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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

Technical Advantages of Urea SCR for Light-Duty and Heavy-Duty Diesel Vehicle Applications

2004-03-08
2004-01-1292
The 2007 emission standards for both light-duty and heavy-duty diesel vehicles remain a challenge. A level of about 90% NOx conversion is required to meet the standards. Technologies that have the most potential to achieve very high NOx conversion at low temperatures of diesel exhaust are lean NOx traps (LNTs) and Selective Catalytic Reduction (SCR) of NOx using aqueous urea, typically known as Urea SCR. The LNT has the advantage of requiring no new infrastructure, and does not pose any new customer compliance issues. However, Urea SCR has high and durable NOx conversion in a wider temperature window, a lower equivalent fuel penalty, and lower system cost. On a technical basis, Urea SCR has the best chance of meeting the 2007 NOx targets. This paper reviews the results of some demonstration programs for both light-and heavy-duty applications.
Technical Paper

System Level Simulation of H2 ICE after Treatment System

2024-04-09
2024-01-2625
Hydrogen Internal Combustion Engines (H2 ICE) are gaining recognition as a nearly emission-free alternative to traditional ICE engines. However, H2 ICE systems face challenges related to thermal management, N2O emissions, and reduced SCR efficiency in high humidity conditions (15% H2O). This study assesses how hydrogen in the exhaust affects after-treatment system components for H2 ICE engines, such as Selective Catalytic Reduction (SCR), Hydrogen Oxidation Catalyst (HOC), and Ammonia Slip Catalyst (ASC). Steady-state experiments with inlet H2 inlet concentrations of 0.25% to 1% and gas stream moisture levels of up to 15% H2O were conducted to characterize the catalyst response to H2 ICE exhaust. The data was used to calibrate and validate system component models, forming the basis for a system simulation.
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.
Journal Article

Impact of Second NH3 Storage Site on SCR NO x Conversion in an Ultra-Low NO x Aftertreatment System

2023-04-11
2023-01-0367
Typical two-site storage-based SCR plant models in literature consider NH3 stored in the first site to participate in NH3 storage, NOx conversion and second site to only participate in NH3 storage passively. This paper focuses on quantifying the impact of stored NH3 in the second site on the overall NOx conversion for an ultra-low NOx system due to intra site NH3 mass transfer. Accounting for this intra site mass transfer leads to better prediction of SCR out NH3 thus ensuring compliance with NH3 coverage targets and improved dosing characteristics of the controller that is critical to achieving ultra-low NOx standard. The stored NH3 in the second site undergoes mass transfer to the first site during temperature ramps encountered in a transient cycle that leads to increased NOx conversion in conditions where the dosing is switched off. The resultant NH3 coverage fraction prediction is critical in dosing control of SCR.
Journal Article

Impact of Hydrothermal and Chemical Aging on SCR Storage Characteristics and NOx Reduction Performance in an Ultra-Low NOx System

2023-04-11
2023-01-0360
This work is a part of medium-duty Low NOx technology development project with a focus on evaluating a combination of engine and advanced aftertreatment for 0.02 g/bhp-hr NOx regulation proposed by CARB (California air resource board). In this project, a control oriented chemical kinetics model of SCR (Selective catalytic reduction) was used in the aftertreatment controller that is susceptible to performance degradation due to hydrothermal and chemical aging. This paper focuses on modeling the NOx conversion and NH3 storage characteristics using a controls oriented SCR plant model which is further used for a model-based urea dosing scheme. A set of steady state reactor tests were used to calibrate the SCR performance at degreened, hydrothermal only and hydrothermal + chemical aging conditions and also to determine inhibition factors related to aging. The resultant model is capable of simulating SCR performance deterioration such as a reduction in NOx conversion and NH3 storage.
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

Fast Diesel Aftertreatment Heat-up Using CDA and an Electrical Heater

2021-04-06
2021-01-0211
Commercial vehicles require fast aftertreatment heat-up in order to move the SCR catalyst into the most efficient temperature range to meet upcoming NOX regulations. Today’s diesel aftertreatment systems require on the order of 10 minutes to heat up during a cold FTP cycle. The focus of this paper is to heat up the aftertreatment system as quickly as possible during cold starts and maintain a high temperature during low load, while minimizing fuel consumption. A system solution is demonstrated using a heavy-duty diesel engine with an end-of-life aged aftertreatment system targeted for 2027 emission levels using various levels of controls. The baseline layer of controls includes cylinder deactivation to raise the exhaust temperature more than 100° C in combination with elevated idle speed to increase the mass flowrate through the aftertreatment system. The combination yields higher exhaust enthalpy through the aftertreatment system.
Technical Paper

Evaluating the Impact of Connected Vehicle Technology on Heavy-Duty Vehicle Emissions

2023-04-11
2023-01-0716
Eco-driving algorithms enabled by Vehicle to Everything (V2X) communications in Connected and Automated Vehicles (CAVs) can improve fuel economy by generating an energy-efficient velocity trajectory for vehicles to follow in real time. Southwest Research Institute (SwRI) demonstrated a 7% reduction in energy consumption for fully loaded class 8 trucks using SwRI’s eco-driving algorithms. However, the impact of these schemes on vehicle emissions is not well understood. This paper details the effort of using data from SwRI’s on-road vehicle tests to measure and evaluate how eco-driving could impact emissions. Two engine and aftertreatment configurations were evaluated: a production system that meets current NOX standards and a system with advanced aftertreatment and engine technologies designed to meet low NOX 2031+ emissions standards.
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.
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