Silicon zeolites

A process offered by Sweden s Munters Zeol employs a large, disk-shaped ceramic rotor that is honeycombed with channels impregnated with a hydrophobic, all-silicon zeolite. Although it does not use carbon, the process is mentioned here because it is aimed at removing low concentrations (below 1,000 ppm) of VOCs from contaminated air streams. When used for this purpose, the impure air flows through one section of the rotor s channels, where the zeolite adsorbs the V(Xs, while heated air or inert gas flows through another section to desorb material previously adsorbed. The assembly rotates continuously so that each channel passes through adsorption and desorption zones alternately. Adsorption typically occurs at 80°-100°F, desorption at 360°F. Reportedly, the process was first offered in the U.S. in 1991 after more than a dozen units had been sold in Europe (Anon., 1991). 

Increasing the surface-to-bulk ratio of the sample to be studied. This is easily done in the case of highly porous materials, and has been exploited for the characterization of supported catalysts, zeolites, sol-gels and porous silicon, to mention a few. 

Figure B3.3.14. Template molecule in a zeolite cage. The CFIA stmcture (periodic in the calculation but only a fragment shown here) is drawn by omitting the oxygens which are positioned approximately halfway along the lines shown coimecting the tetrahedral silicon atoms. The molecule shown is 4-piperidinopiperidine, which was generated from the dicyclohexane motif suggested by computer. Thanks are due to D W Lewis and C R A Catlow for this figure. For fiirther details see [225].

Figure C2.12.1. Origin of ion exchange capacity in zeolites. Since every oxygen atom contributes one negative charge to the tetrahedron incoriDorated in the framework, the silicon tetrahedron carries no net charge while the aluminium tetrahedron carries a net charge of-1 which is compensated by cations M.

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

Examples of the unique insights obtained by solid state NMR applications to materials science include the Si/Al distribution in zeolites, the hydrogen microstructure in amorphous films of hydrogenated silicon, and the mechanism for the zeolite-catalyzed oligomerization of olefins. ... 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable. Incorporating zeolites (crystalline alumina-silica) with the silica/alumina catalyst improves selectivity towards aromatics. These catalysts have both Fewis and Bronsted acid sites that promote carbonium ion formation. An important structural feature of zeolites is the presence of holes in the crystal lattice, which are formed by the silica-alumina tetrahedra. Each tetrahedron is made of four oxygen anions with either an aluminum or a silicon cation in the center. Each oxygen anion with a -2 oxidation state is shared between either two silicon, two aluminum, or an aluminum and a silicon cation. 

The four oxygen anions in the tetrahedron are balanced by the -i-4 oxidation state of the silicon cation, while the four oxygen anions connecting the aluminum cation are not balanced. This results in -1 net charge, which should be balanced. Metal cations such as Na", Mg ", or protons (H" ) balance the charge of the alumina tetrahedra. A two-dimensional representation of an H-zeolite tetrahedra is shown ... 

Aluminum distribution in zeolites is also important to the catalytic activity. An inbalance in charge between the silicon atoms in the zeolite framework creates active sites, which determine the predominant reactivity and selectivity of FCC catalyst. Selectivity and octane performance are correlated with unit cell size, which in turn can be correlated with the number of aluminum atoms in the zeolite framework. ... 

Zeolite is sometimes called molecular sieve. It has a well defined lattice structure. Its basic building blocks are silica and alumina tetrahedra (pyramids). Each tetrahedron (Figure 3-1) consists of a silicon or aluminum atom at the center of the tetrahedron, with oxygen atoms at the four comers. 

The elementary building block of the zeolite crystal is a unit cell. The unit cell size (UCS) is the distance between the repeating cells in the zeolite structure. One unit cell in a typical fresh Y-zeolite lathee contains 192 framework atomic positions 55 atoms of aluminum and 1atoms of silicon. This corresponds to a silica (SiOj) to alumina (AI.O,) molal ratio (SAR) of 5. The UCS is an important parameter in characterizing the zeolite structure. 

As stated above, a typical zeolite consists of silicon and aluminum atoms that are tetrahedrally joined by four oxygen atoms. Silicon is in a +4 oxidation state therefore, a tetrahedron containing silicon is neutral in charge. In contrast, aluminum is in a +3 oxidation state. This indicates that each tetrahedron containing aluminum has a net charge of -1, which must be balanced by a positive ion. 

Unit Cell Size (UCS). The UCS is a measure of aluminum sites or the total potential acidity per unit cell. The negatively-charged aluminum atoms are sources of active sites in the zeolite. Silicon atoms do not... 

An uitrastabie or a dealuminated zeolite (USY) is produced by replacing some of the aluminum ions in the framework with silicon. The conventional technique (Figure 3-9) includes the use of a high temperature (1,300-1,500°F [704-816°C]) steam calcination of... 

In zeolite synthesis (ref. 2) an aqueous mixture containing a silicon source, an aluminum source, an alkali source (usually NaOH) is autoclaved and subjected to hydrothermal treatment. Hydrated Na-ions are then filling the pore system in the as-synthesized zeolite. In the case of relatively high Si/Al zeolites an organic template is required which is usually a tetraalkylammonium compound, applied as the bromide or the hydroxide. 

Figure 2.4 Schematic representation of silicon hydrolysis from the zeolite framework in aqueous alkali hydroxide solution.

Figure 2.5 N2 adsorption isotherms and schematized silicon dissolution (inset) upon alkaline treatment ofZSM-5 zeolites with different framework Si/AI ratios, highlighting the crucial role of framework aluminum.

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