Catalysts catalytic converters

Clearly, the best catalyst for the reduction reactions may not be the best for the oxidation reactions, so two catalysts are combined. The noble metals, although expensive, are particularly useful. Typically, platinum and rhodium are deposited on a fine honeycomb mesh of alumina (AI2O3) to give a large surface area that increases the contact time of the exhaust gas with the catalysts. The platinum serves primarily as an oxidation catalyst and the rhodium as a reduction catalyst. Catalytic converters can be poisoned with certain metals that block their active sites and reduce their effectiveness. Because lead is one of the most serious such poisons, automobiles with catalytic converters must use unleaded fuel. 

However, such a level can still be considered too high for vehicles having 3-way catalytic converters. In fact, results observed in the United States (Benson et al., 1991) and given in Figure 5.20 show that exhaust pollutant emissions, carbon monoxide, hydrocarbons and nitrogen oxides, increase from 10 to 15% when the sulfur level passes from 50 ppm to about 450 ppm. This is explained by an inhibiting action of sulfur on the catalyst though... 

The protection of the environment implies the elimination of lead compounds, first of all because of their individual toxicities and second because these derivatives or their products of decomposition poison catalytic converter catalysts. 

We consider next perhaps the bet understood catalyzed reaction the oxidation of CO over group VIII metal catalysts. The reaction is an important environmental one since it involves the conversion of CO to CO2 in automobile catalytic converters. The mechanism is straightforward ... 

Oxidation. Carbon monoxide can be oxidized without a catalyst or at a controlled rate with a catalyst (eq. 4) (26). Carbon monoxide oxidation proceeds explosively if the gases are mixed stoichiometticaHy and then ignited. Surface burning will continue at temperatures above 1173 K, but the reaction is slow below 923 K without a catalyst. HopcaUte, a mixture of manganese and copper oxides, catalyzes carbon monoxide oxidation at room temperature it was used in gas masks during World War I to destroy low levels of carbon monoxide. Catalysts prepared from platinum and palladium are particularly effective for carbon monoxide oxidation at 323 K and at space velocities of 50 to 10, 000 h . Such catalysts are used in catalytic converters on automobiles (27) (see Exhaust CONTHOL, automotive). 

Some catalyst supports rely on a relatively low surface area stmctural member coated with a layer of a higher surface area support material. The automotive catalytic converter monolith support is an example of this technology. In this appHcation, a central core of multichanneled, low surface area, extmded ceramic about 10 cm in diameter is coated with high surface area partially hydrated alumina onto which are deposited small amounts of precious metals as the active catalytic species. 

Automotive Catalytic Converter Catalysts. California environmental legislation in the early 1960s stimulated the development of automobile engines with reduced emissions by the mid-1960s, led to enactment of the Federal Clean Air Act of 1970, and resulted in a new industry, the design and manufacture of the automotive catalytic converter (50). Between 1974 and 1989, exhaust hydrocarbons were reduced by 87% and nitrogen oxides by 24%. 

In principle, the catalytic converter is a fixed-bed reactor operating at 500—620°C to which is fed 200—3500 Hters per minute of auto engine exhaust containing relatively low concentrations of hydrocarbons, carbon monoxide, and nitrogen oxides that must be reduced significantly. Because the auto emission catalyst must operate in an environment with profound diffusion or mass-transfer limitations (51), it is apparent that only a small fraction of the catalyst s surface area can be used and that a system with the highest possible surface area is required. 

The most widely used exhaust control device consists of a ceramic monolith with a thin-waHed open honeycomb stmcture. The accessible surface of this monolith system is iacreased by applyiag a separate coatiag, a wash coat, of a high surface area material such as gamma-alumiaa with the catalyticaHy active species impregaated iato this washcoat. The catalyst aeeds to oxidize hydrocarboas, coavert CO to CO2, and reduce NO. The whole system forms a catalytic converter that, suitably encased, is placed between the engine and the muffler/silencer unit. 

M ass Transfer. Exhaust gas catalytic treatment depends on the efficient contact of the exhaust gas and the catalyst. During the initial seconds after start of the engine, hot gases from the exhaust valve of the engine pass through the exhaust manifold and encounter the catalytic converter. Turbulent flow conditions (Reynolds numbers above 2000) exist in response to the exhaust stroke of each cylinder (about 6 to 25 times per second) times the number of cylinders. However, laminar flow conditions are reached a short (- 0.6 cm) distance after entering the cell passages of the honeycomb (5,49—52). 

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. 

Fig. 5. Catalytic system designs (11) of (a) basic VOC catalytic converter containing a preheater section, a reactor housing the catalyst, and essential controls, ducting, instmmentation, and other elements (b) a heat exchanger using the cleaned air exiting the reactor to raise the temperature of the incoming process exhaust and (c) extracting additional heat from the exit gases by a secondary heat exchanger.

Beginning with the 1975 U.S. automobiles, catalytic converters were added to nearly all models to meet the more restrictive emission standards. Since the lead used in gasoline is a poison to the catalyst used in the converter, a scheduled introduction of unleaded gasoline was also required. The U.S. petroleum industry simultaneously introduced unleaded gasoline into the marketplace. 

The original Sonogashira reaction uses copper(l) iodide as a co-catalyst, which converts the alkyne in situ into a copper acetylide. In a subsequent transmeta-lation reaction, the copper is replaced by the palladium complex. The reaction mechanism, with respect to the catalytic cycle, largely corresponds to the Heck reaction.Besides the usual aryl and vinyl halides, i.e. bromides and iodides, trifluoromethanesulfonates (triflates) may be employed. The Sonogashira reaction is well-suited for the synthesis of unsymmetrical bis-2xy ethynes, e.g. 23, which can be prepared as outlined in the following scheme, in a one-pot reaction by applying the so-called sila-Sonogashira reaction ... 

The second method used to reduce exliaust emissions incorporates postcombustion devices in the form of soot and/or ceramic catalytic converters. Some catalysts currently employ zeolite-based hydrocarbon-trapping materials acting as molecular sieves that can adsorb hydrocarbons at low temperatures and release them at high temperatures, when the catalyst operates with higher efficiency. Advances have been made in soot reduction through adoption of soot filters that chemically convert CO and unburned hydrocarbons into harmless CO, and water vapor, while trapping carbon particles in their ceramic honeycomb walls. Both soot filters and diesel catalysts remove more than 80 percent of carbon particulates from the exliatist, and reduce by more than 90 percent emissions of CO and hydrocarbons. 

Probably the most significant control technology breakthrough came m 1977, when Volvo released a computer-controlled, fuel-mjected vehicle equipped with a three-way catalyst. The new catalytic converters employed platinum, palladium, and rhodium to simultaneously reduce NO and oxidize CO and HC emissions under carefully controlled oxygen conditions. The new Bosch fuel injection system on the vehicle provided the precise air/fuel control necessary for the new catalyst to perform effectively. The combined fuel control and three-way catalyst system served as the foundation for emissions control on the next generation of vehicles. 

The efficiency of the three-way catalytic converter is also a function of air/fuel ratio. At the stoichiometric air/fiiel ratio of 14.7 kilograms of air per kilogram of fuel, the relative air/fuel ratio known as X equals 1.0. Figure 1 illustrates catalytic converter efficiency for each pollutant as a function of relative air/fuel ratio X (where a positive X indicates a lean mixture and a negative X indicates a rich mixture). The closer the mixture stays to stoichiometric, the more efficient the catalyst at reducing the combined emissions of the three pollutants. 

High levels of sulfur not only form dangerous oxides, but they also tend to poison the catalyst in the catalytic converter. As it flows over the catalyst in the exliaust system, the sulfur decreases conversion efficiency and limits the catalyst s oxygen storage capacity. With the converter working at less than maximum efficiency, the exhaust entering the atmosphere contains increased concentrations, not only of the sulfur oxides but also, of hydrocarbons, nitrogen oxides, carbon monoxides, toxic metals, and particulate matter. 

After each reaction stage, sulfur is removed by condensation so that it does not collect on the catalyst. The temperature in the catalytic converter should be kept over the dew point of sulfur to prevent condensation on the catalyst surface, which reduces activity. 

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