Performance of a NOX Storage/Reduction Catalyst

2009-04-20
2009-01-0631
The performance characteristics of a commercial lean-NOX trap catalyst were evaluated between 200 and 500°C, using H2, CO, and a mixture of both H2 and CO as reductants before and after different high-temperature aging steps, from 600 to 750°C. Tests included NOX reduction efficiency during cycling, NOX storage capacity (NSC), oxygen storage capacity (OSC), and water-gas-shift (WGS) and NO oxidation reaction extents. The WGS reaction extent at 200 and 300°C was negatively affected by thermal degradation, but at 400 and 500°C no significant change was observed. Changes in the extent of NO oxidation did not show a consistent trend as a function of thermal degradation. The total NSC was tested at 200, 350 and 500°C. Little change was observed at 500°C with thermal degradation but a steady decrease was observed at 350°C as the thermal degradation temperature was increased.
Technical Paper

Sulfur Management of NOx Adsorber Technology for Diesel Light-duty Vehicle and Truck Applications

2003-10-27
2003-01-3245
Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure.
Technical Paper

Axial NO2 Utilization Measurements within a Partial Flow Filter during Passive Regeneration

2017-03-28
2017-01-0988
Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.
Technical Paper

Lean Breakthrough Phenomena Analysis for TWC OBD on a Natural Gas Engine using a Dual-Site Dynamic Oxygen Storage Capacity Model

2017-03-28
2017-01-0962
Oxygen storage capacity (OSC) is one of the most critical characteristics of a three-way catalyst (TWC) and is closely related to the catalyst aging and performance. In this study, a dynamic OSC model involving two oxygen storage sites with distinct kinetics was developed. The dual-site OSC model was validated on a bench reactor and a natural gas engine. The model was capable of predicting temperature dependence on OSC with H2, CO and CH4 as reductants. Also, the effects of oxygen concentration and space velocity on the amount of OSC were captured by the model. The validated OSC model was applied to simulate lean breakthrough phenomena with varied space velocities and oxygen concentrations. It is found that OSC during lean breakthrough is not a constant for a particular TWC catalyst and is dependent on space velocity and oxygen concentration. Specifically, breakthrough time exhibits a non-linear, inverse correlation to oxygen flux.
Technical Paper

Development of a Kinetic Model to Evaluate Water Storage on Commercial Cu-Zeolite SCR Catalysts during Cold Start

2017-03-28
2017-01-0968
Commercial Cu-Zeolite SCR catalyst can store and subsequently release significant amount of H2O. The process is accompanied by large heat effects. It is critical to model this phenomenon to design aftertreatment systems and to provide robust tuning strategies to meet cold start emissions and low temperature operation. The complex reaction mechanism of water adsorption and desorption over a Cu-exchanged SAPO-34 catalyst at low temperature was studied through steady state and transient experiments. Steady state isotherms were generated using a gravimetric method and then utilized to predict water storage interactions with respect to feed concentration and catalyst temperature. Transient temperature programmed desorption (TPD) experiments provided the kinetic information required to develop a global kinetic model from the experimental data. The model captures fundamental characteristics of water adsorption and desorption accompanied by the heat effects.
Technical Paper

Decoupling the Interactions of Hydrocarbons and Oxides of Nitrogen Over Diesel Oxidation Catalysts

2011-04-12
2011-01-1137
Oxidation of NO to NO₂ over a Diesel Oxidation Catalyst (DOC) plays an important role in different types of aftertreatment systems, by enhancing NOx storage on adsorber catalysts, improving the NOx reduction efficiency of SCR catalysts, and enabling the passive regeneration of Diesel Particulate Filters (DPF). The presence of hydrocarbon (HC) species in the exhaust is known to affect the NO oxidation performance over a DOC; however, specific details of this effect, including its underlying mechanism, remain poorly understood. Two major pathways are commonly considered to be responsible for the overall effect: NO oxidation inhibition, due to the presence of HC, and the consumption of the NO₂ produced by reaction with hydrocarbons. In this work we have attempted to decouple these two pathways, by adjusting the catalyst inlet concentrations of NO and NO₂ to the thermodynamic equilibrium levels and measuring the composition changes over the catalyst in the presence of HC species.
Technical Paper

High-Performance Grid Computing for Cummins Vehicle Mission Simulation: Architecture and Applications

2011-09-13
2011-01-2268
This paper presents an extension of our earlier work on Cummins Vehicle Mission Simulation (VMS) software. Previously, we presented VMS as a Windows based analysis tool to simulate vehicle missions quickly and to gauge, communicate, and improve the value proposition of Cummins engines to customers. We have subsequently extended this VMS architecture to build a grid-computing platform to support high volume of simulation needs. The building block of the grid-computing version of VMS is an executable file that consists of vehicle and engine simulation models compiled using Real Time Workshop. This executable file integrates MATLAB and Simulink with Java, XML, and JDBC technologies and interacts with the MySQL database. Our grid consists of a cluster of twenty Linux servers with quad-core processors. The Sun Grid Engine software suite that administers this cluster can batch-queue and execute 80 simulations concurrently.
Technical Paper

Reactor System with Diesel Injection Capability for DOC Evaluations

2018-04-03
2018-01-0647
Plug flow reactors, simulating engine exhaust gas, are widely used in emissions control research to gain insight into the reaction mechanisms and engineering aspects that controls activity, selectivity, and durability of catalyst components. The choice of relevant hydrocarbon (HC) species is one of the most challenging factor in such laboratory studies, given the variety of compositions that can be encountered in different application scenarios. Furthermore, this challenge is amplified by the experimental difficulties related to introducing heavier and multi-component HCs and analyzing the reaction products.
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