Catalytic material

Bulk Catalytic Phase Materials Xero- and Aerogels 

An amorphous alumina xerogel is prepared by the nonhydrolytic method according to 

The obtained amorphous hydrated aluminum oxide has a surface area of 640 m g [40]. It remained amorphous up to 973 K and crystallizes to r]-alumina at 1123 K, resulting in a loss of surface to 230 m g . Wetting of this xerogel with water decreases the crystallization temperature to 873 K [41]. 

Combustion volume 1500y 150QK eOOK TOOK 6CBK 

These aspects suggest some analogies with catalytic combustion for GT in terms of (i) a requirement for an activity-stability trade-off for the catalytic materials, (ii) a need to cope with simultaneous homogeneous-heterogeneous reactions coupled with masstransfer effects and (iii) advantages ofconfigurations based on rich combustion. 

Structured catalysts are used in GT and microcombustor applications because of the severe pressure drop constraints combined with the requirement for a fast rate of 

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Bulk catalytic materials, in which the gross composition does not... 

Supported catalysts, in which the active catalytic material is... 

Physical properties affecting catalyst perfoniiance include tlie surface area, pore volume and pore size distribution (section B1.26). These properties regulate tlie tradeoff between tlie rate of tlie catalytic reaction on tlie internal surface and tlie rate of transport (e.g., by diffusion) of tlie reactant molecules into tlie pores and tlie product molecules out of tlie pores tlie higher tlie internal area of tlie catalytic material per unit volume, tlie higher the rate of tlie reaction... 

Catalysis. Kistler explored the catalytic appHcations of aerogels ia the 1930s because of the unique pore characteristics of aerogels (24), but this area of research stayed dormant for about three decades until less tedious procedures to produce the materials were introduced (25,26). Three recent review articles summarize the flurry of research activities since then (63—65). Table 3 is a much abbreviated Hst of what has been cited in these three articles to demonstrate simply the wide range of catalytic materials and reactions that have been studied. 

Bosch and co-workers devised laboratory reactors to operate at high pressure and temperature in a recycle mode. These test reactors had the essential characteristics of potential industrial reactors and were used by Mittasch and co-workers to screen some 20,000 samples as candidate catalysts. The results led to the identification of an iron-containing mineral that is similar to today s industrial catalysts. The researchers recognized the need for porous catalytic materials and materials with more than one component, today identified as the support, the catalyticaHy active component, and the promoter. Today s technology for catalyst testing has become more efficient because much of the test equipment is automated, and the analysis of products and catalysts is much faster and more accurate. 

CatalyticaHy Active Species. The most common catalyticaHy active materials are metals, metal oxides, and metal sulfides. OccasionaHy, these are used in pure form examples are Raney nickel, used for fat hydrogenation, and y-Al O, used for ethanol dehydration. More often the catalyticaHy active component is highly dispersed on the surface of a support and may constitute no more than about 1% of the total catalyst. The main reason for dispersing the catalytic species is the expense. The expensive material must be accessible to reactants, and this requires that most of the catalytic material be present at a surface. This is possible only if the material is dispersed as minute particles, as smaH as 1 nm in diameter and even less. It is not practical to use minute... 

Separability. One of the greatest advantages of a solid catalyst is that it can be separated easily from the products of reaction. To do this successfully requires careful control of the process conditions so that exposure of the catalyst to nonreactant liquids capable of affecting or dissolving either the catalytic material or the support is prevented or rninimi2ed. Solid catalysts typically are used in axial or radial flow beds and multitubular reactors. Many successful commercial processes maintain the reactants and products in the gas phase while in contact with the catalyst to avoid catalyst degradation problems. 

Since catalyst activity is dependent on how much catalytically active surface is available, it is usually desirable to maximi2e both the total surface area of the catalyst and the active fraction of the catalytic material. It is often easier to enlarge the total surface area of the catalyst than to increase the active component s surface area. With proper catalyst design, however, it is possible to obtain a much larger total active surface area for a given amount of metal or other active material in a supported catalyst than can be achieved in the absence of a support. 

Porosity and Pore Size. The same methods used to determine the porosity and pore si2e distribution of the support generally can be used for the catalyst. However, the values found for the catalyst usually ate different from those of the bare support. Porosity could be increased if a part of the support is leached away during preparation of the catalyst, or, more likely, porosity will be decreased because catalytic materials deposited on the support win occupy a part of the support s pore volume. 

Dehydrochlorination of chlorinated derivatives such as 1,1,2-trichloroethane may be carried out with a variety of catalytic materials, including Lewis acids such as aluminum chloride. Refluxing 1,1,2-trichlorethane with aqueous calcium hydroxide or sodium hydroxide produces 1,1-dichloroethylene in good yields (22), although other bases such as magnesium hydroxide have been reported (23). Dehydrochlorination of the 1,1,1-trichloroethane isomer with catalytic amounts of a Lewis acid also yields 1,1-dichloroethylene. Other methods to dehydrochlorinate 1,1,1-trichloroethane include thermal dehydrochlorination (24) and by gas-phase reaction over an alumina catalyst or siUca catalyst (25). 

Pyrolysis Thermal decomposition of 1,1,1,2-tetrachloroethane produces tetrachloroethylene (by disproportionation), hydrogen chloride, and trichloroethylene via dehydrochlorination (111). The yield of the latter is increased in the presence of ferric chloride (112). Other catalytic materials include FeCl —KCl mixture (113), AlCl (6), the complex of AlCl with nitrobenzene (114), activated alumina (3), Ca(OH)2 (115,116), and NaCl (94). 

Various catalytic materials promote dehydrochlorination including AlCl (6,91), AICk-nitrohenzene complex (114), activated alumina (3), and FeCl (112). Chlorination in the presence of anhydrous aluminum chloride gives hexachloroethane. Dry pentachloroethane does not corrode iron at temperatures up to 100°C. It is slowly hydrolyzed by water at normal temperatures and oxidized in the presence of light to give trichloroacetyl chloride. 

Two classes of metals have been examined for potential use as catalytic materials for automobile exhaust control. These consist of some of the transitional base metal series, for instance, cobalt, copper, chromium, nickel, manganese, and vanadium and the precious metal series consisting of platinum [7440-06-4], Pt palladium [7440-05-3], Pd rhodium [7440-16-6], Rh iridium, [7439-88-5], Ir and mthenium [7440-18-8], Ru. Specific catalyst activities are shown in Table 3. 

A key feature of a catalyst is that the catalytic material is not consumed by the chemical oxidation reactions, rather it remains unaltered by the reactions which occur generally on its surface and thus remains available for an infinite number of successive oxidation reactions. 

Fig. 6. Catalyst inhibition mechanisms where ( ) are active catalyst sites the catalyst carrier and the catalytic support (a) masking of catalyst (b) poisoning of catalyst (c) thermal aging of catalyst and (d) attrition of ceramic oxide metal substrate monolith system, which causes the loss of active catalytic material resulting in less catalyst in the reactor unit and eventual loss in performance.

Usually they are employed as porous pellets in a packed bed. Some exceptions are platinum for the oxidation of ammonia, which is in the form of several layers of fine-mesh wire gauze, and catalysts deposited on membranes. Pore surfaces can be several hundred mVg and pore diameters of the order of 100 A. The entire structure may be or catalytic material (silica or alumina, for instance, sometimes exert catalytic properties) or an active ingredient may be deposited on a porous refractory carrier as a thin film. In such cases the mass of expensive catalytic material, such as Pt or Pd, may be only a fraction of 1 percent. 

The 10 volumes in the Series on characterization of particular materials classes include volumes on silicon processir, metals and alloys, catalytic materials, integrated circuit packaging, etc. Characterization is approached from the materials user s point of view. Thus, in general, the format is based on properties, processing steps, materials classification, etc., rather than on a technique. The emphasis of all volumes is on surfaces, interfaces, and thin films, but the emphasis varies depending on the relative importance of these areas for the materials class concerned. Appendixes in each volume reproduce the relevant one-page summaries from the Encyclopedia and provide longer summaries for any techniques referred to that are not covered in the Encyclopedia. 

He became intimately familiar with a wide range of catalytic materials—including aluminum oxide, silica, and clay, as well as nickel, platinum, zinc, and copper—and their role individually and as mixtures 111 effecting chemical transformation. One of Ipatieffs most important lines of research was his breakthrough work on the nature and mechanisms of catalytic promoters on organic reactions. 

Oxidation kinetics over platinum proceeds at a negative first order at high concentrations of CO, and reverts to a first-order dependency at very low concentrations. As the CO concentration falls towards the center of a porous catalyst, the rate of reaction increases in a reciprocal fashion, so that the effectiveness factor may be greater than one. This effectiveness factor has been discussed by Roberts and Satterfield (106), and in a paper to be published by Wei and Becker. A reversal of the conventional wisdom is sometimes warranted. When the reaction kinetics has a negative order, and when the catalyst poisons are deposited in a thin layer near the surface, the optimum distribution of active catalytic material is away from the surface to form an egg yolk catalyst. 

Active heterogeneous catalysts have been obtained. Examples include titania-, vanadia-, silica-, and ceria-based catalysts. A survey of catalytic materials prepared in flames can be found in [20]. Recent advances include nanocrystalline Ti02 [24], one-step synthesis of noble metal Ti02 [25], Ru-doped cobalt-zirconia [26], vanadia-titania [27], Rh-Al203 for chemoselective hydrogenations [28], and alumina-supported noble metal particles via high-throughput experimentation [29]. 

The potential for the use of catalysis in support of sustainability is enormous [102, 103]. New heterogeneous and homogeneous catalysts for improved reaction selectivity, and catalyst activity and stabihty, are needed, for example, new catalytic materials with new carbon modifications for nanotubes, new polymers. 

The principles of application of zeolite membranes at the microlevel can be very similar to those on the particle level, but now at the crystal (micrometer) scale, enclosing the active catalytic material. 

Initial activity is important to ensure fast unloading and loading cycles. The second requirement for repeated use of alanate batteries is long-term stability. Whereas titanium colloids show superior performance in terms of decomposition kinetics, titanium nitride-based materials are superior in long-term stability. The latter can be seen comparing both catalytic materials in several runs (Fig. 19.8). 

For testing and optimizing catalysts, the temperature region just below that where pore diffusion starts to limit the intrinsic kinetics provides a desirable working point (unless equilibrium or selectivity considerations demand working at lower temperatures). In principle, we would like the rate to be as high as possible while also using the entire catalyst efficiently. For fast reactions such as oxidation we may have to accept that only the outside of the particles is used. Consequently, we may decide to use a nonporous or monolithic catalyst, or particles with the catalytic material only on the outside. 

The possibility of obtaining single crystal diffraction patterns from regions of very small diameter can obviously be an important addition to the means for investigating the structures of catalytic materials. The difficulty arises that data on individual small particles is usually, at best, merely suggestive and at worst, completely meaningless. What is normally required is statistical data on the relative frequencies of occurrence of the various structural features. For adequate statistics, it would be necessary to record and analyse very large numbers of diffraction patterns. 

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