Crystal zeolite

Madsen C and Jacobsen C J FI 1999 Nanosized zeolite crystals—convenient control of crystal size distribution by confined space synthesis Chem. Commun. 673-4... 

Activation of zeolites is a dehydration process aceomplished by the application of heat in a high vacuum. Some zeolite crystals show behavior opposite to that of activated carbon in that they selectively adsorb water in the presence of nonpolar solvents. Zeolites can be made to have specifie pore sizes that will increase their seleetive nature due to the size and orientation of the molecules to be adsorbed. Moleeules above a specific size could not enter the pores and therefore would not be adsorbed. 

Jones, A.G., Ejaz, T. and Graham, P., 1999. Direct dynamic observation of phase transformations during zeolite crystal synthesis. In Industrial Crystallization 99. (Rugby Institution of Chemical Engineers). Cambridge, 13-15 September 1999. Paper 95, p. 98. 

Vanadium also promotes dehydrogenation reactions, but less than nickel. Vanadium s contribution to hydrogen yield is 20% to 50% of nickel s contribution, but vanadium is a more severe poison. Unlike nickel, vanadium does not stay on the surface of the catalyst. Instead, it migrates to the inner (zeolite) part of the catalyst and destroys the zeolite crystal structure. Catalyst surface area and activity are permanently lost. 

There are several theories about the chemistry of vanadium poisoning. The most prominent involves conversion of VjOj to vanadic acid (H-iVO ) under regenerator conditions. Vanadic acid, through hydrolysis, extracts the tetrahedral alumina in the zeolite crystal structure, causing it to collapse. 

Steam reacts with VjO, to form volatile vanadic acid. Vanadic acid, through hydrolysis, causes collapse of the zeolite crystal. 

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. 

The sodium in the E-cat is the sum of sodium added with the feed and sodium on the fresh catalyst. A number of catalyst suppliers report sodium as soda (Na20). Sodium deactivates the catalyst acid sites and causes collapse of the zeolite crystal structure. Sodium can also reduce the gasoline octane, as discussed earlier. 

Vanadium in the feed poisons the FCC catalyst when it is deposited on the catalyst as coke by vanadyl porphydrine in the feed. During regeneration, this coke is burned off and vanadium is oxidized to a oxidation state. The vanadium oxide (V O ) reacts with water vapor in the regenerator to vanadic acid, HjVO. Vanadic acid is mobile and it destroys zeolite crystal through acid-catalyzed hydrolysis. Vanadic acid formation is related to the steam and oxygen concentration in the regenerator. 

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. 

Zeolite crystals can be grown in sizes ranging from 0.5 pm to several hundreds pm and often have a characteristic morphology. Thus type A zeolites are cubes,... 

Thus zeolite ZSM-5 can be grown (ref. 15) onto a stainless steel metal gauze as shown in Figure 6. Presumably the zeolite crystals are chemically bonded to the (chromium-) oxide surface layer of the gauze. After template removal by calcination and ion exchange with Cu(II) a structured catalyst is obtained with excellent performance (ref. 15) in DeNOx reactions using ammonia as the reductant. 

The important question how inner and outer surface of the zeolite crystals contribute in the aromatic bromination has been discussed by Sasson et al. (20). Zeolite CaY was recently applied in the bromination (CH2CI2, 20 °C) of benzyl bromide (ref. 25). Selectivity to the 4-bromo derivative was 79% at a conversion of 76%. 

In view of the accessibility of zeolite A (only linear molecules adsorb) the coupling will take place at the outer surface of the zeolite crystals. Indeed, Ag-Y and especially a Ag-loaded amorphous silica-alumina, containing a spectrum of wider pores, mrned out to be much better promoter-agents (ref. 28). The silica-alumina is etched with aqueous NaOH and subsequently exchanged with Ag(I). 

By demetallation, one constituent is preferentially extracted from a preformed zeolite material to form mesoporous zeolite crystals. Existing and emerging demetallation strategies basically comprise dealumination, detitanation, and desilication. 

Figure 2.3 3D-TEM reconstruction of (a) severely steamed and subsequently acid-leached Y zeolite [22] and (b) desilicated ZSM-5 zeolite crystal [24]. The mesopores in the crystal are shown as lighter gray tones.

Figure 2.7 Schematic representation of the partial detem-plation and desilication treatment to tailor mesoporosity development in zeolite crystals.

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

Apart from the above described core-shell catalysts, it is also possible to coat active phases other than zeolite crystals, like metal nanoparticles, as demonstrated by van der Puil et al. [46]. More examples of applications on the micro level are given in Section 10.5, where microreactors and sensor apphcations are discussed. 

Although more recent quantum chemical calculations involving long-range and environmental effects inside zeolite crystals are resulting in similar stabilities for carbenium... 

Soluble species -f nuclei (or zeolite crystals)zeolite A... 

On the intergrowth structure of zeolite crystals as revealed by wide field and confocal fluorescence microscopy of the template removal processes... 

Large zeolite crystals with dimensions of tens and hundreds of micrometers have proven to be irreplaceable as model materials for reactivity and diffusion studies in the field of zeolite science and heterogeneous catalysis [1-3], These large crystallites often possesses complex structures consisting of several intergrown subunits and since the pore orientations of the different elements are not always aligned, this phenomenon can have a considerable effect on the accessibility of the pores in different crystallite regions [4]. 

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