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The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which las smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

Plug-in hybrid electric vehicle (PHEV) technologies have the potential for considerable petroleum consumption reductions, possibly at the expense of increased tailpipe emissions due to multiple “cold” start events and improper use of the engine for PHEV specific operation. PHEVs operate predominantly as electric vehicles (EVs) with intermittent assist from the engine during high power demands. As a consequence, the engine can be subjected to multiple cold start events. These cold start events may have a significant impact on the tailpipe emissions due to degraded catalyst performance and starting the engine under less than ideal conditions. On current hybrid electric vehicles (HEVs), the first cold start of the engine dictates whether or not the vehicle will pass federal emissions tests. PHEV operation compounds this problem due to infrequent, multiple engine cold starts.

A commercial three-way catalyst (TWC) was evaluated for ammonia (NH3) generation on a 2.0-liter BMW lean burn gasoline direct injection engine as a component in a passive ammonia selective catalytic reduction (SCR) system. The passive NH3 SCR system is a potential low cost approach for controlling nitrogen oxides (NOX) emissions from lean burn gasoline engines. In this system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst. NH3 generation was evaluated at different air-fuel equivalence ratios at multiple engine speed and load conditions. Near complete conversion of NOX to NH3 was achieved at λ=0.96 for nearly all conditions studied. At the λ=0.96 condition, HC emissions were relatively minimal, but CO emissions were significant.

We present simulated fuel economy and emissions of city transit buses powered by conventional diesel engines and diesel-hybrid electric powertrains of varying size. Six representative city drive cycles were included in the study. In addition, we included previously published aftertreatment device models for control of CO, HC, NOx, and particulate matter (PM) emissions. Our results reveal that bus hybridization can significantly enhance fuel economy by reducing engine idling time, reducing demands for accessory loads, exploiting regenerative braking, and shifting engine operation to speeds and loads with higher fuel efficiency. Increased hybridization also tends to monotonically reduce engine-out emissions, but tailpipe (post-aftertreatment) emissions are affected by complex interactions between engine load and the transient catalyst temperatures, and the emissions results were found to depend significantly on motor size and details of each drive cycle.

Engine acoustics measured by microphones near the engine have been used in controlled laboratory settings for combustion feedback and even combustion phasing control, but the use of these techniques in a vehicle where many other noise sources exist is problematic. In this study, surface-mounted acoustic emissions sensors are embedded in the block of a 2.0L turbocharged GDI engine, and the signal is analyzed to identify useful feedback features. The use of acoustic emissions sensors, which have a very high frequency response and are commonly used for detecting material failures for health monitoring, including detecting gear pitting and ring scuffing on test stands, enables detection of acoustics both within the range of human hearing and in the ultrasonic spectrum. The high-speed acoustic time-domain data are synchronized with the crank-angle-domain combustion data to investigate the acoustic emissions response caused by various engine events.

Lean gasoline engines offer greater fuel economy than the common stoichiometric gasoline engine, but the current three way catalyst (TWC) on stoichiometric engines is unable to control nitrogen oxide (NOX) emissions in oxidizing exhaust. For these lean gasoline engines, lean NOX emission control is required to meet existing Tier 2 and upcoming Tier 3 emission regulations set by the U.S. Environmental Protection Agency (EPA). While urea-based selective catalytic reduction (SCR) has proven effective in controlling NOX from diesel engines, the urea storage and delivery components can add significant size and cost. As such, onboard NH3 production via a passive SCR approach is of interest. In a passive SCR system, NH3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean operation, NOX passes through the TWC and is reduced by the stored NH3 on the SCR catalyst.

Computational approaches have been limited to examining catalytic processes using models that have been greatly simplified in comparison to real catalysts. Experimental studies, especially on emission treatment catalysts, have primarily focused on fully formulated systems. Thus, there remains a knowledge gap between theory and experiments. We combine the power of theory and experiment for atomistic design of catalytically active sites that can translate the fundamental insights gained directly to a catalyst system suitable for technical deployment. In this article, we describe our results on a model platinum-alumina catalyst that is a common constituent of emission treatment catalysts such as three-way, NOx trap, oxidation, and HC-SCR catalysts. We present theoretical and experimental studies of the oxidation and reactivity of Pt catalyst clusters towards O, CO, and NOx.

High Efficiency Clean Combustion (HECC) strategies such as homogenous charge compression ignition (HCCI) and pre-mixed charge compression ignition (PCCI) offer much promise for the reduction of NOx and PM from diesel engines. While delivering low PM and low NOx, these combustion modes often produce much higher levels of CO and HC than conventional diesel combustion modes. In addition, partially oxygenated species such as formaldehyde (an MSAT) and other aldehydes increase with HECC modes. The higher levels of CO and HCs have the potential to compromise the performance of the catalytic aftertreatment, specifically at low load operating points. As HECC strategies become incorporated into vehicle calibrations, manufacturers need to avoid producing MSATs in higher quantities than found in conventional combustion modes. This paper describes research on two different HECC strategies, HCCI and PCCI.

Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.

The buildup of deposits in EGR coolers causes significant degradation in heat transfer performance, often on the order of 20-30%. Deposits also increase pressure drop across coolers and thus may degrade engine efficiency under some operating conditions. It is unlikely that EGR cooler deposits can be prevented from forming when soot and HC are present. The presence of cooled surfaces will cause thermophoretic soot deposition and condensation of HC and acids. While this can be affected by engine calibration, it probably cannot be eliminated as long as cooled EGR is required for emission control. It is generally felt that “dry fluffy” soot is less likely to cause major fouling than “heavy wet” soot. An oxidation catalyst in the EGR line can remove HC and has been shown to reduce fouling in some applications. The combination of an oxidation catalyst and a wall-flow filter largely eliminates fouling. Various EGR cooler designs affect details of deposit formation.

The combination of advanced combustion with advanced selective catalytic reduction (SCR) catalyst formulations was studied in the work presented here to determine the impact of the unique hydrocarbon (HC) emissions from premixed charge compression ignition (PCCI) combustion on SCR performance. Catalyst core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. The zeolites which form the basis of these catalysts are different with the Cu-based catalyst made on a chabazite zeolite which has smaller pore structures relative to the Fe-based catalyst. Subsequent to exposure, bench flow reactor characterization of performance and hydrocarbon release and oxidation enabled evaluation of overall impacts from the engine exhaust.

Operation of spark-ignition (SI) engines with high levels of charge dilution through exhaust gas recirculation (EGR) achieves significant engine efficiency gains while maintaining stoichiometric operation for compatibility with three-way catalysts. Dilution levels, however, are limited by cyclic variability - including significant numbers of misfires - that becomes more pronounced with increasing dilution. This variability has been shown to have both stochastic and deterministic components. Stochastic effects include turbulence, mixing variations, and the like, while the deterministic effect is primarily due to the nonlinear dependence of flame propagation rates and ignition characteristics on the charge composition, which is influenced by the composition of residual gases from prior cycles.

Plug-in hybrid electric vehicles (PHEV) operate predominantly as electric vehicles (EV) with intermittent assist from the engine. As a consequence, the engine can be subjected to multiple cold start events. These cold start events have a significant impact on tailpipe emissions due to degraded catalyst performance and starting the engine under less than ideal conditions. On current conventional vehicles, the first cold start of the engine dictates whether or not the vehicle will pass federal emissions tests. PHEV operation compounds this problem due to infrequent, multiple engine cold starts. ORNL, in collaboration with the University of Tennessee, developed an Engine-In-the-Loop (EIL) test platform to investigate cold start emissions on a 2.0l Gasoline Turbocharged Direct Injection (GTDI) Ecotec engine coupled to a virtual series hybrid electric vehicle.

Reactivity Controlled Compression Ignition (RCCI) has demonstrated diesel-like or better brake thermal efficiency with significant reductions in nitrogen oxide (NOX) and particulate matter (PM) emissions. Hydrocarbon (HC) and carbon monoxide (CO) emission levels, on the other hand, are higher and similar to those of port-fuel-injected (PFI) gasoline engines. The higher HC and CO emissions combined with the lower exhaust temperatures during RCCI operation present a challenge for current exhaust aftertreatment technologies. The reduction of HC and CO emissions in a lean environment is typically achieved with an oxidation catalyst. In this work, several diesel oxidation catalysts (DOC) with different precious metal loadings were evaluated for effectiveness to control HC and CO emissions from RCCI combustion in a light-duty multi-cylinder engine operating on gasoline and diesel fuels.

Small impurities in the fuel can have a significant impact on the emissions control system performance over the lifetime of the vehicle. Of particular interest in recent studies has been the impact of sodium, potassium, and calcium that can be introduced either through fuel constituents, such as biodiesel, or as lubricant additives. In a collaboration between the National Renewable Energy Laboratory and the Oak Ridge National Laboratory, a series of accelerated aging studies have been performed to understand the potential impact of these metals on the emissions control system. This paper explores the effect of the rate of accelerated aging on the capture of fuel-borne metal impurities in the emission control devices and the subsequent impact on performance. Aging was accelerated by doping the fuel with high levels of the metals of interest. Three separate evaluations were performed, each with a different rate of accelerated aging.

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.

In this research, small, single cylinder engines have been used to simulate larger engines in the areas of aftertreatment, combustion, and fuel formulation effects. The use of small engines reduces overall research cost and allows more rapid experiments to be run. Because component costs are lower, it is also possible to investigate more variations and to sacrifice components for materials characterization and for subsequent experiments. Using small engines in this way is very successful in some cases. In other cases, limitations of the engines influence the results and need to be accounted for in the experimental design and data analysis. Some of the results achieved or limitations found may be of interest to the small engine market, and this paper is offered as a summary of the authors' research in these areas. Research is being conducted in two areas. First, small engines are being used to study the rapid aging and poisoning of exhaust aftertreatment catalysts.

The development of new catalytic materials is still dominated by trial and error methods, even though the experimental and theoretical bases for their characterization have improved dramatically in recent years. Although it has been successful, the empirical development of catalytic materials is time consuming and expensive with no guarantee of success. We have been exploring computationally complex but experimentally simple systems to establish a “catalysis by design” protocol that combines the power of theory and experiment. We hope to translate the fundamental insights directly into a complete catalyst system that is technologically relevant. The essential component of this approach is that the catalysts are iteratively examined by both theoretical and experimental methods.

Lean NOx trap (LNT) catalysts with different formulations have been characterized on a light-duty diesel engine platform. Two in-cylinder regeneration strategies were used during the study. The reductant chemistry differed for both strategies with one strategy having high levels of CO and H2 and the other strategy having a higher hydrocarbon component. The matrix of LNT catalysts that were characterized included LNTs with various sorbate loads and varying ceria content; the sorbate was Ba. Intra-catalyst measurements of exhaust gas composition were obtained at one quarter, one half, and three quarters of the length of the catalysts to better understand the affect of formulation on performance. Exhaust analysis with FTIR allowed measurement of NH3 and thereby, a measurement of N2 selectivity for the catalysts. Although overall NOx conversion increased with increasing sorbate load, the formation of NH3 increased as well.

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/γ-AI2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation.