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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

Using Advanced Emission Control Systems to Demonstrate LEV II ULEV on Light-Duty Gasoline Vehicles

1999-03-01
1999-01-0774
A program to demonstrate the performance of advanced emission control systems in light of the California LEV II light-duty vehicle standards and the EPA's consideration of Tier II emission standards was conducted. Two passenger cars and one light-duty pick-up truck were selected for testing, modification, and emission system performance tuning. All vehicles were 1997 Federal Tier I compliant. The advanced emission control technologies evaluated in this program included advanced three-way catalysts, high cell density substrates, and advanced thermally insulated exhaust components. Using these engine-aged advanced emission control technologies and modified stock engine control strategies (control modifications were made using an ERIC computer intercept/control system), each of the three test vehicles demonstrated FTP emission levels below the proposed California LEV II 193,000 km (120,000 mile) ULEV levels.
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

Study of Modern Application Strategies for Catalytic Aftertreatment Demonstrated on a Production V6 Engine

2001-03-05
2001-01-0925
A study was performed to develop optimum design strategies for a production V6 engine to maximize catalyst performance at minimum pressure loss and at minimum cost. Test results for an advanced system, designed to meet future emission limits on a production V6 vehicle, are presented based on FTP testing. The on-line pressure loss and temperature data serves to explain the functioning of the catalyst.
Technical Paper

Phased Air/Fuel Ratio Perturbation - A Fuel Control Technique for Improved Catalyst Efficiency

2000-03-06
2000-01-0891
This paper describes the results of a study that examined the mechanism of phased perturbation as an emissions control technique. Phased perturbation involves independently controlling the fuel delivered to each bank of a dual bank engine (or each cylinder of a single manifold engine), which allows the two banks to have an adjustable, relative Air/Fuel (A/F) perturbation phase-shift from one another. The phase shifted exhaust is then recombined to achieve a near stoichiometric mixture prior to entering a single underbody catalyst. Phase shifting the exhaust Air/Fuel ratio creates a situation in which both rich exhaust constituents (unburnt hydrocarbons and carbon monoxide) and lean exhaust constituents (oxygen and oxides of nitrogen) arrive at the catalyst at the same time. The results of the study showed that phased perturbation produced a significant effect on A/F control and catalyst THC, CO, and NOx efficiency.
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.
Technical Paper

Nonroad Engine Activity Analysis and Transient Cycle Generation

1999-09-14
1999-01-2800
The United States Environmental Protection Agency (EPA) has initiated Phase I of a regulatory program to control exhaust emissions of nonroad diesel engines over 37 kW. Central to any emissions regulation is the test procedure, which must include an appropriate test cycle. Based on actual in-use speed and estimated torque data collected from an agricultural tractor, a backhoe-loader, and a crawler tractor, three duty cycles were developed. Using an iterative process, comparison of chi-square statistical data was used to identify representative microtrips, segments of engine operation gathered during performance of selected activities. Representative microtrips for specific activities for a particular nonroad application were “strung” together to make up a test cycle. Before accepting the test cycle, data for the cycle was compared to statistical data used to characterize the raw data in an effort to validate that the cycle was representative of the raw data.
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

Fuel Sulfur Effects on a Medium-Duty Diesel Pick-Up with a NOX Adsorber, Diesel Particle Filter Emissions Control System: 2000-Hour Aging Results

2006-04-03
2006-01-0425
Increasing fuel costs and the desire for reduced dependence on foreign oil have brought the diesel engine to the forefront of future medium-duty vehicle applications in the United States due to its higher thermal efficiency and superior durability. One of the obstacles to the increased use of diesel engines in this platform is the Tier 2 emission standards. In order to succeed, diesel vehicles must comply with emissions standards while maintaining their excellent fuel economy. The availability of technologies-such as common rail fuel injection systems, low-sulfur diesel fuel, oxides of nitrogen (NOX) adsorber catalysts or NACs, and diesel particle filters (DPFs)-allows for the development of powertrain systems that have the potential to comply with these future requirements. In support of this, the U.S. Department of Energy (DOE) has engaged in several test projects under the Advanced Petroleum Based Fuels-Diesel Emission Control (APBF-DEC) activity [1, 2, 3, 4, 5].
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

FTP and US06 Performance of Advanced High Cell Density Metallic Substrates as a Function of Varying Air/Fuel Modulation

2003-03-03
2003-01-0819
The influence of catalyst volume, cell density and precious metal loading on the catalyst efficiency were investigated to design a low cost catalyst system. In a first experiment the specific loading was kept constant for a 500cpsi and a 900cpsi substrate. In a second experiment the palladium loading was reduced on the 900cpsi substrate and the same PM loading was applied to a 1200cpsi substrate with lower volume. Finally the loading was further reduced for the 1200cpsi substrate. The following parameters were studied after aging: Catalyst performance of standard cell density compared to high cell density technology Light-off performance and catalyst efficiency as a function of Palladium loading and substrate cell density Catalyst efficiency as a function of AFR biasing The performance of the aged catalysts was investigated in a lambda sweep test and in light-off tests at an engine bench.
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

ERIC - A System to Modify Vehicle Emissions Through Computer Controlled Signal Interception

1999-03-01
1999-01-0773
A computer controlled system capable of intercepting and performing closed-loop control of a vehicle subsystem during targeted modes of operation was developed. The system has been given the acronym ERIC, for Emissions Reduction Intercept and Control system. This study was prompted by the need for the ability to modify engine controls through targeted modes of operation, without altering the majority of engine operation, to assist in the integration of exhaust aftertreatment and engine systems. The general concept and approach for applying the ERIC method, and application of the system to perform targeted, mode-activated EGR control intercept on a 1997 Ford Crown Victoria, are described in this paper. Data are presented that demonstrate how the problem mode was identified, targeted, mapped, and modified. FTP-75 test data are presented to show the impact of this particular application.
Technical Paper

Diesel Catalyst Aging using a FOCAS® HGTR, a Diesel Burner System, to Simulate Engine-Based Aging

2010-04-12
2010-01-1218
The classical approach to prepare engine exhaust emissions control systems for evaluation and certification is to condition the fresh parts by aging the systems on an engine/dynamometer aging stand. For diesel systems this can be a very lengthy process since the estimated service life of the emissions control systems can be several hundred thousand miles. Thus full useful life aging can take thousands of engine bench aging hours, even at elevated temperatures, making aging a considerable cost and time investment. Compared to gasoline engines, diesel engines operate with very low exhaust gas temperatures. One of the major sources of catalyst deactivation is exposure to high temperature [ 1 ].
Technical Paper

Development of a Methodology to Separate Thermal from Oil Aging of a Catalyst Using a Gasoline-Fueled Burner System

2003-03-03
2003-01-0663
Typically, an engine/dynamometer thermal aging cycle contains combinations of elevated catalyst inlet temperatures, chemical reaction-induced thermal excursions (simulating misfire events), and average air/fuel ratio's (AFR's) to create a condition that accelerates the aging of the test part. In theory, thermal aging is predominantly a function of the time at an exposure temperature. Therefore, if a burner system can be used to simulate the exhaust AFR and catalyst inlet and bed temperature profile generated by an engine running an accelerated aging cycle, then a catalyst should thermally age the same when exposed to either exhaust stream. This paper describes the results of a study that examined the aging difference between six like catalysts aged using the Rapid Aging Test (RAT) cycle (an accelerated thermal aging cycle). Three catalysts were aged using a gasoline-fueled engine aging stand; the other three were aged using a computer controlled burner system.
Technical Paper

Detailed Characterization of Particle Emissions from Advanced Internal Combustion Engines

2021-04-06
2021-01-0620
Detailed characterization of particle emissions from three different engine technologies were performed, two of which were advanced technology engines. One of the engines was a nonroad Tier 4 Final emission regulation compliant 6.8L John Deere PSS 6068 diesel engine operated with its production calibration strategy. The other two engine platforms were advanced engine technologies whose controllers were developed by Southwest Research Institute (SwRI). These included a dual fuel Navistar MaxxForce 13L natural gas-diesel engine and a Cummins ISX 15L diesel engine. The dual fuel engine was operated in two distinct modes, conventional dual fuel (CDF) mode and low temperature reactivity controlled compression ignition (RCCI) mode. The Cummins ISX engine was operated using a “hot” or low EGR combustion strategy. For each engine technology, the test campaign involved steady-state test modes ranging from low speed low load to high speed high load conditions.
Technical Paper

Detailed Characterization of Gaseous Emissions from Advanced Internal Combustion Engines

2021-04-06
2021-01-0634
With the advancement of engine technologies and combustion strategies, aftertreatment architectures are expected to evolve as they continue to be the primary emissions mitigation hardware. Some of the engine approaches offer unique challenges and benefits that are not well understood beyond criteria pollutant emissions. As such, there continues to be a need to quantify engine emissions characteristics in pursuit of catalyst technology development and the use of advanced simulation tools. The following study discusses results from an extensive engine emissions assessment for current state-of-the-art technology and novel combustion regimes. The engines tested include a Tier 4 final compliant 6.8 L John Deere PSS 6068 diesel engine, a modified 15 L diesel engine, and a dual fuel 13 L natural gas-diesel engine. The dual fuel engine could operate in conventional positive ignition mode (CDF) or low temperature reactivity-controlled compression ignition mode (RCCI).
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