Dealumination

1 Dealumination Dealumination creates mesopores by removal of a certain amount of the aluminum from the zeolite framework. This method represents the classic alternative route to develop mesoporosity in zeohtes, and mainly comprises two strategies, which are steaming at elevated temperatures and acid leaching. 

Add leaching also allows mesopores to be created by a quite similar mechanism, that is, through the extraction of some aluminum from the framework positions. A typical procedure is slurrying the zeolite in a solution of ethylenediaminetetraacetic acid (EDTA) under reflux conditions for 18h [150]. Afterwards, the zeolite is heated under an inert gas at 1073 K. However, this method has the drawback of preferentially removing the external surface aluminum, leading to a nonuniform composition. 

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Figure C2.12.8. Schematics of tlie dealumination of zeolites. Water adsorbed on a Br( msted site hydrolyses tire Al-O bond and fonns tire first silanol group. The remaining Al-0 bonds are successively hydrolysed leaving a silanol nest and extra-framework aluminium. Aluminium is cationic at low pH.

Catalytic Properties. In zeoHtes, catalysis takes place preferentially within the intracrystaUine voids. Catalytic reactions are affected by aperture size and type of channel system, through which reactants and products must diffuse. Modification techniques include ion exchange, variation of Si/A1 ratio, hydrothermal dealumination or stabilization, which produces Lewis acidity, introduction of acidic groups such as bridging Si(OH)Al, which impart Briimsted acidity, and introducing dispersed metal phases such as noble metals. In addition, the zeoHte framework stmcture determines shape-selective effects. Several types have been demonstrated including reactant selectivity, product selectivity, and restricted transition-state selectivity (28). Nonshape-selective surface activity is observed on very small crystals, and it may be desirable to poison these sites selectively, eg, with bulky heterocycHc compounds unable to penetrate the channel apertures, or by surface sdation. 

Table 3. Vanadium Prepared by Dealuminization with Vacuum Heating ...

Sodium decreases the hydrothermal stability of the zeolite. It also reacts with the zeolite acid sites to reduce catalyst activity. In the regenerator, sodium is mobile. Sodium ions tend to neutralize the strongest acid sites. In a dealuminated zeolite, where the UCS is low (24.22°A to 24.25°A), the sodium can have an adverse affect on the gasoline octane (Figure 3-7). The loss of octane is attributed to the drop in the number of strong acid sites. 

An uitrastabie or a dealuminated zeolite (USY) is produced by replacing some of the aluminum ions in the framework with silicon. The conventional technique (Figure 3-9) includes the use of a high temperature (1,300-1,500°F [704-816°C]) steam calcination of... 

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. 

The previous sections have shown that desihcation of ZSM-5 zeohtes results in combined micro- and mesoporous materials with a high degree of tunable porosity and fuUy preserved Bronsted acidic properties. In contrast, dealumination hardly induces any mesoporosityin ZSM-5 zeolites, due to the relatively low concentration of framework aluminum that can be extracted, but obviously impacts on the acidic properties. Combination of both treatments enables an independent tailoring of the porous and acidic properties providing a refined flexibility in zeolite catalyst design. Indeed, desihcation followed by a steam treatment to induce dealumination creates mesoporous zeolites with extra-framework aluminum species providing Lewis acidic functions [56]. 

Thermal treatments can be applied to modify the properties of a material, for example, dealumination and optimization of crystalHne phases. These techniques do not require oxidants. Oxidative thermal treatments are generally employed to activate molecular sieves, by removing the organic templates employed during synthesis. This is one of the key steps when preparing porous catalysts or adsorbents. In air-atmosphere calcination, the templates are typically combusted between 400... 

MicrocrystalUne zeolites such as beta zeolite suffer from calcination. The crystallinity is decreased and the framework can be notably dealuminated by the steam generated [175]. Potential Br0nsted catalytic sites are lost and heteroatoms migrate to extra-framework positions, leading to a decrease in catalytic performance. Nanocrystals and ultrafine zeolite particles display aggregation issues, difficulties in regeneration, and low thermal and hydrothermal stabilities. Therefore, calcination is sometimes not the optimal protocol to activate such systems. Application of zeolites for coatings, patterned thin-films, and membranes usually is associated with defects and cracks upon template removal. 

Ga-MOR was hydrothermally synthesized by using tetraethylammonium bromide as a template. Ga content was controlled by removing Ga through HCl treatment in the same way as the dealumination of zeolite [1], The numeral at the end of catalyst name stands for Si02/Ga203 ratio in Ga-MOR thus prepared. Ga203/Ga-M0R catalyst was prepared by... 

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

Traditionally, aromatic nitrations have been performed with mixtures of concentrated nitric and sulphuric acids leading to considerable effluent problems associated with the spent acid. A heterogeneous alternative for. sulphuric acid has been reported (Bertea et al., 1995), namely dealuminated Mordenite, which is sufficiently robust to be able to catalyse the vapour-phase nitration of benzene with 65% aqueous nitric acid. 

Metallic nitrates, supported on clays, have been used for nitrations and oxidations. Recent interesting studies involve nitration of 4-hydroxybenzaldehyde with Fe nitrate and KIO montmori I Ionite, in which nuclear nitration was preferentially realized and practically no oxidation of the aldehyde occurred. Even more interesting, simple addition of Fe nitrate to dealuminated or natural clay gave comparable or even better results. A 100% yield was realized at 60 °C with toluene as the solvent (Bekassy et al., 1998). 

Fichtner-Schmittler, H., Lohse, U., Engelhardt, G. et al. (1984) Unit-cell constants of zeolites stabilized by dealumination - determination of al-content from lattice-parameters, Cryst. Res. Technol., 19, Kl. 

To a 500 g sample of acidic, dealuminized mordenite (CBV-20A from PQ Corporation, 1.5 mm diameter extrudates that had been calcined at 540 °C, overnight) was added a solution of 33 ml of 48% HF in 1633 ml of distilled water, and the mix cooled in ice, stirred on a rotary evaporator overnight, then filtered to recover the extruded solids. The extrudates were further washed with distilled water, dried in vacuo at 100 °C, and then calcined at 540 °C, overnight. Analyses of the treated mordenite showed 1.2% fluoride, 0.49 meq/g acidity. Samples were charged to the reactive distillation unit either as 20/40 mesh granules, or as ca. 1.5 mm extrudates. 

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. 

Hydrolysis oftricaprylin in trimethylpentane by Fusarium solani pisi recombinant cutinase immobilized on various zeolites (NaA, NaX, NaY, LZY-82, dealuminated Y) was investigated in order to assess the effect of chemical composition (Si/Al ratio), hydrophilic character and acidity on the catalytic activity [221]. The adsorption of... 

Keywords Two-Dimensional correlation, Infrared spectroscopy, Dealuminated H-Y zeolite, Bronsted acidity, MQ-MAS NMR. 

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