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Aftertreatment system design involves multiple tradeoffs between engine performance, fuel economy, regulatory emission levels, packaging, and cost. Selection of the best design solution (or “architecture”) is often based on an assumption that inherent catalyst activity is unaffected by location within the system. However, this study acknowledges that catalyst activity can be significantly impacted by location in the system as a result of varying thermal exposure, and this in turn can impact the selection of an optimum system architecture. Vehicle experiments with catalysts aged over a range of mild to moderate to severe thermal conditions that accurately reflect select locations on a vehicle were conducted on a chassis dynamometer. The vehicle test data indicated CO and NOx could be minimized with a catalyst placed in an intermediate location.

Internal combustion (IC) engines fueled by hydrogen are among the most efficient means of converting chemical energy to mechanical work. The exhaust has near-zero carbon-based emissions, and the engines can be operated in a manner in which pollutants are minimal. In addition, in automotive applications, hydrogen engines have the potential for efficiencies higher than fuel cells.[1] In addition, hydrogen engines are likely to have a small increase in engine costs compared to conventionally fueled engines. However, there are challenges to using hydrogen in IC engines. In particular, efficient combustion of hydrogen in engines produces nitrogen oxides (NOx) that generally cannot be treated with conventional three-way catalysts. This work presents the results of experiments which consider changes in direct injection hydrogen engine design to improve engine performance, consisting primarily of engine efficiency and NOx emissions.

A Three-Way Catalyst (TWC) model with global TWC kinetics for lean burn DISI engines were developed and validated. The model incorporates kinetics of hydrocarbons and carbon monoxide oxidations, NOx reduction, water-gas and steam reforming and oxygen storage. Ammonia (NH₃) and new nitrous oxide (N₂O) kinetics were added into the model to study NH₃ and N₂O formation in TWC systems. The model was validated over a wide range of engine operating conditions using various types of experimental data from a lean burn automotive SIDI engine. First, well-controlled time-resolved steady state data were used for calibration and initial model tests. In these steady state operations, the engine was switched between lean and rich conditions for NOx emission control. Then, the model was further validated using a large set of time-averaged steady state data. Temperature dependencies of NH₃ and N₂O kinetics in the TWC model were examined and well captured by the model.

Diesel NOx emissions control utilizing combined Lean NOx Trap (LNT) and so-called passive or in-situ Selective Catalytic Reduction (SCR) catalyst technologies (i.e. with reductant species generated by the LNT) has been the subject of several previous papers from our laboratory [ 1 - 2 ]. The present study focuses on hydrocarbon (HC) emissions control via the same LNT+SCR catalyst technology under FTP driving conditions. HC emissions control can be as challenging as NOx control under both current and future federal and California/Green State emission standards. However, as with NOx control, the combined LNT+SCR approach offers advantages for HC emission control over LNT-only aftertreatment. The incremental conversion obtained with the SCR catalyst is shown, both on the basis of vehicle and laboratory tests, to result primarily from HC adsorbed on the SCR catalyst during rich LNT purges that reacts during subsequent lean engine operation.

A laboratory study was performed to assess the effects of sulfur poisoning and desulfation temperature on the NO conversion of a LNT+(Cu/SCR) in-situ system. Four LNT+(Cu/SCR) systems were aged for 4.5 hours without sulfur at 600, 700, 750, and 800°C using A/F ratio modulations to represent 23K miles of desulfations at different temperatures. NO conversion tests were performed on the LNT alone and on the LNT+SCR system using a 60 s lean/5 s rich cycle. The catalysts were then sulfur-poisoned at 400°C and desulfated four times and re-evaluated on the 60/5 tests. This test sequence was repeated 3 more times to represent 100K miles of desulfations. After simulating 23K miles of desulfations, the Cu-based SCR catalysts improved the NO conversion of the LNT at low temperatures (e.g., 300°C), although the benefit decreased as the desulfation temperature increased from 600°C to 800°C.

Effects of fuel cell material properties on water management were numerically investigated using Volume of Fluid (VOF) method in the FLUENT. The results show that the channel surface wettability is an important design variable for both serpentine and interdigitated flow channel configurations. In a serpentine air flow channel, hydrophilic surfaces could benefit the reactant transport to reaction sites by facilitating water transport along channel edges or on channel surfaces; however, the hydrophilic surfaces would also introduce significantly pressure drop as a penalty. For interdigitated air flow channel design, it is observable that liquid water exists only in the outlet channel; it is also observable that water distribution inside GDL is uneven due to the pressure distribution caused by interdigitated structure. An in-situ water measurement method, neutron imaging technique, was used to investigate the water behavior in a PEM fuel cell.

Gasoline turbocharged direct injection (GTDI) engines, such as EcoBoost™ from Ford, are becoming established as a high value technology solution to improve passenger car and light truck fuel economy. Due to their high specific performance and excellent low-speed torque, improved fuel economy can be realized due to downsizing and downspeeding without sacrificing performance and driveability while meeting the most stringent future emissions standards with an inexpensive three-way catalyst. A logical and synergistic extension of the EcoBoost™ strategy is the use of E85 (approximately 85% ethanol and 15% gasoline) for knock mitigation. Direct injection of E85 is very effective in suppressing knock due to ethanol's high heat of vaporization - which increases the charge cooling benefit of direct injection - and inherently high octane rating. As a result, higher boost levels can be achieved while maintaining optimal combustion phasing giving high thermal efficiency.

This study extends research previously reported from our laboratory [SAE 2009-01-0285] on diesel NOx control utilizing a new generation of Lean NOx Trap (LNT) plus in-situ Selective Catalytic Reduction (SCR) catalyst systems. Key findings from this work include 1) evidence for a “non-ammonia” reduction pathway over the SCR catalyst (in addition to the conventional ammonia pathway), 2) high NOx conversions utilizing LNT formulations with substantially lower platinum group metal (PGM) loadings than utilized in earlier systems, 3) ability of the downstream SCR catalyst to maintain high overall system NOx efficiency with aged LNTs, and 4) effectiveness of both Cu- and Fe-zeolite SCR formulations to enhance overall system NOx efficiency. FTP NOx conversion efficiencies in excess of 95% were obtained on two light-duty vehicle platforms with lab-aged catalyst systems, thus showing potential of the LNT+SCR approach for achieving the lowest U.S. emissions standards

Robust on-board diagnosis of emission catalyst performance requires the development of artificially damaged "threshold" catalysts that accurately mimic the performance of damaged catalysts in customer use. The threshold catalysts are used by emissions calibrators to determine fore-aft exhaust oxygen sensor responses that indicate catalyst failure. Rather than rely on traditional trial-and-error processes to generate threshold catalysts, we have used a DFSS (Design For Six-Sigma) approach that explores, at a research level, the relationship between oxygen storage capacity (OSC) of the catalyst (i.e., the fundamental property dictating the response of the aft oxygen sensor) and key process input variables: high-temperature exposure, phosphorus poisoning, and catalyst "recovery."

Ignoring the impact of water condensation leads to incorrect temperature simulation during cold start, and this can lead to questions being raised about the overall accuracy of aftertreatment simulation tools for both temperature and emission predictions. This report provides a mathematical model to simulate the condensation and evaporation of water in exhaust after-treatment devices. The simulation results are compared with experimental data. Simulation results show that the temperature profiles obtained using the condensation model are more accurate than the profiles obtained without using the condensation model. The model will be very useful in addressing questions that concern the accuracy of the simulation tool during cold-start and heating up of catalysts, which accounts for the conditions where tailpipe emission issues are most significant.

A lean-rich hydrothermal aging was used to study the deactivation of Cu-zeolite SCR catalyst that has enhanced stability. Impact of DOC upstream on the SCR catalyst during the lean-rich aging was also investigated. The LR hydrothermal aging was conducted with the presence of hydrocarbon, CO and H₂ at different O₂ levels. It was found that the SCR catalyst was active for the oxidation of CO, H₂ and hydrocarbon, resulting in significant exotherm across the catalyst. In addition to hydrothermal aging, reductive aging, especially the presence of H₂ in the aging gas stream without O₂ presence during the L-R aging, might also contribute to the Cu/zeolite SCR catalyst deactivation. The impacts of DOC upstream on Cu/zeolite SCR catalysts depended on the aging temperatures. At lower aging temperature, the uncompleted oxidation of hydrocarbon and CO on the DOC might cause steam reforming and water-gas shift reactions on the DOC to form reductive gas stream.

The University of Wisconsin-Madison Snowmobile Team designed and constructed a hybrid-electric snowmobile for the 2005 Society of Automotive Engineers' Clean Snowmobile Challenge. Built on a 2003 cross-country touring chassis, this machine features a 784 cc fuel-injected four-stroke engine in parallel with a 48 V electric golf cart motor. The 12 kg electric motor increases powertrain torque up to 25% during acceleration and recharges the snowmobile's battery pack during steady-state operation. Air pollution from the gasoline engine is reduced to levels far below current best available technology in the snowmobile industry. The four-stroke engine's closed-loop EFI system maintains stoichiometric combustion while dual three-way catalysts reduce NOx, HC and CO emissions by up to 94% from stock. In addition to the use of three way catalysts, the fuel injection strategy has been modified to further reduce engine emissions from the levels measured in the CSC 2004 competition.

Phosphorus contamination from engine oil additives has been associated with reduced performance of vehicle-aged exhaust gas catalysts. Identifying phosphorus species on aged catalysts is important for understanding the reasons for catalytic performance degradation. However, phosphorus is present only in small quantities, which makes its detection with bulk analytical techniques difficult. Raman microscopy probes small regions (a few microns in diameter) of a sample, and can detect both crystalline and amorphous materials. It is thus ideal for characterizing phosphates that may have limited distribution in a catalyst. However, suitable Raman spectra for mixed-metal phosphates that might be expected to be present in contaminated catalysts are not generally available.

Presented in this paper is an on-line method for estimating the oxygen storage capacity contained within a catalyst. The oxygen storage capacity of a catalyst changes over time due to catalyst brick temperatures, poisoned catalyst sites, and thermal aging. Information regarding the current oxygen storage capacity of a catalyst is advantageous in the development of robust emission control strategies and on-board diagnostics. The method of collecting the oxygen storage capacity information is extremely important for measurement accuracy and repeatability. Furthermore, the information must be obtained in such a way that it is transparent to the operator and may be implemented on-line during normal drive cycles. This on-line method for estimation of oxygen storage capacity of a catalyst has been demonstrated on a Ford F150 platform with an underbody catalyst.

This research investigates a control system for HCCI engines, where equivalence ratio, fraction of EGR and intake pressure are adjusted as needed to obtain satisfactory combustion. HCCI engine operation is analyzed with a detailed chemical kinetics code, HCT (Hydrodynamics, Chemistry and Transport), that has been extensively modified for application to engines. HCT is linked to an optimizer that determines the operating conditions that result in maximum brake thermal efficiency, while meeting the peak cylinder pressure restriction. The results show the values of the operating conditions that yield optimum efficiency as a function of torque and rpm. The engine has high NOx emissions for high power operation, so the possibility of switching to stoichiometric operation for high torque conditions is considered. Stoichiometric operation would allow the use of a three-way catalyst to reduce NOx emissions to acceptable levels.

A simulated diesel exhaust is treated with a nonthermal plasma discharge under steady state conditions. The plasma effluent is then passed through a sodium zeolite-Y (NaY) catalyst followed by a platinum oxidation catalyst. Detailed FTIR measurements of gas composition are taken before, between, and after the treatment stages. The plasma discharge causes oxidation of NO primarily to NO2, with methyl nitrate and nitric acid byproducts. At the same time, HC is partially oxidized, creating species such as formaldehyde, acetaldehyde, CO and other partial oxidation products. When this mixture passes over the NaY catalyst, part of the NOx is reduced to N2, with the remainder primarily in the form of NO. Methyl nitrate decomposes to form methanol and NOx, and nitric acid is consumed. There is little HC conversion on this catalyst. Small quantities of HCN and N2O are formed. When the mixture then passes over the platinum catalyst, further NOx conversion occurs.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

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.

Meeting upcoming stringent emission standards will require that exhaust gas catalyst systems become active very quickly, function at very high efficiencies and maintain those capabilities at high mileages. This means that contamination of the catalysts by engine oil derived poisons must be minimized. Phosphorus compounds, derived from the zinc dialkyldithio-phosphate (ZDTP) additives that provide antiwear and antioxidant activity, are a principal contaminant that can increase catalyst light off times and reduce catalyst efficiency. Therefore, reducing the concentration of, or eliminating, phosphorus in engine oils is desirable. Doing so, however, requires that oils be reformulated to ensure that wear protection will not be compromised and that oxidation stability will be maintained. To address these concerns, laboratory tests for evaluating oil oxidation and wear performance have been developed and used to evaluate developmental low phosphorus oils.

The aggressive reduction of future diesel engine NOx emission limits forces the heavy- and light-duty diesel engine manufacturers to develop means to comply with stringent legislation. As a result, different exhaust emission control technologies applicable to NOx have been the subject of many investigations. One of these systems is the NOx adsorber catalyst, which has shown high NOx conversion rates during previous investigations with acceptable fuel consumption penalties. In addition, the NOx adsorber catalyst does not require a secondary on-board reductant. However, the NOx adsorber catalyst also represents the most sulfur sensitive emissions control device currently under investigation for advanced NOx control. To remove the sulfur introduced into the system through the diesel fuel and stored on the catalyst sites during operation, specific regeneration strategies and boundary conditions were investigated and developed.