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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.

Compact heat exchangers are commonly used in diesel engines to reduce the temperature of recirculated exhaust gases, resulting in decreased NOx emissions. These exhaust gas recirculation (EGR) coolers experience fouling through deposition of particulate matter (PM) and hydrocarbons (HCs) that reduces the effectiveness of the cooler. Surrogate tubes have been used to investigate the impacts of gas flow rate and coolant temperature on the deposition of PM and HCs. The results indicate that mass deposition is lowest at high flow rates and high coolant temperatures. An oxidation catalyst was investigated and proved to effectively reduce deposition of HCs, but did not reduce overall mass deposition to near-zero levels. Speciation of the deposit HCs showed that a range of HCs from C15 - C25 were deposited and retained in the surrogate tubes.

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.

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.

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.

In a typical automotive SCR system, the urea-water solution is injected into the exhaust gas stream and breaks up into small droplets through the atomization process due to the interaction with the exhaust gas flow. The water vapor is released by vaporization and leaves the urea component in the droplets. The urea component is converted to ammonia and iso-cyanic acid and other species through thermal decomposition and hydrolysis processes. A multi-dimensional CFD model is developed in the present study to simulate injection and mixing in the automotive SCR systems. The urea-water solution is modeled as a bi-component liquid mixture with evaporation laws for each component. A Lagrangian method with spray sub-models is used to track the liquid droplets and the atomization process. The thermal decomposition and hydrolysis processes of the urea and iso-cyanic acid are simulated by simplified two-step reaction mechanisms.

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.

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.

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.

Advanced engine combustion strategies, such as HCCI and SACI, allow engines to achieve high levels of thermal efficiency with low levels of engine-out NOx emissions. To maximize gains in fuel efficiency, HCCI combustion is often run at lean operating conditions. However, lean engine operation prevents the conventional TWC after-treatment system from reaching legislated tailpipe emissions due to oxygen saturation. One potential solution for handling this challenge without the addition of costly NOx traps or on-board systems for urea injection is the passive TWC-SCR concept. This concept includes the integration of an SCR catalyst downstream of a TWC and the use of periods of rich or stoichiometric operation to generate NH3 over the TWC to be stored on the SCR catalyst until it is needed for NOx reduction during subsequent lean operation.

Using exhaust gas recirculation (EGR) as a diluent instead of air allows the use of a conventional three-way catalyst for effective emissions reduction. Cooled EGR can also reduce fuel consumption and NOx emissions, but too much cool EGR leads to combustion instability and misfire. Negative valve overlap (NVO) is explored in the current work as an alternative method of dilution in which early exhaust valve closing causes combustion products to be retained in the cylinder and recompressed near top dead center, before being mixed with fresh charge during the intake stroke. The potential for fuel injection during NVO to extend the dilution limit of spark ignition combustion is evaluated in this work using experiments conducted on a 4-cylinder 2.0 L gasoline direct injection engine with variable intake and exhaust valve timing. The results demonstrate fuel injection during NVO can extend the dilution limit, improve brake specific fuel consumption (BSFC), and reduce CO and NOx emissions.

Selective Catalytic Reduction (SCR) catalysts used in Lean NOx Trap (LNT) - SCR exhaust aftertreatment systems typically encounter alternating oxidizing and reducing environments. Reducing conditions occur when diesel fuel is injected upstream of a reformer catalyst, generating high concentrations of hydrogen (H₂), carbon monoxide (CO), and hydrocarbons to deNOx the LNT. In this study, the functionality of an iron (Fe) zeolite SCR catalyst is explored with a bench top reactor during steady-state and cyclic transient SCR operation. Experiments to characterize the effect of an LNT deNOx event on SCR operation show that adding H₂ or CO only slightly changes SCR behavior with the primary contribution being an enhancement of nitrogen dioxide (NO₂) decomposition into nitric oxide (NO). Exposure of the catalyst to C₃H₆ (a surrogate for an actual exhaust HC mixture) leads to a significant decrease in NOx reduction capabilities of the catalyst.

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.

Degreening is crucial in obtaining a stable catalyst prior to assessing its performance characteristics. This paper characterizes the light-off behavior and conversion efficiency of a Diesel Oxidation Catalyst (DOC) during the degreening process. A platinum DOC is degreened for 16 hours in the presence of actual diesel engine exhaust at 650°C and 10% water (H2O) concentration. The DOC's activity for carbon monoxide (CO) and for total hydrocarbons (THC) conversion is checked at 0, 1, 2, 3, 4, 6, 8, 10, 12, and 16 hours of degreening. Pre-and post-catalyst hydrocarbon species are analyzed via gas chromatography at 0, 4, 8, and 16 hours of degreening. It is found that both light-off temperature and species-resolved conversion efficiencies change rapidly during the first 8 hours of degreening and then stabilize to a large degree. T50, the temperature where the catalyst is 50% active towards a particular species, increases by 14°C for CO and by 11°C for THC through the degreening process.

Premixed compression ignition low-temperature diesel combustion (PCI) can simultaneously reduce particulate matter (PM) and oxides of nitrogen (NOx). Carbon monoxide (CO) and total hydrocarbon (THC) emissions increase relative to conventional diesel combustion, however, which may necessitate the use of a diesel oxidation catalyst (DOC). For a better understanding of conventional and PCI combustion, and the operation of a platinum-based production DOC, engine-out and DOC-out exhaust hydrocarbons are speciated using gas chromatography. As combustion mode is changed from lean conventional to lean PCI to rich PCI, engine-out CO and THC emissions increase significantly. The relative contributions of individual species also change; increasing methane/THC, acetylene/THC and CO/THC ratios indicate a richer combustion zone and a reduction in engine-out hydrocarbon incremental reactivity.

Real-world tailpipe emissions from properly-functioning, model year 1991-94 conventional gasoline-fueled cars associated with vehicle operations not emphasized in the FTP are analyzed. Tailpipe emissions are expressed as the product of three factors: fuel rate, engine-out emissions index, and catalyst pass fraction, which are modeled using empirical data from the FTP-Revision Project and applied to in-use driving survey data to estimate real-world emissions. Average tailpipe emissions due to fuel enrichment in warmed-up vehicles are estimated to be 8 g/mile for CO, and 0.3 g/mile for HC. For NOx, the contribution due to incremental loads on the engine (i.e. air conditioner, grade, high acceleration, and high speed) that are not accounted for in the FTP but are encountered in real-world driving are estimated to be roughly 0.3 g/mile.

Simulation models for second-by-second fuel rate, and engine-out and tailpipe emissions of CO, HC, and NOx from a “composite” car in hot engine and catalyst conditions are presented and tested using Federal Test Procedure Revision Project (FTPRP) data from 15 1991-1994 cars. The models are constructed as a combination of simple science and curve fitting to the FTPRP data. The models are preliminary, the simplest models being presented to illustrate how much can be predicted with very few parameters. Fuel rate and engine out emissions of all three pollutants are accurately predicted. The tailpipe emissions models are only moderately successful, largely because we are only moderately successful in predicting catalyst pass fractions during low power driving. Nevertheless, the composite car shows regular emissions behavior, and these are modeled effectively.

Despite remarkable progress made over the past 30 years, automobiles continue to be a major source of hydrocarbon emissions. The objective of this study is to evaluate whether variable exhaust valve opening (EVO) and exhaust valve closing (EVC) can be used to reduce hydrocarbon emissions. An automotive gasoline engine was tested with different EVO and EVC timings under steady-state and start-up conditions. The first strategy that was evaluated uses early EVO with standard EVC. Although exhaust gas temperature is increased and catalyst light-off time is reduced, the rapid drop in cylinder temperature increases cylinder-out hydrocarbons to such a degree that a net increase in hydrocarbon emissions results. The second strategy that was evaluated uses early EVO with early EVC. Early EVO reduces catalyst light-off time by increasing exhaust gas temperature and early EVC keeps the hydrocarbon-rich exhaust gas from the piston crevice from leaving the cylinder.

NOx reduction efficiency in simulated lean exhaust conditions has been examined for three proprietary catalyst materials using a non-thermal plasma discharge as a pretreatment stage to the catalyst. Using propene as the reducing agent for selective catalytic reduction, 74% reduction of NOx has been observed in the presence of 20 ppm SO2. For sulfur-free simulated exhaust, 84% NOx reduction has been obtained. Results show that the impact of sulfur on the samples examined can vary widely from virtually no effect (< 5%) to more than 20% loss in activity depending on the catalyst. Any loss due to sulfur poisoning appears to be irreversible according to limited measurements on poisoned catalysts exposed to sulfur-free exhaust streams. Catalysts were tested over a temperature range of 473-773K, with the highest activity observed at 773K. Examination of this large temperature window has shown that the optimum C1:NOx ratio changes with temperature.