Catalysts, activity internal structure

Kaolin had little or no cracking activity, and catalyst activity as tested in the laboratory was directly related to silica-alumina gel content. However, the catalyst performed much better in commercial tests than anticipated from laboratory testing. Undoubtedly, this open structure encountered much less severe conditions at the outer surface of the microsphere during regenerations and made internal catalytic surfaces more readily available. This first of the so-called "semisynthetics" was called Nalco 783, and the matrix is still used in many forms some 28 years later.(7,13) Today it is estimated that some 200,000 tons/yr. of kaolin clay is used for cracking catalyst manufacture as reported by Georgia Kaolin Corporation.(24) Figure 10 shows the pore volume distribution for Nalco 783 and two other commercial semisynthetics from that period. 

It has been already emphasized that substitution of heteroelements into the framework of molecular sieves creates acidic sites. Incorporation of transition elements such as Ti, V, Mn, Fe, or Co, which have redox properties, provides molecular sieves with redox active sites that are involved in oxidation reactions (323-332). As mentioned in the beginning of the article, the transition metal-substituted molecular sieves, the so-called redox molecular sieves, exhibit several advantages compared with other types of heterogeneous redox catalysts (1) redox sites are isolated in a well-defined internal structure therefore, oligomerization of the active oxometal species is prevented (this is a major reason for the deactivation of homogeneous catalysts) (2) the site isolation (the so-called microenvironment) of redox centers prevents the leaching of the metal ions, which frequently happens in liquid-phase oxidations catalyzed by conventional transition metal-supported catalysts (3) well-defined cavities and channels of molecular dimensions endow the catalysts with unique performances such as the shape selectivity (and traffic control) toward reactants, intermediates, and/or products. 

There are two classifications of electron donors, internal and external. Electron donors are thus named for their ability to act as Lewis bases and donate electrons to Lewis acid sites. For the TiCls type catalyst, the electron donors are traditionally referred to as just donors and are generally amines, esters, ethers, alcohols, etc. Their roles range from modifying the catalyst site and structure of the TiCL substrate to complexing with the alkyl aluminum either during catalyst preparation or catalyst activation. 

The function of the internal donor in MgCl2-supported catalysts is twofold. One function is to stabilize small primary crystallites of magnesium chloride the other is to control the amount and distribution of TiCU in the final catalyst. Activated magnesium chloride has a disordered structure comprising very small lamellae. Giannini (32) has indicated that, on preferential lateral cleavage surfaces, the magnesium atoms are coordinated with four or five chlorine atoms, as... 

The components in catalysts called promoters lack significant catalytic activity tliemselves, but tliey improve a catalyst by making it more active, selective, or stable. A chemical promoter is used in minute amounts (e.g., parts per million) and affects tlie chemistry of tlie catalysis by influencing or being part of tlie catalytic sites. A textural (structural) promoter, on tlie otlier hand, is used in massive amounts and usually plays a role such as stabilization of tlie catalyst, for instance, by reducing tlie tendency of tlie porous material to collapse or sinter and lose internal surface area, which is a mechanism of deactivation. 

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