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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

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

Advanced Catalyst Solutions for Hydrocarbon Emissions Control During Rich Operation of Lean NOx Trap Systems

2009-04-20
2009-01-0282
The operation of NOx Adsorber catalysts (NAC), also often referred to as Lean NOx Trap catalysts or NOx Storage-reduction catalysts, entails frequent periodic NOx regeneration events. These are accomplished by creating a net reducing, fuel-rich environment in the exhaust. The reduction of hydrocarbon emissions which occur during such fuel-rich events is challenging, due to the oxygen-deficient environment. In order to overcome this limitation, two possibilities exist: (i) oxygen can be stored during lean phase, to be used for hydrocarbon slip oxidation in the subsequent rich phase, or (ii) unreacted hydrocarbons can be trapped during the rich phase and oxidized during the following lean phase. In this work, two groups of catalytic solutions were developed and evaluated for hydrocarbon emission control based on these approaches: an Oxygen Storage Compound (OSC) based catalyst and zeolite-based hydrocarbon trap catalyst.
Technical Paper

Evaluation of Spatially Resolved Performance of NOx Adsorber Catalysts

2009-04-20
2009-01-0275
A novel laboratory methodology has been developed and applied to evaluate performance of NOx Adsorber catalysts, based on the detailed analysis of micro-core samples obtained from various locations in a full-size catalyst. The technique includes a protocol for evaluating various aspects of NOx performance, as well as direct measurements of the amount of sulfur on the catalyst. This method was used to determine the NOx performance and distribution of sulfur loading on several engine aged catalysts. It showed the ability to differentiate poor NOx performance due to insufficient desulfation from that due to thermal degradation. This method further quantifies different forms of sulfur that are present on the catalyst. These forms of sulfur are distinguished by the temperature at which they are removed. In addition, the aspects of sulfur behavior that are important to this technique are discussed.
Technical Paper

Impact of Different Forms of Sulfur Poisoning on Diesel Oxidation Catalyst Performance

2013-04-08
2013-01-0514
Despite drastic reduction of sulfur content in diesel fuel in the recent years, especially with the introduction of Ultra-Low Sulfur Diesel (ULSD), sulfur poisoning remains one of the most significant factors impacting performance of various catalysts in diesel aftertreatment systems. This is because even with ULSD, cumulative exposure of a catalyst over its lifetime in a heavy-duty diesel system may amount to kilograms of sulfur. In this study, we have found that the impact of sulfur poisoning on the performance of various diesel oxidation catalysts (DOC) strongly depends on the catalyst's operation history. For example, exposing a DOC to limited amounts of freshly deposited sulfur in bench reactor testing was shown to have a substantial detrimental effect. On the other hand, several samples which returned from vehicle or test-cell aging with high sulfur loading, have shown no signs of poisoning.
Technical Paper

Hydrocarbon Poisoning of Cu-Zeolite SCR Catalysts

2012-04-16
2012-01-1096
The effects of propylene (C₃H₆) and dodecane (n-C₁₂H₂₆) exposure on the NH₃-based selective catalytic reduction (SCR) performance of two Cu-exchanged zeolite catalysts were investigated. The first sample was a model Cu/beta zeolite sample and the second a state-of-the-art Cu/zeolite sample, with the zeolite material characterized by relatively small pores. Overall, the state-of-the-art sample performed better than the model sample, in terms of hydrocarbon inhibition (which was reduced) and N₂O formation (less formed). The state-of-the-art sample was completely unaffected by dodecane at temperatures lower than 300°C, and only slightly inhibited (less than 5% conversion loss), for standard SCR, by C₃H₆. There was no evidence of coke formation on this catalyst with C₃H₆ exposure. The model sample was more significantly affected by hydrocarbon exposure. With C₃H₆, inhibition is associated with its partial oxidation intermediates adsorbed on the catalyst surface.
Technical Paper

SCR Architectures for Low N2O Emissions

2015-04-14
2015-01-1030
The high global warming potential of nitrous oxide (N2O) led to its inclusion in the list of regulated greenhouse gas (GHG) pollutants [1, 2]. The mitigation of N2O on aftertreatment catalysts was shown to be ineffective as its formation and decomposition temperatures do not overlap. Therefore, the root causes for N2O formation were investigated to enable the catalyst architectures and controls development for minimizing its formation. In a typical heavy-duty diesel exhaust aftertreatment system based on selective catalytic reduction of NOx by ammonia derived from urea (SCR), the main contributors to tailpipe N2O are expected to be the undesired reaction between NOx and NH3 over SCR catalyst and NH3 slip in to ammonia slip catalyst (ASC), part of which gets oxidized to N2O.
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.
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

Catalyst Sulfur Poisoning and Recovery Behaviors: Key for Designing Advanced Emission Control Systems

2017-01-10
2017-26-0133
Advanced emission control systems for diesel engines usually include a combination of Diesel Oxidation Catalyst (DOC), Diesel Particulate Filter (DPF), Selective Catalytic Reduction (SCR), and Ammonia Slip Catalyst (ASC). The performance of these catalysts individually, and of the aftertreatment system overall, is negatively affected by the presence of oxides of sulfur, originating from fuel and lubricant. In this paper, we illustrated some key aspects of sulfur interactions with the most commonly used types of catalysts in advanced aftertreatment systems. In particular, DOC can oxidize SO2 to SO3, collectively referred to as SOx, and store these sulfur containing species. The key functions of a DOC, such as the ability to oxidize NO and HC, are degraded upon SOx poisoning. The impact of sulfur poisoning on the catalytic functions of a DPF is qualitatively similar to DOC.
Technical Paper

Mechanistic Studies of the Catalytic Chemistry of NOx in Laboratory Plasma-Catalyst Reactors

2000-10-16
2000-01-2965
Several reactor systems have been used to study the catalytic chemistry of a particular proprietary zeolitic catalyst in conditions that mimic those found in light-duty diesel exhaust after a non-thermal plasma generator. Very similar catalytic results were obtained with NO + plasma or NO2 as the source of NOx using propene (C3H6) as the reductant. The formation of nitrogen, carbon dioxide, and other products were studied from 150°C to 250°C using a He balance gas and NOx in the form of NO2. The results demonstrate that nitrogen is formed by the selective catalytic reduction of NO2 by propene. The highest activity for N2 formation from NO2 was near 50% conversion at 200°C for a space velocity of 12,600 h-1. The NOx conversion by adsorption and by catalytic reduction was quantified. By performing studies with and without the presence of water, a clear separation in behavior between adsorption processes and catalytic reaction was observed.
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.
Technical Paper

Experimental Determination of the Kinetics of Diesel Soot Oxidation by O2 - Modeling Consequences

2003-03-03
2003-01-0833
Several complementary experimental techniques were applied to investigate kinetics of diesel soot oxidation by O2 in an attempt to provide accurate data for modeling of the Diesel Particulate Filters regeneration process. For two diesel soot samples with measurably different properties, it was shown that the complexity of their overall kinetic behavior was due to an initial period of rapidly changing reactivity. This initial high reactivity was understood not to be related to the SOF, and was quantitatively correlated to the extent of soot pre-oxidation. This initial reactivity can affect the averaged apparent kinetic parameters, for example resulting in the lower apparent activation energy values. After the initial soot pre-oxidation, which consumed ∼10-25% of carbon, the remaining soot was behaving very uniformly, producing linear Arrhenius plots in a remarkably broad range of temperatures (330-610°C) and integral conversions (up to 90%).
Journal Article

Hydrocarbon Storage on Small-Pore Cu-Zeolite SCR Catalyst

2013-04-08
2013-01-0508
In this study we investigated the interaction of short- and long-chain hydrocarbons (HCs), represented by propene (C₃H₆) and n-dodecane (n-C₁₂H₂₆), respectively, with a state-of-the-art small-pore Cu-Zeolite SCR catalyst. By varying HC adsorption conditions, we determined that physisorption was the primary mechanism for some minor HC storage at low temperatures (≺ 200°C), while chemical transformation was involved in more substantial HC storage at higher temperatures (200-400°C). The latter was evidenced by the oxygen-dependent and thermally activated nature of the storage process, and further confirmed by the carbon-rich composition of the deposits. The nature of HC-derived deposits of different origins and amounts was further probed using the standard SCR reaction at kinetically challenging conditions (at 200°C), as well by ammonia adsorption/desorption experiments.
Journal Article

Mitigation of Platinum Poisoning of Cu-Zeolite SCR Catalysts

2013-04-08
2013-01-1065
A typical diesel exhaust emission control system for meeting the US EPA 2010 regulations includes one or more platinum-group metal (PGM)-containing catalysts, located upstream of an SCR unit. However, as was previously reported in literature, under certain operating conditions PGM elements can get transferred onto the downstream SCR catalyst, resulting in the loss of its NOx conversion efficiency. In the same studies, the effect of Pt poisoning was found to be mitigated by catalyst treatment at 850°C, presumably due to Pt volatilization and migration. In the present study, we have explored the process of Pt poisoning mitigation, and identified that the recovery can take place at lower temperatures, reducing the risk of hydrothermal damage to the catalyst.
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

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

Axially Resolved Performance of Cu-Zeolite SCR Catalysts

2012-04-16
2012-01-1084
In this work, an alternative method is proposed and validated for quantifying the axial performance of a state-of-the-art Cu zeolite SCR catalyst. Catalyst cores of a standard length, with varying lengths of wash-coated regions were used to axially resolve the functional performance of the SCR catalyst. This proposed method was validated by quantifying the catalyst entrance and exit effects, as well as the effect of non-uniform wash-coat loading densities. This method is less susceptible to some of the complications highlighted in the previous studies, such as flow uniformity between channels, as well as radiative heating effects, since the product gases are sampled across the entire monolith cross-section rather than through a single catalyst channel. The specific catalyst functions quantified include: NO and NH₃ oxidation, NH₃ storage capacity, as well as NOx conversion efficiency.
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.
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