Zeolites framework composition

The big advantage of the ordered mesoporous material is that it has a high surface area and a large pore volume. The big disadvantage may be that its wall is amorphous, and is not ordered at the atomic level. This results in its poor performances low hydrothermal stability and low catalytic acid strength, although there are many methods available to improve those performances. Simultaneously, the amorphous wall makes the modification chemistry on the wall much easier, which allowed the various wall compositions to be synthesized successfully. In contrast, the extension of zeolite framework compositions is difficult because of the limits of their critical crystalline structures at the atomic level. 

Silica Oxide to Alumina Oxide Ratio (SAR) is used to describe the framework composition of zeolite. 

Kerr (7-9) has shown the critical role of the calcination environment and bed geometry in the formation of USY zeolites ("deep bed" vs."shallow bed"calcination). Ward (10) prepared USY zeolites by calcining ammonium Y zeolites in flowing steam. The work done by Kerr and Maher et al. (11) has clearly demonstrated that USY zeolites are formed as a result of aluminum expulsion from the framework at high temperatures in the presence of steam. The nature of the non-framework aluminum species has not been completely clarified. Obviously, their composition will be strongly affected by the preparation procedure of the USY zeolite. Table II shows different oxi-aluminum species assumed to be formed during thermal dealumination of the zeolite framework. 

The connectivity (topology) of the zeolite framework is characteristic for a given zeolite type, whereas the composition of the framework and the type of extra-framework species can vary. Each zeolite structure type is denoted by a three-letter code [4], As an example, Faujasite-type zeolites have the structure type FAU. The pores and cages of the different zeolites are thus formed by modifications of the TO4 connectivity of the zeolite framework. 

Fries rearrangement, 18 336, 337 isomerization and transalkylation of alky-laromatics, 18 329 epoxide transformations, 18 351-352 hydration and ammonolysis of ethylene oxide, 18 351, 352 isomerization, 18 351 framework composition, 33 226-228 hydrogenation, dehydrogenation, and related reactions, 18 360-365 dehydrocyclization of s-ethylphenyl using zeolites and carbonyl sulfide, 18 364, 365... 

The characteristics of aluminophosphate molecular sieves include a univariant framework composition with Al/P = 1, a high degree of structural diversity and a wide range of pore sizes and volumes, exceeding the pore sizes known previously in zeolite molecular sieves with the VPI-5 18-membered ring material. They are neutral frameworks and therefore have nil ion-exchange capacity or acidic catalytic properties. Their surface selectivity is mildly hydrophilic. They exhibit excellent thermal and hydrothermal stability, up to 1000 °C (thermal) and 600 °C (steam). 

In the metal aluminophosphate (MeAPO) family the framework composition contains metal, aluminum and phosphorus [27]. The metal (Me) species include the divalent forms of Co, Fe, Mg, Mn and Zn and trivalent Fe. As in the case of SAPO, the MeAPOs exhibit both structural diversity and even more extensive composihonal variation. Seventeen microporous structures have been reported, 11 of these never before observed in zeoUtes. Structure types crystallized in the MeAPO family include framework topologies related to the zeolites, for example, -34 (CHA) and -35 (LEV), and to the AIPO4S, e.g., -5 and -11, as well as novel structures, e.g., -36 (O.Snm pore) and -39 (0.4nm pore). The MeAPOs represent the first demonstrated incorporation of divalent elements into microporous frameworks. 

Si NMR provides quantitative information about the framework composition, and framework Si/Al ratio is an important parameter used to tune the catalyst property. Zeolite acidity is directly related to the amount of framework Al. Framework Si/Al ratio can directly be obtained from just Si NMR alone. Si/Al ratio can be calculated from Si NMR intensities if the resonances due to different Q (nAl) species are well-resolved using Eq. (4.10), assuming there is no Al-O-Al bonds present ... 

For multi-component systems it seems intuitive that single-component diffusion and adsorption data would enable one to predict which component would be selectively passed through a membrane. This is only the case where molecular sieving is observed for all other separations where the molecules interact with one another and with the zeolite framework their behavior is determined by these interactions. Differences in membrane properties such as quahty, microstructure, composition and modification can also play a large role in the observed separation characteristics. In many cases, these properties can be manipulated in order to tailor a membrane for a specific apphcation or separation. 

Introductory Chapter 1 provides a historical overview of molecular sieve materials. Chapter 2 covers the definition of a zeolite and describes their basic and composite building units and how they are linked in zeolite frameworks. It defines pores, channels, cages and cavities and it gives references for finding detailed... 

The cation plays a prominent structure-directing role in zeolite crystallization. The unique structural characteristics of zeolite frameworks containing polyhedral cages (62, 63) have led to the postulate that the cation stabilizes the formation of structural subunits which are the precursors or nucleating species in crystallization. The many zeolite compositions and complex cation base systems studied allow a test of the structuredirecting role of the cation and the cation templating concept. Table I summarizes the cation base systems from which zeolites have been synthesized. The systems used before 1969 are indicated to illustrate the number and complexities of new cation systems investigated since that time. Table II presents a summary of zeolite framework structure types, the cation systems in which they have been formed, and a proposal for a cation specificity for the formation of each framework type. A similar... 

The conversion rates of n-hexane are shown as a function of the crystallinity parameter Qai for different temperatures. We found that the catalytical activity increases simultaneously with the increased crystallinity of the composites, the crystallization products. According this linear correlation it can be concluded that the catalytical active sites, the acidic centers in the zeolitic framework, are always, independent of the crystal content of the composite material, accessible for educt of the test reaction, the n-hexane molecules. This leads to the assumption that the crystallization must start on the interface (at the phase border) between the solution (contains the alkalinity and the template) and the solid (porous glass) surface and has to carry on to the volume phase of the glass resulting finally in complete transformed granules. 

Two categories of mesoporous solids are of special interest M41S type materials and pillared or delaminated derivatives of layered zeolite precursors (pillared zeolites in short). The M41S family, first reported in early 1990 s [1], has been extensively studied [2,3]. These materials exhibit broad structural and compositional diversity coupled with relative ease of preparation, which provides new opportunities for applications as catalysts, sorption and support media. The second class owes its existence to the discovery that some zeolite crystallizations can produce a lamellar intermediate phase, structurally resembling zeolites but lacking complete 3-dimensional connectivity in the as-synthesized form [4]. The complete zeolite framework is obtained from such layered zeolite precursor as the layers become fused, e.g. upon calcination. The layers posses zeolitic characteristics such as strong acidity and microporosity. Consequently, mesoporous solids derived from layered zeolite precursors have potentially attractive characteristics different from M41S and the zeolite species... 

Equation (IS) provides the zeolite chemist with a powerful quantitative method for the determination of framework composition of zeolites. By comparing (Si/A1)NMR values with the results of chemical analysis, which gives bulk composition, the amount of nonframework (six-coordinated) aluminum can be calculated. This is of particular value in the study of chemically modified zeolites (see Sections III,J-III,M). 

All the zeolite/carbon composites prepared by these methods were treated with an excess amount of 46% aqueous HF solution at room temperature for 3h and subsequently refluxed in concentrated HC1 solution at 60°C for 3h to dissolve the zeolite framework. The solution was filtered and the insoluble fraction was extensively washed with water. Finally, the resultant insoluble carbon was air-dried at 120°C overnight. 

The total exchange capacity (TEC) of an aluminosilicate zeolite is a function of the framework composition that is, the Si/Al ratio. It is easy to obtain a numerical relation between the TEC, C, in milliequivalent per gram, and the number of A1 atoms per framework unit cell, NAl [5]... 

Third, the relative intensities of the Si(nAl) signals in realuminated samples are strikingly different from those in the as-prepared zeolites with the same framework composition, which means that the distribution of Si and A1 in the treated zeolites is different. This is a consequence of the different site selectivities discussed above, but also of the fact that both the original Si(OAl) sites and the Si(OAl) sites created during ultrastabilization are available for A1 substitution. 

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