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The steam reforming of CH4 plays a crucial role in the high-temperature activity of natural gas three-way catalysts. Despite existing reports on sulfur inhibition in CH4 steam reforming, there is a limited understanding of sulfur storage and removal dynamics under various lambda conditions. In this study, we utilize a 4-Mode sulfur testing approach to elucidate the dynamics of sulfur storage and removal and their impact on three-way catalyst performance. We also investigate the influence of sulfur on CH4 steam reforming by analyzing CH4 conversions under dithering, rich, and lean reactor conditions. In the 4-Mode sulfur test, saturating the TWC with sulfur at low temperatures emerges as the primary cause of significant three-way catalyst performance degradation. After undergoing a deSOx treatment at 600 °C, NOx conversions were fully restored, while CH4 conversions did not fully recover.

Multiple areas in the U.S. continue to struggle with achieving National Ambient Air Quality Standards for ozone. These continued issues highlight the need for further reductions in NOX emission standards in multiple industry sectors, with heavy-duty on-highway engines being one of the most important areas to be addressed. Starting in 2014, CARB initiated a series of technical demonstration programs aimed at examining the feasibility of achieving up to a 90% reduction in tailpipe NOX, while at the same time maintaining a path towards GHG reductions that will be required as part of the Heavy-Duty Phase 2 GHG program. These programs culminated in the Stage 3 Low NOX program, which demonstrated low NOX emissions while maintaining GHG emissions at levels comparable to the baseline engine.

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.

Diesel oxidation catalyst (DOC) is one of the critical catalyst components in modern diesel aftertreatment systems. It mainly converts unburned hydrocarbon (HC) and CO to CO2 and H2O before they are released to the environment. In addition, it also oxidizes a portion of NO to NO2, which improves the NOx conversion efficiency via fast SCR over the downstream selective catalytic reduction (SCR) catalyst. HC light-off tests, with or without the presence of NOx, has been typically used for DOC evaluation in laboratory. In this work, we aim to understand the influences of DOC light-off experimental conditions, such as initial temperature, initial holding time, HC species, with or without the presence of NOx, on the DOC HC light-off behavior. The results indicate that light-off test with lower initial temperature and longer initial holding time (at its initial temperature) leads to higher DOC light-off temperature.

The prediction accuracy of a three-way catalyst (TWC) model is highly associated with the ability of the model to incorporate the reaction kinetics of the emission process as a lambda function. In this study, we investigated the O2 and H2 concentration profiles of TWC reactions and used them as critical inputs for the development of a global TWC model. We presented the experimental data and global kinetic model showing the impact of thermal degradation on the performance of the TWC. The performance metrics investigated in this study included CH4, NOx, and CO conversions under lean, rich, and dithering light-off conditions to determine the kinetics of oxidation reactions and reduction/reforming/water-gas shift reactions as a function of thermal aging. The O2 and H2 concentrations were measured using mass spectrometry to track the change in the oxidation state of the catalyst and to determine the mechanism of the reactions under these light-off conditions.

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.

Upcoming, stricter diesel exhaust emissions standards will likely require aftertreatment architectures with multiple diesel exhaust fluid (DEF) introduction locations. Managing NH3 slip with technologies such as an ammonia slip catalyst (ASC) will continue to be critical in these future aftertreatment systems. In this study, we evaluate the impact of SO2 exposure on a state-of-the-art commercially available ASC. SO2 is co-fed at 0.5 or 3 ppmv to either approximate or accelerate a real-world exhaust SO2 impact. ASC performance during sulfur co-feeding is measured under a wide variety of simulated real-world conditions. Results indicate that the loss of NO conversion during SCR is dependent on the cumulative SO2 exposure, regardless of the inlet SO2 concentration. Meanwhile, N2O formation under SCR conditions is nonlinearly affected by SO2 exposure, with formation increasing during 0.5 ppmv SO2 exposure but decreasing in the presence of 3 ppmv SO2.

Accelerated aging of automotive gasoline emissions catalysts has been performed on bench engines for decades. The EPA regulations include an accelerated aging cycle called the Standard Bench Cycle (SBC) that is modeled on the RAT-A cycle developed by GM Corp. and published in 1988. However, this cycle cannot be used for diesel aftertreatment components because it is based on stoichiometric operation, whereas diesel engines typically operate under excess air (lean) conditions. The need for accelerated aging cycles for diesel emissions systems can be illustrated by considering that the full useful life (FUL) requirement in the United States for an on-highway truck is 435,000 miles, and an off-road application may be 8,000 hours. With the recent CARB Omibus legislation, the durability duration will be increasing for on-road applications by as much as 80 percent in the next decade.

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.

Stoichiometric natural gas engines with three-way catalysts emit less NOx and CH4 due to their higher efficiency compared to lean-burn natural gas engines. Although hydrothermal aging of three-way catalysts has been extensively studied, a deeper understanding beyond hydrothermal aging is needed to explain real-world performance, especially for natural gas engines with near-zero NOx emissions. In this investigation, field-aged three-way catalysts were characterized to identify the contribution of chemical aging to their overall performance. It was found that the sulfur species on the field-aged TWCs were entirely distributed along the catalyst length, showing a decreasing trend, whereas phosphorous contamination was mainly observed at the inlet section of the three-way catalysts, and the phosphorous concentration declined sharply along the axial length.

Water injection is an effective method for knock control in spark-ignition engines. However, the requirement of a separate water source and the cost and complexity associated with a fully integrated system creates a limitation of this method to be used in volume production engines. The engine exhaust typically contains 10-15% water vapor by volume which could be condensed and potentially stored for future use. In this study, the exhaust condensate composition was assessed for its use as an effective replacement for distilled water. Specifically, condensate samples were collected pre and post-three-way catalyst (TWC) and analyzed for acidity and composition. The composition of the pre and post-TWC condensates was found to be similar however, the pre-TWC condensate was mildly acidic. The mild acidity has the potential to corrode certain components in the intake air circuit.

As agencies and governing bodies evaluate the feasibility of reduced emission standards, additional focus has been placed on technology durability. This is seen in proposed updates, which would require Original Equipment Manufacturers (OEMs) to certify engine families utilizing a full useful life (FUL) aftertreatment system. These kinds of proposed rulings would place a heavy burden on the manufacturer to generate FUL components utilizing traditional engine aging methods. Complications in this process will also increase the product development effort and will likely limit the amount of aftertreatment durability testing. There is also uncertainty regarding the aging approach and the representative impact compared to field aged units. Existing methodologies have evolved to account for several deterioration mechanisms that, when controlled, can be utilized to create a flexible aging protocol. As a result, these methodologies provide the necessary foundation for continued development.

With the conclusion of the California Air Resources Board (CARB) Stage 1 Ultra-Low NOX program, there continues to be a commitment for identifying potential pathways to demonstrate 0.02 g/hp-hr NOX emissions. The Stage 1 program focused on achieving the Ultra-Low NOX (ULN) levels utilizing a turbo-compound (TC) engine, which required the integration of novel catalyst technologies and a supplemental heat source. While the aftertreatment configuration provided a potential solution to meet the ULN target, a complicated approach was required to overcome challenges from low temperature exhaust. The Stage 3 program leverages a different engine architecture more representative of the broader heavy-duty industry to meet the Phase 2 Greenhouse Gas (GHG) targets and to simplify the ULN aftertreatment solution. The following work will discuss the aftertreatment technology evaluation, down selection criteria, and the emission results for the candidate ULN systems

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.

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.

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.

Three-way catalysts have been used in a variety of stoichiometric natural gas engines for emission control. During real-world operation, these catalysts have experienced a large number of temporary and permanent deactivations including thermal aging and chemical contamination. Thermal aging is typically induced either by high engine-out exhaust temperatures or the reaction exotherm generated on the catalysts. Chemical contamination originates from various inorganic species such as Phosphorous (P) and Sulfur (S) that contain in engine fluids, which can poison and/or mask the catalyst active components. Such deactivations are quite difficult to simulate under laboratory conditions, due to the fact that multiple deactivation modes may occur at the same time in the real-world operations. In this work, a set of field-aged TWCs has been analyzed through detailed laboratory research in order to identify and quantify the real-world aging mechanisms.

Diesel engines are facing increased competition from gasoline engines in the light-duty and small non-road segments, primarily due to the high relative cost of emissions control systems for lean-burn diesel engines. Advancements in gasoline engine technology have decreased the operating cost advantage of diesels and the relatively high initial-cost disadvantage is now too large to sustain a strong business position. SwRI has focused several years of research efforts toward enabling diesel engine combustion systems to operate at stoichiometric conditions, which allows the application of a low-cost three-way catalyst emission control system which has been well developed for gasoline spark-ignited engines. One of the main barriers of this combustion concept is the result of high smoke emissions from poor fuel/air mixing.

Cummins has recently launched next-generation aftertreatment technology, the Single ModuleTM aftertreatment system, for medium-duty and heavy-duty engines used in on-highway and off-highway applications. Besides meeting EPA 2010+ and Euro VI regulations, the Single ModuleTM aftertreatment system offers 60% volume and 40% weight reductions compared to current aftertreatment systems. In this work, we present model-based approaches that were systematically adopted in the design and development of the Cummins Single ModuleTM aftertreatment system. Particularly, a variety of analytical and experimental component-level and system-level validation tools have been used to optimize DOC, DPF, SCR/ASC, as well as the DEF decomposition device.

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.