Catalytic converters, heterogeneous catalysts

One problem with heterogeneous catalysis is that the solid catalyst is easily poisoned. Foreign materials deposited on the catalytic surface during the reaction reduce or even destroy its effectiveness. A major reason for using unleaded gasoline is that lead metal poisons the Pt-Rh mixture in the catalytic converter. 

Microporous catalysts are heterogeneous catalysts used in catalytic converters and for many other specialized applications, because of their very large surface areas and reaction specificity. Zeolites, for example, are microporous aluminosilicates (see Section 14.19) with three-dimensional structures riddled with hexagonal channels connected by tunnels (Fig. 13.38). The enclosed nature of the active sites in zeolites gives them a special advantage over other heterogeneous catalysts, because an intermediate can be held in place inside the channels until the products form. Moreover, the channels allow products to grow only to a particular size. 

Catalysts can be poisoned, or inactivated. A common cause of such poisoning is the adsorption of a molecule so tightly to the catalyst that it seals the surface of the catalyst against further reaction. Some heavy metals, especially lead, are very potent poisons for heterogeneous catalysts, which is why lead-free gasoline must be used in engines fitted with catalytic converters. The elimination of... 

Heterogeneous catalysts are the active ingredients in automobile catalytic converters. When combustion occurs in an automobile engine, side reactions generate small amounts of undesired products. Some carbon atoms end up as poisonous CO rather than CO2. Another reaction that takes place at the high temperatures and pressures in automobile engines is the conversion of N2 to NO. Furthermore, the combustion process fails to bum all the hydrocarbons. Hydrocarbons, CO, and NO all are undesirable pollutants that can be removed from exhaust gases... 

Heterogeneous catalysts are used to convert solid coal into gasoline and other chemicals. Solid coal is not easily transformed into hydrocarbon chains, so the conversion requires two general steps gasification followed by catalytic hydrocarbon-forming reactions. Coal is first gasified by reaction with steam ... 

The potential importance of homogeneous catalytic reactions in synthesis gas transformations (i.e., hydrogenation of carbon monoxide) has been widely recognized in recent years. In the first place, such systems could provide structural and mechanistic models for the currently more important, but more difficult to study, heterogeneous catalysts. Secondly, product selectivity is generally more readily achievable with homogeneous catalysts, and this would be an obviously desirable feature in an efficient process converting synthesis gas to useful chemicals and fuels. 

A heterogeneous catalyst is in a different phase or state of matter than the reactants. Most commonly, the catalyst is a solid and the reactants are liquids or gases. These catalysts provide a surface for the reaction. The reactant on the surface is more reactive than the free molecule. Many times these homogeneous catalysts are finely divided metals. Chemists use an iron catalyst in the Haber process, which converts nitrogen and hydrogen gases into ammonia. The automobile catalytic converter is another example. 

True/False. An automobile catalytic converter is an example of a heterogeneous catalyst. 

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... 

FIGURE 12.19 The gases exhausted from an automobile engine pass through a catalytic converter where air pollutants such as unburned hydrocarbons (CjHy), CO, and NO are converted to C02, H20, N2, and 02. The photo shows a cutaway view of a catalytic converter. The beads are impregnated with the heterogeneous catalyst. 

The transition metals iron and copper have been known since antiquity and have played an important role in the development of civilization. Iron, the main constituent of steel, is still important as a structural material. Worldwide production of steel amounts to some 800 million tons per year. In newer technologies, other transition elements are useful. For example, the strong, lightweight metal titanium is a major component in modern jet aircraft. Transition metals are also used as heterogeneous catalysts in automobile catalytic converters and in the industrial synthesis of essential chemicals such as sulfuric acid, nitric acid, and ammonia. 

Biocatalysis is a rather special case, somewhere between homogeneous and heterogeneous catalysis. In most cases, the biocatalyst is an enzyme - a complex protein that catalyzes the reactions in living cells. Enzymes are extremely effident catalysts. An enzyme typically completes 1000 catalytic cycles in one second. Compared to this, conventional homogeneous and heterogeneous catalysts are slow and inefficient (100-10000 cydes per hour). Speed, however, is not the only advantage enzymes specialize in converting one specific reactant into another... 

Heterogeneous catalysts are present in a different physical state from the reactants. A typical heterogeneous catalytic reaction involves a solid surface onto which molecules in a fluid phase temporarily attach themselves in such a way to favor a rapid reaction. Catalytic converters in cars utilize heterogeneous catalysis to break down harmful chemicals in exhaust. 

B Catalysts provide an alternate mechanism in both directions, but do not alter equilibrium (I is false, II is true). The kinetic energy of molecules increases with temperature, so the energy of their collisions increases also (III is true). Catalytic converters contain a heterogeneous catalyst (IV is false). 

Figure 1.2 A few illustrative examples of chemicals and classes of chemicals that are manufactured by homogeneous catalytic processes. In 1.6 low-pressure methanol synthesis by a heterogeneous catalyst is one of the steps. In 1.9 it is ethylene that is converted to acetaldehyde. In 1.7 all the available building blocks may be used.

Several heterogeneous catalysts have been developed for the hydroxylation of alkanes under mild conditions.68,69 One of them is the bi-catalytic system, which combines the ability of palladium to convert hydrogen and oxygen to hydrogen peroxide, with the capability of the iron ions to activate the hydrogen peroxide to hydroxylate hydrocarbons.70 Iron oxide and palladium supported on silica have been used as efficient catalysts for the oxidation of cyclohexane to the alcohol and ketone, via the in situ generation of hydrogen peroxide in an acetone solvent.71... 

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