Crystal structures zeolite catalysts

Vanadium also promotes dehydrogenation reactions, but less than nickel. Vanadium s contribution to hydrogen yield is 20% to 50% of nickel s contribution, but vanadium is a more severe poison. Unlike nickel, vanadium does not stay on the surface of the catalyst. Instead, it migrates to the inner (zeolite) part of the catalyst and destroys the zeolite crystal structure. Catalyst surface area and activity are permanently lost. 

The sodium in the E-cat is the sum of sodium added with the feed and sodium on the fresh catalyst. A number of catalyst suppliers report sodium as soda (Na20). Sodium deactivates the catalyst acid sites and causes collapse of the zeolite crystal structure. Sodium can also reduce the gasoline octane, as discussed earlier. 

Zeolites are used in various applications such as household detergents, desiccants and as catalysts. In the mid-1960s, Rabo and coworkers at Union Carbide and Plank and coworkers at Mobil demonstrated that faujasitic zeolites were very interesting solid acid catalysts. Since then, a wealth of zeolite-catalyzed reactions of hydrocarbons has been discovered. Eor fundamental catalysis they offer the advantage that the crystal structure is known, and that the catalytically active sites are thus well defined. The fact that zeolites posses well-defined pore systems in which the catalytically active sites are embedded in a defined way gives them some similarity to enzymes. 

According to the chemical analysis and coordination distances, the Rietveld refinement of the crystal structure at room temperature revealed 1.2 Co2+ atoms per unit cell at the Col and Co2 sites, whereas the 1.4 Ag+ cations are spread over the Co3 site, from now on referred to as Ag5 for clarity, and two new sites, Ag2 and Ag3, located near Co2 in the 10-membered ring (Fig. 3). In addition, for this catalyst the presence of Ag° clusters outside the zeolite structure was recognized by the detection of a strong reflection at about 40° 28. In agreement with the lower Ag content, in Ag2.7Co2.8AF the Ag3 site... 

Because of the large demand for p-xylene, another method is now being used by Amoco to increase the percentage of the para isomer in mixed xylenes. They are heated at 300°C with an acidic zeolite catalyst, which equilibrates the three xylenes to an o,m,p ratio of 10 72 18%. The para isomer is separated by fractional crystallization, whereas the o,m mixture is reisomerized with the catalyst to produce more para product. Theoretically, all the xylenes could be transformed into the desired para isomer. The zeolite catalyst has the following structure. 

Tlhe importance of zeolites in research on heterogeneous catalysis is A based mainly on the fact that the structure of the active surface is a defined part of the crystal structure and does not represent a more or less severe lattice defect as most catalyst surfaces do. The crystal structure, and therefore the structure of the zeolite surface, can be determined by x-ray diffraction. Knowledge of this structure allows the construction of simple models of the distribution of electric fields in the holes of the zeolite by which wide ranges of experimental results can be explained, as is shown by the pioneering work of Barrer 1-5) and Kiselev 6-9) on calculation of the heats of adsorption of various substances. 

Zeolite samples that were exhaustively treated were gray in color (materials A). Portions of each treated catalyst (0.3 gram) were calcined at 500°C in oxygen for 6 hours, giving a white product (material B). X-ray analysis showed no deterioration in crystal structure on treatment with TMS and subsequent calcination. Surface area measurements using N2 adsorption at — 196°C and the Point B method are also given in Table I. The value for HY zeolite, activated as described, prior to TMS treatment was 840 m2/gram. 

The paper deals with some new data concerning the state of the metal after reduction and the catalytic functions of zeolite catalysts containing nickel and platinum. By using the molecular sieve selectivity in the hydrogenation of mesitylene it has been proved that metal (platinum) is contained in the volume of the zeolite crystal. The temperature dependence of the formation of nickel crystals was investigated. The aluminosilicate structure and the zeolite composition influence mainly the formation of the metal surface which determines the catalytic activity. In the hydrocracking of cumene and disproportionation of toluene a bifunctional action of catalysts has been established. Hydrogen retarded the reaction. 

When studying the properties of a particular zeolitic catalyst it is not sufficient to consider the overall crystal structure in terms of a space group and pore dimensions. It is also essential to know factors such as the degree of... 

Many but not all catalysts are porous materials in which most of the surface area is internal. It is sometimes convenient to speak of the structure and texture of such materials. The structure is defined by the distribution in space of the atoms or ions in the material part of the catalyst and, in particular, by the distribution at the surface. The texture is defined by the detailed geometry of the void space in the particles of catalyst. Porosity is a concept related to texture and refers to the pore space in a material. With zeolites, however, much of the porosity is determined by the crystal structure. 

Zeolites are crystalline aluminosilicates that are used as catalysts and that have a particular chemical and physical structure (Decroocq, 1984 Goursot et al., 1997). They are highly porous crystals veined with sub-microscopic channels. The channels contain water (hence the bubbling at high temperatures), which can be eliminated by heating (combined with other treatments) without altering the crystal structure (Occelli and Robson, 1989). 

CONTENTS Introduction, Thom H. Dunning, Jr. Electronic Structure Theory and Atomistic Computer Simulations of Materials, Richard P. Messmer, General Electric Corporate Research and Development and the University of Pennsylvania. Calculation of the Electronic Structure of Transition Metals in Ionic Crystals, Nicholas W. Winter, Livermore National Laboratory, David K. Temple, University of California, Victor Luana, Universidad de Oviedo and Russell M. Pitzer, The Ohio State University. Ab Initio Studies of Molecular Models of Zeolitic Catalysts, Joachim Sauer, Central Institute of Physical Chemistry, Germany. Ab Inito Methods in Geochemistry and Mineralogy, Anthony C. Hess, Battelle, Pacific Northwest Laboratories and Paul F. McMillan, Arizona State University. 

Zeolite-P, as an excellent catalyst, is one of the most useful high-siUca zeolites. The crystal structure of zeolite-P has been comprehensively determined. However, the previously elucidated structures contain no open bonds and carmot explain why a large number of silanol groups are present in zeoHte-p. 

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