Alumina catalyst supports

Figure 8 Foam as a catalyst support (alumina impregnated with Cs2S04.V205).

The potential of rare earth compounds as catalytically active phases and promoters in pollution control, catalytic combustion, polymer production and in the fuel and chemical manufacture and thermal stabilizers for catalyst supports (alumina, silica-alumina, titania) need to be mentioned. Application of rare earths in alternate fuels technology (Fisher-Tropsch Processes, natural gas to transport fuel pathways) is also promising. 

Representative yields of trans-decalin as a function of conversion are shown in Figs. 4 and 5. These experiments included two different feeds (naphthalene and tetralin), two different catalyst supports (alumina and charcoal), and a range of temperatures. Figure 4 shows that ruthenium is highly selective for the formation of ci -deoalin. In the... 

Catalyst Support Alumina. The support used exclusively in commercial naphtha reforming catalysts is alumina. As previously mentioned, the Pt/KL-zeolite might be used for dehydrocyclization of linear C6-C8 paraffins, but not for straight-run naphthas reforming. 

In the palladium-alkyl nitrite system, the gas phase synthesis of diallqrl carbonates has mainly been studied and not many examples are known concerning the liquid phase variants. For catalyst supports, alumina, activated carbon.f and Li-Al-0(spinel)f were successfully utilized in dimethyl carbonate synthesis (Table 4). 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Ethjlben ne Synthesis. The synthesis of ethylbenzene for styrene production is another process in which ZSM-5 catalysts are employed. Although some ethylbenzene is obtained direcdy from petroleum, about 90% is synthetic. In earlier processes, benzene was alkylated with high purity ethylene in liquid-phase slurry reactors with promoted AlCl catalysts or the vapor-phase reaction of benzene with a dilute ethylene-containing feedstock with a BF catalyst supported on alumina. Both of these catalysts are corrosive and their handling presents problems. 

Catalytic properties are dependent on physical form, principally the exposed surface area which is a function of particle size. Industrial PGM catalysts are in the form of finely divided powder, wine, or gauze, or supported on substrates such as carbon or alumina (see Catalysis Catalysts, supported). 

Sodium alumiaate is widely used in the preparation of alumina-based catalysts. Aluminosilicate [1327-36-2] can be prepared by impregnating siHca gel with alumiaa obtained from sodium alumiaate and aluminum sulfate (41,42). Reaction of sodium alumiaate with siHca or siHcates has produced porous crystalline alumiaosiHcates which are useful as adsorbents and catalyst support materials, ie, molecular sieves (qv) (43,44). 

Gibbsite is aii important technical product and world production, predominantly by the Bayer process, is more than 50 million metric tons aimuaHy. Alost (90%) is calcined to alumina [1344-28-1 j, Al202, to be used for aluminum production. Tlie remainder is used by the chemical industry as filler for paper, plastics, rubber, and as the starting material for the preparation of various aluminum compounds, alumina ceramics, refractories, polishing products, catalysts, and catalyst supports. 

Gelatinous boehmite, called alumina gel in commeicial use, is used in the piepaiation of adsorbents, desiccants (qv), catalysts, and catalyst supports (see Catalysts, SUPPORTBd). A significant amount is used in pharmaceutical preparations. 

Alkali moderation of supported precious metal catalysts reduces secondary amine formation and generation of ammonia (18). Ammonia in the reaction medium inhibits Rh, but not Ru precious metal catalyst. More secondary amine results from use of more polar protic solvents, CH OH > C2H5OH > Lithium hydroxide is the most effective alkah promoter (19), reducing secondary amine formation and hydrogenolysis. The general order of catalyst procUvity toward secondary amine formation is Pt > Pd Ru > Rh (20). Rhodium s catalyst support contribution to secondary amine formation decreases ia the order carbon > alumina > barium carbonate > barium sulfate > calcium carbonate. 

A few industrial catalysts have simple compositions, but the typical catalyst is a complex composite made up of several components, illustrated schematically in Figure 9 by a catalyst for ethylene oxidation. Often it consists largely of a porous support or carrier, with the catalyticaHy active components dispersed on the support surface. For example, petroleum refining catalysts used for reforming of naphtha have about 1 wt% Pt and Re on the surface of a transition alumina such as y-Al203 that has a surface area of several hundred square meters per gram. The expensive metal is dispersed as minute particles or clusters so that a large fraction of the atoms are exposed at the surface and accessible to reactants (see Catalysts, supported). 

Transition aluminas are good catalyst supports because they are inexpensive and have good physical properties. They are mechanically stable, stable at relatively high temperatures even under hydrothermal conditions, ie, in the presence of steam, and easily formed in processes such as extmsion into shapes that have good physical strength such as cylinders. Transition aluminas can be prepared with a wide range of surface areas, pore volumes, and pore size distributions. 

Most catalyst supports are simply nearly inert platforms that help stabilize the dispersion of the catalyticaHy active phase. Sometimes, however, the supports play a direct catalytic role, as exemplified by the alumina used in supported Pt and RePt catalysts for naphtha reforming. 

A selective poison is one that binds to the catalyst surface in such a way that it blocks the catalytic sites for one kind of reaction but not those for another. Selective poisons are used to control the selectivity of a catalyst. For example, nickel catalysts supported on alumina are used for selective removal of acetjiene impurities in olefin streams (58). The catalyst is treated with a continuous feed stream containing sulfur to poison it to an exacdy controlled degree that does not affect the activity for conversion of acetylene to ethylene but does poison the activity for ethylene hydrogenation to ethane. Thus the acetylene is removed and the valuable olefin is not converted. 

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. 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

A great many materials have been used as catalyst supports in hydrogena-tion, but most of these catalyst have been in a quest for an improved system. The majority of catalyst supports are some form of carbon, alumina, or silica-alumina. Supports such as calcium carbonate or barium sulfate may give better yields of B in reactions of the type A- B- C, exemplified by acetylenes- cjs-olefins, apparently owing to a weaker adsorption of the intermediate B. Large-pore supports that allow ready escape of B may give better selectivities than smaller-pore supports, but other factors may influence selectivity as well. 

Top silica-supported catalysts bottom alumina-supported catalysts left 25,000 space velocity and right 95,000 space velocity... 

A ceramic monolith catalyst support, cordierite, consisting of silica, alumina and magnesium oxide. The purpose of this is to provide support, strength and stability over a wide temperature range. 

Figure 5.24. Alumina comes in many different forms, y-Al203 being the most often used catalyst support.

Figure 9.13. Preparation of a bifunctional Pt/Al203 catalyst. The alumina support is impregnated with an aqueous solution of hexachloroplatinic acid (H2PtCl6) and HCl.The competitive adsorption between C and...

Suppose you prepared an iron oxide catalyst supported on an alumina support. Your aim is to use the catalyst in the metallic form, but you want to keep the iron particles as small as possible, with a degree of reduction of at least 50%. Hence, you need to know the particle size of the iron oxide in the unreduced catalyst, as well as the size of the iron particles and their degree of reduction in the metallic state. Refer to Chapters 4 and 5 to devise a strategy to obtain this information. (Unfortunately for you, it appears that electron microscopy and X-ray diffraction do not provide useful data on the unreduced catalyst.)... 

In ecent years the utility of extended X-ray absorption fine structure UXAFS) as a probe for the study of catalysts has been clearly demonstrated (1-17). Measurements of EXAFS are particularly valuable for very highly dispersed catalysts. Supported metal systems, in which small metal clusters or crystallites are commonly dispersed on a refractory oxide such as alumina or silica, are good examples of such catalysts. The ratio of surface atoms to total atoms in the metal clusters is generally high and may even approach unity in some cases. 

Figure 9. Spectra of CO adsorbed on Co+ 8% Mo/A1.0 catalysts supported on (A.) Aero 1000 alumina and (6.) Filtrol 90 alumina. Co concentrations as indicated on spectra.

Partial oxidation reactions are usually carried out over transition metal oxides capable of changing their valent state during their interaction with reacting molecules. Naturally, zeolites with their alumina-silicate composition did not prove themselves as good oxidation catalysts. They failed also to serve as efScient catalyst supporters, since transition metals being introduced into the zeolite matrix lose their ability to activate dioxygen [3,4],... 

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