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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.

Premixed low temperature combustion (LTC) in diesel engines simultaneously reduces soot and NOx at the expense of increased hydrocarbon (HC) and CO emissions. The use of biodiesel in the LTC regime has been shown to produce lower HC emissions than petroleum diesel; however, unburned methyl esters from biodiesel are more susceptible to particulate matter (PM) formation following atmospheric dilution due to their low volatility. In this study, the efficacy of a production-type diesel oxidation catalyst (DOC) for the conversion of light hydrocarbons species and heavier, semi-volatile species like those in unburned fuel is examined. Experimental data were taken from a high speed direct-injection diesel engine operating in a mid-load, late injection partially premixed LTC mode on ultra-low sulfur diesel (ULSD) and neat soy-based biodiesel (B100). Gaseous emissions were recorded using a conventional suite of analyzers and individual light HCs were measured using an FT-IR analyzer.

This paper analyzes and compares reactor and engine behavior of a diesel oxidation catalyst (DOC) in the presence of conventional diesel exhaust and low temperature premixed compression ignition (PCI) diesel exhaust. Surrogate exhaust mixtures of n-undecane (C11H24), ethene (C2H4), CO, O2, H2O, NO and N2 are defined for conventional and PCI combustion and used in the gas flow reactor tests. Both engine and reactor tests use a DOC containing platinum, palladium and a hydrocarbon storage component (zeolite). On both the engine and reactor, the composition of PCI exhaust increases light-off temperature relative to conventional combustion. However, while nominal conditions are similar, the catalyst behaves differently on the two experimental setups. The engine DOC shows higher initial apparent HC conversion efficiencies because the engine exhaust contains a higher fraction of trappable (i.e., high boiling point) HC.

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.

A dielectric barrier discharge device has been built to test nonthermal plasma discharges for simulated diesel exhaust NOx removal. The device has also been tested with selected catalysts located after the plasma. Emissions are measured by conventional automotive emission analyzers, plus FTIR. Dielectric barrier discharges without catalyst convert input NO to a mix of NO2, HONO, HNO3, and organic nitrates. At 30 J/l energy deposition, approximately 26% of the input NO is “lost”. Some of the hydrocarbon input is converted to a variety of species, including CO, CO2, aldehydes, and alcohols. A Cu-ZSM catalyst after the plasma device eliminates the apparent NOx conversion seen with the bare plasma. This indicates that the apparent NOx conversion of the bare plasma is actually conversion to some (unmeasured) species which can be reconverted to NOx by the Cu-ZSM catalyst. Placing a proprietary catalyst within the plasma results in significant NOx conversion.

Nonthermal plasma discharges in combination with catalysts are being developed for diesel aftertreatment. NOx conversion has been shown over several different catalyst materials. Particulate removal has also been demonstrated. The gas phase chemistry of the plasma discharge is described. The plasma is oxidative. NO is converted to NO2, CH3ONO2 and HNO3. Hydrocarbons are partially oxidized resulting in aldehydes and CO along with various organic species. Soot will oxidize if it is held in the plasma. When HC is present, SO2 is not converted to sulfates. Suitable plasma-catalysts can achieve NOx conversion over 70%, with a wider effective temperature range than non-plasma catalysts. NOx conversion requires HC and O2. Electrical power consumption and required exhaust HC levels increase fuel consumption by several percent. A plasma catalyst system has demonstrated over 90% particulate removal in vehicle exhaust.

A diesel fuel and air diffusion flame burner system has been designed for laboratory simulation of diesel exhaust gas. The system consists of mass flow controllers and a fuel pump, and employs several unique design and construction features. It produces particulate emissions with size, number distribution, and morphology similar to diesel exhaust. At the same time, it generates NOx emissions and HC similar to diesel. The system has been applied to test plasma discharges. Different design discharge devices have been tested, with results indicating the importance of testing devices with soot and moisture. Both packed bed reactor and flat plate dielectric barrier discharge systems remove some soot from the gas, but the designs tested are susceptible to soot fouling and related electrical failures. The burner is simple and stable, and is suitable for development and aging of plasma and catalysts systems in the laboratory environment.

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.

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.

An early-design methodology for predicting both expected fuel economy and catalyst-out CO, HC and NOx concentrations during arbitrarily-defined transient cycles is presented. The methodology is based on utilizing a vehicle-powertrain model with embedded maps of fully warmed up engine-out performance and emissions, and appropriate temperature-dependent correction factors to account for not fully warmed up conditions during transients. Similarly, engine-out emissions are converted to catalyst-out emissions using conversion efficiencies based on the catalyst brick temperature. A crucial element of the methodology is hence the ability to predict heat flows and component temperatures in the engine and the exhaust system during transients, consistent with the data available during concept definition and early design phases.

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.

There is a need for an efficient, durable technology to reduce NOx emissions from oxidative exhaust streams such as those produced by compression-ignition, direct-injection (CIDI) diesel or lean-burn gasoline engines. A partnership formed between the DOE Office of Advanced Automotive Technology, Pacific Northwest National Laboratory, Oak Ridge National Laboratory and the USCAR Low Emission Technologies Research and Development Partnership is evaluating the effectiveness of a non-thermal plasma in conjunction with catalytic materials to mediate NOx and particulate emissions from diesel fueled light duty (CIDI) engines. Preliminary studies showed that plasma-catalyst systems could reduce up to 70% of NOx emissions at an equivalent cost of 3.5% of the input fuel in simulated diesel exhaust. These studies also showed that the type and concentration of hydrocarbon play a key role in both the plasma gas phase chemistry and the catalyst surface chemistry.

Previously reported experiments revealed the presence of a small number of clusters or very small particles in the effluent of a nonthermal plasma reactor when treating a simulated engine exhaust mixture. These clusters are smaller than 7 nm. The quantity of clusters is orders of magnitude smaller than the particulate diesel or gasoline engine exhaust typically contains. In this report, we describe further experiments designed to determine the chemical composition of the clusters. Clusters were collected on the surface of a silicon substrate by exposing it to the effluent flow for extended time periods. The resulting deposits were analyzed by high mass resolution SIMS and by XPS. The SIMS analysis reveals NH4+, CH6N+, SO-, SO2-, SO3- and HSO4- ions. XPS reveals the presence of N and S at binding energies consistent with that of ammonium sulfate.

NOx reduction efficiency under simulated lean burn conditions is examined for a non-thermal plasma in combination with borosilicate glass, alumina, titania, Cu-ZSM-5 and Na-ZSM-5. The non-thermal plasma alone or with a packed bed of borosilicate glass beads converts NO to NO2 and partially oxidizes hydrocarbons. Alumina and Na-ZSM-5 reduce a maximum of 40% and 50% of NOx respectively; however, the energy cost is high for Na- ZSM-5. Cu-ZSM-5 converts less than 20% with a very high energy consumption. The anatase form of titania reduces up to 35% of NOx at a relatively high energy consumption (150J/L) when the catalyst is contained in the plasma region, but does not show any appreciable conversion when placed downstream from the reactor. This phenomenon is explained by photo-activation of anatase in the plasma.

Previous work done at the University of Michigan shows the capability of the vacuum-insulated catalytic converter (VICC) to retain heat during soak and the resulting benefits in reducing cold start emissions. This paper provides an improved version of the design which overcomes some of the shortcomings of the previous model and further improves the applicability and benefits of VICC. Also, newer materials have been evaluated and their effects on heat retention and emissions have studied using the 1-D after treatment model. Cold start emissions constitute around 60% to 80% of all the hydrocarbon and CO emissions in present day vehicles. The time taken to achieve the catalyst light-off temperature in a three-way catalytic converter significantly affects the emissions and fuel efficiency. The current work aims at developing a method to retain heat in catalytic converter, thus avoiding the need for light-off and reducing cold start emissions effectively.

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.