Zeolite Bronsted-acid sites

In the case of H-SSZ-24, the values of the pre-exponential factor experimentally obtained (see Table 5.4) do not agree with the values theoretically predicted by the equation for a jump diffusion mechanism of transport in zeolites with linear channels, in the case of mobile adsorption [6,26], Furthermore, the values obtained for the activation energies are not representative of the jump diffusion mechanism. As a result, the jump diffusion mechanism is not established for H-SSZ-24. This affirmation is related to the fact that in the H-SSZ-24 zeolite Bronsted acid sites were not clearly found (see Figure 4.4.) consequently p- and o-xylene do not experience a strong acid-base interaction with acid sites during the diffusion process in the H-SSZ-24 channels, and, therefore, the hopping between sites is not produced. 

Once a carbenium ion is formed by either of the mechanisms described above, it can desorb as an olefin and restoring the zeolite Bronsted acid site ... 

S. P. Greatbanks, I. W. Hillier, N. A. Burton, and P. Sherwood, /. Chem. Phys., 105, 3770 (1996). Adsorption of Water and Methanol on Zeolite Bronsted Acid Sites An Ab Initio, Embedded Cluster Study Including Electron Correlation. 

The polarizability of zeolitic Bronsted acidic sites has been calculated using a classical electrostatic interaction scheme and compared to silanol. A larger effective polarizability has also been found for the bridged OH group with a Si cation, even in absence of the Lewis-acid promotion of silanol by Al. ... 

Factors other tlian tire Si/Al ratio are also important. The alkali-fonn of zeolites, for instance, is per se not susceptible to hydrolysis of tire Al-0 bond by steam or acid attack. The concurrent ion exchange for protons, however, creates Bronsted acid sites whose AlO tetraliedron can be hydrolysed (e.g. leading to complete dissolution of NaA zeolite in acidic aqueous solutions). 

Acid-treated clays were the first catalysts used in catalytic cracking processes, but have been replaced by synthetic amorphous silica-alumina, which is more active and stable. Incorporating zeolites (crystalline alumina-silica) with the silica/alumina catalyst improves selectivity towards aromatics. These catalysts have both Fewis and Bronsted acid sites that promote carbonium ion formation. An important structural feature of zeolites is the presence of holes in the crystal lattice, which are formed by the silica-alumina tetrahedra. Each tetrahedron is made of four oxygen anions with either an aluminum or a silicon cation in the center. Each oxygen anion with a -2 oxidation state is shared between either two silicon, two aluminum, or an aluminum and a silicon cation. 

Bronsted acid sites in HY-zeolites mainly originate from protons that neutralize the alumina tetrahedra. When HY-zeolite (X- and Y-zeolites... 

The isomorphic substituted aluminum atom within the zeolite framework has a negative charge that is compensated by a counterion. When the counterion is a proton, a Bronsted acid site is created. Moreover, framework oxygen atoms can give rise to weak Lewis base activity. Noble metal ions can be introduced by ion exchanging the cations after synthesis. Incorporation of metals like Ti, V, Fe, and Cr in the framework can provide the zeolite with activity for redox reactions. 

Figure 3.53. IR transmission absorption spectrum of pyridine adsorbed on partly dehydroxylated HY zeolite (Van Bekkum et al, 1991) B = Bronsted acid sites L = Lewis acid sites.

Two-Dimensional correlation analysis to study Bronsted acid sites in zeolites... 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

The shift of the acidic OH-band due to the interaction of the Bronsted acid sites with hexane reactant is clearly accompanied by the appearance of the absorption bands in the vCh region (fig. 2). The Av0h, C6 values listed in table 1 suggest that the apparent acidity of the ZSM-5 and mordenite samples is distinctly different (113-116 and 85-94 cm 1 shifts, respectively) and significantly higher than that of the zeolite Y samples (41-52 cm"1). 

It can be observed that very small integrated areas were obtained for ethane and ethylene (catalyst with 3 wt.%) and ethane (catalyst with 2 wt.%), contrasting with high integrated area referring to ethylene in the catalyst with 2 wt.% of gallium, which is probably due to cracking reactions with zeolite s Bronsted acid sites that in this catalyst... 

Kubica et al45 also investigated the effect of platinum-modified zeolites on the decalin reaction. They found that the addition of Pt enhances the catalyst activity. The initial isomerization was increased 3 times, which can be interpreted in terms of a change in the reaction initiation. In addition to initiation by a PC step over Bronsted acid sites, as proposed for H-form zeolites, a bifunctional initiation path... 

Pyridine sorption studies have shown the presence of both Bronsted and Lewis acid sites in USY zeolites, although to a lesser extent than in the corresponding HY zeolite (51,53). Acidity is maintained even after strong dehydroxylation of USY-B at 820°C. Rehydration of the calcined material did not regenerate significantly Bronsted acid sites, due to irreversible changes in the zeolite framework (51). 

Several reaction pathways for the cracking reaction are discussed in the literature. The commonly accepted mechanisms involve carbocations as intermediates. Reactions probably occur in catalytic cracking are visualized in Figure 4.14 [17,18], In a first step, carbocations are formed by interaction with acid sites in the zeolite. Carbenium ions may form by interaction of a paraffin molecule with a Lewis acid site abstracting a hydride ion from the alkane molecule (1), while carbo-nium ions form by direct protonation of paraffin molecules on Bronsted acid sites (2). A carbonium ion then either may eliminate a H2 molecule (3) or it cracks, releases a short-chain alkane and remains as a carbenium ion (4). The carbenium ion then gets either deprotonated and released as an olefin (5,9) or it isomerizes via a hydride (6) or methyl shift (7) to form more stable isomers. A hydride transfer from a second alkane molecule may then result in a branched alkane chain (8). The... 

Infrared Spectroscopy Characterization of Zeolitic Systems 129 Bronsted Acid Site Distribution... 

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