Of dealuminated

Figure 2. The effect of dealumination by EDTA over MOR (Si/Al=5.0) for ethyle-nediamine synthesis.

An amorphous component such as silica-alumina is added to the catalyst, for a sort of pre-cracking of the large molecules (greater than about C25), which cannot enter the zeolite pores. The smaller fragments may then react in the zeolite. Middle distillates maximum yield is achieved by the use of dealuminated Y zeolites. 

In view of catalytic potential applications, there is a need for a convenient means of characterization of the porosity of new catalyst materials in order to quickly target the potential industrial catalytic applications of the studied catalysts. The use of model test reactions is a characterization tool of first choice, since this method has been very successful with zeolites where it precisely reflects shape-selectivity effects imposed by the porous structure of tested materials. Adsorption of probe molecules is another attractive approach. Both types of approaches will be presented in this work. The methodology developed in this work on zeolites Beta, USY and silica-alumina may be appropriate for determination of accessible mesoporosity in other types of dealuminated zeolites as well as in hierarchical materials presenting combinations of various types of pores. 

This could be a result of dealumination of the catalysts in the presence of water formed in the thermal pyrolysis of woody biomass. 

Besides di- and poly-saccharides, zeolites have been applied for hydrolysis of simple glycosides as described by Le Strat and Morreau.132 Methyl a- and /i-D-glucopyrano-sides were treated with water in the presence of dealuminated HY faujasite with an Si/Al ratio of 15, at temperatures ranging between 100 and 150 °C. It was observed that the reaction rate for the (i glycoside was about 5-6 times higher than that for the oc anomer, a result that might arise from the shape-selective properties of the zeolite and stereoelectronic effects on the surface of the solid. 

J.-F. Chapat, A. Finiels, J. Joffre, and C. Moreau, Synthesis of butyl-a and / -d-glucopyranosides in the presence of dealuminated H-Y faujasites Kinetic study, mechanism, stereoelectronic effects, and microreversibility principle, /. Catal., 185 (1999) 445—453. 

Seeding technique. Al-free Ti-beta obtained by use of dealuminated zeolite-beta seeds Fluoride method. Al-free Ti-beta synthesis from a reaction mixture containing TEAOH and fluoride ions (HF) at near-neutral pH. Gel composition Ti02 60SiO2 32.9NEt4OH 32.9HF 20H2O 457.5 H20. Crystallization at 413 K with rotation of the autoclave (60 rpm)... 

Combination of thermal and chemical dealumination. This is a two-step method which was applied in the preparation of aluminum-deficient mordenite (4,5) and Y zeolites (28,29). In some instances the two-step treatment was repeated on the same material, in order to obtain a higher degree of dealumination (5,28). 

A modification of the above cyclic method has proved more effective in the dealumination of Y zeolites. An almost aluminum-free, Y-type structure was obtained by using a process involving the following steps a) calcination, under steam, of a low-soda (about 3 wt.% Na O), ammonium exchanged Y zeolite b) further ammonium exchange of the calcined zeolite c) high-temperature calcination of the zeolite, under steam d) acid treatment of the zeolite. Steps a) and c) lead to the formation of ultrastable zeolites USY-A and USY-B, respectively. Acid treatment of the USY-B zeolite can yield a series of aluminum-deficient Y zeolites with different degrees of dealumination, whose composition depends upon the conditions of the acid treatment. Under severe reaction conditions (5N HC1, 90°C) an almost aluminum-free Y-type structure can be obtained ("silica-faujasite") (28,29). 

SURFACE COMPOSITION AND DEPTH PROFILE OF DEALUMINATED ZEOLITES (43,44)... 

Aluminum-deficient Y zeolites prepared by partial removal of aluminum with a chelating agent (e.g. EDTA) also show improved thermal and hydrothermal stability compared to the parent zeolite. The optimum stability was found in the range of 25 to 50 percent of framework A1 extraction (8). However, the maximum degree of dealumination is also affected by the SiO /Al O ratio in the parent zeolite a higher ratio appears to allow more advanced dealumination without loss of crystallinity (8,25,45). Above 50 or 60 percent dealumination, significant loss of crystallinity was observed. Calcination of the aluminum-deficient zeolite resulted in a material with a smaller unit cell size and lower ion-exchange capacity compared to the parent zeolite. 

Sorption. The sorption properties of aluminum-deficient mordenite are strongly affected by the dealumination procedure used and by the degree of dealumination. Materials prepared by procedures that do not involve high temperature treatments show a relatively high sorption capacity for water (15,70), due to the presence of silanol groups, which are hydrophilic centers. However, aluminum-deficient mordenite zeolites prepared by methods requiring heat treatment show a lower sorption capacity for water due to fewer silanol groups. This was shown by Chen (71), who studied the sorption properties of aluminum-deficient mordenite prepared by the two-step method. 

The formation of such bonds during the heat treatment of dealuminated mordenite has also been suggested by Rubinshtein et al. (72-74), in some instances without the intermediate formation of SiOH groups. The hydrophobic nature of the zeolite also increases with progressive dealumination. Chen (71) has shown that aluminum-deficient mordenite zeolites with SiO /Al O ratios over 80 absorb little or no water at low pressure. These highly silicious zeolites are truly hydrophobic and in this respect are similar to highly silicious zeolites prepared by direct synthesis (e.g. ZSM-5) (75). 

Degree of dealumination. Moderate dealumination generally increases the catalytic activity or leaves it unchanged, while advanced dealumination leads to a decrease in activity. Such a decrease is due to a loss of active sites with advanced framework dealumination. 

M. Neamtu, C. Catrinescu and A. Kettrup, Effect of dealumination of iron(III)-exchanged Y. zeolites on oxidation of Reactive Yellow 84 azo dye in the presence of hydrogen peroxide. Appl. Catal. B Environ., 51 (2004) 149-157. 

The other advantage of dealumination is improved coke selectivity. Vlhile coke selectivity correlates with unit cell size, the correlation is different than the one for octane, and there is no correlation between coke selectivity and sodium content 5). 

DEALUMINATIQN OF ZEOLITE Y Dealumination is an important process to improve the thermal stability and resistance to acid of zeolite. This is one of the main techniques for preparing zeolite catalysts (US-Y). New pores (mesopores) have been introduced during hydrothermal treatment (Fig.4), which were directly confirmed by electron microscopy. The density of mesopores depended on the degree of dealumination and the size distribution of mesopores... 

In Fig. 2.1.6.6, the FTIR spectra of the Jacobsen ligand (a), the Jacobsen catalyst (bj, and the immobilized manganese salen complex in the cages of dealuminated faujasite zeolite (c) are compared. While spectra a and b have been measured using the standard KBr technique, the spectrum c of the ship in a bottle catalyst has been recorded using a self-supported wafer. The bands at wavenumbers 1466 cm, 1434 cm" , 1399 cm" and 1365 cm" in spectrum c can be assigned to the... 

The mechanism of dealumination of the zeolitic framework and the nature of extra-framework Al ... 

It has been shown before that the removal of aluminum from the framework leads to very marked narrowing of NMR signals. When no A1 is present, the Si(4Si) lines are very narrow indeed ( 0.7 ppm). Fyfe et al. (84-88) studied the effect of dealumination on linewidths of Si(4 Si) signals in several zeolites. They found that substantial line narrowing occurs at Si/Al > 100, which indicates that the effect must be long range in nature. They suggest (86) that it is caused by a chemical shift interaction due to distribution of Al in the second-nearest and further coordination shells of silicon. 

The extent of dealumination was found (166) to be limited by the degree of ammonium exchange of the starting material, and also to depend on the temperature and water vapor pressure during treatment. Depending on the conditions, any desired composition of the product up to Si/Al 8 could be... 

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