Zeolites manufacture

The reported surface area is the combined surface area of zeolite and matrix. In zeolite manufacturing, the measurement of the zeolite surface area is one of the procedures used by catalyst suppliers to control quality. The surface area is commonly determined by the amount of nitrogen adsorbed by the catalyst. 

Synthetic zeolites and other molecular sieves are important products to a number of companies in the catalysis and adsorption areas and numerous applications, both emerging and well-established, are encouraging the industrial synthesis of the materials. There are currently no more than a few dozen crystalline microporous structures that are widely manufactured for commercial use, in comparison to the hundreds of structures that have been made in the laboratory. See Chapter 2 for details on zeolite structures. The highest volume zeolites manufactured are two of the earliest-discovered materials zeolite A (used extensively as ion exchangers in powdered laundry detergents) and zeolite Y (used in catalytic cracking of gas oil). 

A number of reagents containing oxide components are used in zeolite manufacture [19]. Silica is provided by addihon of sodium or other alkali silicate solutions, precipitated, colloidal, or fumed silica, or tetraalkylorthosihcate (alkyl = methyl, ethyl) and certain mineral silicates such as clays and kaolin. Alumina is provided as sodium aluminate, aluminum sulfate soluhon, hydrous aluminum oxides such as pseudo boehmite, aluminum nitrate, or aluminum alkoxides. Additional alkali is added as hydroxide or as halide salts, while organic amines and/or... 

Molecular exchange between the crystallites and the intercrystalline space may, however, be controlled by processes other than ordinary diffusion. A substantial retardation of molecular exchange may be caused by transport resistances on the external surface of the crystallites. It has been shown in PFG NMR studies that such surface barriers may be brought about during the process of zeolite manufacturing (e.g. by hydrothermal treatment) [1,6] and by coke depositions [1,7]. In this case, irrespective of possibly large rates of molecular redistribution within the crystallites, the rate of molecular escape out of the crystallites may be slowed down dramatically. In effect, in this case, the product molecules should be distributed essentially homogeneously over the whole space of the individual crystallites. 

Other common applications of colloidal gases include solid foams, such as those occurring in the areas of food (leavened breads), geology (pumice stone, zeolites), manufacturing (polystyrene foam, polyurethane foam), and personal care... 

Color Zeohte has to he white powder. The degree of whiteness depends on the method and standard used in the measurement (CIE LAB-Hunter MgO, BaS04, CIBA as white standard). Although BaS04 as a secondary standard [56] is more stable than MgO, the latter, due to its diffuse reflartance, is better for powdered materials. The zeolite manufacturing standard demands the refl ance against MgO to be ... 

Zeolites. A large and growing industrial use of aluminum hydroxide and sodium alurninate is the manufacture of synthetic zeoHtes (see Molecular sieves). ZeoHtes are aluminosiHcates with Si/Al ratios between 1 and infinity. There are 40 natural, and over 100 synthetic, zeoHtes. AH the synthetic stmctures are made by relatively low (100—150°C) temperature, high pH hydrothermal synthesis. For example the manufacture of the industriaHy important zeoHtes A, X, and Y is generaHy carried out by mixing sodium alurninate and sodium sHicate solutions to form a sodium alurninosiHcate gel. Gel-aging under hydrothermal conditions crystallizes the final product. In special cases, a small amount of seed crystal is used to control the synthesis. 

Molecular sieves are an adsorbent that is produced by the dehydration of naturally occurring or synthetic zeolites (crystalline alkali-metal aluminosilicates). The dehydration leaves inter-crystalline cavities into which normal paraffin molecules are selectively retained and other molecules are excluded. This process is used to remove normal paraffins from gasoline fuels for improved combustion. Molecular sieves are used to manufacture high-purity solvents. 

The molecular sieve process uses synthetically manufactured. solid crystalline zeolite in a dry bed to remove gas impurities. The crystalline... 

Zeolites employed in the manufacture of the FCC catalyst are synthetic versions of naturally occurring zeolites called faujasites. There are about 40 known natural zeolites and over 150 zeolites that have been synthesized. Of this number, only a few have found commercial applications. Table 3-1 shows properties of the major synthetic zeolites. 

A freshly manufactured zeolite has a relatively high UCS in the range of 24.50°A to 24.75°A. The thermal and hydrothermal environment of the regenerator extracts alumina from the zeolite structure and, therefore, reduces its UCS. The final UCS level depends on the rare earth and sodium level of the zeolite. The lower the sodium and rare earth content of the fresh zeolite, the lower UCS of the equilibrium catalyst (E-cat). 

Sodium Content. The sodium on the catalyst originates either from zeolite during its manufacture or from the FCC feedstock. It is important for the fresh zeolite to contain very low amounts of sodium. 

The filler is a clay incorporated into the catalyst to dilute its activity. Kaoline [A. 2(OH)2, Si205] is the most common clay used in the FCC catalyst. One FCC catalyst manufacturer uses kaoline clay as a skeleton to grow the zeolite in situ. 

In the manufacturing of USY catalyst, the zeolite, clay, and binder are slurried together. If the binder is not active, an alumina component having catalytic properties may also be added. The well-mixed slurry solution is then fed to a spray dryer. The function of a spray dryer is to form microspheres by evaporating the slurry solution, through the use of atomizers, in the presence of hot air. The type of spray dr er and the drying conditions determine the size and distribution of catalyst particles. 

Improved crystallinity by producing more uniform zeolite crystals, FCC catalyst manufacturers have greater control over the zeolite acid site distribution. In addition, there is an upward trend in the quantity of zeolite being included in the catalyst. 

Faujasite is a naturally occurring mineral, having a specific crystalline, alumina-silicate structure, used in the manufacturing of the FCC catalyst. Zeolite faujasite is a synthetic form of the mineral. 

Rare Earth is a generic name used for the 14 metallic elements of the lanthanide series used in the manufacturing of FCC catalyst to improve stability, activity, and gasoline selectivity of the zeolite. 

Zeolite is a synthetic crystalline alumina-silicate material used in the manufacturing of FCC catalyst. 

External treatment also meant the removal of calcium and magnesium hardness by zeolite softening using either a variety of silcate-based, natural zeolites [such as analcite, (Na AljS O, 2 2H20)], or manufactured carbon zeolites. 

Today n-paraffms are exclusively produced from the corresponding distillation cuts of paraffin-rich oils with the use of molecular sieves. Molecular sieves are synthetically manufactured aluminum silicates of the zeolite type, which after dehydration have hollow spaces of specific diameters with openings of specific diameters. The molecules are then able to penetrate the openings in the correct size and form and are held in the hollow spaces by electrostatic or van der Waals forces. The diameter of the zeolite type used for the production of paraffins is 5 A and is refined so that the n-paraffins (C5-C24) can penetrate the hollow spaces while the iso- and cyclic paraffins are unable to pass through [15]. 

Zeoliltes seem particularly suited to take over the job and in fact are doing so already for aromatic alkylation. Thus in ethylbenzene manufacture (from benzene and ethene) modern processes apply zeolites (H-ZSM-5, H-Y) as the catalyst, substituting conventional processes based on AICI3 or BF3-on-alumina catalysis. Substantial waste reductions are achieved. 

To overcome the limitations of natural zeolites a whole range of synthetic zeolites have been manufactured since the 1950s. These have tailored pore sizes and tuned acidities, as well as often incorporating other metal species. The basic synthesis involves mixing a source of silica, usually sodium silicate or colloidal Si02, with a source of alumina, often sodium aluminate, and a base such as sodium hydroxide. The mixture is heated at temperatures up to 200 °C under autogenous pressure for a period of a few days to a few weeks to allow crystallization of the zeolite. 

Base catalysis is another area which has received a recent stimulus from developments in materials science and microporous solids in particular. The Merk company, for example, has developed a basic catalyst by supporting clusters of cesium oxide in a zeolite matrix [13]. This catalyst system has been developed to manufacture 4-methylthiazole from acetone and methylamine. 

Some companies are successfully integrating chemo- and biocatalytic transformations in multi-step syntheses. An elegant example is the Lonza nicotinamide process mentioned earlier (.see Fig. 2.34). The raw material, 2-methylpentane-1,5-diamine, is produced by hydrogenation of 2-methylglutaronitrile, a byproduct of the manufacture of nylon-6,6 intermediates by hydrocyanation of butadiene. The process involves a zeolite-catalysed cyciization in the vapour phase, followed by palladium-catalysed dehydrogenation, vapour-pha.se ammoxidation with NH3/O2 over an oxide catalyst, and, finally, enzymatic hydrolysis of a nitrile to an amide. 

In the recent past the potential of zeolites in the manufacture of fine chemicals has received considerable attention. High-Si zeolites can have Hammet s acidity function Ho of -12.8 which is close to those for superacids. MCM (Mobil Catalytic Materials) have opened up new vistas due to larger pore sizes. 

The use of zeolites can also be very helpful in removing a reaction product that unfavourably influences the yield of the desired product. Thus, in the manufacture of antibiotic cefoxitin, the amide acylation results in the generation of HCI, which can be removed by the addition of molecular sieve 3 A or 4 A, which has a large capacity for HCI (Weinstock, 1986). Other examples are reactions in which products like methanol or water retard the rate and prevent the reaction to reach the desired degree of completion. Molecular sieves capture methanol or water very well. 

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