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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.
Journal Article

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 LaboratoryTM (ECTO-LabTM) 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 an 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.
Technical Paper

Unregulated Emissions Characterization and Comparison for Two Off-Road Applications: A DPF and Non-DPF Engine

2022-03-29
2022-01-0587
As governmental agencies focus on low levels of the oxides of nitrogen (NOx) emissions compliance, new off-road applications are being reviewed for both regulated and unregulated emissions to understand the technological challenges and requirements for improved emissions performance. The California Air Resources Board (CARB) has declared its intention to pursue more stringent NOX standards for the off-road market. As part of this effort, CARB initiated a program to provide a detailed characterization of emissions meeting the current Tier 4 off-road standards [1]. This work focused on understanding the off-road market, establishing a current technology emissions baseline, and performing initial modeling on potential low NOx solutions. This paper discusses a part of this effort, focuses on the emissions characterization from two non-road engine platforms, and compares the emissions species from different approaches designed to meet Tier 4 emissions regulations.
Technical Paper

The Diesel Aftertreatment Accelerated Aging Cycle Protocol: An Advanced Aftertreatment Case Study

2020-09-15
2020-01-2210
As agencies and governing bodies evaluate the feasibility of reduced emission standards, additional focus has been placed on technology durability. This is seen in proposed updates, which would require Original Equipment Manufacturers (OEMs) to certify engine families utilizing a full useful life (FUL) aftertreatment system. These kinds of proposed rulings would place a heavy burden on the manufacturer to generate FUL components utilizing traditional engine aging methods. Complications in this process will also increase the product development effort and will likely limit the amount of aftertreatment durability testing. There is also uncertainty regarding the aging approach and the representative impact compared to field aged units. Existing methodologies have evolved to account for several deterioration mechanisms that, when controlled, can be utilized to create a flexible aging protocol. As a result, these methodologies provide the necessary foundation for continued development.
Technical Paper

Post-Mortem Analysis of DAAAC and Conventionally Aged Aftertreatment Systems

2023-10-31
2023-01-1656
Upcoming regulations from CARB and EPA will require diesel engine manufacturers to validate aftertreatment durability with full useful life aged components. To this end, the Diesel Aftertreatment Accelerated Aging Cycle (DAAAC) protocol was developed to accelerate aftertreatment aging by accounting for hydrothermal aging, sulfur, and oil poisoning deterioration mechanisms. Two aftertreatment systems aged with the DAAAC protocol, one on an engine and the other on a burner system, were directly compared to a reference system that was aged to full useful life using conventional service accumulation. After on-engine emission testing of the fully aged components, DOC and SCR catalyst samples were extracted from the aftertreatment systems to compare the elemental distribution of contaminants between systems. In addition, benchtop reactor testing was conducted to measure differences in catalyst performance.
Technical Paper

Optimization of Surfactant and Catalyst Modified Urea-Water Solution Formulation for Deposit Reduction in SCR Aftertreatment Systems

2022-03-29
2022-01-0541
Selective Catalytic Reduction is the primary method of NOX emission abatement in lean-burn internal combustion. This process requires the decomposition of a 32.5 wt. % urea-water solution (UWS) to provide ammonia as a reducing agent for NOX, but at temperatures < 250 °C the injection of UWS is limited due to the formation of harmful deposits within an aftertreatment system and decreased ammonia production. Previous work has sufficiently demonstrated that the addition of surfactant and a urea/isocyanic acid (HNCO) decomposition catalyst to UWS can significantly decrease deposit formation within an aftertreatment system. The objective of this work was to further optimize the modified UWS formulation by investigating different types and concentrations of surfactants and titanium-based urea/HNCO catalyst. Because there is a correlation between surface tension and water evaporation, it was theorized that minimizing the surface tension of UWS would result in decreased deposit formation.
Technical Paper

Oil Consumption Pathway Impact on SCR-on-Filter Functional Performance and Lubricant Derived Ash Characteristics

2021-04-06
2021-01-0578
SCR-on-filter, or SCRoF, is an emerging technology for different market segments and vehicle applications. The technology enables simultaneous particulate matter trapping and NOX reduction, and provides thermal management and aftertreatment packaging benefits. However, there is little information detailing the lubricant derived exposure effects on functional SCR performance. A study was conducted to evaluate the impact of various oil consumption pathways on a light duty DOC and SCRoF aftertreatment system. This aftertreatment system was aged utilizing an engine test bench modified to enable increased oil consumption rates via three unique oil consumption pathways. The components were characterized for functional SCR performance, ash morphology, and ash deposition characteristics. This included utilizing techniques, such as SEM / EDS, to evaluate the ash structures and quantify the ash elemental composition.
Journal Article

Meeting Future NOX Emissions Over Various Cycles Using a Fuel Burner and Conventional Aftertreatment System

2022-03-29
2022-01-0539
The commercial vehicle industry continues to move in the direction of improving brake thermal efficiency while meeting more stringent diesel engine emission requirements. This study focused on demonstrating future emissions by using an exhaust burner upstream of a conventional aftertreatment system. This work highlights system results over the low load cycle (LLC) and many other pertinent cycles (Beverage Cycle, and Stay Hot Cycle, New York Bus Cycle). These efforts complement previous works showing system performance over the Heavy-Duty FTP and World Harmonized Transient Cycle (WHTC). The exhaust burner is used to raise and maintain the Selective Catalytic Reduction (SCR) catalyst at its optimal temperature over these cycles for efficient NOX reduction. This work showed that tailpipe NOX is significantly improved over these cycles with the exhaust burner.
Technical Paper

Low NOx Emissions Performance after 800,000 Miles Aging Using CDA and an Electric Heater

2024-07-02
2024-01-3011
Engine and aftertreatment solutions have been identified to meet the upcoming ultra-low NOX regulations on heavy duty vehicles in the United States and Europe. These standards will require changes to current conventional aftertreatment systems for dealing with low exhaust temperature scenarios while increasing the useful life of the engine and aftertreatment system. Previous studies have shown feasibility of meeting the US EPA and California Air Resource Board (CARB) requirements. This work includes a 15L diesel engine equipped with cylinder deactivation (CDA) and an aftertreatment system that was fully DAAAC aged to 800,000 miles. The aftertreatment system includes an e-heater (electric heater), light-off Selective Catalytic Reduction (LO-SCR) followed by a primary aftertreatment system containing a DPF and SCR.
Journal Article

Low Ambient Temperature Impact on a Low NOX Demonstration System

2023-04-11
2023-01-0361
In 2020, CARB adopted the low NOX omnibus ruling, which provided revisions to on-road heavy duty engine compliance standards and certification practices. As part of the updates to the regulation, CARB has introduced a new in-use vehicle testing process that broadens the operation modes tested and considers the manufacturer’s intended vehicle application. Compared to the previous method, or the Not-to-Exceed approach, cold start and low ambient temperature provisions were included as part of the updates. The inclusion of low temperature operation requires the OEMs to design a robust engine and aftertreatment package that extends NOX conversion performance. The following work discusses the NOX emissions performance impact in a low temperature ambient environment. The engine and aftertreatment system evaluated was designed to comply with CARB’s low NOX regulations. The cycles tested included the CARB Southern NTE cycle and an FTP-LLC protocol.
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.
Journal Article

Investigation into Low-Temperature Urea-Water Solution Decomposition by Addition of Titanium-Based Isocyanic Acid Hydrolysis Catalyst 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 selective catalytic reduction (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 was to expand the knowledge base of a potential third option, which entails chemical modification of UWS by addition of a titanium-based urea/isocyanic acid (HNCO) decomposition catalysts and/or surfactant to the fluid. Physical solid mixtures of urea with varying concentrations of ammonium titanyl oxalate (ATO), oxalic acid, and titanium dioxide (TiO2) were generated, and the differences in NH3 and CO2 produced upon thermal decomposition were quantified.
Technical Paper

Further Advances in Demonstration of a Heavy-Duty Low NOX System for 2027 and Beyond

2024-04-09
2024-01-2129
Multiple areas in the U.S. continue to struggle with achieving National Ambient Air Quality Standards for ozone. These continued issues highlight the need for further reductions in NOX emission standards in multiple industry sectors, with heavy-duty on-highway engines being one of the most important areas to be addressed. Starting in 2014, CARB initiated a series of technical demonstration programs aimed at examining the feasibility of achieving up to a 90% reduction in tailpipe NOX, while at the same time maintaining a path towards GHG reductions that will be required as part of the Heavy-Duty Phase 2 GHG program. These programs culminated in the Stage 3 Low NOX program, which demonstrated low NOX emissions while maintaining GHG emissions at levels comparable to the baseline engine.
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

DAAAC Protocol for Durability Demonstration of Diesel Aftertreatment Systems: Emissions Performance Validation

2022-08-30
2022-01-1015
Aftertreatment durability demonstration is a required validation exercise for on-road medium and heavy-duty diesel engine certification. The demonstration is meant to validate emissions compliance for the engine and aftertreatment system at full useful life or FUL. Current certification practices allow engine manufacturers to complete partial aging and then extrapolate emissions performance results to FUL. While this process reduces the amount of service accumulation time, it does not consider changes in the aftertreatment deterioration rate. Rather, deterioration is assumed to occur at a linear rate, which may lead to false conclusions relating to emissions compliance. With CARB and EPA’s commitment to the reduction of criteria emissions, emphasis has also been placed on revising the existing certification practices. The updated practices would require engine manufacturers to certify with an aftertreatment system aged to FUL.
Technical Paper

Continuous Oil Consumption Measurement Using Laser Induced Breakdown Spectroscopy

2022-03-29
2022-01-0581
This paper describes a new method for measuring oil consumption using laser induced breakdown spectroscopy (LIBS). LIBS focuses a high energy laser pulse on a sample to form a transient plasma. As the plasma cools, each element produces atomic emission lines which can be used to identify and quantify the elements present in the original sample. In this work, a LIBS system was used on simulated engine exhaust with a focus on quantifying the inorganic components (termed ash) of the particulate emissions. Because some of the metallic elements in the ash almost exclusively result from lube oil consumption, their concentrations can also be correlated to an oil consumption rate. Initial testing was performed using SwRI’s Exhaust Composition Transient Operation Laboratory®(ECTO-Lab®) burner system so that oil consumption and ash mass could be precisely controlled.
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.
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