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Urea-selective catalytic reduction (SCR) catalysts are the leading aftertreatment technology for diesel engines, but there are major challenges associated with meeting future NOx emission standards, especially under transient drive cycle conditions that include large swings in exhaust temperatures. Here we present a simplified, transient, one-dimensional integral model of NOx reduction by NH₃ on a commercial small-pore Cu-zeolite urea-SCR catalyst for which detailed kinetic parameters have not been published. The model was developed and validated using data acquired from bench reactor experiments on a monolith core, following a transient SCR reactor protocol. The protocol incorporates NH₃ storage, NH₃ oxidation, NO oxidation and three global SCR reactions under isothermal conditions, at three space velocities and at three NH₃/NOx ratios.

In order to further characterize and optimize the performance of Selective Catalytic Reduction (SCR) aftertreatment systems used on heavy-duty diesel engines, an accurately calibrated high-fidelity multi-step global kinetic SCR model and a reduced order estimator for on-board diagnostic (OBD) and control are desirable. In this study, a Cu-zeolite SCR catalyst from a 2010 Cummins ISB engine was experimentally studied in a flow reactor using carefully designed protocols. A 2-site SCR model describing mass transfer and the SCR chemical reaction mechanisms is described in the paper. The model was calibrated to the reactor test data sets collected under temperatures from 200 to 425 °C and SCR space velocities of 60000, 90000, and 120000 hr-1. The model parameters were calibrated using an optimization code to minimize the error between measured and simulated NO, NO₂, N₂O, and NH₃ gas concentration time histories.

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.

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.

A hybrid LNT+SCR system is used to control NOx from a light-duty diesel engine with in-cylinder regeneration controls. A diesel oxidation catalyst and diesel particulate filter are upstream of the LNT and SCR catalysts. Ultraviolet (UV) adsorption spectroscopy performed directly in the exhaust path downstream of the LNT and SCR catalysts is used to characterize NH3 production and utilization in the system. Extractive exhaust samples are analyzed with FTIR and magnetic sector mass spectrometry (H2) as well. Furthermore, standard gas analyzers are used to complete the characterization of exhaust chemistry. NH3 formation increases strongly with extended regeneration (or “over regeneration”) of the LNT, but the portion of NOx reduction occurring over the SCR catalyst is limited by the amount of NH3 produced as well as the amount of NOx available downstream of the LNT. Control of lean-rich cycling parameters enables control of the ratio of NOx reduction between the LNT and SCR catalysts.

Two hybrid powertrain configurations, including parallel and series hybrids, were simulated for fuel economy, component energy loss, and emissions control in Class 8 trucks over both city and highway driving conditions. A comprehensive set of component models describing engine fuel consumption, emissions control, battery energy, and accessory power demand interactions was developed and integrated with the simulated hybrid trucks to identify heavy-duty (HD) hybrid technology barriers. The results show that series hybrid is absolutely negative for fuel-economy improvement of long-haul trucks due to an efficiency penalty associated with the dual-step conversions of energy (i.e. mechanical to electric to mechanical).

Reliable means for on-board detection of particulate filter failures or malfunctions are needed to meet diagnostics (OBD) requirements. Detecting these failures, which result in tailpipe particulate matter (PM) emissions exceeding the OBD limit, over all operating conditions is challenging. Current approaches employ differential pressure sensors and downstream PM sensors, in combination with particulate filter and engine-out soot models. These conventional monitors typically operate over narrowly-defined time windows and do not provide a direct measure of the filter’s state of health. In contrast, radio frequency (RF) sensors, which transmit a wireless signal through the filter substrate provide a direct means for interrogating the condition of the filter itself.

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.

A computational study using multi-dimensional CFD modeling was performed to investigate the effects of physical properties on diesel engine combustion characteristics with bio-diesel fuels. Properties of typical bio-diesel fuels that were either calculated or measured are used in the study and the simulation results are compared with those of conventional diesel fuels. The sensitivity of the computational results to individual physical properties is also investigated, and the results provide information about the desirable characteristics of the blended fuels. The properties considered in the study include liquid density, vapor pressure, surface tension, liquid viscosity, liquid thermal conductivity, liquid specific heat, latent heat, vapor specific heat, vapor diffusion coefficient, vapor viscosity and vapor thermal conductivity. The results show significant effects of the fuel physical properties on ignition delay and burning rates at various engine operating conditions.

A prototype three-way catalyst (TWC) with NOX storage component 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 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. Adding a NOX storage component to a TWC provides two benefits in the context of a passive SCR system: (1) enabling longer lean operation by storing NOX upstream and preserving NH3 inventory on the downstream SCR catalyst; and (2) increasing the quantity and rate of NH3 production during rich operation.

In-cylinder blending of gasoline and diesel to achieve Reactivity Controlled Compression Ignition (RCCI) has been shown to reduce NOX and particulate matter (PM) emissions while maintaining or improving brake thermal efficiency as compared to conventional diesel combustion (CDC). The RCCI concept has an advantage over many advanced combustion strategies in that the fuel reactivity can be tailored to the engine speed and load allowing stable low-temperature combustion to be extended over more of the light-duty drive cycle load range. Varying the premixed gasoline fraction changes the fuel reactivity stratification in the cylinder providing further control of combustion phasing and pressure rise rate than the use of EGR alone. This added control over the combustion process has been shown to allow rapid engine operating point exploration without direct modeling guidance.

An engine-aftertreatment computational model was developed to support in-loop performance simulations of tailpipe emissions and fuel consumption associated with a range of heavy-duty (HD) truck drive cycles. For purposes of this study, the engine-out exhaust dynamics were simulated with a combination of steady-state engine maps and dynamic correction factors that accounted for recent engine operating history. The engine correction factors were approximated as dynamic first-order lags associated with the thermal inertia of the major engine components and the rate at which engine-out exhaust temperature and composition vary as combustion heat is absorbed or lost to the surroundings. The aftertreatment model included catalytic monolith components for diesel exhaust oxidation, particulate filtration, and selective catalytic reduction of nitrogen oxides (NOx) with urea.

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.

To quantify the fuel economy (FE) effect of some common vehicle accessories or alterations, a compact passenger sedan and a sport utility vehicle (SUV) were subjected to SAE J2263 coastdown procedures. Coastdowns were conducted with low tire pressure, all windows open, with a roof top or hitch-mounted cargo carrier, and with the SUV pulling an enclosed cargo trailer. From these coastdowns, vehicle dynamometer coefficients were developed which enabled the execution of vehicle dynamometer experiments to determine the effect of these changes on vehicle FE and emissions over standard drive cycles and at steady highway speeds. In addition, two minivans were subjected to coastdowns to examine the similarity in derived coefficients for two duplicate vehicles of the same model. The FE penalty associated with the rooftop cargo box mounted on the compact sedan was as high as 25-27% at higher speeds, where the aerodynamic drag is most pronounced.

The leading approach for reduction of NOx from diesel engines is selective catalytic reduction employing urea as a reductant (NH₃- or urea-SCR). For passenger vehicles, the best known NH₃-SCR catalysts are Cu-ZSM-5 and Fe-ZSM-5 and have been shown to function very well in a narrow temperature range. This technology is not directly transferable to off-road diesel engines which operate under a different duty cycle resulting in exhaust with different fractions of components than are present in passenger vehicle emissions. Our results show that Cu-ZSM-5 exhibits 90% NOx reduction efficiency in 250-450°C range while Fe-ZSM-5 is highly effective in 350-550°C range for off-road engines. However, a combination of these catalysts cannot efficiently reduce NOx in 150-650°C which is the desirable range for deployment in off-road diesel engines. In our efforts to increase the effective range of these catalysts, we initiated efforts to modify these catalysts by catalyst promoters.

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.

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.

Previously reported work with a full-scale ethanol-SCR system featuring a Ag-Al2O3 catalyst demonstrated that this particular system has potential to reduce NOx emissions 80-90% for engine operating conditions that allow catalyst temperatures above 340°C. A concept explored was utilization of a fuel-borne reductant, in this case ethanol “stripped” from an ethanol-diesel micro-emulsion fuel. Increased tailpipe-out emissions of hydrocarbons, acetaldehyde and ammonia were measured, but very little N2O was detected. In the current increment of work, a number of light alcohols and other hydrocarbons were used in experiments to map their performance with the same Ag-Al2O3 catalyst. These exploratory tests are aimed at identification of compounds or organic functional groups that could be candidates for fuel-borne reductants in a compression ignition fuel, or could be produced by some workable method of fuel reforming.

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.

Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. Using an accelerated aging procedure, a set of production exhaust systems from a 2011 Ford F250 equipped with a 6.7L diesel engine have been aged to an equivalent of 150,000 miles of thermal aging and metal exposure. These exhaust systems included a diesel oxidation catalyst (DOC), selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ULSD containing no measureable metals, B20 containing sodium, B20 containing potassium and B20 containing calcium. Metals levels were selected to simulate the maximum allowable levels in B100 according to the ASTM D6751 standard. Analysis of the aged catalysts included Federal Test Procedure emissions testing with the systems installed on a Ford F250 pickup, bench flow reactor testing of catalyst cores, and electron probe microanalysis (EPMA).