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Ammonia/urea-SCR is a mature technology, applied worldwide for the control of NOx emissions in combustion exhausts from thermal power plants, cogeneration units, incinerators and stationary diesel engines and more recently also from mobile sources. However a greater DeNOx activity at low temperatures is desired in order to meet more and more restrictive legislations. In this paper we report transient and steady state data collected over commercial Fe-ZSM-5 and V₂O₅-WO₃/TiO₂ catalysts showing high NOx reduction efficiencies in the 200 - 350°C T-range when NO and ammonia react with nitrates, e.g., in the form of an aqueous solution of ammonium nitrate. Under such conditions a new reaction occurs, the so-called "Enhanced SCR" reaction, 2 NH₃ + 2 NO + NH₄NO₃ → 3 N₂ + 5 H₂O.

In the next years, the upcoming emission legislations are expected to introduce further restrictions on the admittable level of pollutants from vehicles measured on homologation cycles and real drive tests. In this context, the strict control of pollutant emissions at the cold start will become a crucial point to comply with the new regulation standards. This will necessarily require the implementation of novel strategies to speed-up the light-off of the reactions occurring in the after-treatment system, since the cold start conditions are the most critical one for cumulative emissions. Among the different possible technological solutions, this paper focuses on the evaluation of the potential of a burner system, which is activated before the engine start. The hypothetical burner exploits the lean combustion of an air-gasoline mixture to generate a high temperature gas stream which is directed to the catalyst section promoting a fast heating of the substrate.

Selective Catalytic Reduction (SCR) systems are nowadays widely applied for the reduction of NOx emitted from Diesel engines. The typical process is based on the injection of aqueous urea in the exhaust gases before the SCR catalyst, which determines the production of the ammonia needed for the catalytic reduction of NOx. However, this technology is affected by two main limitations: a) the evaporation of the urea water solution (UWS) requires a sufficiently high temperature of the exhaust gases and b) the formation of solid deposits during the UWS evaporation is a frequent phenomenon which compromise the correct operation of the system. In this context, to overcome these issues, a technology based on the injection of gaseous ammonia has been recently proposed: in this case, ammonia is stored at the solid state in a cartridge containing a Strontium Chloride salt and it is desorbed by means of electrical heating.

In this paper, a model-based linear estimator and a non-linear control law for an Fe-zeolite urea-selective catalytic reduction (SCR) catalyst for heavy duty diesel engine applications is presented. The novel aspect of this work is that the relevant species, NO, NO2 and NH3 are estimated and controlled independently. The ability to target NH3 slip is important not only to minimize urea consumption, but also to reduce this unregulated emission. Being able to discriminate between NO and NO2 is important for two reasons. First, recent Fe-zeolite catalyst studies suggest that NOx reduction is highly favored by the NO 2 based reactions. Second, NO2 is more toxic than NO to both the environment and human health. The estimator and control law are based on a 4-state model of the urea-SCR plant. A linearized version of the model is used for state estimation while the full nonlinear model is used for control design.

A number of oxidation catalysts have been prepared using different types of advanced support materials such as ceria-zirconia, silica-titania, spinels and perovskites. Active metals such as Pd and Au-Pd were loaded by conventional impregnation techniques and/or deposition-precipitation methods. A liquid hydrocarbon delivery system was designed and implemented for the catalyst test benches in order to simulate the diesel engine exhaust environment. The activity of fresh (no degreening) catalysts was evaluated with traditional CO and light hydrocarbons (C2H4, C3H6) as well as with heavy hydrocarbons such as C10 H22.

Transient and steady-state kinetic data are herein presented to analyze the inhibiting effect of ammonia on the NH₃-SCR of NO at low temperatures over a Fe-zeolite commercial catalyst for vehicles. It is shown that in SCR converter models a rate expression accounting for NH₃ inhibition of the Standard SCR reaction is needed in order to predict the specific dynamics observed both in lab-scale and in engine test bench runs upon switching on and off the ammonia feed. Two redox, dual site kinetic models are developed which ascribe such inhibition to the spill-over of ammonia from its adsorption sites, associated with the zeolite, to the redox sites, associated with the Fe promoter. Better agreement both with lab-scale intrinsic kinetic runs and with engine test-bench data, particularly during transients associated with dosing of ammonia to the SCR catalyst, is obtained assuming slow migration of NH₃ between the two sites.

It is estimated that operating continuously on a B20 fuel containing the current allowable ASTM specification limits for metal impurities in biodiesel could result in a doubling of ash exposure relative to lube-oil-derived ash. The purpose of this study was to determine if a fuel containing metals at the ASTM limits could cause adverse impacts on the performance and durability of diesel emission control systems. An accelerated durability test method was developed to determine the potential impact of these biodiesel impurities. The test program included engine testing with multiple DPF substrate types as well as DOC and SCR catalysts. The results showed no significant degradation in the thermo-mechanical properties of cordierite, aluminum titanate, or silicon carbide DPFs after exposure to 150,000 mile equivalent biodiesel ash and thermal aging. However, exposure of a cordierite DPF to 435,000 mile equivalent aging resulted in a 69% decrease in the thermal shock resistance parameter.

An experimental and modeling study was conducted to study the passive regeneration of a catalyzed particulate filter (CPF) by the oxidation of particulate matter (PM) via thermal and Nitrogen dioxide/temperature-assisted means. Emissions data in the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR and a diesel oxidation catalyst (DOC) - catalyzed particulate filter (CPF) in the exhaust system was measured and used for this study. A series of experiments was conducted to evaluate the performance of the DOC, CPF and DOC+CPF configurations at various engine speeds and loads.

Steady-state particulate loading experiments were conducted on an advanced production catalyzed particulate filter (CPF), both with and without a diesel oxidation catalyst (DOC). A heavy-duty diesel engine was used for this study with the experiments conducted at 20, 40, 60 and 75 % of full load (1120 Nm) at rated speed (2100 rpm). The data obtained from these experiments were used and are necessary for calibrating the MTU 1-D 2-Layer CPF model. These experimental and modeling results were compared to previous research conducted at MTU that used the same engine but an earlier development version of the combination of DOC and CPF. The motivation for the comparison of the two systems was to determine whether the reformulated production catalysts performed as good or better than the early development catalysts. The results were compared to understand the filtration and oxidation differences between the two DOC+CPF and the CPF-only aftertreatment systems.

Model-based control strategies are important for meeting the dual objective of maximizing NOx reduction and minimizing NH3 slip in urea-SCR catalysts. To be implementable on the vehicle, the models should capture the essential behavior of the system, while not being computationally intensive. This paper discusses the adequacy of two different reduced order SCR catalyst models and compares their performance with a higher order model. The higher order model assumes that the catalyst has both diffusion and reaction kinetics, whereas the reduced order models contain only reaction kinetics. After describing each model, its parameter identification and model validation based on experiments on a Navistar I6 7.6L engine are presented. The adequacy of reduced order models is demonstrated by comparing the NO, NO2 and NH3 concentrations predicted by the models to their concentrations from the test data.

Various gold catalysts were prepared using commercial and in-house fabricated advanced catalyst supports that included mesoporous silica, mesoporous alumina, sol-gel alumina, and transition metal oxides. Gold nanoparticles were loaded on the supports by co-precipitation, deposition-precipitation, ion exchange and surface functionalization techniques. The average gold particle size was ∼20nm or less. The oxidation activity of the prepared catalysts was studied using carbon monoxide and light hydrocarbons (ethylene, propylene and propane) in presence of water and CO2 and the results are presented.

A one-dimensional model simulating the oxidation of CO, HC, and NO was developed to predict the gaseous emissions downstream of a diesel oxidation catalyst (DOC). The model is based on the conservation of mass, species, and energy inside the DOC and draws on past research literature. Steady-state experiments covering a wide range of operating conditions (exhaust temperatures, flow rates and gaseous emissions) were performed, and the data were used to calibrate and validate the model. NO conversion efficiencies of 50% or higher were obtained at temperatures between 300°C and 350°C. CO conversion efficiencies of 85% or higher and HC conversion efficiencies of 75% or higher were found at every steady state condition above 200°C. The model agrees well with the experimental results at temperatures from 200°C to 500°C, and volumetric flow rates from 8 to 42 actual m3/min.

This paper describes two independent studies on γ-alumina as a plasma-activated catalyst. γ-alumina (2.5 - 4.3 wt%) was coated onto the surface of mesoporous silica to determine the importance of aluminum surface coordination on NOx conversion in conjunction with nonthermal plasma. Results indicate that the presence of 5- and 6- fold aluminum coordination sites in γ-alumina could be a significant factor in the NOx reduction process. A second study examined the effect of changing the reducing agent on NOx conversion. Several hydrocarbons were examined including propene, propane, isooctane, methanol, and acetaldehyde. It is demonstrated that methanol was the most effective reducing agent of those tested for a plasma-facilitated reaction over γ-alumina.

A slipstream of exhaust from a Caterpillar 3126B engine was diverted into a plasma-catalytic NOx control system in the space velocity range of 7,000 to 100,000 hr-1. The stream was first fed through a non-thermal plasma that was formed in a coaxial cylinder dielectric barrier discharge reactor. Plasma treated gas was then passed over a catalyst bed held at constant temperature in the range of 573 to 773 K. Catalysts examined consisted of γ-alumina, indium-doped γ-alumina, and silver-doped γ-alumina. Road and rated load conditions resulted in engine out NOx levels of 250 - 600 ppm. The effects of hydrocarbon level, catalyst temperature, and space velocity are discussed where propene and in one case ultra-low sulfur diesel fuel (late cycle injection) were the reducing agents used for NOx reduction. Results showed NOx reduction in the range of 25 - 97% depending on engine operating conditions and management of the catalyst and slipstream conditions.

In the last years, as a response to the more and more restrictive emission legislation, new devices (SRC, DOC, NOx-trap, DPF) have been progressively introduced as standard components of modern after-treatment system for Diesel engines. In addition, the adoption of electrical heating is nowadays regarded with interest as an effective solution to promote the light-off of the catalyst at low temperature, especially at the start-up of the engine and during the low load operation of the engine typical of the urban drive. In this work, a state-of-the-art 48 V electrical heated catalyst is considered, in order to investigate its effect in increasing the abatement efficiency of a standard DOC. The electrical heating device considered is based on a metallic support, arranged in a spiral layout, and it is heated by the Joule effect due to the passage of the electrical current.

In this study, a DOC catalyst was experimentally studied in an engine test cell with a2010 Cummins 6.7L ISB diesel and a production aftertreatment system. The test matrix consisted of steady state, active regeneration with in-cylinder fuel dosing and transient conditions. Conversion efficiencies of total hydrocarbon (THC), CO, and NO were quantified under each condition. A previously developed high-fidelity DOC model capable of predicting both steady state and transient active regeneration gaseous emissions was calibrated to the experimental data. The model consists of a single 1D channel where mass and energy balance equations were solved for both surface and bulk gas regions. The steady-state data were used to identify the activation energies and pre-exponential factors for CO, NO and HC oxidation, while the steady-state active regeneration data were used to identify the inhibition factors. The transient data were used to simulate the thermal response of the DOC.

In this paper the low temperature reduction process of nitrates stored at high temperatures over model Pt-Ba/Al2O3 LNT catalysts using both H2 and C3H6 is analyzed. The results indicate that over the Pt-Ba/Al2O3 catalyst the reduction of stored NOx with both H2 and C3H6 occurs at temperature below those corresponding to their thermal stability. Accordingly, the reduction process occurs through a Pt-catalyzed surface reaction, which does not involve, as a preliminary step, the thermal decomposition of the adsorbed NOx species. The occurrence of such a pathway also requires the co-presence of the storage element and of the noble metal on the same support.

The primary goal of this project was to design and implement an oxidation catalyst specific to a high-performance spark ignited two stroke engines to reduce vehicle-out emissions. The primary challenges of two stroke catalysis at high loads include controlling the catalytic reaction temperature as well as minimizing the increase in exhaust back pressure due to the addition of a catalyst. Reaction temperature is difficult to control due to high HC and CO concentrations paired with an excess of oxygen in the exhaust stream. By limiting catalyst conversion efficiency, the reaction temperatures were controlled. Two stroke engines are also inherently sensitive to changes in exhaust back pressure and therefore location and sizing of the catalyst are key design considerations. Because of these challenges significant effort was directed toward developing the two-stroke specific catalyst design process.

The objective of this research was to study the effects of a CCRT®, henceforth called Diesel Oxidation Catalyst - Catalyzed Particulate Filter (DOC-CPF) system on particulate and gaseous emissions from a heavy-duty diesel engine (HDDE) operated at Modes 11 and 9 of the old Environmental Protection Agency (EPA) 13-mode test cycle Emissions characterized included: total particulate matter (TPM) and components of carbonaceous solids (SOL), soluble organic fraction (SOF) and sulfates (SO4); vapor phase organics (XOC); gaseous emissions of total hydrocarbons (HC), carbon monoxide (CO), oxides of nitrogen (NOx), nitric oxide (NO) and nitrogen dioxide (NO2), oxygen (O2) and carbon dioxide (CO2); and particle size distributions at normal dilution ratio (NDR) and higher dilution ratio (HDR). Significant reductions were observed for TPM and SOL (>90%), SOF (>80%) and XOC (>70%) across the DOC-CPF at both modes.

The Society of Automotive Engineers' (SAE) Clean Snowmobile Challenge 2004 (CSC 2004) was held at Michigan Technological University in Houghton, Michigan, from March 15 - 20, 2004. The Clean Snowmobile Challenge has been a competition in the SAE Collegiate Design Series since 2000, and began in Jackson Hole, Wyoming, as a response to rising concerns about snowmobiling in environmentally-sensitive areas. Teams from fifteen universities competed in CSC 2004. The winning snowmobile (sled) was developed by the University of Wisconsin, Madison, and featured a four-stroke engine with electronic fuel injection (EFI), a two-stage tuned muffler, and catalytic exhaust aftertreatment. A hybrid-electric design was used to increase the snowmobile's powertrain output and improve acceleration. [8] Teams should be competitive in all events to gain enough points to win the competition.