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Technical Paper

Water-Gas-Shift Catalyst Development and Optimization for a D-EGR® Engine

2015-09-01
2015-01-1968
Dedicated Exhaust Gas Recirculation (D-EGR®) technology provides a novel means for fuel efficiency improvement through efficient, on-board generation of H2 and CO reformate [1, 2]. In the simplest form of the D-EGR configuration, reformate is produced in-cylinder through rich combustion of the gasoline-air charge mixture. It is also possible to produce more H2 by means of a Water Gas Shift (WGS) catalyst, thereby resulting in further combustion improvements and overall fuel consumption reduction. In industrial applications, the WGS reaction has been used successfully for many years. Previous engine applications of this technology, however, have only proven successful to a limited degree. The motivation for this work was to develop and optimize a WGS catalyst which can be employed to a D-EGR configuration of an internal combustion engine. This study consists of two parts.
Technical Paper

Use of Nitric Acid to Control the NO2:NOX Ratio Within the Exhaust Composition Transient Operation Laboratory Exhaust Stream

2020-04-14
2020-01-0371
The Exhaust Composition Transient Operation Laboratory (ECTO-Lab) is a burner system developed at Southwest Research Institute (SwRI) for simulation of IC engine exhaust. The current system design requires metering and combustion of nitromethane in conjunction with the primary fuel source as the means of NOX generation. While this method affords highly tunable NOX concentrations even over transient cycles, no method is currently in place for dictating the speciation of nitric oxide (NO) and nitrogen dioxide (NO2) that constitute the NOX mixture. NOX generated through combustion of nitromethane is dominated by NO, and generally results in a NO2:NOX ratio of <5 %. Generation of any appreciable quantities of NO2 is therefore dependent on an oxidation catalyst to oxidize a fraction of the NO to NO2.
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.
Technical Paper

SCR Deactivation Study for OBD Applications

2012-04-16
2012-01-1076
Selective catalytic reduction (SCR) catalysts will be used to reduce oxides of nitrogen (NOx) emissions from internal combustion engines in a number of applications. 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.
Video

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

2012-06-18
Selective Catalytic Reduction (SCR) catalysts are used to reduce NOx emissions from internal combustion engines in a variety 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 a Fe-zeolite formulation. This work describes NH3 storage capacity measurement data as a function of aging time and temperature. Addressing one objective of the work, these data can be used in model-based control algorithms to calculate the current NH3 storage capacity of an SCR catalyst operating in the field, based on time and temperature history. The model-based control then uses the calculated value for effective DEF control and prevention of excessive NH3 slip. Addressing a second objective of the work, accelerated thermal aging of SCR catalysts may be achieved by elevating temperatures above normal operating temperatures.
Technical Paper

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

2012-04-16
2012-01-1077
Selective Catalytic Reduction (SCR) catalysts are used to reduce NOx emissions from internal combustion engines in a variety of applications. 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 a Fe-zeolite formulation. This work describes NH₃ storage capacity measurement data as a function of aging time and temperature. Addressing one objective of the work, these data can be used in model-based control algorithms to calculate the current NH₃ storage capacity of an SCR catalyst operating in the field, based on time and temperature history. The model-based control then uses the calculated value for effective DEF control and prevention of excessive NH₃ slip. Addressing a second objective of the work, accelerated thermal aging of SCR catalysts may be achieved by elevating temperatures above normal operating temperatures.
Technical Paper

Investigation of Urea Derived Deposits Composition in SCR Systems and Their Potential Effect on Overall PM Emissions

2016-04-05
2016-01-0989
Ideally, complete thermal decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea thermal decomposition reaction includes the formation of isocyanic acid as an intermediate product. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid, biuret, melamine, ammeline, ammelide, and dicyandimide [1,2,3,4]. These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions, can create oligomers such as melam, melem, and melon [5, 6] that are difficult to remove from exhaust systems. Deposits can affect the efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow.
Technical Paper

Investigation of Urea Derived Deposits Composition in SCR Systems

2016-10-17
2016-01-2327
Ideally, complete decomposition of urea should produce only two products in active Selective Catalytic Reduction (SCR) systems: ammonia and carbon dioxide. In reality, urea decomposition reaction is a two-step process that includes the formation of ammonia and isocyanic acid as intermediate products via thermolysis. Being highly reactive, isocyanic acid can initiate the formation of larger molecular weight compounds such as cyanuric acid (CYN), biuret (BIU), melamine (MEL), ammeline (AML), ammelide (AMD), and dicyandimide (DICY). These compounds can be responsible for the formation of deposits on the walls of the decomposition reactor in urea SCR systems. Composition of these deposits varies with temperature exposure, and under certain conditions can create oligomers that are difficult to remove from exhaust pipes. Deposits can affect efficiency of the urea decomposition, and if large enough, can inhibit the exhaust flow and negatively impact ammonia distribution on the SCR catalyst.
Technical Paper

Investigation Into Improved Low-Temperature Urea-Water Solution Decomposition by Addition of Titanium-Based Isocyanic Acid Hydrolysis Catalysts and Surfactant

2020-04-14
2020-01-1316
Mitigation of urea deposit formation and improved ammonia production at low exhaust temperatures continues to be one of the most significant challenges for current generation SCR aftertreatment systems. Various technologies have been devised to alleviate these issues including: use of alternative reductant sources and thermal treatment of the urea-water solution (UWS) pre-injection. The objective of this work is to expand the knowledge base of a potential third option, which entails chemical modification of UWS by addition of titanium-based urea/isocyanic acid (HNCO) decomposition catalysts and/or surfactants to the fluid. Physical mixtures of urea and varying concentrations of ammonium titanyl oxalate (ATO), oxalic acid, and titanium dioxide (TiO2) were generated, and the differences in NH3 and CO2 production were evaluated.
Technical Paper

Identifying Limiters to Low Temperature Catalyst Activity

2015-04-14
2015-01-1025
The drive to more fuel efficient vehicles is underway, with passenger car targets of 54.5 mpg fleet average by 2025. Improving engine efficiency means reducing losses such as the heat lost in the exhaust gases. However, reducing exhaust temperature makes it harder for emissions control catalysts to function because they require elevated temperatures to be active. Addressing this conundrum was the focus of the work performed. The primary objective of this work was to identify low temperature limiters for a variety of catalyst aftertreatment types. The ultimate goal is to reduce catalyst light-off temperatures, and the knowledge needed is an understanding of what prevents a catalyst from lighting off, why, and how it may be mitigated. Collectively these are referred to here as low temperature limiters to catalyst activity.
Technical Paper

Fuel Reforming and Catalyst Deactivation Investigated in Real Exhaust Environment

2019-04-02
2019-01-0315
Increased in-cylinder hydrogen levels have been shown to improve burn durations, combustion stability, HC emissions and knock resistance which can directly translate into enhanced engine efficiency. External fuel reformation can also be used to increase the hydrogen yield. During the High-Efficiency, Dilute Gasoline Engine (HEDGE) consortium at Southwest Research Institute (SwRI), the potential of increased hydrogen production in a dedicated-exhaust gas recirculation (D-EGR) engine was evaluated exploiting the water gas shift (WGS) and steam reformation (SR) reactions. It was found that neither approach could produce sustained hydrogen enrichment in a real exhaust environment, even while utilizing a lean-rich switching regeneration strategy. Platinum group metal (PGM) and Ni WGS catalysts were tested with a focus on hydrogen production and catalyst durability.
Technical Paper

Effects of Catalyst Formulation on Vehicle Emissions With Respect to Gasoline Fuel Sulfur Level

1999-10-25
1999-01-3675
Proposed emissions standards will require that emissions control systems function at extremely high efficiency. Recently, studies have shown that elevated gasoline fuel sulfur levels (GFSL) can impair catalytic converter efficiency. In this study, a variety of tri-metal catalysts were evaluated to determine if formulation changes could reduce emissions sensitivity to GFSL. Catalysts with elemental composition similar to an OEM, but with double the precious metal (PM) loading, were evaluated using 38 and 620 ppm GFSL. Doubling the PM loading significantly reduced catalyst sensitivity to sulfur. Doubling the rhodium loading, at the expense of the platinum loading, significantly improved NOx emission sulfur sensitivity.
Technical Paper

Deposit Reduction in SCR Aftertreatment Systems by Addition of Ti-Based Coordination Complex to UWS

2019-04-02
2019-01-0313
Formation of urea-derived deposits in selective catalytic reduction (SCR) aftertreatment systems continues to be problematic at temperatures at and below 215 °C. Several consequences of deposit formation include: NOx and NH3 slip, exhaust flow maldistribution, increased engine backpressure, and corrosion of aftertreatment components. Numerous methods have been developed to reduce deposit formation, but to date, there has been no solution for continuous low-temperature dosing of Urea-Water Solution (UWS). This manuscript presents a novel methodology for reducing low-temperature deposit formation in SCR aftertreatment systems. The methodology described herein involves incorporation and dissolution of an HNCO hydrolysis catalyst directly into the UWS. HNCO is a transient species formed by the thermolysis of urea upon injection of UWS into the aftertreatment system.
Technical Paper

Comparison of Accelerated Ash Loading Methods for Gasoline Particulate Filters

2018-09-10
2018-01-1703
Recent legislation enacted for the European Union (EU) and the United States calls for a substantial reduction in particulate mass (and number in the EU) emissions from gasoline spark-ignited vehicles. The most prominent technology being evaluated to reduce particulate emissions from a gasoline vehicle is a wall flow filter known as a gasoline particulate filter (GPF). Similar in nature to a diesel particulate filter (DPF), the GPF will trap and store particulate emissions from the engine, and oxidize said particulate with frequent regeneration events. The GPF will also collect ash particles in the wall flow substrate, which are metallic components that cannot be oxidized into gaseous components. Due to high temperature operation and frequent regeneration of the GPF, the impact of ash on the GPF has the potential to be substantially different from the impact of ash on the DPF.
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.
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

Achieving Ultra Low NOX Emissions Levels with a 2017 Heavy-Duty On-Highway TC Diesel Engine - Comparison of Advanced Technology Approaches

2017-03-28
2017-01-0956
The 2010 emissions standards for heavy-duty engines have established a limit of oxides of nitrogen (NOX) emissions of 0.20 g/bhp-hr. However, the California Air Resource Board (ARB) projects that even when the entire on-road fleet of heavy-duty vehicles operating in California is compliant with 2010 emission standards, the National Ambient Air Quality Standards (NAAQS) requirement for ambient particulate matter (PM) and Ozone will not be achieved without further reduction in NOX emissions. The California Air Resources Board (CARB) funded a research program to explore the feasibility of achieving 0.02 g/bhp-hr NOX emissions.
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