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Ammonia adsorption on the catalyst surface is a crucial step in the selective catalytic reduction of nitrogen oxides over zeolites with NH3 as the reducing agent. In this study, two small pore zeolites with chabazite frameworks, H-SSZ-13 and Cu exchanged SSZ-13, are examined. Adsorption of NH3 on the zeolite causes changing electrical properties of the material. They can be detected by a radio frequency based technique. We have found that with this method it is possible to determine the amount of adsorbed NH3 on these catalysts, examining both the influences of temperature and NH3/NO feed gas ratio. At constant temperature, a fairly linear correlation between the resonance frequency and the amount of adsorbed ammonia was observed. Furthermore, this method also allows differentiation between some of the NH3 adsorption sites.

A laboratory study was performed to assess the potential capability of TWC+LNT/SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. It was assumed that the exhaust system would need a close-coupled (CC) TWC, an underbody (U/B) TWC, and a third U/B LNT/SCR converter to satisfy the emission standards on the FTP and US06 tests while allowing lean operation for improved fuel economy during select driving conditions. Target levels for HC, CO, and NOx during lean/rich cycling were established. Sizing studies were performed to determine the minimum LNT/SCR volume needed to satisfy the NOx target. The ability of the TWC to oxidize the HC during rich operation through steam reforming was crucial for satisfying the HC target.

A laboratory study was performed to assess the potential capability of passive TWC+SCR systems to satisfy the Tier 2, Bin 2 emission standards for lean-burn gasoline applications. In this system, the TWC generates the NH3 for the SCR catalyst from the feedgas NOx during rich operation. Therefore, this approach benefits from high feedgas NOx during rich operation to generate high levels of NH3 quickly and low feedgas NOx during lean operation for a low rate of NH3 consumption. It was assumed that the exhaust system needed to include a close-coupled (CC) TWC, an underbody (U/B) TWC, and an U/B SCR converter to satisfy the emission standards during the FTP and US06 tests while allowing lean operation for improved fuel economy during select driving conditions. Target levels for HC, CO, and NOx during lean/rich cycling were established. With a 30 s lean/10 s rich cycle and 200 ppm NO lean, 1500 ppm NO rich and the equivalent of 3.3 L of SCR volume were required to satisfy the NOx target.

Fouling in EGR coolers occurs because of the presence of soot and condensable species (such as hydrocarbons) in the gas stream. Fouling leads to one of two possible outcomes: stabilization of effectiveness and plugging of the gas passages within the cooler. Deposit formation in the cooler under high-temperature conditions results in a fractal deposit that has a characteristic thermal conductivity of ∼0.033 W/m*K and a density of 0.0224 g/cm3. Effectiveness becomes much less sensitive to changes in thermal resistance as fouling proceeds, creating the appearance of “stabilization” even in the presence of ongoing, albeit slow, deposit growth. Plugging occurs when the deposit thermal resistance is several times lower because of the presence of large amounts of condensed species. The deposition mechanism in this case appears to be soot deposition into a liquid film, which results in increased packing efficiency and decreased void space in the deposit relative to high-temperature deposits.

All high-pressure exhaust gas recirculation (EGR) coolers become fouled during operation due to thermophoresis of particulate matter and condensation of hydrocarbons present in diesel exhaust. In some EGR coolers, fouling is so severe that deposits form plugs strong enough to occlude the gas passages thereby causing a complete failure of the EGR system. In order to better understand plugging and means of reducing its undesirable performance degradation, EGR coolers exhibiting plugging were requested from and provided by industry EGR engineers. Two of these coolers contained glassy, brittle, lacquer-like deposits which were analyzed using gas chromatography-mass spectrometry (GC-MS) which identified large amounts of oxygenated polycyclic aromatic hydrocarbons (PAHs). Another cooler exhibited similar species to the lacquer but at a lower concentration with more soot.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOx emissions standards. Exhaust gas laden with particulate matter flows through the EGR cooler which causes deposits to form through thermophoresis and condensation. The low thermal conductivity of the resulting deposit reduces the effectiveness of the EGR system. In order to better understand this phenomenon, industry-provided coolers were characterized using neutron tomography. Neutrons are strongly attenuated by hydrogen but only weakly by metals which allows for non-destructive imaging of the deposit through the metal heat exchanger. Multiple 2-D projections of cooler sections were acquired by rotating the sample around the axis of symmetry with the spatial resolution of each image equal to ∼70 μm. A 3-D tomographic set was then reconstructed, from which slices through the cooler sections were extracted across different planes.

A number of studies have identified a tendency for exhaust gas recirculation (EGR) coolers to foul to a steady-state level and subsequently not degrade further. One possible explanation for this behavior is that the shear force imposed by the gas velocity increases as the deposit thickens. If the shear force reaches a critical level, it achieves a removal of the deposit material that can balance the rate of deposition of new material, creating a stabilized condition. This study reports efforts to observe removal of deposit material in-situ during fouling studies as well as an ex-situ removal through the use of controlled air flows. The critical gas velocity and shear stress necessary to cause removal of deposit material is identified and reported. In-situ observations failed to show convincing evidence of a removal of deposit material. The results show that removal of deposit material requires a relatively high velocity of 40 m/s or higher to cause removal.

Exhaust gas recirculation (EGR) cooler fouling has become a significant issue for compliance with NOX emissions standards and has negative impacts on cooler sizing and engine performance. In order to improve our knowledge of cooler fouling as a function of engine operating parameters and to predict and enhance performance, 19 tube-in-shell EGR coolers were fouled using a 5-factor, 3-level design of experiments with the following variables: (1) EGR flow rate, (2) EGR inlet gas temperature, (3) coolant temperature, (4) soot level, and (5) hydrocarbon concentration. A 9-liter engine and ULSD fuel were used to form the cooler deposits. Coolers were run until the effectiveness stabilized, and then were cooled down to room temperature and run for an additional few hours in order to measure the change in effectiveness due to shut down. The coolers were cut open and the mass per unit area of the deposit was measured as a function of distance down the tube.

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).

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.

An advanced diesel aftertreatment system utilizing Selective Catalytic Reduction (SCR) with urea for lean nitrogen oxides (NOx) control was tested on a 2.7L V6 Land Rover vehicle to demonstrate the capability of achieving Tier 2 Bin 5 and lower emission standards for light-duty trucks. SCR washcoat was applied to a diesel particulate filter (DPF) to perform NOx and particulate reduction simultaneously. Advanced SCR systems employed both traditional SCR catalysts and SCR-coated filters (SCRF) to improve the NOx reduction efficiency. The engine-out NOx level was adjusted by modifying the EGR (Exhaust Gas Recirculation) calibration. Cold start NOx performance was improved by SCR warm-up strategy and urea over injection. This study showed the advanced SCR system could tolerate higher NH₃ storage in the SCR catalyst, resulting in overall higher NOx conversion on the FTP-75 test cycle.

Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300°C. These stored HCs inhibit or block NOx-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NOx conversion begins at between 100° and 200°C. When exposure to unburned fuel occurs at higher temperatures (250°-400°C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NOx conversion is inhibited until it is heated to 400°C.

A laboratory flow reactor study was utilized to determine the durability impact of alkali metal (Na and K) exposure on three Pt/Pd-based diesel oxidation catalysts (DOC), two vanadium-based selective catalytic reduction (SCR) catalysts, and two Cu/zeolite-based SCR catalysts. All catalyst samples were contaminated by direct deposition of Na or K by an incipient wetness technique. The activity impact on the contaminated DOCs was accomplished by evaluating for changes in CO and HC light-off. The activity impact on the contaminated SCR catalysts was accomplished by evaluating for changes in the Standard SCR Reaction, the Fast SCR Reaction, the Ammonia Oxidation Reaction, and the Ammonia Storage Capacity. Contamination levels of 3.0 wt% Na was found to have a higher negative impact on Pt-based and zeolite containing DOCs for T-50 CO and HC light-off.

Urea selective catalytic reduction (SCR) catalysts have the capability to deliver the high NOx conversion efficiencies required for future emission standards. However, the potential for the occasional over-temperature can lead to the irreversible deactivation of the SCR catalyst. On-board diagnostics (OBD) compliance requires monitoring of the SCR function to make sure it is operating properly. Initially, SCR catalyst performance metrics such as NOx conversion, NH3 oxidation, NH3 storage capacity, and BET surface area are within normal limits. However, these features degrade with high temperature aging. In this work, a laboratory flow reactor was utilized to determine the impact on these performance metrics as a function of aging condition. Upon the completion of a full time-at-temperature durability study, four performance criteria were established to help determine a likely SCR failure.

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).

Advanced Cu-zeolite based SCR (selective catalytic reduction) catalyst technologies were evaluated in a laboratory reactor as a component of a diesel LNT (lean NOx trap) plus in-situ SCR system (i.e., NH3 generation over the LNT vs injection via urea). New-generation LNT formulations, with lower desulfation temperatures and improved durability characteristics relative to previous LNTs, were also evaluated. The combined new-generation LNT+Cu-zeolite SCR systems showed a much wider temperature window of high NOx conversion compared to either LNT catalysts alone or LNT+SCR systems utilizing Fe-zeolite SCR catalysts. The new-generation Cu-zeolite SCR catalysts retained high activity even after repeated exposure to high-temperature rich DeSOx conditions in a laboratory 3-mode aging cycle simulating 120,000 mile vehicle driving.

For diesel applications, cold start accounts for a large amount of the total NOx emissions during a typical Federal Test Procedure (FTP) for light-duty vehicles and is a key focus for reducing NOx emissions. A common form of diesel NOx aftertreatment is selective catalytic reduction (SCR) technology. For cold start NOx improvement, the SCR catalyst would be best located as the first catalyst in the aftertreatment system; however, engine-out hydrocarbons and no diesel oxidation catalyst (DOC) upstream to generate an exotherm for desulfation can result in degraded SCR catalyst performance. Recent advances in vanadia-based SCR (V-SCR) catalyst technology have shown better low temperature NOx performance and improved thermal durability. Three V-SCR technologies were tested for their thermal durability and low-temperature NOx performance, and after 600°C aging, one technology showed low-temperature performance on par with state-of-the-art copper-zeolite SCR (Cu-SCR) technology.

Copper/zeolite catalysts are the leading urea SCR catalysts for NOx emission treatment in diesel applications. Sulfur poisoning directly impacts the overall SCR performance and is still a durability issue for Cu/zeolite SCR catalysts. Most studies on sulfur poisoning of Cu/zeolite SCR catalysts have been based on SO2 as the poisoning agent. It is important to investigate the relative poisoning effects of SO3, especially for systems with DOCs in front of Cu/zeolite SCR catalysts. It was observed that SCR activity was significantly reduced for samples poisoned by SO3 vs. those poisoned by SO2. The sulfur was released mainly as SO2 for both samples poisoned by SO2 and SO3. The temperatures and the magnitudes of released SO2 peaks however, were very different between the samples poisoned by SO2 vs. SO3. The results indicate that sulfur poisoning by SO2 and SO3 are not equivalent, with different poisoning mechanisms and impacts.

Diesel aftertreatment systems configured with a diesel oxidation catalyst (DOC) upstream of an urea selective catalytic reduction (SCR) catalyst run the risk of precious metal contamination. During active diesel particulate filter (DPF) regeneration events, the DOC bed temperature can reach up to 850°C. Under these conditions, precious metal (especially Pt) can be volatized and then deposited on a downstream SCR catalyst. In this paper, the impact of ultra-low contamination of platinum group metals (PGM) on the SCR catalyst was studied. A method based on precious metal volatilization of a Pt-rich DOC at 850°C and under lean gas conditions was employed to contaminate downstream FeSCR and CuSCR formulations. The contamination resulted in poor NOx conversion (via NOx remake) and excessive N2O formation. The precious metal volatilization method was employed to screen various Pt/Pd based DOCs to avoid contamination of the downstream FeSCR.

This paper discusses the poisoning of a selective catalytic reduction (SCR) catalyst by trace levels of platinum originating from an upstream diesel oxidation catalyst (DOC). A diesel aftertreatment system consisting of a DOC, urea based SCR Catalyst and a DPF was aged and evaluated on a 6.4 liter diesel engine dynamometer. The SCR catalyst system consisted of an Fe-zeolite catalyst followed by a Cu-zeolite catalyst. After approximately 400 hours of engine operation at varied exhaust flow rates and temperatures, deactivation of the SCR catalyst was observed. A subsequent detailed investigation revealed that the Cu catalyst was not deactivated and the front half of the Fe-based catalyst showed severe deactivation. The deactivated portion of the catalyst showed high activity of NH3 conversion to NOx and N2O formation. The cause of the deactivation was identified to be the presence of trace Pt contamination.