Catalysis by zeolites and molecular sieves

Meriaudeau and Naccache conclude the volume with a concise description of skeletal isomerization of butenes catalyzed by medium-pore zeolites and molecular sieves. This isomerization is a relatively new industrial process. and it is remarkable how fast a good fundamental understanding of it has developed in a few years the chapter is an account of catalysis by well-defined acidic groups in pores that exert a subtle control over catalyst performance, including selectivity. It is a story that was deeply appreciated by Werner Haag. 

Sorption into, release from and diffusion inside microporous and mesoporous materials are of paramount interest in view of separation processes and catalysis by zeolites and related structures. Thus, volume 7 of the handbook-like series Molecular Sieves - Science and Technology is exclusively devoted to the phenomena of adsorption into, desorption out of and diffusion in the pores of zeolite crystalhtes. 

In the above discussion, we have presumed that the tortuosity factor t is characteristic of the pore structure but not of the diffusing molecules. However, when the size of the diffusing molecule begins to approach the dimensions of the pore, one expects the solid to exert a retarding influence on the flux and this effect may also be incorporated in the tortuosity factor. This situation is likely to be significant in dealing with catalysis by zeolites (molecular sieves). 

Although a number of books now contain chapters or sections dealing with zeolites, this subject has been the primary focus in very few volumes. The most noteworthy of these is the treatise by D. W. Breck, Zeolite Molecular Sieves, published by Wiley in 1974. The earliest modem ones are the Russian texts on Molecular Sieves and Their Use, published by V. A. Sokolov, N. S. Torocheshnikov, and N. V. Kel tsev in 1964, and S. P. Zhdanov s Chemistry of Zeolites in 1968. Other significant works include the 1976 ACS Monograph on Zeolite Chemistry and Catalysis edited by J. A. Rabo, and the volume on Zeolites and Clay Minerals as Sorbents and Molecular Sieves by R. M. Barrer, published in England in 1978. 

Catalysis by zeolites is a rapidly expanding field. Beside their use in acid catalyzed conversions, several additional areas can be identified today which give rise to new catalytic applications of zeolites. Pertinent examples are oxidation and base catalysis on zeolites and related molecular sieves, the use of zeolites for the immobilization of catalytically active guests (i.e., ship-in-the-bottle complexes, chiral guests, enzymes), applications in environmental protection and the development of catalytic zeolite membranes. Selected examples to illustrate these interesting developments are presented and discussed in the paper. 

The major activities in the science and application of zeolite catalysts are still observed in the field of (shape selective) acid catalysis. However, additional thrust areas can be clearly identified today, viz. zeolites in oxidation or base catalysis, applications in environmental protection, catalysis by ship-in-the-bottle complexes, to enumerate just a few. Many aspects of zeolite catalysis have been covered in a number of recent review articles [e g., 1-6] including the potential catalytic applications of ultra-large pore molecular sieves [7]. Hence there is no real need, nor would it be feasible on the limited number of pages allotted to this review, to cover every aspect fi om the huge amount of work done recently in the field. Rather, the authors restricted themselves to selected topics in catalysis by zeolites which, in their own view, deserve particular attention in the years to come. 

The use of microporous solid catalysts such as zeolites and related molecular sieves has an additional benefit in organic synthesis. The highly precise organization and discrimination between molecules by molecular sieves endows them with shape-selective properties [12] reminiscent of enzyme catalysis. The scope of molecular sieve catalysis has been considerably extended by the discovery of ordered mesoporous materials of the M41S type by Mobil scientists [13,14]. Furthermore, the incorporation of transition metal ions and complexes into molecular sieves extends their catalytic scope to redox reactions and a variety of other transition metal-catalyzed processes [15,16]. 

One of the main factors determining the effectiveness of zeolites for catalysis and molecular sieving is their stability under working conditions. In many cases the deposition of carbonaceous compounds terminates a zeolite s lifetime, and therefore quantitative information about the localization of such coke deposits and the intensity of the mass transfer resistances they cause is of supreme importance for optimizing zeolite regeneration and replacement. Comparison of the quantities Ti ,ra and as determined by PFG NMR provides a straight-... 

The method outUned above was initially investigated for the introduction of isolated Ti(IV) sites onto a sihca substrate for use in selective oxidation catalysis. Since the development of a silica-supported Ti(lV) epoxida-tion catalyst by Shell in the 1970s, titania-sihca materials have attracted considerable attention [135,136]. Many other titania-sihca materials have been studied in this context including, but not hmited to, TSl and TS2 (titanium-substituted molecular sieves), Ti-/i (titanium-substituted zeolite). 

Zeolite catalysts play a vital role in modern industrial catalysis. The varied acidity and microporosity properties of this class of inorganic oxides allow them to be applied to a wide variety of commercially important industrial processes. The acid sites of zeolites and other acidic molecular sieves are easier to manipulate than those of other solid acid catalysts by controlling material properties, such as the framework Si/Al ratio or level of cation exchange. The uniform pore size of the crystalline framework provides a consistent environment that improves the selectivity of the acid-catalyzed transformations that form C-C bonds. The zeoHte structure can also inhibit the formation of heavy coke molecules (such as medium-pore MFl in the Cyclar process or MTG process) or the desorption of undesired large by-products (such as small-pore SAPO-34 in MTO). While faujasite, morden-ite, beta and MFl remain the most widely used zeolite structures for industrial applications, the past decade has seen new structures, such as SAPO-34 and MWW, provide improved performance in specific applications. It is clear that the continued search for more active, selective and stable catalysts for industrially important chemical reactions will include the synthesis and application of new zeolite materials. 

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

A number of conferences have now been held whose focus has been molecular sieve zeolites. The International Zeolite Association will have held the Fifth International Conference on Zeolites in Naples in June, 1980. The first such conference was organized by R. M. Barrer in London in 1967, and was followed by others in Worcester, Massachusetts in 1970, Zurich in 1973, and Chicago in 1977. Preceding these were the All-Union Conferences held in the USSR in 1961 and 1964 other European conferences have included the First All-Union Conference - on Molecular Sieves in Catalysis held in Novosibirsk in 1976, the Symposium on Zeolites held in Szeged, Hungary in 1978, and the Symposium on Catalysis by... 

Once the multi-step reaction sequence is properly chosen, the bifunctional catalytic system has to be defined and prepared. The most widely diffused heterogeneous bifunctional catalysts are obtained by associating redox sites with acid-base sites. However, in some cases, a unique site may catalyse both redox and acid successive reaction steps. It is worth noting that the number of examples of bifunctional catalysis carried out on microporous or mesoporous molecular sieves is not so large in the open and patent literature. Indeed, whenever it is possible and mainly in industrial patents, amorphous porous inorganic oxides (e.g. j -AEOi, SiC>2 gels or mixed oxides) are preferred to zeolite or zeotype materials because of their better commercial availability, their lower cost (especially with respect to ordered mesoporous materials) and their better accessibility to bulky reactant fine chemicals (especially when zeolitic materials are used). Nevertheless, in some cases, as it will be shown, the use of ordered and well-structured molecular sieves leads to unique performances. 

All these aspects were thoroughly discussed by lecturers and participants during the round table organized during the Poitiers School on The Future Trends in Zeolite Applications . Special emphasis was placed on the role played by the sites at the external surface (pockets, etc.) or at the pore mouth, by mesopores, extraframework aluminum species, as well as by the polarity of reactant and product molecules. Other important topics dealt with the remarkable catalytic properties of BEA zeolites for fine chemical synthesis, the potential of mesoporous molecular sieves, zeolitic membranes and the role of combinatorial catalysis in the development of zeolite catalysts. It is our hope that the fruits of these discussions will appear in the literature or even better as new and environmentally friendly products or processes. 

Thus, in ammonia synthesis, mixed oxide base catalysts allowed new progress towards operating conditions (lower pressure) approaching optimal thermodynamic conditions. Catalytic systems of the same type, with high weight productivity, achieved a decrease of up to 35 per cent in the size of the reactor for the synthesis of acrylonitrile by ammoxidation. Also worth mentioning is the vast development enjoyed as catalysis by artificial zeolites (molecular sieves). Their use as a precious metal support, or as a substitute for conventional silico-aluminaies. led to catalytic systems with much higher activity and selectivity in aromatic hydrocarbon conversion processes (xylene isomerization, toluene dismutation), in benzene alkylation, and even in the oxychlorination of ethane to vinyl chloride. 

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