Exhaust emission

The potential advantages of LPG concern essentially the environmental aspects. LPG s are simple mixtures of 3- and 4-carbon-atom hydrocarbons with few contaminants (very low sulfur content). LPG s contain no noxious additives such as lead and their exhaust emissions have little or no toxicity because aromatics are absent. This type of fuel also benefits often enough from a lower taxation. In spite of that, the use of LPG motor fuel remains static in France, if not on a slightly downward trend. There are several reasons for this situation little interest from automobile manufacturers, reluctance on the part of automobile customers, competition in the refining industry for other uses of and fractions, (alkylation, etherification, direct addition into the gasoline pool). However, in 1993 this subject seems to have received more interest (Hublin et al., 1993). 

The implementation of very effective devices on vehicles such as catalytic converters makes extremely low exhaust emissions possible as long as the temperatures are sufficient to initiate and carry out the catalytic reactions however, there are numerous operating conditions such as cold starting and... 

Benson, J.D. et al. (1991), Effects of gasoline sulfur level on mass exhaust emissions . SAE paper No. 91-2323, International fuels and lubricants meeting, Toronto, Ontario. 

Typical examples of gaseous samples include automobile exhaust, emissions from industrial smokestacks, atmospheric gases, and compressed gases. Also included with gaseous samples are solid aerosol particulates. 

Environmental Aspects. Airborne particulate matter (187) and aerosol (188) samples from around the world have been found to contain a variety of organic monocarboxyhc and dicarboxyhc acids, including adipic acid. Traces of the acid found ia southern California air were related both to automobile exhaust emission (189) and, iadirecfly, to cyclohexene as a secondary aerosol precursor (via ozonolysis) (190). Dibasic acids (eg, succinic acid) have been found even ia such unlikely sources as the Murchison meteorite (191). PubHc health standards for adipic acid contamination of reservoir waters were evaluated with respect to toxicity, odor, taste, transparency, foam, and other criteria (192). BiodegradabiUty of adipic acid solutions was also evaluated with respect to BOD/theoretical oxygen demand ratio, rate, lag time, and other factors (193). 

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. 

Additional research for both ethanol and methanol showed that the amount of ignition improver could be reduced by systems increa sing engine compression (63). Going from 17 1 to 21 1 reduced the amount of TEGDN requited for methanol from 5% by volume to 3%. Ignition-improved methanol exhibited very low exhaust emissions compared to diesels particulate emissions were eliminated except for small amounts associated with engine oil, NO was even lower with increased compression, and CO and hydrocarbons were also below diesel levels. 

The products manufactured are predominantiy paraffinic, free from sulfur, nitrogen, and other impurities, and have excellent combustion properties. The very high cetane number and smoke point indicate clean-burning hydrocarbon Hquids having reduced harmful exhaust emissions. SMDS has also been proposed to produce chemical intermediates, paraffinic solvents, and extra high viscosity index (XHVI) lubeoils (see Lubrication and lubricants) (44). 

In 1957, Ethyl Corp. announced anew antiknock compound, methylcyclopentadienyknanganese tricarbonyl [12108-13-3] (MMT). MMT is almost as effective as lead on a per gram of metal basis, but because manganese was more expensive than lead, MMT was not widely used until limits were placed on the lead content of gasoline. MMT was used in unleaded fuel between 1975 and 1978. After a large fleet test suggested that MMT could increase exhaust emissions because it interfered with catalysts and oxygen sensors, EPA banned its use in unleaded fuel in 1978. MMT is used in Canada in unleaded fuel. 

Table 7. Federal Light-Duty Exhaust Emission Standards...

Table 9. Effect of Fuel Composition Change on Exhaust Emissions ...

Table 12. Federal Heavy-Duty Truck Exhaust Emission Standards, g/(kWh) ...

Although the naturally occurring concentration of ozone at the earth s surface is low, the distribution has been altered by the emission of pollutants, primarily by automobiles but also from industrial sources which lead to the formation of ozone. The strategy for controlling ambient ozone concentrations arising from automobile exhaust emissions is based on the control of hydrocarbons, CO, and NO via catalytic converters. As a result, peak ozone levels in Los Angeles, for instance, have decreased from 0.58 ppm in 1970 to 0.33 ppm in 1990, despite a 66% increase in the number of vehicles. 

Particulate Matter Other Phan Systemic Poisons. SUica and asbestos dust produce fibrosis. SUicon carbide, carbon (other than exhaust emissions), and emery are iuert dusts. Many organic dusts, eg, poUen, wood, and resius, cause aUergic reactions. Acids, alkaUes, fluorides, and chromates are irritants. 

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). 

Exhaust emissions of CO, unbumed hydrocarbons, and nitrogen oxides reflect combustion conditions rather than fuel properties. The only fuel component that degrades exhaust is sulfur the SO2 concentrations ia emissions are directly proportional to the content of bound sulfur ia the fuel. Sulfur concentrations ia fuel are determined by cmde type and desulfurization processes. Specifications for aircraft fuels impose limits of 3000 —4000 ppm total sulfur but the average is half of these values. Sulfur content ia heavier fuels is determined by legal limits on stack emissions. 

The first commercial supersonic transport, the Concorde, operates on Jet A1 kerosene but produces unacceptable noise and exhaust emissions. Moreover, it is limited in capacity to 100 passengers and to about 3000 miles in range. At supersonic speed of Mach 2, the surfaces of the aircraft are heated by ram air. These surfaces can raise the temperature of fuel held in the tanks to 80 °C. Since fuel is the coolant for airframe and engine subsystems, fuel to the engine can reach 150°C (26). An HSCT operated at Mach 3 would place much greater thermal stress on fuel. To minimize the formation of thermal oxidation deposits, it is likely that fuel deflvered to the HSCT would have to be deoxygenated. 

Uses. MTBE and related ethers are used to add octane to gasoline. It also adds oxygen to the gasoline, which allows for more efficient combustion, and therefore less carbon monoxide and unbumed hydrocarbon ia the exhaust emissions (11,24). 

In the United States, federal regulations require automobile manufacturers to certify that vehicles are ia compliance with exhaust emission standards when tested under specific test procedures. 

Table 1. Federal Exhaust Emission Standards for Conventionally Fueled Passenger Cars and Light Trucks, g/km...

Test Procedure. To comply with emission standards, representative vehicles must be mn for 80,000 km (Appendix IV of the Eederal Test Procedure (ETP)) (3). The first 6,400 km are considered a break-in portion. Exhaust emissions are measured each 8,000 km between approximately 6,400 and 80,000 km of accumulation and a deterioration factor (DE) of emissions is calculated. A DE of 1.15 for HC indicates that HC emissions increased by 15% between 6,400 and 80,000 km, and were within the 80,000 km standard. This DE is appHed to the 6,400 km emission test data points for all other model variations of the family of vehicles represented by the 80,000 km durabiUty car. 

Beyond the catalytic ignition point there is a rapid increase in catalytic performance with small increases in temperature. A measure of catalyst performance has been the temperature at which 50% conversion of reactant is achieved. For carbon monoxide this is often referred to as CO. The catalyst light-off property is important for exhaust emission control because the catalyst light-off must occur rehably every time the engine is started, even after extreme in-use engine operating conditions. 

On-Board Diagnostics. State of California regulations require that vehicle engines and exhaust emission control systems be monitored by an on-board system to assure continued functional performance. The program is called OBD-II, and requires that engine misfire, the catalytic converter, and the evaporative emission control system be monitored (101). The U.S. EPA is expected to adopt a similar regulation. 

Emission Control Technologies. The California low emission vehicle (LEV) standards has spawned iavestigations iato new technologies and methods for further reducing automobile exhaust emissions. The target is to reduce emissions, especially HC emissions, which occur during the two minutes after a vehicle has been started (53). It is estimated that 70 to 80% of nonmethane HCs that escape conversion by the catalytic converter do so during this time before the catalyst is fully functional. 

J. D. Benson and co-workers. Effects of Gasoline Sulfur on Mass Exhaust Emissions—-Autoj Oil Air Quality Improvement Research Program, SAE 912323, Society of Automotive Engineers, Warrendale, Pa., 1991. 

M. J. Heim rich, L. R. Smith, andj. Kitowski, Cold-Start IPydrocarbon Collection for Advanced Exhaust Emission Control, SAE 920847, Society of... 

Once an undesirable material is created, the most widely used approach to exhaust emission control is the appHcation of add-on control devices (6). Eor organic vapors, these devices can be one of two types, combustion or capture. AppHcable combustion devices include thermal iaciaerators (qv), ie, rotary kilns, Hquid injection combusters, fixed hearths, and uidi2ed-bed combustors catalytic oxidi2ation devices flares or boilers/process heaters. Primary appHcable capture devices include condensers, adsorbers, and absorbers, although such techniques as precipitation and membrane filtration ate finding increased appHcation. A comparison of the primary control alternatives is shown in Table 1 (see also Absorption Adsorption Membrane technology). 

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