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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.
Journal Article

Visual, Thermodynamic, and Electrochemical Analysis of Condensate in a Stoichiometric Spark-Ignited EGR Engine

The objectives of this project were to investigate the corrosivity of condensate in a stoichiometric spark-ignited (SI) engine when running exhaust gas recirculation (EGR) and to determine the effects of sulfur-in-fuel on corrosion. A 2.0 L turbocharged direct-injected SI engine was operated with low-pressure EGR for this study. The engine was instrumented for visual, thermodynamic, and electrochemical analyses to determine the potential for corrosion at locations where condensation was deemed likely in a low-pressure loop EGR (LPL-EGR) engine. The electrochemical analysis was performed using multi-electrode array (MEA) corrosion probes. Condensate was also collected and analyzed. These analyses were performed downstream of both the charge air cooler (CAC) and the EGR cooler. It was found that while conditions existed for sulfuric acid to form with high-sulfur fuel, no sulfuric acid was detected by any of the measurement methods.
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

Polycyclic Aromatic Hydrocarbons in Diesel Engine Exhaust Both with and without Aftertreatment

Since the conception of the internal combustion engine, smoky and ill-smelling exhaust was prevalent. Over the last century, significant improvements have been made in improving combustion and in treating the exhaust to reduce these effects. One group of compounds typically found in exhaust, polycyclic aromatic hydrocarbons (PAH), usually occurs at very low concentrations in diesel engine exhaust. Some of these compounds are considered carcinogenic, and most are considered hazardous air pollutants (HAP). Many methods have been developed for sampling, handling, and analyzing PAH. For this study, an improved method for dilute exhaust sampling was selected for sampling the PAH in diesel engine exhaust. This sampling method was used during transient engine operation both with and without aftertreatment to show the effect of aftertreatment.
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 Improved Low-Temperature Urea-Water Solution Decomposition by Addition of Titanium-Based Isocyanic Acid Hydrolysis Catalysts 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 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

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.
Journal Article

Extension of Analytical Methods for Detailed Characterization of Advanced Combustion Engine Emissions

Advanced combustion strategies used to improve efficiency, emissions, and performance in internal combustion engines (IC) alter the chemical composition of engine-out emissions. The characterization of exhaust chemistry from advanced IC engines requires an analytical system capable of measuring a wide range of compounds. For many years, the widely accepted Coordinating Research Council (CRC) Auto/Oil procedure[1,2] has been used to quantify hydrocarbon compounds between C1 and C12 from dilute engine exhaust in Tedlar polyvinyl fluoride (PVF) bags. Hydrocarbons greater than C12+ present the greatest challenge for identification in diesel exhaust. Above C12, PVF bags risk losing the higher molecular weight compounds due to adsorption to the walls of the bag or by condensation of the heavier compounds. This paper describes two specialized exhaust gas sampling and analytical systems capable of analyzing the mid-range (C10 - C24) and the high range (C24+) hydrocarbon in exhaust.
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

Dilute Measurement of Semi-Volatile Organic Compounds (SVOC) from a Heavy-Duty Diesel Engine

Semi-volatile organic compounds (SVOC) are a group of compounds in engine exhaust that either form during combustion or are part of the fuel and lubricating oil. Since these compounds occur at very low concentrations in diesel engine exhaust, the methods for sampling, handling, and analyzing these compounds are critical to obtaining good results. An improved dilute exhaust sampling method was used for sampling and analyzing SVOC in engine exhaust, and this method was performed during transient engine operation. A total of 22 different SVOC were measured using a 2012 medium-duty diesel engine. This engine was equipped with a stock diesel oxidation catalyst (DOC), a diesel particulate filter (DPF), and a selective catalytic reduction (SCR) catalyst in series. Exhaust concentrations for SVOC were compared both with and without exhaust aftertreatment. Concentrations for the engine-out SVOC were significantly higher than with the aftertreatment present.
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.