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Video

SCR Deactivation Kinetics for Model-Based Control and Accelerated Aging Applications

2012-06-18
This paper forms the third of a series and presents results obtained during the testing and development phase of a dedicated range extender engine designed for use in a compact class vehicle. The first paper in this series used real world drive logs to identify usage patterns of such vehicles and a driveline model was used to determine the power output requirements of a range extender engine for this application. The second paper presented the results of a design study. Key attributes for the engine were identified, these being minimum package volume, low weight, low cost, and good NVH. A description of the selection process for identifying the appropriate engine technology to satisfy these attributes was given and the resulting design highlights were described. The paper concluded with a presentation of the resulting specification and design highlights of the engine. This paper will present the resulting engine performance characteristics.
Video

Brief Investigation of SCR High Temperature N2O Production

2012-06-18
Nitrous Oxide (N2O) is a greenhouse gas with a Global Warming Potential (GWP) of 298-310 [1,2] (298-310 times more potent than carbon dioxide (CO2)). As a result, any aftertreatment system that generates N2O must be well understood to be used effectively. Under low temperature conditions, N2O can be produced by Selective Catalytic Reduction (SCR) catalysts. The chemistry is reasonably well understood with N2O formed by the thermal decomposition of ammonium nitrate [3]. Ammonium nitrate and N2O form in oxides of nitrogen (NOx) gas mixtures that are high in nitrogen dioxide (NO2)[4]. This mechanism occurs at a relatively low temperature of about 200°C, and can be controlled by maintaining the nitric oxide (NO)/NO2 ratio above 1. However, N2O has also been observed at relatively high temperatures, in the region of 500°C.
Video

SCR Deactivation Study for OBD Applications

2012-06-18
Selective catalytic reduction (SCR) catalysts will be used to reduce oxides of nitrogen (NOx) emissions from internal combustion engines in a number of applications [1,2,3,4]. Southwest Research Institute® (SwRI)® performed an Internal Research & Development project to study SCR catalyst thermal deactivation. The study included a V/W/TiO2 formulation, a Cu-zeolite formulation and an Fe-zeolite formulation. This work describes NOx timed response to ammonia (NH3) transients as a function of thermal aging time and temperature. It has been proposed that the response time of NOx emissions to NH3 transients, effected by changes in diesel emissions fluid (DEF) injection rate, could be used as an on-board diagnostic (OBD) metric. The objective of this study was to evaluate the feasibility and practicality of this OBD approach.
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

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.
Technical Paper

Combination of Mixed Metal Oxides with Cu-Zeolite for Enhanced Soot Oxidation on an SCRoF

2021-09-05
2021-24-0071
A push for more stringent emissions regulations has resulted in larger, increasingly complex aftertreatment solutions. In particular, oxides of nitrogen (NOX) and particulate matter (PM) have been controlled using two separate systems, selective catalytic reduction (SCR) and the catalyze diesel particulate filter (CDPF), or the functionality has been combined into a single device producing the SCR on filter (SCRoF). The SCRoF forgoes beneficial NO2 production present in the CDPF to avoid NH3 oxidation which occurs when using platinum group metals (PGM) for oxidation. In this study, mixed-metal oxides are shown to oxidize NO to NO2 without appreciable NH3 oxidation. This selectivity leads to enhanced performance when combined with a typical Cu-zeolite catalyst.
Technical Paper

A Controls Overview on Achieving Ultra-Low NOx

2020-04-14
2020-01-1404
The California Air Resources Board (CARB)-funded Stage 3 Heavy-Duty Low NOX program focusses on evaluating different engine and after-treatment technologies to achieve 0.02g/bhp-hr of NOX emission over certification cycles. This paper highlights the controls architecture of the engine and after-treatment systems and discusses the effects of various strategies implemented and tested in an engine test cell over various heavy-duty drive cycles. A Cylinder De-Activation (CDA) system enabled engine was integrated with an advanced after-treatment controller and system package. Southwest Research Institute (SwRI) had implemented a model-based controller for the Selective Catalytic Reduction (SCR) system in the CARB Stage 1 Low-NOX program. The chemical kinetics for the model-based controller were further tuned and implemented in order to accurately represent the reactions for the catalysts used in this program.
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.
Technical Paper

Evaluation of Cylinder Deactivation on a Class 8 Truck over Light Load Cycles

2020-04-14
2020-01-0800
Selective Catalytic Reduction (SCR) systems provide excellent NOX control for diesel engines provided the exhaust aftertreatment inlet temperature remains at 200° C or higher. Since diesel engines run lean, extended light load operation typically causes exhaust temperatures to fall below 200° C and SCR conversion efficiency diminishes. Heated urea dosing systems are being developed to allow dosing below 190° C. However, catalyst face plugging remains a concern. Close coupled SCR systems and lower temperature formulation of SCR systems are also being developed, which add additional expense. Current strategies of post fuel injection and retarded injection timing increases fuel consumption. One viable keep-warm strategy examined in this paper is cylinder deactivation (CDA) which can increase exhaust temperature and reduce fuel consumption.
Journal Article

Model-Based Estimation and Control System Development in a Urea-SCR Aftertreatment System

2008-04-14
2008-01-1324
In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.
Journal Article

Measurement of Dioxin and Furan Emissions during Transient and Multi-Mode Engine Operation

2011-04-12
2011-01-1158
This study analyzed the impact of transient and multi-mode engine conditions on emissions of dioxins and furans from a variety of diesel aftertreatment configurations. Exhaust aftertreatment systems included combinations of diesel oxidation catalyst, diesel particulate filter, and either Cu/zeolite or Fe/zeolite selective catalytic reduction catalyst. EPA method TO-9A was modified for proportional exhaust gas sampling, whereas EPA method 0023A was modified for raw exhaust gas sampling. Dioxin and furan emissions were first measured with modified method TO-9A during Federal Test Procedure transient cycles, but no toxic dioxins or furans were detected. Measurements were then taken with modified method 0023A during Ramped Mode Cycles-Supplemental Emissions Test experiments. Because more rigorous pre-cleaning and sample extraction procedures were used with this method and lower detection limits were achieved by the analytical laboratory, some dioxin and furan congeners were detected.
Journal Article

Boosting Simulation of High Efficiency Alternative Combustion Mode Engines

2011-04-12
2011-01-0358
Four high-efficiency alternative combustion modes were modeled to determine the potential brake thermal efficiency (BTE) relative to a traditional lean burn compression ignition diesel engine with selective catalytic reduction (SCR) aftertreatment. The four combustion modes include stoichiometric pilot-ignited gasoline with EGR dilution (SwRI HEDGE technology), dual fuel premixed compression ignition (University of Wisconsin), gasoline partially premixed combustion (Lund University), and homogenous charge compression ignition (HCCI) (SwRI Clean Diesel IV). For each of the alternative combustion modes, zero-D simulation of the peak torque condition was used to show the expected BTE. For all alternative combustion modes, simulation showed that the BTE was very dependent on dilution levels, whether air or EGR. While the gross indicated thermal efficiency (ITE) could be shown to improve as the dilution was increased, the required pumping work decreased the BTE at EGR rates above 40%.
Journal Article

Brief Investigation of SCR High Temperature N2O Production

2012-04-16
2012-01-1082
Nitrous Oxide (N₂O) is a greenhouse gas with a Global Warming Potential (GWP) of 298-310 (298-310 times more potent than carbon dioxide (CO₂)). As a result, any aftertreatment system that generates N₂O must be well understood to be used effectively. Under low temperature conditions, N₂O can be produced by Selective Catalytic Reduction (SCR) catalysts. The chemistry is reasonably well understood with N₂O formed by the thermal decomposition of ammonium nitrate. Ammonium nitrate and N₂O form in oxides of nitrogen (NOx) gas mixtures that are high in nitrogen dioxide (NO₂). This mechanism occurs at a relatively low temperature of about 200°C, and can be controlled by maintaining the nitric oxide (NO)/NO₂ ratio above 1. However, N₂O has also been observed at relatively high temperatures, in the region of 500°C.
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.
Technical Paper

Preparation and Testing of an Electric Competition Vehicle

1991-08-01
911684
A Dodge Omni electric car was prepared for competition in an electric “stock car” 2-hour endurance event: the inaugural Solar and Electric 500 Race, April 7, 1991. This entry utilized a series-wound, direct-current 21-hp electric motor controlled by an SCR frequency and pulse width modulator. Two types of lead-acid batteries were evaluated and the final configuration was a set of 16 (6-volt each) deep-cycle units. Preparation involved weight and friction reduction; suspension modification; load, charge and temperature instrumentaltion; and electrical interlock and collision safety systems. Vehicle testing totalled 15 hours of operation. Ranges observed in testing with the final configuration were from 30 to 52 miles for loads of 175 to 90 amperes. These were nearly constant, continuous discharge cycles. The track qualifying speed (64mph) was near the 68 mph record set by the DEMI Honda at the event on the one-mile track.
Journal Article

Impact of Biodiesel Impurities on the Performance and Durability of DOC, DPF and SCR Technologies

2011-04-12
2011-01-1136
It is estimated that operating continuously on a B20 fuel containing the current allowable ASTM specification limits for metal impurities in biodiesel could result in a doubling of ash exposure relative to lube-oil-derived ash. The purpose of this study was to determine if a fuel containing metals at the ASTM limits could cause adverse impacts on the performance and durability of diesel emission control systems. An accelerated durability test method was developed to determine the potential impact of these biodiesel impurities. The test program included engine testing with multiple DPF substrate types as well as DOC and SCR catalysts. The results showed no significant degradation in the thermo-mechanical properties of cordierite, aluminum titanate, or silicon carbide DPFs after exposure to 150,000 mile equivalent biodiesel ash and thermal aging. However, exposure of a cordierite DPF to 435,000 mile equivalent aging resulted in a 69% decrease in the thermal shock resistance parameter.
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.
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.
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