Zeolites crystalline structures

The XRD patterns of the Cu/beta catalyst as a function of temperature/time interval are plotted in Fig. 5.2. At temperatures below 800 °C (Scan number = 16 in Fig. 5.2), the change in intensity of all the diffraction peaks that correspond to the beta zeolite framework structure follows nearly the same trend as seen on the parent beta zeolite. Above this temperature however, the intensity of all peaks decreases rapidly. The zeolite crystalline structure completely collapses and... 

Adsorbents Table 16-3 classifies common adsorbents by structure type and water adsorption characteristics. Structured adsorbents take advantage of their crystalline structure (zeolites and sllicalite) and/or their molecular sieving properties. The hydrophobic (nonpolar surface) or hydrophihc (polar surface) character may vary depending on the competing adsorbate. A large number of zeolites have been identified, and these include both synthetic and naturally occurring (e.g., mordenite and chabazite) varieties. 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable.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 zeolites with applications to FCC are Type X, Type Y, and ZSM-5. Both X and Y zeolites have essentially the same crystalline structure. The X zeolite has a lower silica-alumina ratio than the Y zeolite. The X zeolite also has a lower thermal and hydrothermal... 

The most common classes of solid adsorbents are Zeolites and Silicagels. The main difference between the two is the way they are built. Zeolites have a crystalline structure and therefore a certain pore size. Silicagel have a pore... 

Figure 236. Crystalline structure of different Zeolite types...

ITQ-21 presents excellent catalytic properties for the production of cumene, being more active and stable towards deactivation and presenting lower selectivity to NPB than a comparable beta zeolite. The benefits of ITQ-21 can be directly related to its open three-dimensional crystalline structure that favors diffusion of the products and minimizes undesired consecutive reactions. 

Gibbs energy minimization has also predicted negative isobaric expansion coefficients for certain crystalline zeolite framework structures, which subsequently were confirmed experimentally [6], Many solids show negative thermal expansion at very low temperatures, including even some alkali halides (Barron and White (Further reading)). Many other solids on heating expand in some directions and contract in others. 

Zeolites are alumino-silicate materials containing extensive channels which connect cavities throughout giant three-dimensional crystalline structures. 

Loss of crystalline structure as a function of temperature can also be measured ex situ by performing the heat treatment and then determining the change in zeolite content by X-ray diffraction. Such an analysis is shown in Figure 4.43 for... 

The most commonly employed crystalline materials for liquid adsorptive separations are zeolite-based structured materials. Depending on the specific components and their structural framework, crystalline materials can be zeoUtes (silica, alumina), silicalite (silica) or AlPO-based molecular sieves (alumina, phosphoms oxide). Faujasites (X, Y) and other zeolites (A, ZSM-5, beta, mordenite, etc.) are the most popular materials. This is due to their narrow pore size distribution and the ability to tune or adjust their physicochemical properties, particularly their acidic-basic properties, by the ion exchange of cations, changing the Si02/Al203 ratio and varying the water content. These techniques are described and discussed in Chapter 2. By adjusting the properties almost an infinite number of zeolite materials and desorbent combinations can be studied. 

Leflaive, P., Dubreuil, A.G., Gaullet, P., Patarin, J., and Paillaud, J.L (2005) Process for separation by selective adsorption on a solid containing a zeolite with a crystalline structure analogous to lM-12. F.R. Patent 2,877,237. 

In view of the breadth of NMR spectroscopy in heterogeneous catalysis, no attempt has been made in this review to cover the field comprehensively the reader is directed to other reviews for complementary information (7-P). This review is focused on zeolite catalysts, in part because of their crystalline structures and in part because of their widespread use in industrial catalysis. 

In the simplest study of this type, Al-ghamdi and Mark [138] studied reinforcement of PDMS by two zeolites of different pore sizes. The zeolites were a zeolite 3A (pore diameter 3 A) and a zeolite 13X (pore diameter 10 A), both with a cubic crystalline structure. They were simply blended into hydroxyl-terminated chains of PDMS which were subsequently end-linked with tetraethoxysilane to form an elastomeric network. These elastomers were studied by equilibrium stress-strain measurements in elongation at 25°C. Both zeolites increased the modulus and related mechanical properties of the elastomer, but the effect was larger for the zeolite with the larger pore size. 

The crystalline structure of modified zeolites determine a number of properties which are specific and favorable for catalytic reactions. The complete or partial loss of crystalline structure during catalytic reactions or regeneration is in most cases accompanied by decreased catalytic activity. Thermal stability or structural stability characteristics are therefore suitable for evaluating such catalysts or supported catalysts. 

Variation in the Parameters of the Crystalline Structure of Zeolites during Adsorption... 

The high thermal stability of zeolites and related micro-porous solids is one of their most attractive features. Whilst it Is clear that materials with organic components cannot withstand ultra-high temperatures, quite respectable compositional stability can be achieved. Thus the [Er(TMA)] polymer mentioned above shows no weight loss in its TGA curve before 550°C. However for porous solids another key issue is that of structural stability. Many open framework coordination polymers lose their crystalline structure upon mild heating, or even evacuation, through loss of guest molecules. 

Zeolitic Catalyst—Since the early 1960s. modern cracking catalysts contain a silica-alumina crystalline structured material called zeolite. This zeolite is commonly called a molecular sieve. The admixture of a molecular sieve in with the base clay matrix imparts desirable cracking selectivities. 

On the other hand, a remarkable difference between catalysis by Y and 13 zeolites has been found for the Claisen-Sohmidt condensation of acetophenone and benzaldehyde (Table 5). When the cross aldolic reaction is carried out in the presence of HY, together with the expected trans and ois chalcones 5, the 3,3-diphenylpropiophenone 6 is also formed, this product being not detected on 13 zeolites. A likely explanation for the absence of 6 using zeolite beta is that the crystalline structure of this zeolite exerte a spatial constraint making difficult the formation of a big size molecule like 6, especially in the smaller channel. Similar effects due steno limitations on 6 catalysis have been found for the formation of multi-branched products during the cracking of alkanes (ref 8). 

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