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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.

Ultrasound is attractive for medical imaging in space because scanners can be small, lightweight, low power, and have minimal electromagnetic emissions. In addition, unlike conventional 2-D ultrasound. 3-D ultrasound allows an operator with no diagnostic skills to collect high-quality scans that can be interpreted by a remote expert. This allows 3-D ultrasound to be used effectively in remote locations. These capabilities are illustrated by the MUSTPAC-1, a portable 3-D ultrasound telemedicine system recently developed for the U.S. military. Design, implementation, and field experiences with the MUSTPAC-1 are discussed, and extensions for use in space are proposed.

Fuel cell vehicles are entering the automotive market with significant potential benefits to reduce harmful greenhouse emissions, facilitate energy security, and increase vehicle efficiency while providing customer expected driving range and fill times when compared to conventional vehicles. One of the challenges for successful commercialization of fuel cell vehicles is transitioning the on-board fuel system from liquid gasoline to compressed hydrogen gas. Storing high pressurized hydrogen requires a specialized structural pressure vessel, significantly different in function, size, and construction from a gasoline container. In comparison to a gasoline tank at near ambient pressures, OEMs have aligned to a nominal working pressure of 700 bar for hydrogen tanks in order to achieve the customer expected driving range of 300 miles.

With new legislation and federal regulation for vehicle emission levels, automotive and truck manufacturers have been prompted to focus on emission control technologies that limit the level of exhaust pollutants. One of the primary pollutants, especially from diesel engines, is oxides of nitrogen (NOx). One possible solution to this pollution challenge is to design a more efficient internal combustion engine, which would require better engine operating parameter controls. However, there are limitations associated with such tight engine management. This need has led researchers and engineers to focus on the development of exhaust aftertreatment devices that will reduce NOx emissions with current diesel engines. An optimum aftertreatment device must be unaffected by exhaust-gas impurity poisoning such as sulfur products, and must have minimal impact on vehicle operations and fuel economy.

We present here a phenomenological analysis of a cascade of two-step discharge-catalyst reactors. That is, each step of the cascade consists of a discharge reactor in series with a catalyst bed. These reactors are intended for use in the reduction of tailpipe emission of NOx from diesel engines. The discharge oxidizes NO to NO2, and partially oxidizes HC. The NO2 then reacts on the catalyst bed with hydrocarbons and partially oxidized HCs and is reduced to N2. The cascade may be essential because the best catalysts for this purpose that we have also convert significant fractions of the NO2 back to NO. As we show, reprocessing the gas may not only be necessary, but may also result in energy savings and increased device reliability.

Brønsted acidity of solution ion-exchanged and solid-state exchanged zeolites was compared for NaY, BaY, CaY, NaX, and CaX zeolites. These materials were chosen because they all exhibit catalytic activity in SCR of NOx in combination with a non-thermal plasma. Brønsted acidity was characterized qualitatively with retinol as an indicator dye. Our results show that the solid-state exchange using a chloride salt creates zeolites with lower acidity than zeolites obtained by conventional solution ion-exchange. NO2 adsorption was also found to create a significant quantity of acid sites at room temperature and a slight increase in acidity at 200°C. We speculate that the acid sites created by NO2 adsorption, because of their vicinity to metal cation sites in the zeolite, may lead to preferential reactions that lead to NOx reduction. BaY made by solution ion-exchange and BaY made by solid-state exchange using a chloride salt were tested for NOx reduction in a plasma-catalyst reactor system.

Projected NOx and fuel costs are compared for a plasma-catalyst system and an active lean NOx catalyst system. Comparisons are based on modeling of FTP cycle performance. The model uses steady state laboratory device characteristics, combined with measured vehicle exhaust data to predict NOx conversion efficiency and fuel economy penalties. The plasma system uses a proprietary catalyst downstream of a plasma discharge. The active lean NOx catalyst uses a catalyst along with addition of hydrocarbons to the exhaust. For the plasma catalyst system, NOx conversion is available over a wide temperature range. Increased electrical power improves conversion but degrades vehicle fuel economy; 10 J/L energy deposition costs roughly 3% fuel economy. Improved efficiency is also available with larger catalyst size or increased exhaust hydrocarbon content. For the active lean NOx system, NOx conversion is available only in a narrow temperature range.

A double dielectric barrier discharge reactor driven by an alternating voltage is a relatively simple approach to promote oxidation of NO to NO2 for subsequent reduction in a catalyst bed. The chemical performance of such a non-thermal plasma reactor is determined by its current and electric field behavior in the gap, and by the fraction of the current carried by electrons, because the key reactants which initiate the NO oxidation and accompanying chemical changes are produced there, mostly by electron impact. We have tried to determine by models and experiments the bounds on performance of double dielectric barrier reactors and guidelines for optimization. Models reported here predict chemical results from time-resolved applied voltage and series sense capacitor data.

Recent work has shown that energy efficiencies as well as yields and selectivities of the NOx reduction reaction can be enhanced by combining a plasma discharge with select catalysts. While analysis of gas phase species with a chemiluminescent NOx meter and mass spectrometer show that significant removal of NOx is achieved, high background concentrations of nitrogen preclude the measurement of nitrogen produced from NOx reduction. Results presented in this paper show that N2 from NOx reduction can be measured if background N2 is replaced with helium. Nitrogen production results are presented for a catalyst system where the catalyst is in the plasma region and where the catalyst is downstream from the plasma. The amount of N2 produced is compared with the amount of NOx removed as measured by the chemiluminescent NOx meter. The measured nitrogen from NOx reduction accounts for at least 40% of the total NOx removed for both reactor configurations.

Diesel particulate samples were collected from a light duty engine operated at a single speed-load point with a range of biodiesel and conventional fuel blends. The oxidation reactivity of the samples was characterized in a laboratory reactor, and BET surface area measurements were made at several points during oxidation of the fixed carbon component of both types of particulate. The fixed carbon component of biodiesel particulate has a significantly higher surface area for the initial stages of oxidation, but the surface areas for the two particulates become similar as fixed carbon oxidation proceeds beyond 40%. When fixed carbon oxidation rates are normalized to total surface area, it is possible to describe the oxidation rates of the fixed carbon portion of both types of particulates with a single set of Arrhenius parameters. The measured surface area evolution during particle oxidation was found to be inconsistent with shrinking sphere oxidation.

NOx reduction under simulated lean burn conditions was studied using a non-thermal plasma in combination with zeolite and alumina catalysts. The influence of temperature and plasma treatment on the catalytic performance was investigated. Zeolite catalyst B showed high activity in the 150-300°C temperature region. Alumina Catalyst D was most active at temperatures higher than 250°C. In addition, the alumina catalyst was effective in oxidation of aldehydes formed during plasma treatment of the reaction mixture. When the reaction was carried out over a catalyst bed consisting of separate layers of the zeolite and alumina catalysts, the catalyst temperature range for significant NOx reduction was expanded to 150-500°C.

Proposed vehicle emissions regulations for the near future have prompted automotive manufactures and component suppliers to focus heavily on developing more efficient exhaust aftertreatment devices to lower emissions from spark and compression ignition engines. One of the primary pollutants from lean-burn engines, especially from diesels, are oxides of nitrogen (NOx). Current three-way catalytic converters will not have adequate performance to meet future emission reduction requirements. Therefore, there is a need for researchers and engineers to develop efficient exhaust aftertreatment devices that will reduce NOx emissions from lean-burn engines. These devices must have very high conversion of NOx gases, be unaffected by exhaust-gas impurity such as sulfur, and have minimal impact on vehicle operations and fuel economy. An effective technology for NOx control that is currently receiving a lot of attention is a non-thermal plasma system.

With ever more stringent CO2 emissions mandates, many automobile manufacturers are seeking the fuel economy benefits of diesel and lean-burn gasoline engines. At the same time the emissions standards that diesel and gasoline engines will have to meet in the next decade continue to reduce. Proposed solutions for meeting the stringent emissions standards all appear to have limitations, such as propensities to poisoning from sulfur, narrow operating temperature windows, and requirements for controls that give rapid rich excursions. Non-thermal plasma-catalyst systems have shown good performance in bench testing while being largely unaffected by these same issues. A two-stage system with a unique non-thermal plasma reactor combined with a zeolite-based catalyst has been constructed and shown to work over a wide temperature range.

The Office of Heavy Vehicle Technologies supports research to enable high-efficiency diesel engines to meet future emissions regulations, thus clearing the way for their use in light trucks as well as continuing as the most efficient powerplant for freight-haulers. Compliance with Tier 2 emission regulations for light-duty vehicles will require effective exhaust emission controls (aftertreatment) for diesels in these applications. Diesel-powered heavy trucks face a similar situation for the 2007 regulations announced by EPA in December 2000. DOE laboratories are working with industry to improve emission control technologies in projects ranging from application of new diagnostics for elucidating key mechanisms, to development and evaluation of prototype devices. This paper provides an overview of these R&D efforts, with examples of key findings and developments.

Two analytical tools for failure predictions in free-expansion tube hydroforming, namely “Process Window Diagram” (PWD) and forming limit curve (FLC), are discussed in this paper. The PWD represents the incipient failure conditions of buckling, wrinkling and bursting of free-expansion tube hydroforming processes in the plane of process parameters, e.g. internal pressure versus axial compression. The PWD is a useful tool for design engineers to quickly assess part producibility and process design for tube hydroforming. An attempt is also made to draw the differences between FLCs for sheet and tube so that the appropriate FLC could be used to estimate the bursting or fracture limits in free-expansion tube hydroforming processes.

Conventional diesel engines will continue to hold a vital role in the heavy- and medium-duty markets for the transportation of goods along with many other uses. The ability to offset traditional diesel fuels with low-net-carbon biofuels could have a significant impact on reducing the carbon footprint of these vehicles. A prior study screened several hundred candidate biofuel blendstocks based on required diesel blendstock properties and identified 12 as the most promising. Eight representative biofuel blendstocks were blended at a 30% volumetric concentration with EPA certification ultra-low-sulfur diesel (ULSD) and were investigated for emissions and fuel efficiency performance. This study used a single cylinder engine (based on the Ford 6.7L engine) using Conventional Diesel Combustion (CDC), also known as Mixing Control Compression Ignition (MCCI). The density, cetane number, distillation curve and sooting tendency (using the yield sooting index method) of the fuels were measured.

Synergies between various catalytic converters such as SCR and DPF are vital to the success of an integrated aftertreatment system for simultaneous NO and particulate matter control in diesel engines. Several issues such as hydrocarbon poisoning, thermal aging and other coupled aftertreatment dynamics need to be addressed to develop an effective emission control system. This work is significant especially in an integrated DPF-SCR aftertreatment scenario where the SCR catalyst on the filter substrate is exposed to un-burnt diesel hydrocarbons during active regeneration of the particulate filter. This paper reports an experimental and modeling study to understand the effect of hydrocarbons on a Fe-zeolite urea-SCR catalyst. Several bench-reactor tests to understand the inhibition of NO oxidation, to characterize hydrocarbon storage and to investigate the impact of hydrocarbons on SCR reactions were conducted.

Aftertreatment modeling capabilities are an important part of the diesel engine manufacturer's efforts to meet the quickly approaching EPA 2007 heavy-duty emissions regulations. A critical, yet poorly understood, component of particulate filter modeling is the representation of the soot oxidation rate. This term directly influences most of the macroscopic phenomenon of interest, including filtration efficiency, heat transfer, back pressure, and filter regeneration. Intrinsic soot cake properties such as packing density, permeability and heat transfer coefficients remain inadequately characterized (1). The work reported in this paper involves subgrid modeling techniques which may prove useful in resolving these inadequacies. The technique involves the use of a lattice Boltzmann modeling approach. This approach resolves length scales which are orders of magnitude below those typical of a standard computational fluid dynamics (CFD) representation of an aftertreatment device.

We present data in this paper showing that non-thermal plasma in combination with heterogeneous catalysis is a promising technique for the treatment of NOx in diesel exhaust. Using a commonly available zeolite catalyst, sodium Y, to treat synthetic diesel exhaust we report approximately 50% chemical reduction of NOx over a broad, representative temperature range. We have measured the overall efficiency as a function of the temperature and hydrocarbon concentration. The direct detection of N2 and N2O when the background gas is replaced by helium confirms that true chemical reduction is occurring.

The NOx reduction performance under lean conditions over γ-alumina was evaluated using a micro-reactor system and a non-thermal plasma-equipped bench test system. Various alumina samples were obtained from alumina manufacturers to assess commercial alumina materials. In addition, γ-alumina samples were synthesized at Caterpillar with a sol-gel technique in order to control alumina properties. The deNOx performances of the alumina samples were compared. The alumina samples were characterized with analytical techniques such as inductively coupled plasma (ICP) emission spectroscopy, temperature programmed desorption (TPD) and surface area measurements (BET) to understand physical and chemical properties. The information derived from these techniques was correlated with the NOx reduction performance to identify key parameters of γ-alumina for optimizing materials for lean-NOx and plasma assisted catalysis.