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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

Thermodynamic Systems for Tier 2 Bin 2 Diesel Engines

2013-04-08
2013-01-0282
Light duty vehicle emission standards are getting more stringent than ever before as stipulated by US EPA Tier 2 Standards and LEV III regulations proposed by CARB. The research in this paper sponsored by US DoE is focused towards developing a Tier 2 Bin 2 Emissions compliant light duty pickup truck with class leading fuel economy targets of 22.4 mpg “City” / 34.3 mpg “Highway”. Many advanced technologies comprising both engine and after-treatment systems are essential towards accomplishing this goal. The objective of this paper would be to discuss key engine technology enablers that will help in achieving the target emission levels and fuel economy. Several enabling technologies comprising air-handling, fuel system and base engine design requirements will be discussed in this paper highlighting both experimental and analytical evaluations.
Technical Paper

The Impact of Lubricant and Fuel Derived Sulfur Species on Efficiency and Durability of Diesel NOx Adsorbers

2004-10-25
2004-01-3011
Global emission legislations for diesel engines are becoming increasingly stringent. While the exhaust gas composition requirements for prior iterations of emission legislation could be met with improvements in the engine's combustion process, the next issue of European, North American and Japanese emission limits greater than 2005 will require more rigorous measures, mainly employment of exhaust gas aftertreatment systems. As a result, many American diesel OEMs are considering NOx adsorbers as a means to achieve 2007+ emission standards. Since the efficacy of a NOx adsorber over its lifetime is significantly affected by sulfur (“sulfur poisoning”), forthcoming reductions in diesel fuel sulfur (down to 15 ppm), have raised industry concerns regarding compatibility and possible poisoning effects of sulfur from the lubricant.
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

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

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

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

Sooted Diesel Engine Oil Pumpability Studies as the Basis of a New Heavy Duty Diesel Engine Oil Performance Specification

2002-05-06
2002-01-1671
Changing diesel engine emission requirements for 2002 have led many diesel engine manufacturers to incorporate cooled Exhaust Gas Recirculation, EGR, as a means of reducing NOx. This has resulted in higher levels of soot being present in used oils. This paper builds on earlier work with fresh oils and describes a study of the effect of highly sooted oils on the low temperature pumpability in diesel engines. Four experimental diesel engine oils, of varying MRV TP-1 viscosities, were run in a Mack T-8 engine to obtain a soot level ranging between 6.1 and 6.6%. These sooted oils were then run in a Cummins M11 engine installed in a low temperature cell. Times to lubricate critical engine components were measured at temperatures ranging between -10 °C and -25 °C. A clear correlation was established between the MRV TP-1 viscosity of a sooted oil and the time needed to lubricate critical engine components at a given test temperature.
Journal Article

Smart Sensing and Decomposition of NOx and NH3 Components from Production NOx Sensor Signals

2011-04-12
2011-01-1157
Production NO sensors have a strong cross-sensitivity to ammonia which limits their use for closed-loop SCR control and diagnostics since increases in sensor output can be caused by either gas component. Recently, Ammonia/NO Ratio (ANR) perturbation methods have been proposed for determining the dominant component in the post-SCR exhaust as part of the overall SCR control strategy, but these methods or the issue of sensor cross-sensitivity have not been critically evaluated or studied in their own right. In this paper the dynamic sensor direct- and cross-sensitivities are estimated from experimental FTIR data (after compensating for the dynamics of the gas sampling system) and compared to nominal values provided by the manufacturer. The ANR perturbation method and the use of different input excitations are then discussed within an analytical framework, and applied to experimental data from a large diesel engine.
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.
Technical Paper

Quantitative Flow-Reactor Study of Diesel Soot Oxidation Process

2002-05-06
2002-01-1684
Advanced flow-reactor capabilities created at Cummins were applied to the study of the diesel particulate matter (soot) oxidation process. This approach complemented the on-engine studies with a number of important features, including accurate control of gas composition and soot layer temperature. Using the developed methodology for quantitative soot oxidation studies in a broad range of temperatures (200-700°C), an initial set of experiments was performed to compare the behavior of the real and model soot samples under the identical conditions (10%vol. of O2, 0-15%vol. of H2O). It was found that presence of H2O vapor synergistically enhances the rate of oxidation by O2 of the diesel soot sample. However, the behavior of the model soot sample (carbon black) was virtually not affected by H2O. Kinetic analysis of the obtained results revealed an unusual type of behavior, with the activation energy of soot oxidation increasing in the course of the experiment.
Journal Article

Powertrain Cycle for Emission Certification

2012-09-24
2012-01-2059
In August of 2011, the US Environmental Protection Agency issued new Green House Gas (GHG) emissions regulations for heavy duty vehicles. These regulations included new procedures for the evaluation of hybrid powertrains and vehicles. One of the hybrid options allows for the evaluation of an engine plus a hybrid transmission (a powertrain). For this type of testing, EPA has proposed simulating a vehicle following the hybrid vehicle test procedures, including the use of the vehicle cycles and the A to B comparison testing - as required for the full vehicle evaluation option. This paper proposes an alternative approach by defining a powertrain cycle. The powertrain cycle is based on the heavy duty engine emissions cycle - the transient FTP cycle. Simulation and test results are presented showing similar performance over the engine and vehicle cycles. This approach offers several advantages as compared to the procedure described in EPA's GHG rule.
Technical Paper

New Insights into the Unique Operation of Small Pore Cu-Zeolite SCR Catalyst: Overlapping NH3 Desorption and Oxidation Characteristics for Minimizing Undesired Products

2014-04-01
2014-01-1542
An operational challenge associated with SCR catalysts is the NH3 slip control, particularly for commercial small pore Cu-zeolite formulations as a consequence of their significant ammonia storage capacity. The desorption of NH3 during increasing temperature transients is one example of this challenge. Ammonia slipping from SCR catalyst typically passes through a platinum based ammonia oxidation catalyst (AMOx), leading to the formation of the undesired byproducts NOx and N2O. We have discovered a distinctive characteristic, an overlapping NH3 desorption and oxidation, in a state-of-the-art Cu-zeolite SCR catalyst that can minimize NH3 slip during temperature transients encountered in real-world operation of a vehicle.
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

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

Meeting the US Heavy-Duty EPA 2010 Standards and Providing Increased Value for the Customer

2010-10-05
2010-01-1934
The paper will discuss the design and development of heavy-duty diesel engines to meet the US EPA 2010 on-highway standards - 0.2 g/HP-hr NOx and 0.01 g/HP-hr particulate matter (PM). In meeting these standards a combination of in-cylinder control and aftertreatment control for both NOx and particulate has been used. For NOx control, a combination of cooled exhaust gas recirculation (EGR) and selective catalytic reduction (SCR) is used. The SCR catalyst uses copper zeolite to achieve high levels of NOx conversion efficiency with minimal ammonia slip and unparalleled thermal durability. For particulate control, a diesel particulate filter (DPF) with upstream oxidation catalyst (DOC) is used. While the DPF may be actively regenerated when required, it operates predominantly with passive regeneration - enabled by the high NOx levels between the engine and the DPF, associated with high efficiency SCR systems and NO₂ production across the DOC.
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.
Technical Paper

Impact of Sulfur-Oxides on the Ammonia Slip Catalyst Performance

2014-04-01
2014-01-1545
The ammonia slip catalyst (ASC), typically composed of Pt oxidation catalyst overlaid with SCR catalyst, is employed for the mitigation of NH3 slip originating from SCR catalysts. Oxidation and SCR functionalities in an ASC can degrade through two key mechanisms i) irreversible degradation due to thermal aging and ii) reversible degradation caused by sulfur-oxides. The impact of thermal aging is well understood and it mainly degrades the SCR function of the ASC and increases the NH3 conversion to undesired products [1]. This paper describes the impact of sulfur-oxides on critical functions of ASC and on NH3 oxidation activity and selectivity towards N2, NOx and N2O. Furthermore impact of desulfation under selected conditions and its extent of ASC performance recovery is explained.
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.
Technical Paper

Future Challenges for Engine Manufacturers in View of Future Emissions Legislation

2017-05-10
2017-01-1923
Countries around the world are expected to continue to adopt more stringent emissions standards for heavy-duty markets for both oxides of nitrogen (NOx) and greenhouse gases (GHG). While there is uncertainty about the timing and extent of these regulations, it is clear that significant reductions will be required to address urban air pollution and climate change concerns. The rate and pace of technology evolution and how it will affect the energy pathways for commercial transportation and industrial use are dependent on multiple variables such as national energy and environmental policies and public-private partnerships. Although it adds complexity, the engine system has great potential to evolve as it continues to be highly integrated into the super system for which it is producing power. This paper examines the potential opportunities and challenges for engine manufacturers to continue to be the supplier of power to vehicles and equipment of the future.
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