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Extensive vehicle fleet testing has demonstrated that use of MMT can reduce net tailpipe out emissions. The use of fuel containing the octane-enhancing, emission-reducing fuel additive leads to manganese oxide deposits in the vehicle exhaust system. Studies of the physical and chemical effects of manganese oxide deposits on the performance of catalytic converters conclusively demonstrated that MMT does not adversely affect catalytic converters and, in fact, protected the converters from phosphorus and zinc. Despite the overwhelming evidence that MMT is compatible with catalytic converters and vehicle emission control systems, concerns have recently been raised about the effect of manganese oxides on OBD-II catalytic converter monitoring.

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.

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.

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.

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.

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.

This paper describes a method for accurately measuring sulfur oxides in automotive exhaust. In this method, the exhaust from a car is diluted with ambient air, then introduced into a large bag filled with clean dry air. The temperature, pressure, and humidity of the diluted exhaust are measured, along with the concentrations of hydrocarbons, carbon monoxide, carbon dioxide, SO2, and sulfates. Bag concentrations are related to the exhaust by using the sulfur/carbon ratio of the fuel. Established instrumental methods are used for the carbon compounds. The sulfur dioxide in the diluted exhaust gas is measured by the West-Gaeke method, which involves collecting a gaseous sample in a scrubber containing potassium tetrachloromecurate. The sulfates are collected on a particulate filter and measured by a new colorimetric method. The techniques we have developed have been applied to both non-catalyst and catalyst-equipped cars. These studies have shown that: 1.

The Clean Air Act of 1990 requires on-board diagnostics (OED) capabilities on all new vehicles. These diagnostic systems monitor the performance of engine and emission system components and inform the vehicle operator when component or system degradation could significantly impact emissions. Acceptable operation of the monitor requires proper treatment of system variables. Fuel composition is one of many possible variables that must be considered for monitoring components directly in the exhaust stream. Recently, the octane enhancing, emissions reducing additive methylcyclopentadienyl manganese tricarbonyl (MMT) was reintroduced into unleaded gasoline in the U.S. Prior to reintroduction, the additive underwent extensive testing to demonstrate that use of MMT does not adversely affect vehicle emissions or the operation of emission systems such as OBD. However, questions have been raised about the influence of the additive on OBD systems.

Emissions regulations for 2007 will likely require engine manufacturers to use a diesel particulate filter (DPF) to meet particulate matter (PM) emission requirements. With the lower operating temperatures of light-duty diesel engines, some form of catalyst will be required to facilitate oxidation of accumulated soot PM to regenerate the DPF. This catalyst can either be permanently applied to the filter substrate in the manufacturing process, or be continuously delivered via the diesel fuel. In this study we examined the impact of using both forms of catalyst. A recently published study of the fuel-borne catalyst additive MMT [1] (Methylcyclopentadienyl Manganese Tricarbonyl), reviewed the performance of MMT in conjunction with an uncatalyzed DPF [2].

In designing fuel economy oils, two useful approaches are reduction of viscosity and incorporation of friction reducers. To achieve viscosity reduction without incurring problems of high oil consumption and possible interference with catalyst or oxygen sensor performance, the use of part-synthetic lubricants can be helpful. In this way, oil volatility (therefore oil consumption) is reduced and fuel economy is improved without incurring engine operating penalties. Friction reducers also can be used to improve fuel economy. The combination of these approaches furnishes the benefits of both. Laboratory and road testing of such combinations show important fuel economy benefits in normal vehicle operation, greater than those achievable from either approach alone. In addition, all other engine performance requirements are completely met. This advance in engine oil formulation technology, which opens up new possibilities to both vehicle manufacturers and consumers, is being further pursued.

MMT (methylcyclopentadienyl manganese tricarbonyl) is an antiknock additive for unleaded gasoline, which is now required for cars equipped with catalytic converters. Because of its effectiveness, MMT is economically attractive compared with achieving antiknock quality by refinery processing. Use of MMT in gasoline at a concentration of 0.125 g of contained manganese per gallon provides, on the average, about 2 road octane numbers. Compared to processing, this could represent a savings in crude oil of about 1%. Like other antiknocks, the economic attractiveness of MMT is greatest at low concentrations. Extensive road and dynamometer engine tests have shown that use of MMT in the recommended concentration range is compatible with general aspects of car operation--octane number requirement, exhaust valve and spark plug durability, and exhaust gas recycle for NOx control. Moreover, beneficial effects in exhaust valve guide and seat wear have been observed with MMT in some tests.

The long-term durability of a vehicle's exhaust catalyst is essential for emission control. Catalyst durability can be affected by a variety of factors including engine oil consumption. During normal engine operation, some of the lubricating oil is combusted. The deposition of combustion products from phosphorus containing lubricant additives on the catalyst can adversely affect catalyst durability. In an attempt to minimize the impact of oil consumption on additive performance, engines have been designed to reduce oil consumption and oils are being formulated with lower concentrations of phosphorus compounds. However, these phosphorus compounds protect the engine from excessive wear and cannot be easily removed from lubricant oil due to concerns over engine durability. The use of a phosphorus scavenger is an approach that works together with engine design to minimize catalyst deterioration.