Dealuminated zeolites, similarity

The fact that catalysts prepared from hydrothermally and chemically dealuminated zeolites are similar may be related to the catalyst... 

The order of activity was HY > HBEA > HMOR for the dealuminated zeolites but HMOR and HBEA have nearly similar activity. 

The third kind of spectrum, pictured on Figure 7c, is found on dealuminated zeolites Y15 and Y 5 at medium and high nickel loadings. This spectrum reveals that only a small part of nickel is stabilized in the cationic sites. But the bands at 23460 cm-1 and 5500 cm-1 are inconsistent with an octahedral coordination. Such bands may be attributed to coordinatively unsaturated nickel ions. A similar type of nickel species was recently found on an alumina surface after moderate heating (16) with characteristic bands at 5830 and 23500 cm 1. 

Figure 16. Dealumination of zeolite Na-Y using SiClk vapor studied by 27Al-MAS NMR at 104,2 MHz. Key a, parent Na-Y zeolite b, after treatment with SiClk and moderate washing with dilute acid and c, a sample similar to b, but after extensive washing. (Reproduced from Ref. 30. Copyright 1982, American Chemical...

Reaction with chelating agents. Such reactions have been used primarily for partial dealumination of Y zeolites. In 1968, Kerr (8,21) reported the preparation of aluminum-deficient Y zeolites by extraction of aluminum from the framework with EDTA. Using this method, up to about 50 percent of the aluminum atoms was removed from the zeolite in the form of a water soluble chelate, without any appreciable loss in zeolite crystallinity. Later work (22) has shown that about 80 percent of framework aluminum can be removed with EDTA, while the zeolite maintains about 60 to 70 percent of its initial crystallinity. Beaumont and Barthomeuf (23-25) used acetylacetone and several amino-acid-derived chelating agents for the extraction of aluminum from Y zeolites. Dealumination of Y zeolites with tartaric acid has also been reported (26). A mechanism for the removal of framework aluminum by EDTA has been proposed by Kerr (8). It involves the hydrolysis of Si-O-Al bonds, similar to the scheme in Figure 1A, followed by formation of a soluble chelate between cationic, non-framework aluminum and EDTA. 

More recently, dealumination was achieved by fluorination of zeolites at ambient temperature with a dilute fluorine-in-air stream, followed by high-temperature calcination (102). The suggested reaction mechanism involves the formation of different aluminum-fluorine compounds along with zeolites containing hydroxyl and fluorine nests. During the high-temperature calcination, it is assumed that silica insertion occurs, similar to the scheme in Figure IB. 

The infrared spectra of EDTA-dealuminated Y zeolites show bands in the OH stretching region similar to those encountered in HY zeolites at about 3750, 3640 and 3540 cm (50,54). However, the OH groups responsible for the 3640 and 3540 cm bands in the spectra of the aluminum-deficient zeolites... 

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). 

Macedo et al. [227] studied HY zeolites dealuminated by steaming, and found that the strength of intermediate sites decreased with increasing dealumination for Si/Al ratios varying from 8 to greater than 100. For comparison, isomorphously substituted HY, which is free of extra-framework cationic species, possesses more acid sites than conventionally dealuminated solids with a similar framework Si/Al ratio [227], This is because some of the extra-framework aluminum species act as charge-compensating cations and therefore decrease the number of potential acid sites. 

It is also of interest to use MAS NMR for the study of the thermal treatment of zeolites which are not in the ammonium-exchanged form. In an X-ray study, Pluth and Smith (179) found electron density at the center of the sodalite cages in dehydrated zeolites Ca-A and Sr-A and attributed this to a partial occupancy of these sites by a four-coordinated aluminous species. No such effect was found in zeolite A exchanged with monovalent cations. Corbin et al. (180) used 27A1 MAS NMR to examine commercial samples of K-A, Na-A and (Ca,Na)-A, as received (see Fig. 41). For K-A and Na-A, only framework tetrahedral Al species were observed, with chemical shifts of 57 and 52 ppm respectively. However, in (Ca,Na)-A an additional intense resonance at 78 ppm, typical of AlfOH) but definitely not due to framework aluminum, was also found (see Fig. 41). A much weaker signal, also at 78 ppm, was detected in zeolite Sr-A its intensity increased greatly on heating the sample to 550°C. Freude et al. (183) came to very similar conclusions in their NMR study of heat-treated zeolite Ca-A. They found that maximum framework dealumination occurs at 500°C and corresponds to ac. 17% of total Al. 

Monodirectional 12 membered ring zeolites (offretite, L, mordenite and 0) are very inefficient as catalysts for formaldehyde benzene condensation to give diphenylmethane, esterification of phenylacetio acid with equimolar amounts of ethanol, Friedel-Crafts acylation of 3-phenylpropanoyl chloride with anisole and Claisen-Schmidt condensation of acetophenone with benzaldehyde. This fact has been attributed to diffusional constraints of organic compounds inside the channels. By contrast, the behaviour of the tridireotional f zeolite is very similar to that of dealuminated HY zeolites, inoreasing the turnover of the acid sites with the framework Si-to-Al ratio. 

Finally, the influence of the framework Si-to-Al ratio is clearly observed by increases upon dealumination of the turnover frequency (TOF) per framework A1 calculated from the MAS NMR data, for the series of HYD and 13 zeolites, Moreover, similar TOF values are found for HYD and 13 zeolites, being in general slightly higher for the second zeolite. 

This would indicate that (3 has stronger acid sites than dealuminated HYD samples, something which agrees with IR data of both solids, where the wavenumber of the accesible acidic hydroxy groups is 3620-3630 cm-1 on dealuminated HY, and 3612 cm- in HJ3 zeolites (ref. 8), A similar conclusion was reached by measuring the desorption of pyridine on these two types of large pore zeolites. 

As a numerical example, consider a partially dealuminated H-Y zeolite that contains 32 Alf/u.c., all of which are isolated, and 8 extraframework Al cations/u.c. This example is similar to the case of the partially dealuminated H-ZSM-20 zeolite in Figure 6 if one assumes that most of the extraframework Al is present in the cationic form. If the extraframework Al is complexed such that each Al has an equivalent charge of +2, 16 protons would be required to balance the framework charge. Here it is assumed that the cationic extraframework... 

Reaction mechanism It is generally admitted that, over zeolites, acetylation of arenes with AA is catalysed by protonic acid sites. Comparison of the activity of a series of dealuminated HBEA samples allows one to exclude any direct participation of Lewis acid sites in 2-MN acetylation with AA. Indeed, two HBEA samples with similar protonic acidities but with very different concentrations of Lewis acid sites (170 and 16 pmol g ) have practically the same acylating activity.1271 The role of Brpnsted sites is also clearly expressed in Spagnol et a/.131... 

The initial rate of 2-MN acetylation depends on the framework Si/Al ratio of the zeolite catalyst.[27] For a series of dealuminated BEA samples (by treatment with hydrochloric acid or with ammonium hexafluorosilicate), the acetylation rate passes through a maximum for a number of framework A1 atoms per unit cell (/VA() between 1.5 and 2.0 (Si/Al ratio between 30 and 40). The activity of the protonic sites (i.e. the TOF) increases significantly with Si/Al from 420 h 1 for Si/Al = 15 to 2650 h 1 for Si/Al = 90. It should be noted that similar TOF values could be expected from the next nearest neighbour (NNN) model. Indeed all the framework A1 atoms of the zeolite (hence all the corresponding protonic acid sites) are isolated for Si/Al ratio 10.5. Therefore the acid strength of the protonic sites is then maximal as well as their activity.[57,58] This was furthermore found for m-xylcnc isomerization over the same series of BEA zeolites.1271 This increase in TOF for... 

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