1.1. Catalyst Operating Conditions in Engine Exhaust
Spark-ignition and diesel engines are a major source of urban air pollution. The spark-ignition engine exhaust gases contain oxides of nitrogen (NO and small amounts of N02-collectively referred to as NOx), carbon monoxide (CO) and organic compounds, which are unburnt or partially burnt hydrocarbons (HC). Compression-ignition (diesel) engine exhaust contains smaller amounts of CO and HC, their main problem being the particulate emissions. The relative amounts depend on engine technology and operating conditions. Table 1 gives indicative values of the operating conditions for exhaust aftertreatment catalysts met in different technology engine types.
As shown in Table 1, in diesel engine exhausts, the
concentrations of NOx are comparable to those from SI engines. Diesel hydrocarbon emissions are, how ever, significantly lower than those from SI engines. The hydrocarbons in the exhaust may also condense to form white smoke during engine startup and warm up. Specific hydrocarbon compounds in diesel engines exhaust are the source of characteristic diesel colour. Diesel engines are also a source of particulate emissions. About 0.1-0.5% of the fuel is emitted as small particulates (0.1 jLm mean size), which consist primarily of soot with some additional adsorbed hydrocarbon material. Carbon monoxide emissions of diesel engines are insignificant because of the
abundancy of oxygen in diesel combustion.
Use of alcohol fuels in either of these engines substantially increases aldehyde emissions. Aldehydes would be another significant pollutant if these fuels were to be used in quantities comparable to gasoline and diesel.
Currently used fuels, gasoline and diesel, contain sulfur: gasoline in small amounts «600 ppm weight S), diesel fuel in larger amounts (0.01-0.3% w.). In diesel engines the sulfur is oxidized to produce sulfur dioxide, S02, a fraction of which can be oxidized to sulfur trioxide, S03, which combines with water to form a sulfuric acid aerosol. In gasoline engines H2S is produced in small amounts as a by-product of the reactions occurring in a 3WCC during oxygen deficiency conditions.
Improvements in engine design and fuel manage
ment have led to substantial lowering of raw emission
figures during the last decades. Further reductions in exhaust emissions can be obtained by removing pollutants from the exhaust gases in the engine exhaust system. Devices developed to achieve this result are usually assisted by catalysts, and include catalytic converters (oxidizing catalysts for HC, CO and SOF of HC, three-way catalysts for the simultaneous reduction of all three pollutants) and catalytically assisted traps or filters for the diesel particulate.
The temperature of exhaust gas in a warmed-up
spark-ignition engine can vary from 300 to 400°C during idle, to about lOOO°Cin full load operation. Modern spark ignition engines usually operate at
oscillating AI F, close to stoichiometric, as a result of
the feedback lambda control system. The exhaust gas
may therefore contain modest amounts of oxygen (when lean), or more substantial amounts of CO (when rich of stoichiometric). Lean burn engines,
operating in the range 14.5 < AI F < 22, are also
produced in limited numbers, mainly in Japan. Diesel
engines, on the other hand, operate significantly leaner, and load is controlled by the amount of fuel injected in a fairly constant (at constant speed) quantity of air. The diesel exhaust gas, therefore, contains substantial oxygen and is at lower tempera tures (l00-700°C). Removal of gaseous pollutants from exhaust after it leaves the engine cylinder can be either thermal or catalytic. However, thermal oxida tion requires temperatures of the order of 600-700°C and high residence times of the order of 50 ms, and thus has limited applicability. I
Table 2 summarizes the application of various catalyst categories in different engine types to convert the regulated automobile pollutants, which will be reviewed in this paper. Catalytic oxidation of CO and hydrocarbons in the exhaust can be achieved at temperatures as low as 220°C. On the other hand, the only efficient methods known for the removal of NO
from exhaust gas either at stoichiometric or lean AI F
conditions, involve catalytic processes.' Consump
tion of NO by the reducing species present in the exhaust such as CO, hydrocarbons or H2 is the preferred catalytic process. This is the case in 3WCCs for SI engines. NOx reduction in oxygen rich conditions is currently achieved by catalysts which promote NO-hydrocarbons reactions in lean burn or diesel exhaust gas. In the latter case, additional amounts of hydrocarbons are usually injected in the exhaust gas to ensure high NO conversion efficiency.
Particulates in the diesel exhaust gas stream may be removed by a particulate filter (trap). Due to the small particle size involved (order of 0.2 J.l.m), mechanical filtration is the most effective trapping method. The accumulation of mass within the filter and the increase in exhaust manifold pressure during filter operation are major development problems. Diesel particulates, once trapped, can be burned up either by initiating oxidation within the filter with an external heat source, or by using a catalytically coated filter or, better, a fuel doped with some type of catalytic fuel additive. Reliable regeneration of diesel particulate filters remains a major challenge for diesel engine emission control.
1.2. Fuel Effects
The role of fuel composition and properties as an additional factor in reducing air pollutant emissions is widely recognized and discussed. In this discussion, two main streams are evident: improvement of the traditional fuels (reformulated fuels) and the intro duction of alternative fuels. Improving traditional fuels has two different performance aspects:
1. To maintain engine and emissions control
equipment in the best possible order during a vehicle's useful life. For example, sulfur in fuel can clearly affect the efficiency of catalyst conversion systems.
2. To further lower the engine out and, subse
quently, catalyst out exhaust emissions.
The following parameters have been, and are being, studied extensively for their relationship with exhaust and evaporative emissions: aromatics content (clearly related to benzene emissions), olefins content (strong effect on butadiene emissions), benzene content, boiling range (T50, T90-signifi cant effect on HC emissions), vapour pressure (high RVP leads to breakthrough of canister control systems) and content of oxygenated compounds (mainly lower CO emissions, MTBE may increase formaldehyde emissions).
Fuel improvements could enable the legislator to
drastically reduce atmospheric concentrations of HC and (to a lesser extent) NOx emissions. However, such issues should seriously consider the dual role of NOx in ozone formation. In areas with low atmospheric HC-NOx ratios, reducing NOx can increase ozone
formation, whereas for high atmospheric HC-NOx ratio areas, reducing NOx decreases ozone.' In a recent U.S. study it was stated that in 2005 the light duty vehicles will contribute 5-9% of peak ground level 03 values in three US cities. This contribution could be lowered by 25% by switching to reformu lated gasoline. Afterwards the effect becomes appre ciably smaller; also the effect strongly depends on the local pollutant mix.
Compressed natural gas (CNG) as a fuel for internal combustion engines is mainly composed of methane (from 60 to 99% by volume, depending on different sources). Although methane is a greenhouse gas, it does not contribute to the formation of photochemical smog and this is the reason that the U.S. legislation excludes methane from the regulated emissions. Thus, ULEV standards may be more easily attained by the use of CNG. However, if total hydrocarbon emissions are controlled, as in the EC legislation, special catalysts must be developed able to convert methane at relatively low temperatures."
Liquified petroleum gas (LPG) has some advan
tages over gasoline regarding engine-out emissions which, however, essentially disappear with the introduction of the closed loop control three-way catalyst system.?
Methanol is used as a component of fuels for S.1. engines (M85 or MIOO). The main thrust behind California/U.S. interest in methanol is future trans port energy supply and the potential for lowering photooxidants. Its use results in a clear reduction of HC emissions (of the order of 30-40%), less or no benzene emissions and acceptable methanol and formaldehyde concentrations in the air. Depending on the source material for methanol production, greenhouse gases can range from favorable or equal to, to very much worse than petrol. However, methanol fuelled vehicle exhaust also contains significant amounts of photochemically reactive alde hydes (primarily formaldehyde). Previous studies6,7 have shown that maximum air quality benefit from methanol fuel can be obtained, provided that exhaust emissions of formaldehyde are kept to very low levels. The California Air Resources Board has enacted a
15mg/mile formaldehyde emission standard for
methanol-fuelled vehicles and the requirement that this standard be met for at least 5 years or 50,000 miles of vehicle use.