Aluminum distributions in zeolites

Aluminum distribution in zeolites is also important to the catalytic activity. An inbalance in charge between the silicon atoms in the zeolite framework creates active sites, which determine the predominant reactivity and selectivity of FCC catalyst. Selectivity and octane performance are correlated with unit cell size, which in turn can be correlated with the number of aluminum atoms in the zeolite framework. ... 

The major effect of new advanced techniques on catalyst structure is found in zeolite catalysis. NMR techniques, especially MASNMR, have helped to explain aluminum distribution in zeolites and to increase our understanding of critical parameters in zeolite synthesis and crystallization. MASNMR, combined with TEM, STEM, XPS, and diagnostic catalytic reaction probes, has advanced our knowledge of the critical relationship between the structure and reactivity patterns of zeolites in the chemical fuels industry. Throughout the symposium upon which this book is based, many correlations were evident between theoretical quantum mechanical calculations and the structures elucidated by these techniques. 

The main result of extensive simulations of A1 placement in the FAU-framework topology is that random insertion of A1 into the structure, subject to Loewenstein s rule and to a weaker second neighbor Al-Al repulsion term, does not reproduce the measured Si-nAl distribution patterns [4]. The details of the aluminum distributions are therefore determined by additional or different factors. This is consistent with Melchior s model of FAU-framework construction from pre-formed 6-iing units [47,48], The simulation results also highlight the likely limitations of quantum mechanical studies of aluminum T-site preferences. If the factors controlling the aluminum distributions in zeolites X and Y are also at work in other systems, purely energetic arguments will likely have limited direct relevance for application to real materials. 

Kennedy, G.J., Afeworki, M., and Hong, S.B. 2002. Probing the non-random aluminum distribution in zeolite merlinoite with ultra-high-field (18.8 T) A1 and Si MAS NMR. Micropor. Mesopor. Mater. 52 55-59. 

The location of boron or aluminum sites in zeolites is of utmost importance to an understanding of the catalytic properties. Due to the inherent long-range disorder of the distribution of these sites in most zeolites, it is difficult to locate them by diffraction methods. The aforementioned methods to measure heteronuclear dipolar interactions can be utilized to determine the orientation between the organic SDA and A1 or B in the framework. The SDA location may be obtained by structure refinement or computational modeling. For catalytic reactions, the SDA must be removed from the pores system by calcination. 

In contrast to the stabilization of monovalent exchange cations in zeolites the structural aspects of stabilization of multivalent metal exchange cations are not quite clear. For example, the ion exchange position for bivalent metal cations should be formed by two lattice Al atoms. According to the traditional point of view the aluminum distribution over zeolite lattice is predominantly stochastic. It creates a variety of mutual localization of two nearest lattice Al atoms and results in a number of possible ion exchange structures for the bivalent cation stabilization. On the other hand, it is evident that structural peculiarities of bivalent metal cations stabilization influence the adsorption ability and catalytic reactivity of the cation. 

The next stage of characterization focuses upon the different phases present within the catalyst particle and their nature. Bulk, component structural information is determined principally by x-ray powder diffraction (XRD). In FCC catalysts, for example, XRD is used to determine the unit cell size of the zeolite component within the catalyst particle. The zeolite unit cell size is a function of the number of aluminum atoms in the framework and has been related to the coke selectivity and octane performance of the catalyst in commercial operations. Scanning electron microscopy (SEM) can provide information about the distribution of crystalline and chemical phases greater than lOOnm within the catalyst particle. Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) can be used to obtain information on crystal transformations, decomposition, or chemical reactions within the particles. Cotterman, et al describe how the generation of this information can be used to understand an FCC catalyst system. 

Dealuminated Y zeolites which have been prepared by hydrothermal and chemical treatments show differences in catalytic performance when tested fresh however, these differences disappear after the zeolites have been steamed. The catalytic behavior of fresh and steamed zeolites is directly related to zeolite structural and chemical characteristics. Such characteristics determine the strength and density of acid sites for catalytic cracking. Dealuminated zeolites were characterized using X-ray diffraction, porosimetry, solid-state NMR and elemental analysis. Hexadecane cracking was used as a probe reaction to determine catalytic properties. Cracking activity was found to be proportional to total aluminum content in the zeolite. Product selectivity was dependent on unit cell size, presence of extraframework alumina and spatial distribution of active sites. The results from this study elucidate the role that zeolite structure plays in determining catalytic performance. 

As shown in Figure 7, calcined zeolites with similar unit cell sizes demonstrate different octane-producing behavior. Hence, structural characteristics such as extraframework aluminum and spatial distribution of acid sites are important factors affecting zeolite acidity. After steaming, the octane behaviors of AFS and USY zeolites are similar reflecting similarities in zeolite acidities. 

These calculations yield, subject to some simplifying assumptions, relative T-site alumimun substitution energies computed (1) for the thermodynamic equilibrium state, (2) at zero K and (3) for models devoid of non-firamework species. Framework zeolites, metastable structures, are produced under luetic control and if, as indicated by the most recent calculations, the relative T-site substitution energies for the (Cerent sites are not grossly disparate, the actual distributions in reed materitds will be determined by the particular conditions of synthesis. As the molecular-level mechanisms of zeolite sjmthesis remain obscure, we especially need some experimental indicator of which sites are actually adopted by aluminum in real MFI-framework materials. 

Mordenite is a naturally occurring zeolite that has a Si Al ratio near ten. Synthetic mordenites also have this same narrow range Si Al ratio, a fact that suggests that the aluminum atoms are distributed in an orderly manner in this zeolite rather than in the presumed random orientation in the other zeolites. The central feature of mordenite is a slightly oval shaped 12-ring with a 0.67 x 0.7 run... 

Scherzer concluded that in the USY formed from NH4Y through high-temperature water-vapor treatment, the aluminum exists in three forms (1) in the USY framework, (2) outside the framework as 6-coordinated octahedral Al, (3) on the USY surface as differently coordinated Al which results in surface Al enrichment. The Al in the USY framework produces B acid centers, and although the number of the acid centers is smaller than that of the parent Y zeolite, the strength and distribution of these centers may favor cracking catalytic reactions more. 

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