Exchangeable acid sites

Catalyst Co content (mmol) Non exchanged acid sites (mmol) Reaction rate (mmol/min) Cyclohexane conversion (%) Adipic acid yield (%)... 

Figure C2.12.2. Fonnation of Br0nsted acid sites in zeolites. Aqueous exchange of cation M witli an ammonium salt yields tlie ammonium fonn of tlie zeolite. Upon tliennal decomposition ammonia is released and tire proton remains as charge-balancing species. Direct ion-exchange of M witli acidic solutions is feasible for high-silica zeolites.

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 Sites. Acidic zeoHtes have outstanding catalytic activity. The hydrogen form may be produced by ammonium ion exchange, foUowed by thermal deammoniation. The unsolvated proton forms an OH group with a bridging O ... 

A rare-earth-exchanged zeolite increases hydrogen transfer reactions. In simple terms, rare earth forms bridges between two to three acid sites in the catalyst framework. In doing so, the rare earth protects... 

It is believed that clay minerals promote organic reactions via an acid catalysis [2a]. They are often activated by doping with transition metals to enrich the number of Lewis-acid sites by cationic exchange [4]. Alternative radical pathways have also been proposed [5] in agreement with the observation that clay-catalyzed Diels-Alder reactions are accelerated in the presence of radical sources [6], Montmorillonite K-10 doped with Fe(III) efficiently catalyzes the Diels-Alder reaction of cyclopentadiene (1) with methyl vinyl ketone at room temperature [7] (Table 4.1). In water the diastereoselectivity is higher than in organic media in the absence of clay the cycloaddition proceeds at a much slower rate. 

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. 

Since spillover phenomena have been most directly sensed through the use of IR in OH-OD exchange [10] (in addition, in the case of reactions of solids, to phase modification), we used this technique to correlate with the catalytic results. One of the expected results of the action of Hjp is the enhancement of the number of Bronsted sites. FTIR analysis of adsorbed pyridine was then used to determine the relative amounts of the various kinds of acidic sites present. Isotopic exchange (OH-OD) experiments, followed by FTIR measurements, were used to obtain direct evidence of the spillover phenomena. This technique has already been successfully used for this purpose in other systems like Pt mixed or supported on silica, alumina or zeolites [10]. Conner et al. [11] and Roland et al. [12], employed FTIR to follow the deuterium spillover in systems where the source and the acceptor of Hjp were physically distinct phases, separated by a distance of several millimeters. In both cases, a gradient of deuterium concentration as a function of the distance to the source was observed and the zone where deuterium was detected extended with time. If spillover phenomena had not been involved, a gradientless exchange should have been observed. 

Szanyi et al., using again in situ IR-TPD coupled skills, studied the effect of acid sites on the catalytic activities of a series of H+-modified Na-Y zeolites in the non-thermal plasma assisted NO reduction reaction using a simulated diesel engine exhaust gas mixture. The acid sites were formed by NH ion exchange and subsequent heat treatment of a NaY zeolite. The catalytic activities of these H+- modified NaY zeolites... 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

The acidic character of 5A zeolite as a function of the calcium content has been explored by different techniques propylene adsorption experiments, ammonia thermodesorption followed by microgravimetry and FTIR spectroscopy. Propylene is chemisorbed and slowly transformed in carbonaceous compounds (coke) which remain trapped inside the zeolite pores. The coke quantities increase with the Ca2+ content. Olefin transformation results from an oligomerization catalytic process involving acidic adsorption sites. Ammonia thermodesorption studies as well as FTIR experiments have revealed the presence of acidic sites able to protonate NH3 molecules. This site number is also correlated to the Ca2+ ion content. As it has been observed for FAU zeolite exchanged with di- or trivalent metal cations, these sites are probably CaOH+ species whose vas(OH) mode have a spectral signature around 3567 cm"1. 

Di or trivalent cations are able to induce the dissociation of coordinated water molecules to produce acidic species such as MOH+ (or MOH2+ for trivalent metal cations) and H+. Several infrared studies concerning rare-earth or alkali-earth metal cation exchanged Y zeolites have demonstrated the existence of such species (MOH+ or MOH2+) [3, 4, 5, 6]. However, the literature is relatively poor concerning the IR characterization of these acidic sites for LTA zeolites. The aim of the present work is to characterize 5A zeolite acidity by different techniques and adsorption tests carried on 5A zeolite samples with different ion exchange. 

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. 

NH4 ion-exchange capacity, taken as the concentration of Bronsted acid sites... 

In spite of the nominal absence of Bronsted acid sites, it is possible to introduce copper species in the S-l matrix by following an ion-exchange procedure. The unit cell of the S-l can be written as follow [1] ... 

The type of treatment applied significantly affected the benzene/naphthalene (B/N) product ratio (Fig. 6). Thus, treatment with oxalic and citric acids, steaming plus HC1 washing, and partial Cs-exchanged increased the B/N ratio with respect to the untreated sample. In the first three cases, this effect may be explained by a preferential removal of the acid sites at the external zeolite surface, where naphthalene is predominantly formed [6], The reason of the increased B/N ratio in the 3Mo/CsHZ5 sample still needs to be elucidated, but a decrease in surface acidity in combination with an enhanced shape selectivity effect due to presence of voluminous Cs+ cations inside the micropores (a decrease in Vmicrop was noticed in Table 1) may be hypothesized. 

The NH4-Beta-300 (Zeolyst International, number denote Si02/Al203 molar ratio) was transformed to corresponding proton form using a step calcination procedure at 500 °C. H-Beta-300 was partially modified with Fe by repeated ion-exchange method (Fe(III)nitrate). The surface areas as well as acidities (Bronsted and Lewis acid sites) of Fe-Beta (iron content - 0.1 wt %) were determined by nitrogen adsorption and pyridine desorption at 250, 350 and 450 °C using FTIR spectroscopy [6]. 

The transformation of n-hexadecane was carried out in a fixed-bed reactor at 220°C under a 30 bar total pressure on bifunctional Pt-exchanged HBEA catalysts differing only by the zeolite crystallites size. The activities of the catalysts and especially the reaction scheme depended strongly on the crystallites size. Monobranched isomers were the only primary reaction products formed with the smallest crystallites, while cracking was the main reaction observed with the biggest crystallites. This was explained in terms of number of zeolite acidic sites encountered by the olefinic intermediates between two platinum particles. 

The method of metal introduction should significantly affect the degree of proximity between the Pt and acidic sites, hence the catalytic properties. In a previous study, the behavior of Pt/MCM-22 samples in n-hexane transformation was explored by Martins et al. [11]. In this study the same reaction was used in order to evaluate the influence of the mode of Pt introduction. Three 1 wt.% Pt/MCM-22 samples were prepared, differing by the mode of platinum introduction ion exchange, incipient wetness impregnation or mechanical mixture of the zeolite with Pt/Al203. 

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