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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.

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.

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.

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.

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.

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.

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.

Particulate matter (PM) and NOX are two major pollutants generated by diesel engines. Modern diesel aftertreatment systems include selective catalytic reduction (SCR) technology that helps reduce tailpipe NOX emissions when coupled with diesel exhaust fluid (DEF/urea) injection. However, this process also results in the formation of urea derived byproducts that can influence non-volatile particle number (PN) measurement conducted in accordance with the European Union (EU) Particle Measurement Program (PMP) protocol. In this program, an experimental investigation of the impact of DEF injection on tailpipe PN and its implications for PMP compliant measurements was conducted using a 2015 model year 6.7 L diesel engine equipped with a diesel oxidation catalyst, diesel particulate filter and SCR system. Open access to the engine controller was available to manually override select parameters.

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.

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.

This project’s objective was to generate experimental data to evaluate the impact of metals doped B20 on diesel particle filter (DPF) ash loading and performance compared to that of conventional petrodiesel. The effect of metals doped B20 vs. conventional diesel on a DPF was quantified in a laboratory controlled accelerated ash loading study. The ash loading was conducted on two DPFs – one using ULSD fuel and the other on B20 containing metals dopants equivalent to 4 ppm B100 total metals. Engine oil consumption and B20 metals levels were accelerated by a factor of 5, with DPFs loaded to 30 g/L of ash. Details of the ash loading experiment and on-engine DPF performance evaluations are presented in the companion paper (Part I). The DPFs were cleaned, and ash samples were taken from the cleaned material. X-ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD) were conducted on the ash samples.

The project objective was to generate experimental data to evaluate the impact of metals doped B20 on DPF ash loading and performance compared to that of conventional petrodiesel. Accelerated ash loading was conducted on two DPFs – one exposed to regular diesel fuel and the other to B20 containing metal dopants equivalent to 4 ppm B100 total metals (currently total metals are limited to 10 ppm in ASTM D6751, the standard for B100). Periodic performance evaluations were conducted on the DPFs at 10 g/L ash loading intervals. After the evaluations at 30 g/L, the DPF was cleaned with a commercial DPF cleaning machine and another round of DPF evaluations were conducted. A comparison of the effect of ash loading with the two fuels and DPF cleaning is presented. The metals doped B20 fuel resulted in ash that was similar to that deposited when exposed to ULSD (lube oil ash) and exhibited similar ash cleaning removal efficiency.

A novel urea evaporation and mixing device has been developed to improve the overall performance of a urea-SCR system. The device was tested with a MY2007 Cummins ISB 6.7L diesel engine equipped with an SCR aftertreatment system. Test results show that the device effectively improved the overall NO conversion efficiency of the SCR catalyst over both steady-state and transient engine operating conditions, while NH₃ slip from the catalyst decreased.

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.

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.

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.

A push for more stringent emissions regulations has resulted in larger, increasingly complex aftertreatment solutions. In particular, oxides of nitrogen (NOX) and particulate matter (PM) have been controlled using two separate systems, selective catalytic reduction (SCR) and the catalyze diesel particulate filter (CDPF), or the functionality has been combined into a single device producing the SCR on filter (SCRoF). The SCRoF forgoes beneficial NO2 production present in the CDPF to avoid NH3 oxidation which occurs when using platinum group metals (PGM) for oxidation. In this study, mixed-metal oxides are shown to oxidize NO to NO2 without appreciable NH3 oxidation. This selectivity leads to enhanced performance when combined with a typical Cu-zeolite catalyst.

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.