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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.

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.

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.

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.

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.

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.

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.

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.

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.

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.