Heterogeneous zeolites

The Propylur process converts low value light hydrocarbons enriched in olefins into petrochemicals such as propylene and is based on a shape-selective heterogeneous zeolitic catalyst of the ZSM-5 type. 

Whereas superaeid (HF/BF3, HF/SbF, HF/TaF FS03FI/SbF3, etc.)-eatalyzed hydroearbon transformations were first explored in the liquid phase, subsequently, solid aeid eatalyst systems, sueh as those based on Nafion-H, longer-chain perfluorinated alkanesulfonic acids, fluorinated graphite intercalates, etc. were also developed and utilized for heterogeneous reactions. The strong acidic nature of zeolite catalysts was also successfully explored in cases such as FI-ZSM-5 at high temperatures. 

Volume 104 Equilibria and Dynamics of Gas Adsorption on Heterogeneous Solid Surfaces edited by W. Rudzihski, W.A. Steele and G. Zgrablich Volume 105 Progress in Zeolite and Microporous Materials... 

Some work has also been achieved with heterogeneous catalysis. These catalysts include Amberlyst-15, Nafion-H, montmorillonite KSF clay, ferrihydrite silica gel aerogels containing 11-13% iron, silica sulfuric acid, and zeolites. ... 

The vapor-phase Badger process (Eigure 10-2), which has been commercialized since 1980, can accept dilute ethylene streams such as those produced from ECC off gas. A zeolite type heterogeneous catalyst is used in a fixed bed process. The reaction conditions are 420°C and 200-300 psi. Over 98% yield is obtained at 90% conversion." Polyethylbenzene (polyalkylated) and unreacted benzene are recycled and join the fresh feed to the reactor. The reactor effluent is fed to the benzene fractionation system to recover unreacted benzene. The bottoms... 

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. 

Sulfur is widely distributed as sulfide ores, which include galena, PbS cinnabar, HgS iron pyrite, FeS, and sphalerite, ZnS (Fig. 15.11). Because these ores are so common, sulfur is a by-product of the extraction of a number of metals, especially copper. Sulfur is also found as deposits of the native element (called brimstone), which are formed by bacterial action on H,S. The low melting point of sulfur (115°C) is utilized in the Frasch process, in which superheated water is used to melt solid sulfur underground and compressed air pushes the resulting slurry to the surface. Sulfur is also commonly found in petroleum, and extracting it chemically has been made inexpensive and safe by the use of heterogeneous catalysts, particularly zeolites (see Section 13.14). One method used to remove sulfur in the form of H2S from petroleum and natural gas is the Claus process, in which some of the H2S is first oxidized to sulfur dioxide ... 

In this chapter, we Hmit ourselves to the topic of zeolite membranes in catalysis. Many types of membranes exist and each membrane has its specific field where it can be appHed best. Comparing polymeric and inorganic membranes reveals that for harsher conditions and high-temperature applications, inorganic membranes outperform polymeric membranes. In the field of heterogeneous catalYsis, elevated temperatures are quite common and therefore this is a field in which inorganic membranes could find excellent applications. 

Proceedings of the 2" International FEZA (Federation of the European Zeolite Associations) Conference, Taormina, Italy, September 1-5, 2002 edited by R. Aiello, G. Giordano and F.Testa Volume 143 Scientific Bases for the Preparation of Heterogeneous Catalysts... 

Zeolites form a unique class of oxides, consisting of microporous, crystalline aluminosilicates that can either be found in nature or synthesized artificially [J.M. Thomas, R.G. Bell and C.R.A. Catlow in Handbook of Heterogeneous Catalysis (Ed. G. Ertl, H. Knbzinger and J. Weitkamp) (1997), Vol. 1, p. 206, VCH, Weinheim.]. The zeolite framework is very open and contains channels and cages where cations, water and adsorbed molecules may reside and react. The specific absorption properties of zeolites are used in detergents, toothpaste, and desiccants, whereas their acidity makes them attractive catalysts. 

Acidic, high area silica-almnina had received substantial attention in ICC 1, 52-58). Perhaps the most dramatic change in the subsequent catalytic literature was the debut of zeolites. Why acid catalyzed reactions are so much faster on zeolites than on silica-alumina has been extensively discussed but probably not conclusively. One should be able to know the exact structures of catalytic sites in zeolites, but initial hopes that this would do wonders for mechanistic imderstanding have not been fully realized. Super acids and carbonium ions came into heterogeneous catalysis from homogeneous chemistry and in special cases reaction via carbonium ions seems to occur. 

Zeolites have led to a new phenomenon in heterogeneous catalysis, shape selectivity. It has two aspects (a) formation of an otherwise possible product is blocked because it cannot fit into the pores, and (b) formation of the product is blocked not by (a) but because the transition state in the bimolecular process leading to it cannot fit into the pores. For example, (a) is involved in zeolite catalyzed reactions which favor a para-disubstituted benzene over the ortho and meso. The low rate of deactivation observed in some reactions of hydrocarbons on some zeoUtes has been ascribed to (b) inhibition of bimolecular steps forming coke. 

The reader is referred the recent book by Bell and Pines [2] for a more complete overview of the various methods and objectives in NMR studies of solid acids and other heterogeneous catalysis. In the present contribution we illustrate the application of H, and MAS NMR to two archetypal solid acids, Brpnsted sites in zeolites and solid metal halides such as aluminum chloride and bromide powders which exhibit "Lewis superacidity". An important characteristic of the more recent work is the integration of quantum chemical calculations into the design and interpretation of the NMR experiments. 

Zeolites. In heterogeneous catalysis porosity is nearly always of essential importance. In most cases porous materials are synthesized using the above de.scribed sol-gel techniques resulting in so-called amorphous catalysts. Porosity is introduced in the agglomeration process in which the sol is transformed into a gel. From X-ray Diffraction patterns it is clear that the material shows only weak broad lines, characteristic of non-crystalline materials. Silica and alumina are typical examples. Zeolites are an exception they are crystalline materials but nevertheless exhibit high (micro) porosity. Zeolites belong to the class of molecular sieves, which are porous solids with pores of molecular dimensions, i.e., typically the pore diameter ranges from 0.3 to 10 nm. Examples of molecular sieves are carbons, oxides and zeolites. 

The hydroamination of alkenes has been performed in the presence of heterogeneous acidic catalysts such as zeolites, amorphous aluminosilicates, phosphates, mesoporous oxides, pillared interlayered clays (PILCs), amorphous oxides, acid-treated sheet silicates or NafioN-H resins. They can be used either under batch conditions or in continuous operation at high temperature (above 200°C) under high pressure (above 100 bar). 

An alternative that has received a great deal of attention in recent years is the immobilisation of a chiral catalyst on a nonsoluble support (polystyrene resins, silica gel, zeolites, etc.), thereby creating a chiral heterogeneous catalyst. Unlike homogeneous catalysts, these supported complexes can be recovered from the... 

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