Exhaust catalysts for

Purely adiabatic fixed-bed reactors are used mainly for reactions with a small heat of reaction. Such reactions are primarily involved in gas purification, in which small amounts of noxious components are converted. The chambers used to remove NO, from power station flue gases, with a catalyst volume of more than 1000 m3, are the largest industrial adiabatic reactors, and the exhaust catalyst for internal combustion engines, with a catalyst volume of ca. 1 L, the smallest. Typical applications in the chemical industry include the methanation of traces of CO and CO2 in NH3 synthesis gas, as well as the hydrogenation of small amounts of unsaturated compounds in hydrocarbon streams. The latter case requires accurate monitoring and regulation when hydrogen is in excess, in order to prevent complete methanation due to an uncontrolled temperature runaway. 

In the past few years the tudy of morphology changes undergone by supported Rh particles during oxidation / reduction thermal treatments has attracted considerable attention (refs 1-4). These phenomena are of particular importance in the deactivation of automotive exhaust catalysts for which rhodium is the main active Ingredient for the reduction of NO. 

The Clean Air Act Amendments of 1970, which followed the original Clean Air Act of 1967, set national air quality standards for six criteria air pollutants NOx, SOx, ozone, carbon monoxide (CO), particulates and lead. The result was the removal of lead from gasoline and the installation of emission control technologies, including baghouse filters for particulate control, wet and dry scrubbers for SOx control and automobile exhaust catalysts for controlling hydrocarbons (HC), CO and NOx. As a consequence, lead emissions have been dramatically reduced, SOx emissions are being controlled, and automobile CO, HC and NOx emissions have decreased by nearly a factor of 10 (over uncontrolled emissions). In spite of these dramatic improvements, in 1989 approximately 130 million people in the U.S. lived in 96 areas which did not meet air quality standards either in ozone, in carbon monoxide, or in both [2]. 

Lead sesquioxide is used as an oxidation catalyst for carbon monoxide ia exhaust gases (44,45) (see Exhaust control), as a catalyst for the preparation of lactams (46) (see Antibiotics, P-lactams), ia the manufacture of high purity diamonds (47) (see Carbon, diamond-natural), ia fireproofing compositions for poly(ethylene terephthalate) plastics (48), ia radiation detectors for x-rays and nuclear particles (49), and ia vulcanization accelerators for neoprene mbber (50). 

Cordierite [12182-53-5] Mg Al Si O g, is a ceramic made from talc (25%), kaolin (65%), and Al O (10%). It has the lowest thermal expansion coefficient of any commercial ceramic and thus tremendous thermal shock resistance. It has traditionally been used for kiln furniture and mote recently for automotive exhaust catalyst substrates. In the latter, the cordierite taw materials ate mixed as a wet paste, extmded into the honeycomb shape, then dried and fired. The finished part is coated with transition-metal catalysts in a separate process. 

Catalyst Function. Automobile exhaust catalysts are perfect examples of materials that accelerate a chemical reaction but are not consumed. Reactions are completed on the catalyst surface and the products leave. Thus the catalyst performs its function over and over again. The catalyst also permits reactions to occur at considerably lower temperatures. For instance, CO reacts with oxygen above 700°C at a substantial rate. An automobile exhaust catalyst enables the reaction to occur at a temperature of about 250°C and at a much faster rate and in a smaller reactor volume. This is also the case for the combustion of hydrocarbons. 

Design considerations and costs of the catalyst, hardware, and a fume control system are direcdy proportional to the oven exhaust volume. The size of the catalyst bed often ranges from 1.0 m at 0°C and 101 kPa per 1000 m /min of exhaust, to 2 m for 1000 m /min of exhaust. Catalyst performance at a number of can plant installations has been enhanced by proper maintenance. Annual analytical measurements show reduction of solvent hydrocarbons to be in excess of 90% for 3—6 years, the equivalent of 12,000 to 30,000 operating hours. When propane was the only available fuel, the catalyst cost was recovered by fuel savings (vs thermal incineration prior to the catalyst retrofit) in two to three months. In numerous cases the fuel savings paid for the catalyst in 6 to 12 months. 

G. R. Lester, andJ. C. Summers "Poison-Resistant Catalyst for Purification of Web Offset Press Exhaust," presented at Air Pollution Control... 

The metallic catalysts for exliaust pollution control are designed to perform three functions. The air/fuel ratio employed in combustion engines creates exhaust products which are a mixture of hydrocarbons, carbon oxides, and niU ogen oxides. These must be rendered environmentally innocuous by reactions on the catalyst such as... 

The main use of rhodium is with platinum in catalysts for oxidation of automobile exhaust emissions. In the chemical industry, it is used in catalysts for the manufacture of ethanoic acid, in hydroformylation of alkenes and the synthesis of nitric acid from ammonia. Many applications of iridium rely on... 

Laboratory catalyst testing is sometimes done under conditions that are far removed from exhaust gas conditions, and can be a very unreliable guide to the utility of a catalyst. For instance, noble metals may rank below base metal oxides in oxidation activity at low temperatures, but the ranking reverses at high temperatures. These and other hazards were pointed out by Schlatter et al. (53). Laboratory catalyst testing is usually done by the catalyst manufacturers, resulting in the rejection of a vast majority of formulations. 

The relatively high cost and lack of domestic supply of noble metals has spurred considerable efforts toward the development of nonnoble metal catalysts for automobile exhaust control. A very large number of base metal oxides and mixtures of oxides have been considered, especially the transition metals, such as copper, chromium, nickel, manganese, cobalt vanadium, and iron. Particularly prominent are the copper chromites, which are mixtures of the oxides of copper and chromium, with various promoters added. These materials are active in the oxidation of CO and hydrocarbons, as well as in the reduction of NO in the presence of CO (55-59). Rare earth oxides, such as lanthanum cobaltate and lanthanum lead manganite with Perovskite structure, have been investigated for CO oxidation, but have not been tested and shown to be sufficiently active under realistic and demanding conditions (60-63). Hopcalities are out-... 

So the question should never be (nor has it ever been) one of choosing between all catalytic chemists studying ortho-para hydrogen conversion, molecular orbitals and the like, or all catalytic chemists studying fuel synthesis and exhaust catalysts a healthy society is a judiciously balanced society, and the concern for relevance is one for a shift toward greater dedication in the direction of the most vital needs for the survival and health of the kinetic system of human society. 

The effect of alkali addition on the adsorption of NO on metal surfaces is of great importance due to the need of development of efficient catalysts for NO reduction in stationary and automotive exhaust systems. Similar to CO, NO always behaves as an electron acceptor in presence of alkalis. 

Reactions involving the catalytic reduction of nitrogen oxides are of major environmental importance for the removal of toxic emissions from both stationary and automotive sources. As shown in this section electrochemical promotion can affect dramatically the performance of Rh, Pd and Pt catalysts (commonly used as exhaust catalysts) interfaced with YSZ, an O2 ion conductor. The main feature is strong electrophilic behaviour, i.e. enhanced rate and N2 selectivity behaviour with decreasing Uwr and , due to enhanced NO dissociation. 

Unbumt gasoline and cracked hydrocarbons such as ethylene and propylene are also substantial constituents of exhaust. Gasoline contains additives such as benzene, toluene and branched hydrocarbons to achieve the necessary octane numbers. The direct emission of these volatile compounds, e.g. at gas stations, is a significant source of air pollution. Leaded fuels, containing antiknock additions such as tetra-ethyl-lead, have been abandoned because lead poisons both human beings and the three-way exhaust catalyst, especially for the removal of NO by rhodium. 

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