Zeolites crystallization mechanism

Figure 12.2 (a) Three different zeolite crystallization mechanisms. (Reproduced with per-... 

The section on crystallization comprises zeolite synthesis, kinetics and mechanism of formation, stability relationships, recrystallization processes as well as the genesis of natural zeolites. Recent advances in this field have been surveyed, and some new perspectives have been outlined in the review by E. M. Flanigen. Most of the studies in this field are still empirical because of the complexity of the systems involved. Considerable progress has been made, however, towards a better understanding of the processes and mechanisms governing zeolite crystallization. It is not unreasonable to expect that conditions for synthesizing new zeolite structure types can eventually be predicted. 

Zhdanov (1) describes the mechanism of zeolite crystallization in terms of a quasiequilibrium between the solid and liquid phase in gels and emphasizes that the formation and growth of nuclei occurs in the liquid phase. 

Zeolite crystallization can be interpreted in terms of a ripening mechanism. The initially formed gel consists of amorphous dispersed particles of the order of 100-300 A in size. Growth of these particles to approximately 1000 A occurs during the induction period after which zeolite crystals appear imbedded in the amorphous gel matrix. This is especially evident in electron microscopic studies of gel solids (66,88). Ciric comments on the observation of growing crystals imbedded in gel particles which, as the crystals grow, tend to shrink together, resulting in coalescence (74)-... 

Progress in zeolite crystallization in the last several years has been mostly in the experimental realm and has resulted in several new synthetic zeolites and compositional variants of previously known structures. Theoretical advances have come more slowly but are significant. Until the elucidation of zeolite structures in the last decade or so, structural interpretation of crystallization phenomena was not possible. As additional physical and chemical techniques are applied to the complex structural chemistry of zeolite crystallization, our understanding of the mechanism increases, and the extent of empiricism in synthesis decreases. Areas of investigation still unexplored that should add considerable understanding... 

It was possible for two of the systems chosen that the nucleation and crystallization activation energies could be determined separately by distinguishing the induction period and crystal growth period in the overall crystallization process. Of the two hypotheses proposed for zeolite crystallization, in the gel phase or from the solution phase, the data support the latter hypothesis for crystal growth with the crystal-liquid surface enhancing the nucleation process in seeded systems. The precise mechanism of nucleation in unseeded systems remains to be determined. 

It is well known that the elements in framework of zeolite molecular sieves greatly influence the properties and behaviors of these materials [1-3], The introduction of heteroatoms into the framework has become one of most active fields in study of zeolites. The investigations were mostly focused on the methods to introduce heteroatoms into the framework (for examples, hydrothermal synthesis and post-synthesis), the mechanisms for incorporations, the effect of heteroatoms on the acid-base properties and the catalytic features of modified samples [1-10]. Relatively less attention was paid to the effect of treatment process on the porous properties of samples although the incorporation of heteroatoms, especially by the so-called post-synthesis, frequently changes the distribution of pore size. Recently, we incorporated Al, Ga and B atoms into zeolites (3 by the post-synthesis in an alkaline medium named alumination, galliation and boronation, respectively. It was found that different trivalent elements inserted into the [3 framework at quite different level. The heteroatoms with unsuitable atom size and poor stability in framework were less introduced, leading to that a considerable amount of framework silicon were dissolved under the action of base and the mesopores in zeolite crystal were developed. As a typical case, the boronation of zeolites (3 and the accompanied formation of mesopores are reported in the present paper. 

Mintova et al. studied deposition of zeolite A on various cellulose fibers pretreated chemically and/or mechanically [151]. It was shown that the amount of zeolite deposited was controllable by suitable fiber pretreatment with ball-milling or with diethyl ether under ultrasonic action. The reactive high-concentration hydroxyl groups on the structurally loosened celluloses seem to interact with aluminosilicate species and thus promote the formation of nuclei for zeolite crystallization. Pretreatment of natural cellulose fibers with alkali provides another simple route for anchoring preformed zeolite crystallites onto the cellulose surface. 

Mechanism of Rapid Zeolite Crystallizations and Its Applications to Catalyst Synthesis... 

ECR-1 is a true boundary phase between two compatible structures - mazzite and mordenite - which normally crystallize with greatly disparate Si/Al ratios (3.4 and >5 respectively). Yet ECR-1 has an Si/Al ratio identical to mazzite, even though half of its component sheets are structurally characteristic of mordenite (in the structure proposal). This compositional incompatibility is further reflected in the almost complete lack of mixtures of mazzite with mordenite in the experiments so far completed. The ongoing search for ECR-1 with mordenite overgrowths is therefore an important objective in the understanding of crystallization mechanisms in this system, with particular interest in the possible compositional variation between all three component zeolites. 

It is anticipated that the continued apphcation of sophisticated NMR spectroscopy to solution and solid phases with the development of diffraction techniques to study the early stages of zeolite crystallization may ultimately clarify the problems of the mechanisms whereby zeolites are formed. 

The mechanism of the diffusion within ZSM-5 zeolite crystal is thought to be analogous to that of impurities in the lattice of metals. This analogy gives the relation of the intracrystalline diffusivity, A to the molecular size and the pore size, as follows ... 

In the early days of XPS the first applications of the technique to zeolites were dealing with the determination of Si/Al ratios calculated using equation (23) and their comparison with bulk values [14-16]. This of course allowed to detect important compositional gradients in the surface region, a piece of information which is related to the mechanism of zeolite synthesis and which is technically important in order to monitor the concentration of Brdnsted acid sites on the external surface of the zeolite crystals. The measurement of... 

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