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Technical Paper

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

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

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.
Technical Paper

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

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

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

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

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 Low-Temperature Urea-Water Solution Decomposition by Addition of Titanium-Based Isocyanic Acid Hydrolysis Catalyst and Surfactant

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 Reforming and Catalyst Deactivation Investigated in Real Exhaust Environment

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

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

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

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

Detailed Characterization of Criteria Pollutant Emissions from D-EGR® Light Duty Vehicle

In this study, the criteria pollutant emissions from a light duty vehicle equipped with Dedicated EGR® technology were compared with emissions from an identical production GDI vehicle without externally cooled EGR. In addition to the comparison of criteria pollutant mass emissions, an analysis of the gaseous and particulate chemistry was conducted to understand how the change in combustion system affects the optimal aftertreatment control system. Hydrocarbon emissions from the vehicle were analyzed usin g a variety of methods to quantify over 200 compounds ranging in HC chain length from C1 to C12. The particulate emissions were also characterized to quantify particulate mass and number. Gaseous and particulate emissions were sampled and analyzed from both vehicles operating on the FTP-75, HWFET, US06, and WLTP drive cycles at the engine outlet location.
Technical Paper

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

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

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.
Journal Article

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

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.
Technical Paper

Achieving Tier 2 Bin 5 Emission Levels with a Medium Duty Diesel Pick-Up and a NOX Adsorber, Diesel Particulate Filter Emissions System-Exhaust Gas Temperature Management

Increasing fuel costs and the desire for reduced dependence on foreign oil has 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. The main obstacle to the increased use of diesel engines in this platform is the upcoming extremely stringent, Tier 2 emission standard. 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, NOX adsorber catalysts (NAC), and diesel particle filters (DPFs) allow the development of powertrain systems that have the potential to comply with these future requirements. In meeting the Tier 2 emissions standards, the heavy light-duty trucks (HLDTs) and medium-duty passenger vehicles (MDPVs) will face the greatest technological challenges. In support of this, the U.S.