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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.

Dynamic Skip Fire (DSF®) has been shown to significantly reduce CO2 on gasoline engines and has been in mass production since 2018. Diesel Dynamic Skip Fire (dDSF™) builds upon the technology and extends it to diesel engine applications. dDSF is an advanced cylinder deactivation technology that allows the deactivation of any number of cylinders dynamically to deliver the requested torque while maintaining acceptable noise, vibration, and harshness (NVH) performance. NOx regulations are becoming progressively more stringent on light, medium and heavy-duty (HD) diesel engines. Meeting low NOx standards is becoming increasingly challenging, especially in lightly loaded operating conditions where maintaining ideal aftertreatment system efficiency is difficult. Most existing techniques to increase aftertreatment temperatures at low loads incur a fuel consumption penalty, which increases greenhouse gas emissions.

For renewable fuels to displace petroleum, they must be compatible with emissions control devices. Pure biodiesel contains up to 5 ppm Na + K and 5 ppm Ca + Mg metals, which have the potential to degrade diesel emissions control systems. This study aims to address these concerns, identify deactivation mechanisms, and determine if a lower limit is needed. Accelerated aging of a production exhaust system was conducted on an engine test stand over 1001 h using 20% biodiesel blended into ultra-low sulfur diesel (B20) doped with 14 ppm Na. This Na level is equivalent to exposure to Na at the uppermost expected B100 value in a B20 blend for the system full-useful life. During the study, NOx emissions exceeded the engine certification limit of 0.33 g/bhp-hr before the 435,000-mile requirement.

In this contribution, nuanced changes of a commercial Cu-SSZ-13 catalyst with hydrothermal aging, which have not been previously reported, as well as their corresponding impact on SCR functions, are described. In particular, a sample of Cu-SSZ-13 was progressively aged between 550 to 900°C and the changes of performance in NH3 storage, oxidation functionality and NOx conversion of the catalyst were measured after hydrothermal exposure at each temperature. The catalysts thus aged were further characterized by NH3-TPD, XRD and DRIFTS techniques for structural changes. Based on the corresponding performance and structural characteristics, three different regimes of hydrothermal aging were identified, and tentatively as assigned to “mild”, “severe” and “extreme” aging. Progressive hydrothermal aging up to 750°C decreased NOx conversion to a small degree, as well as NH3 storage and oxidation functions.

The high global warming potential of nitrous oxide (N2O) led to its inclusion in the list of regulated greenhouse gas (GHG) pollutants [1, 2]. The mitigation of N2O on aftertreatment catalysts was shown to be ineffective as its formation and decomposition temperatures do not overlap. Therefore, the root causes for N2O formation were investigated to enable the catalyst architectures and controls development for minimizing its formation. In a typical heavy-duty diesel exhaust aftertreatment system based on selective catalytic reduction of NOx by ammonia derived from urea (SCR), the main contributors to tailpipe N2O are expected to be the undesired reaction between NOx and NH3 over SCR catalyst and NH3 slip in to ammonia slip catalyst (ASC), part of which gets oxidized to N2O.

In this work, an alternative method is proposed and validated for quantifying the axial performance of a state-of-the-art Cu zeolite SCR catalyst. Catalyst cores of a standard length, with varying lengths of wash-coated regions were used to axially resolve the functional performance of the SCR catalyst. This proposed method was validated by quantifying the catalyst entrance and exit effects, as well as the effect of non-uniform wash-coat loading densities. This method is less susceptible to some of the complications highlighted in the previous studies, such as flow uniformity between channels, as well as radiative heating effects, since the product gases are sampled across the entire monolith cross-section rather than through a single catalyst channel. The specific catalyst functions quantified include: NO and NH₃ oxidation, NH₃ storage capacity, as well as NOx conversion efficiency.

Mitigation of ammonia slip from SCR system is critical to meeting the evolving NH₃ emission standards, while achieving maximum NOx conversion efficiency. Ammonia slip catalysts (ASC) are expected to balance high activity, required to oxidize ammonia across a broad range of operating conditions, with high selectivity of converting NH₃ to N₂, thus avoiding such undesirable byproducts as NOx or N₂O. In this work, new insights into the behavior of an advanced ammonia slip catalyst have been developed by using accelerated progressive catalyst aging as a tool for catalyst property interrogation. The overall behavior was deconstructed to several underlying functions, and referenced to an active but non-selective NH₃ oxidation function of a diesel oxidation catalyst (DOC) and to the highly selective but minimally active NH₃ oxidation function of an SCR catalyst.

A prototype 2007 ISL Cummins diesel engine equipped with a diesel oxidation catalyst (DOC), diesel particle filter (DPF), variable geometry turbocharger (VGT), and cooled exhaust gas recirculation (EGR) was tested at Southwest Research Institute (SwRI) under a high-load accelerated durability cycle for 1000 hours with B20 soy-based biodiesel blends and ultra-low sulfur diesel (ULSD) fuel to determine the impact of B20 on engine durability, performance, emissions, and fuel consumption. At the completion of the 1000-hour test, a thorough engine teardown evaluation of the overhead, power transfer, cylinder, cooling, lube, air handling, gaskets, aftertreatment, and fuel system parts was performed. The engine operated successfully with no biodiesel-related failures. Results indicate that engine performance was essentially the same when tested at 125 and 1000 hours of accumulated durability operation.

Conventional diesel fuel (1) has been on the market for decades and used successfully to run diesel engines of all sizes in many applications.* In order to reduce emissions and to foster energy source diversity, new fuels such as alternative and renewable, as well as new formulations, have entered the market. These include biodiesel, gas-to-liquid, and alternative formulations by states such as California. Performance variations in fuel economy, emissions, and compatibility for these fuels have been evaluated and debated. In some cases, contradictory views have surfaced. “Renewable” and “clean” designations have been interchanged. Adding to the confusion, results from one fuel in one type of engine, such as an older heavy-duty engine, is at times compared to that of another type, such as a modern light-duty engine.

The influence of various diesel fuel properties on the steady state emissions and performance of a Cummins light-duty (ISB) engine modified for single cylinder operation has been studied at the mid-load “cruise” operating condition. Designed experiments involving independent manipulation of both fuel properties and engine control parameters have been used to build statistical engine response models. The models were then applied to optimize for the minimum fuel consumption subject to specific constraints on emissions and mechanical limits and also to estimate the optimum engine control parameter settings and fuel properties. The study reveals that under the high EGR, diffusion-burn dominated conditions encountered during the experiments, NOx is impacted by cetane number and the distillation characteristics. Lower T50 (mid-distillation temperature) resulted in simultaneous reductions in both NOx and smoke, and higher cetane number provided an additional small NOx benefit.

Empirical models for engine-out oxides of Nitrogen (NOx) and smoke emissions have been developed for the purpose of minimizing transient emissions while maintaining transient response. Three major issues have been addressed: data acquisition, data processing and modeling method. Real and virtual transient parameters have been identified for acquisition. Accounting for the phase shift between transient engine events and transient emission measurements has been shown to be very important to the quality of model predictions. Several methods have been employed to account for the transient transport delays and sensor lags which constitute the phase shift. Finally several different empirical modeling methods have been used to determine the most suitable modeling method for transient emissions. These modeling methods include several kinds of neural networks, global regression and localized regression.

The operation of NOx Adsorber catalysts (NAC), also often referred to as Lean NOx Trap catalysts or NOx Storage-reduction catalysts, entails frequent periodic NOx regeneration events. These are accomplished by creating a net reducing, fuel-rich environment in the exhaust. The reduction of hydrocarbon emissions which occur during such fuel-rich events is challenging, due to the oxygen-deficient environment. In order to overcome this limitation, two possibilities exist: (i) oxygen can be stored during lean phase, to be used for hydrocarbon slip oxidation in the subsequent rich phase, or (ii) unreacted hydrocarbons can be trapped during the rich phase and oxidized during the following lean phase. In this work, two groups of catalytic solutions were developed and evaluated for hydrocarbon emission control based on these approaches: an Oxygen Storage Compound (OSC) based catalyst and zeolite-based hydrocarbon trap catalyst.

A novel laboratory methodology has been developed and applied to evaluate performance of NOx Adsorber catalysts, based on the detailed analysis of micro-core samples obtained from various locations in a full-size catalyst. The technique includes a protocol for evaluating various aspects of NOx performance, as well as direct measurements of the amount of sulfur on the catalyst. This method was used to determine the NOx performance and distribution of sulfur loading on several engine aged catalysts. It showed the ability to differentiate poor NOx performance due to insufficient desulfation from that due to thermal degradation. This method further quantifies different forms of sulfur that are present on the catalyst. These forms of sulfur are distinguished by the temperature at which they are removed. In addition, the aspects of sulfur behavior that are important to this technique are discussed.

In this work fuel dilution of engine oil, and the impact of biodiesel fuel on dilution, were examined. New emissions requirements have driven the adoption of a range of aftertreatment systems for diesel engines. These aftertreatment devices in many cases have specific requirements for exhaust composition and temperature. Meeting these requirements can lead to fuel dilution of the engine oil. Measurement of fuel dilution of engine oil can be challenging, and in this study a new strategy for utilizing Fourier Transform Infrared Spectroscopy (FTIR) was examined. A synthetic component of aviation oil, pentaerythritol ester (PE), was found to be a very useful tracer for measuring dilution with ultra low sulfur diesel (ULSD), but not useful for measuring dilution with B20. Fuel dilution and evaporation rates were measured for both ULSD and for a blend of biodiesel and ULSD (B20).

A 2002 Cummins ISM engine was modified to be optimized for operation on gas-to-liquid (GTL) fuel and advanced emission control devices. The engine modifications included increased exhaust gas recirculation (EGR), decreased compression ratio, and reshaped piston and bowl configuration. The emission control devices included a deNOx filter and a diesel particle filter. Over the transient test, the emissions met the 2007 standards. In July 2004, the modified engine was installed into a Class 8 tractor for use by a grocery fleet. Chassis emission testing of the modified vehicle was conducted at the National Renewable Energy Laboratory's (NREL) Renewable Fuels and Lubricants (ReFUEL) facility. Testing included hot and cold replicate Urban Dynamometer Driving Schedule (UDDS) and New York Composite (NYComp) cycles and several steady-state points. The objective of the testing was to demonstrate the vehicle's with the modified engine.