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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.

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.

This paper reports on DaimlerChrysler's participation in the Ad Hoc Diesel Fuels Test Program. This program was initiated by the U.S. Department of Energy and included major U.S. auto makers, major U.S. oil companies, and the Department of Energy. The purpose of this program was to identify diesel fuels and fuel properties that could facilitate the successful use of compression ignition engines in passenger cars and light-duty trucks in the United States at Tier 2 and LEV II tailpipe emissions standards. This portion of the program focused on minimizing engine-out particulates and NOx by using selected fuels, (not a matrix of fuel properties,) in steady state dynamometer tests on a modern, direct injection, common rail diesel engine.

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.

The variability in gasoline energy content, though most frequently not a consumer concern, is an issue of concern for vehicle manufacturers in demonstrating compliance with regulatory requirements. Advancements in both vehicle technology, test methodology, and fuel formulations have increased the level of visibility and concern with regard to the energy content of fuels used for regulatory testing. The R factor was introduced into fuel economy calculations for vehicle certification in the late 1980s as a means of addressing batch-to-batch variations in the heating value of certification fuels and the resulting variations in fuel economy results. Although previous studies have investigated values of the R factor for modern vehicles through experimentation, subsequent engine studies have made clear that it is difficult to distinguish between the confounding factors that influence engine efficiency when R is being studied experimentally.

Lean NOx Trap (LNT) catalysts are capable of reducing NOx in lean exhaust from diesel engines. NOx is stored on the catalyst during lean operation; then, under rich exhaust conditions, the NOx is released from and reduced by the catalyst. The process of NOx release and reduction is called regeneration. One method of obtaining the rich conditions for regeneration is to inject additional fuel into the engine cylinders while throttling the engine intake air flow to effectively run the engine at rich air:fuel ratios; this method is called “in-cylinder” regeneration. In-cylinder regeneration of LNT catalysts has been demonstrated and is a candidate emission control technique for commercialization of light-duty diesel vehicles to meet future emission regulations. In the study presented here, a 1.7-liter diesel engine with a LNT catalyst system was used to evaluate in-cylinder regeneration techniques.

Measuring axial exhaust species concentration distributions within a wall-flow aftertreatment device provides unique and significant insights regarding the performance of complex devices like the SCR-on-filter. In this particular study, a less complex aftertreatment configuration which includes a DOC followed by two uncoated partial flow filters (PFF) was used to demonstrate the potential and challenges. The PFF design in this study was a particulate filter with alternating open and plugged channels. A SpaciMS [1] instrument was used to measure the axial NO2 profiles within adjacent open and plugged channels of each filter element during an extended passive regeneration event using a full-scale engine and catalyst system. By estimating the mass flow through the open and plugged channels, the axial soot load profile history could be assessed.

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.

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.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with nitrogen oxides (NOx) emissions standards. In order to better understand fouling mechanisms, eleven field-aged EGR coolers provided by seven different engine manufacturers were characterized using a suite of techniques. Microstructures were characterized using scanning electron microscopy (SEM) and optical microscopy following mounting the samples in epoxy and polishing. Optical microscopy was able to discern the location of hydrocarbons in the polished cross-sections. Chemical compositions were measured using thermal gravimetric analysis (TGA), differential thermal analysis (DTA), gas chromatography-mass spectrometry (GC-MS), x-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS) and x-ray diffraction (XRD). Mass per unit area along the length of the coolers was also measured.

As the fuel economy regulations increase in stringency, many manufacturers are implementing start-stop operation to enhance vehicle fuel economy. During start-stop operation, the engine shuts off when the vehicle is stationary for more than a few seconds. When the brake is released by the driver, the engine restarts. Depending on traffic conditions, start-stop operation can result in fuel savings from a few percent to close to 10%. Gasoline direct injection (GDI) engines are also increasingly available on light-duty vehicles. While GDI engines offer fuel economy advantages over port fuel injected (PFI) engines, they also tend to have higher PM emissions, particularly during start-up transients. Thus, there is interest in evaluating the effect of start-stop operation on PM emissions. In this study, a 2.5L GDI vehicle was operated over the FTP75 drive cycle.

One challenge in meeting emission regulations with catalytic aftertreatment systems is maintaining the proper catalyst temperatures that enable the catalytic devices to perform the emissions reduction. In this study, in-cylinder techniques are used to actively control the temperature of a catalyzed diesel particulate filter (DPF) in order to raise the DPF temperature to induce particulate oxidation. The performance of four strategies is compared for two different starting DPF temperatures (150°C and 300°C) on a 4-cylinder 1.7-liter diesel engine. The four strategies include: (1) addition of extra fuel injection early in the combustion cycle for all four cylinders, (2) addition of extra fuel injection late in the combustion cycle for all four cylinders, (3) operating one-cylinder with extra fuel injection early in the combustion cycle, and (4) operating one-cylinder with extra fuel injection late in the combustion cycle.

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 poisoning of diesel oxidation catalysts (DOCs) by the engine oil additive zinc dialkyldithiophosphate (ZDDP) is investigated in the present study. A 517cc single-cylinder diesel engine is used to accelerate the phosphorus poisoning of DOCs by artificially increasing the ZDDP consumption to approximately 700 times normal operation by three different methods. These include lube-oil doped fuel, intake manifold, and exhaust manifold injection with lube-oil containing an elevated level of ZDDP. The deactivation of DOCs under these conditions is characterized by a variety of physical and chemical techniques. Surface composition and structure of the poisoned catalysts analyzed with SEM-EDS show differences depending on the method of ZDDP introduction. Exhaust manifold injection produces a zinc phosphate glaze which masks the surface to species diffusion. Fuel and intake manifold injection methods produce chemically absorbed phosphorus on the catalyst washcoat surface.

The U.S. Department of Energy’s Co-Optimization of Fuels and Engines initiative (Co-Optima) aims to simultaneously transform both transportation fuels and engines to maximize performance and energy efficiency. Researchers from across the DOE national laboratories are working within Co-Optima to develop merit functions for evaluating the impact of fuel formulations on the performance of advanced engines. The merit functions relate overall engine efficiency to specific measurable fuel properties and will serve as key tools in the fuel/engine co-optimization process. This work focused on developing a term for the Co-Optima light-duty boosted spark ignition (SI) engine merit function that captures the effects of fuel composition on emissions control system performance. For stoichiometric light-duty SI engines, the majority of NOx, NMOG, and CO emissions occur during cold start, before the three-way catalyst (TWC) has reached its “light-off” temperature.

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.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOx emissions standards. This paper reports results of a study of fundamental aspects of EGR cooler fouling. An apparatus and procedure were developed to allow surrogate EGR cooler tubes to be exposed to diesel engine exhaust under controlled conditions. The resulting fouled tubes were removed and analyzed. Volatile and non-volatile deposit mass was measured for each tube. Thermal diffusivity of the deposited soot cake was measured by milling a window into the tube and using the Xenon flash lamp method. The heat capacity of the deposit was measured at temperatures up to 430°C and was slightly higher than graphite, presumably due to the presence of hydrocarbons. These measurements were combined to allow calculation of the deposit thermal conductivity, which was determined to be 0.041 W/mK, only ∼1.5 times that of air and much lower than the 304 stainless steel tube (14.7 W/mK).

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.