Emissions, automotive exhaust

Vehicle Emissions. Gasohol has some automotive exhaust emissions benefits because adding oxygen to a fuel leans out the fuel mixture, producing less carbon monoxide [630-08-2] (CO). This is tme both for carbureted vehicles and for those having electronic fuel injection. 

In the outdoor environment, the high concentrations of sulfur and nitrogen oxides from automotive and industrial emissions result in a corrosion having both soluble and insoluble corrosion products and no pacification. The results are clearly visible on outdoor bronze sculpture (see Airpollution Exhaust CONTROL, automotive Exhaust conthol, industrial). 

Automotive Emission Control Catalysts. Air pollution (qv) problems caused by automotive exhaust emissions have been met in part by automotive emission control catalysts (autocatalysts) containing PGMs. In the United States, all new cars have been requited to have autocatalyst systems since 1975. In 1995, systems were available for control of emissions from both petrol and diesel vehicles (see Exhaust control, automotive). 

Serious research in catalytic reduction of automotive exhaust was begun in 1949 by Eugene Houdry, who developed mufflers for fork lift trucks used in confined spaces such as mines and warehouses (18). One of the supports used was the monolith—porcelain rods covered with films of alumina, on which platinum was deposited. California enacted laws in 1959 and 1960 on air quality and motor vehicle emission standards, which would be operative when at least two devices were developed that could meet the requirements. This gave the impetus for a greater effort in automotive catalysis research (19). Catalyst developments and fleet tests involved the partnership of catalyst manufacturers and muffler manufacturers. Three of these teams were certified by the California Motor Vehicle Pollution Control Board in 1964-65 American Cyanamid and Walker, W. R. Grace and Norris-Thermador, and Universal Oil Products and Arvin. At the same time, Detroit announced that engine modifications by lean carburation and secondary air injection enabled them to meet the California standard without the use of catalysts. This then delayed the use of catalysts in automobiles. 

Evaluation of Catalysts As Automotive Exhaust Treatment Devices," Report of the Catalyst Panel to the Committee on Motor Vehicle Emissions, National Academy of Sciences, Washington, D.C., 1973. 

Challenges in Control of Emission from Automotive Exhaust... 

Table 10.2. Emission standards (g km" ) for automotive exhaust from gasoline-fueled cars.

One of the most straightforward methods to reduce carbon dioxide emissions is to enhance the fuel efficiency of engines. The three-way catalyst, although very successful at cleaning up automotive exhaust, dictates that engines operate at air-to-fuel ratios of around 14.7 1. Unfortunately, this is not the optimum ratio with respect to fuel efficiency, which is substantially higher under lean-burn conditions at A/F ratios of about 20 1, where the exhaust becomes rich in oxygen and NOx reduction is extremely difficult (Fig. 10.1). 

Hammer, T. (2002) Non-thermal plasma application to the abatement of noxious emissions in automotive exhaust gases, Plasma Sources Sci. Technol. 11, A196-A201. 

Ciambelli, P Corbo, P Migliardini, F. Potentialities and limitations of lean de-NOx catalysts in reducing automotive exhaust emissions, Catal. Today, 2000, Volume 59, Issues 3-4. 279-286... 

More recently Cass, Boone and Macias constructed a very detailed carbon inventory for Metropolitan Los Angeles in order to estimate the amount of primary elemental and organic carbon in this urban area ( ). Over 50 source types were included in this emission Inventory. A particulate lead emission inventory was also constructed and used as a tracer for primary automotive exhaust. They compared the ratio of organic carbon to elemental carbon and lead from the emission estimates to that measured in the atmosphere during winter mornings. In that study the sampling time and location were chosen in order to measure... 

Pt-Rh/AROs catalysts are widely used in automotive-exhaust emission control. In these systems, Pt is generally used for the oxidation of CO and hydrocarbons and Rh is active for the reduction of nitric oxide to N2. HRTEM and AEM show two discrete particle morphologies and Pt-Rh alloy particles (Lakis et al 1995). EM studies aimed at understanding the factors leading to deactivation, surface segregation of one metal over the other and SMSI are limited. There are great opportunities for EM studies, in particular, of surface enrichment, and defects and dislocations in the complex alloy catalysts as sites for SMSI. 

Emission studies show that lead is only a small part of the automotive pollution problem. Prior to control, hydrocarbon emissions were more than 40 times and the oxides of nitrogen emissions more than 15 times the emission of the lead compounds. Obviously, however, legislation will result in the eventual elimination of lead from gasoline. The removal of lead, besides eliminating a possible toxic pollutant, simplifies the problem of handling other automotive exhaust pollutants in that catalytic exhaust chambers perform much better in the absence of lead contaminant. All emission standards become particularly severe in 1975 and 1980. The particulate standards are equivalent to 1 gram Pb/gal in 1975 and 0.3 gram Pb/gal in 1980. Since the particulates include all solid materials, tolerable lead levels will be less than indicated above. 

Another important application of heterogeneous catalysts is in automobile catalytic converters. Despite much work on engine design and fuel composition, automotive exhaust emissions contain air pollutants such as unburned hydrocarbons (CxHy), carbon monoxide, and nitric oxide. Carbon monoxide results from incomplete combustion of hydrocarbon fuels, and nitric oxide is produced when atmospheric nitrogen and oxygen combine at the high temperatures present in an... 

Another debatable approach to pollution control involves the methods currently used to reduce hydrocarbons and CO in automotive exhausts. The need to control CO is based on its direct health effects while the need to control the hydrocarbons is based on their interactions with the N02 photolytic cycle which leads to elevated concentrations of N02, 03, peroxyacyl nitrates, and aerosols. The solution adopted was to increase the efficiency of the combustion process, thereby reducing hydrocarbon and CO emissions. Unfortunately, the method adopted also leads to dramatic increases in NO emissions. When this increase in NO was objected to, the answer came back that increased NO in the atmosphere is beneficial since it rapidly reacts with and destroys ozone, one of the very health-related substances requiring control. This is another example of failure to view the total air pollution system. Of course NO destroys 03, but one product of this reaction is N02 which is also detrimental to health. Furthermore, this N02 is the beginning point of sunlight absorption which leads to all the products of photochemical interactions. In a certain location excess NO will tend to reduce 03 levels. However, downstream of these locations excess N02 will promote more photochemical reactions and perhaps even higher ozone levels. In part this nonsolution to automotive pollution may be a major cause of the substantial increases in ozone in many areas during the past few years. This automotive example clearly illustrates the need for in-depth analysis when plans are made to change any part of the system of air pollution. Decisions based on such an analysis are all the more important because the tradeoffs involve human health and welfare. 

Complete oxidation of hydrocarbons in air is a useful method for atmospheric purification, and has been sucessfully applied in automotive exhaust control. An important new area is the catalytic control of the emissions of volatile organic compounds (VOC) in a more general sense [1]. Many sources, low concentrations and wide temperature ranges can be involved. 

Automotive Exhaust Gases in Los Angeles, Vehicle Emissions I. SAE Progress in Technology Series (1964) 6, 7-16. 

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