Organic catalysis over zeolites: A perspective on reaction paths within micropores

The framework topology of zeolite beta

Zeolites have proved to be valuable technical catalysts in petrochemistry and in oil processing. The characteristic properties of zeolites, such as acidity, shape-selectivity and thermal stability also enable them to be used for highly selective synthesis in the fields of chemical intermediates and fine chemicals. This interesting area of application has grown continuously in recent years. The present article summarizes the various standard types of reaction involved in organic syntheses which can be catalyzed by zeolites; these include, inter alia, electrophilic and nucleophilic substitution reactions, isomerization of double bonds and carbon skeletons, as well as addition, elimination and hydrogenation reactions.

Zeolites: Catalysts for Organic Syntheses

The tetrahedral framework structure of zeolite beta is disordered along (001). The disordered structure is related by a/3 and/or b/3 displacements on (001) planes to three ordered polytype structures with triclinic, monoclinic, and tetragonal symmetry. Three mutually perpendicular 12-ring channel systems are characteristic of the three ordered polytypes and the disordered beta structure. The proposed framework structures are consistent with the known diffraction, sorption an cation exchange properties of zeolite beta.

In the 26 years since the term “shape-selective catalysis” was coined by P. B. Weisz and V. J. Frilette [1] to describe the unique catalytic properties of small pore molecular sieve zeolites, great strides in the use of shape-selective zeolites have been made, both scientifically and technologically. Since then, in addition to small pore zeolites, synthetic medium pore zeolites, such as ZSM-5 [2], ZSM-11 [3], ZSM-22 [4], ZSM-23 [5], ZSM-35 [6], ZSM-38 [7], ZSM-48 [8], etc., have been discovered. The availability of these synthetic medium pore zeolites has expanded the realm of “shape selectivity” beyond the original discovery of selective conversion of straight chain molecules to include certain branched molecules, single-ring aromatics, naphthenes, and nonhydrocarbons with a critical molecular dimension smaller than about 6 A.

W.J. Rohrbaugh

Papers

The framework topology of ZSM-23: A high silica zeolite