Exhaust-gas catalytic converter

The lead alkyls and scavengers contained in fuels cause rapid poisoning ol exhaust gas catalytic converters. They are tolerated only in trace quantities in fuels for vehicles having that equipment. The officially allowed content is 0.013 g Pb/1, but the contents observed in actual practice are less than 0.005 g Pb/1. 

Figure 14.14 Catalyst carriers in the form of bulk materials for power stations and as a honeycomb structure for vehicle exhaust gas catalytic converters...

Emissions from automobiles could be decreased with improvements in the design of combustion chambers and the computer control of combustion mixtures. Exhaust-gas catalytic converters can also limit emissions. 

The most well-known type of heterogeneous catalyst is the exhaust-gas catalytic converter found in vehicles with gasoline engines. It eliminates combustion... 

Three-way catalysts used in exhaust-gas catalytic converters of automobiles contain platinum, palladium, rhodium, zirconium, and cerium. Oki et al. have developed a method which concentrates these metals by means of a two-step crushing procedure (Kim et al., 2010 Oki et al. 2010). The process makes it possible to increase concentration of rare-earth metals by a factor of five by first demolishing the honeycomb structure, and then peeling off the surface. To date, no process leading to recovery of individual rare-earth metals has been described. 

In this work reactor modeling and experimentation have been combined to study the warm-up period of exhaust gas catalytic converters. The influence of structural modifications may be effectively studied numerically provided that an accurate model for the catalytic converter is available. Such a model can guide the converter design provided that the description of the chemical reaction kinetics is tuned for the catalyst at hand. 

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). 

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). 

Reduction of exhaust emissions is being tackled in two ways by engineers, including precombustion and postcombustion technology. One of the most effective methods now being researched and adopted includes use of synthetic fuel made from natural gas. This fuel is crystal clear, and just like water, it has no aromatics, contains no sulfur or heavy metals, and when used with a postcombustion device such as a catalytic converter any remaining NO, or other emissions can be drastically reduced. Estimates currently place the cost of this fuel at 1.50 per gallon, with availability in 2004 to meet the next round of stiff EPA exhaust emission standards. 

Emission control from heavy duty diesel engines in vehicles and stationary sources involves the use of ammonium to selectively reduce N O, from the exhaust gas. This NO removal system is called selective catalytic reduction by ammonium (NH3-SGR) and it is additionally used for the catalytic oxidation of GO and HGs.The ammonia primarily reacts in the SGR catalytic converter with NO2 to form nitrogen and water. Excess ammonia is converted to nitrogen and water on reaction with residual oxygen. As ammonia is a toxic substance, the actual reducing agent used in motor vehicle applications is urea. Urea is manufactured commercially and is both ground water compatible and chemically stable under ambient conditions [46]. 

At the heart of an automotive catalytic converter is a catalyzed monolith which consists of a large number of parallel channels in the flow direction whose walls are coated with a thin layer of catalyzed washcoat. The monolith catalyst brick is wrapped with mat, steel shell and insulation to minimize exhaust gas bypassing and heat loss to the surroundings. 

Even though the usual catalytic converter of the exhaust of the standard drive train is omitted, there are also net increases in the chemical industry. The increased demand is for the expensive coating of the electrode-membrane unit (MEA) and the catalysts needed for gas preparation (reformer). 

Unavoidable loss of gas is compensated via a feed valve for supplying virgin nitrogen into the circulation pipe. The exhaust gas of the process has to be bypassed for purification. After the separation of dust by a filter, the gas is heated to 400 °C for the catalytic combustion of the side products. The gas is then cooled down, and the excess oxygen is catalytically converted to water by using hydrogen. For economic reasons, the gas flow will recover the heat via a heat exchanger and then be cooled down by a gas cooler. 

When hydrogen combines with the metal alloy (in granular form or particles), an exothermic reaction occurs. The gas is thus stored in these metal particles until some heat is applied to release the hydrogen and build up the pressure in the tanks. When a metal hydride absorbs hydrogen, heat is given off. A hydride cold-start heater can be developed that instantly heats an automobile s catalytic converter when the car is started to dramatically reduce overall exhaust pollution up to 80%. 

Schauer et al. (1999) reported ethylbenzene in a diesel-powered medium-duty truck exhaust at an emission rate of 470 pg/km. California Phase II reformulated gasoline contained ethylbenzene at a concentration of 12,800 mg/kg. Gas-phase tailpipe emission rates from gasoline-powered automobiles with and without catalytic converters were 4.18 and 434.0 mg/km, respectively (Schauer et al, 2002). 

Before 1970 there was very little unleaded gasoline on the market, but by 1974 all gas stations were offering it. In 1974, unleaded fuel had become a necessity for most new cars because of their catalytic converters placed in the exhaust system. These contain platinum or palladium compounds that act as a surface catalyst to bum the hydrocarbons more completely. But lead coats the platinum and palladium and deactivates the converters, so unleaded gas must be used. Up to 4 g/gal of lead could be used in the 1970s, but this was decreased to 0.1 g by 1986. Since 1995 no leaded gas could be used in the U.S. Fig. 7.6 shows the dramatic shift from leaded to unleaded gas between 1975 and 1992. 

Recent emission control system development in the automotive industry has been directed mainly towards the use of three-way or dual bed catalytic converters, This type of converter system not only oxidizes the hydrocarbons (HC) and carbon monoxide (CO) in the exhaust gas but will also reduce the nitrous oxides (NO ). An integral part of this type of system is the exhaust oxygen sensor which is used to provide feedback for closed loop control of the air-fuel ratio. This is necessary since this type of catalytic converter system operates efficiently only when the composition of the exhaust gas is very near the stoichiometric point. 

The following, well-acceptable assumptions are applied in the presented models of automobile exhaust gas converters Ideal gas behavior and constant pressure are considered (system open to ambient atmosphere, very low pressure drop). Relatively low concentration of key reactants enables to approximate diffusion processes by the Fick s law and to assume negligible change in the number of moles caused by the reactions. Axial dispersion and heat conduction effects in the flowing gas can be neglected due to short residence times ( 0.1 s). The description of heat and mass transfer between bulk of flowing gas and catalytic washcoat is approximated by distributed transfer coefficients, calculated from suitable correlations (cf. Section III.C). All physical properties of gas (cp, p, p, X, Z>k) and solid phase heat capacity are evaluated in dependence on temperature. Effective heat conductivity, density and heat capacity are used for the entire solid phase, which consists of catalytic washcoat layer and monolith substrate (wall). 

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