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Journal Article

Removal of Hydrocarbons and Particulate Matter Using a Vanadia Selective Catalytic Reduction Catalyst: An Experimental and Modeling Study

The use of vanadia selective catalytic reduction (V-SCR) catalysts for NOX reduction from diesel engine exhaust is well known. These catalysts are also active for hydrocarbon (HC) and particulate matter (PM) oxidation. This dual functionality (oxidation and reduction) of V-SCR catalysts can help certain applications achieve the legislative limits with an improved margin. In this work, NOX reduction, HC and CO oxidation over V-SCR were studied independently and simultaneously in microreactor tests. The effect of various parameters (HC speciation, concentration, ANR, and NO₂/NOX ratio) was investigated and the data was used to develop a kinetic model. Oxidation of CO, C₃H₆, and n-C₁₀H₂₂ is first order in CO/HC, while C₇H₈ oxidation is less than first order in C₇H₈. All these reactions were zero order in O₂. Oxidation activity decreased in order: C₇H₈ ≻ n-C₁₀H₂₂ ≻ C₃H₆ ≻ CO. HC oxidation was inhibited by NH₃.
Journal Article

NOx and PM Reduction from Diesel Exhaust Using Vanadia SCRF®

Future heavy-duty diesel (HDD) engines are designed to have higher engine out NOx, for improved fuel economy, while reduction of the emission control technology footprint is also desired. Consequently, higher NOx reduction across compact emission control systems is required. Selective catalytic reduction (SCR) catalyst coating combined with a wall flow particulate filter (SCRF®1) is a technology that enables abatement of NOx emissions in addition to oxidation of soot from diesel engine exhausts. Vanadia based-SCR is well known for NOx reduction and is active for hydrocarbon (HC) and particulate matter (PM) oxidation. This dual functionality (oxidation and reduction reactions) of the V.SCR catalysts plus the filtration achieved by the filter substrate can help certain diesel engine applications achieve the legislative limits with a reduced packaging volume.
Technical Paper

Modeling of Dual Layer Ammonia Slip Catalysts (ASC)

In recent years, ammonia slip catalysts (ASC) are being used downstream of an SCR system to minimize the ammonia slip. The dual-layer ASC is more attractive for its bi-functionality in reducing the ammonia and NOX emissions. It consists of two layers with the upper layer comprising a component with SCR functionality and the lower layer a PGM containing catalyst with oxidation functionality. Thus, both oxidation and SCR reactions take place in two different layers and are interlinked by the inter-layer mass transfer mechanism. In addition, adsorption and desorption kinetics between the gas and solid phases play a significant role. Mathematically, the overall system is a complex system of mass, momentum and energy transfer equations with temporal and spatial variables in both axial and radial directions. In this work, we focus on devising a suitable, computationally inexpensive model for such ASCs to be efficiently used for design, control and system optimization studies.
Technical Paper

Fe-Zeolite SCR Model Development, Validation and Application

Selective Catalytic Reduction (SCR) technology has been widely studied for removal of NOX from the exhaust of diesel engines. To design and optimize diesel engine aftertreatment systems including an SCR catalyst component, a reliable SCR model is a very useful tool, to aid in system integration and control algorithm testing. In this paper, the development of a one-dimensional numerical model for a Fe-Zeolite-based SCR catalyst (hydrothermally aged for 100 hours at 650°C in 10% H₂O in air) is presented, followed by its validation and application. The resulting model is capable of predicting NOX reduction efficiency under various operating conditions as a function of gas hourly space velocity (SV), temperature, NO₂/NOX ratio and NH₃ to NOX (ANR) ratios; NH₃ slip and N₂O formation are also correctly predicted by the model. Extensive validation of the model has been carried out against engine test data for both steady state light-off and the heavy-duty FTP transient cycle (HD-FTP).
Technical Paper

Experimental and Computational Study of DOC on CSF for Heavy Duty Diesel Applications

For diesel exhaust aftertreatment applications with space limitations, as well as to move the selective catalytic reduction system (SCR) to a warmer location closer to the engine, DOC on CSF technology can be used. This technology combines the diesel oxidation catalyst (DOC) and catalyzed soot filter (CSF) functionalities in one component, thereby enabling volume reduction. DOC on CSF maintains the abatement of hydrocarbon (HC), carbon monoxide (CO), and particulate matter (PM), and the oxidation of nitric oxide (NO) to nitrogen dioxide (NO2) for passive soot oxidation and fast SCR reaction of NOx on a downstream SCR catalyst. In this study, the performance of DOC on CSF was compared to a DOC + bare diesel particulate filter (DPF) and a DOC + CSF system, to understand the performance benefits and challenges. All the components were optimized individually for their respective functions. The DOC on CSF was optimized for NO oxidation and passive soot oxidation performance.
Technical Paper

Engine Performance of Cu- and Fe-Based SCR Emission Control Systems for Heavy Duty Diesel Applications

Since early 2010, most new medium- and heavy-duty diesel vehicles in the US rely on urea-based Selective Catalytic Reduction (SCR) technology for meeting the most stringent regulations on nitrogen oxides (NOx) emissions in the world today. Catalyst technologies of choice include Copper (Cu)- and Iron (Fe)-based SCR. In this work, the performances of Fe-SCR and Cu-SCR were investigated in the most commonly used DOC + CSF + SCR system configuration. Cu-SCR offered advantages over Fe-SCR in terms of low temperature conversion, NO₂:NOx ratio tolerance and NH₃ slip, while Fe-SCR demonstrated superior performance under optimized NO₂:NOx ratio and at higher temperatures. The Cu-SCR catalyst displayed less tolerance to sulfur (S) exposure. Reactor testing has shown that Cu-SCR catalysts deactivate at low temperature when poisoned by sulfur.
Journal Article

Effect of Coolant Exposure on Diesel Exhaust Aftertreatment Performance

Aftertreatment devices are exposed to exhaust poisons from fuel, oil and coolant. Studies on fuel- and lubricant-based poisoning have been widely published. However, diesel oxidation catalyst (DOC) and catalyzed soot filter (CSF) performance after exposure to constituents of coolant is not fully understood. Exhaust gas recirculation (EGR) cooler failure can cause a coolant leak into the exhaust that can reach the exhaust aftertreatment system. Coolant contains elements that can cause deterioration of aftertreatment components. This study focuses on the poisoning effect of coolant on the performance of a DOC + CSF system. The coolant introduction simulates an engine failure such as an EGR cooler internal fracture. DOC NO oxidation, quenching and hydrocarbon (HC) slip control performance during active regenerations are evaluated after slow and after consecutive fast coolant introduction and compared to the performance before the coolant exposure.
Journal Article

Development of SCR on High Porosity Substrates for Heavy Duty and Off-Road Applications

Selective Catalytic Reduction (SCR) catalysts have been demonstrated as an effective solution for controlling NOx emissions from diesel engines. There is a drive to reduce the overall packaging volume of the aftertreatment system for these applications. In addition, more active SCR catalysts will be needed as the applications become more challenging: e.g. lower temperatures and higher engine out NOx, for fuel consumption improvements. One approach to meet the challenges of reduced volume and/or higher NOx reduction is to increase the active site density of the SCR catalyst by coating higher amount of SCR catalyst on high porosity substrates (HPS). This approach could enable the reduction of the overall packaging volume while maintaining similar NOx conversion as compared to 2010/2013 systems, or improve the NOx reduction performance for equivalent volume and NH3 slip.
Technical Paper

Development and Validation of a Cu-Zeolite SCR Catalyst Model

A one-dimensional numerical model for a Cu-zeolite SCR catalyst has been developed. The model is based on kinetics developed from laboratory microreactor data for the various NH₃-NOX reactions, as well as for NH₃ oxidation. The kinetic scheme used is discussed and evidence for it presented. The model is capable of predicting the conversion of NO and NO₂, NH₃ slip and the formation of N₂O, as well as effects associated with NH₃ storage and desorption. To obtain a good prediction of catalyst temperature during cold start tests, it was found necessary to include storage and desorption of H₂O in the model; storage of H₂O is associated with a sizable exotherm and the subsequent desorption of this water produces a correspondingly large endotherm.
Technical Paper

After-Treatment Systems to Meet China NS VI, India BS VI Regulation Limits

Future emissions regulations proposed for the Asian automotive industry (BS VI regulations for India and NS VI regulations for China) are strict and similar to EU VI regulations. As a result, they will require both advanced NOx control as well as advanced Particulate Matter (PM) control. This will drive implementation of full Catalyzed Diesel Particulate Filter (cDPF) and simultaneous NOx control using Selective Catalytic Reduction (SCR) technologies. In this work, we present the performance of various Diesel Oxidation Catalyst (DOC), cDPF, SCR and Ammonia slip catalyst (ASC) systems utilizing the World Harmonized Transient Cycle (WHTC). Aftertreatment Systems (ATS) required for both active and passive filter regeneration applications will be discussed. The sensitivity of key design parameters like catalyst technology, PGM loading, catalyst sizing to meet the regulation limits has been investigated.