Large-pore Titanium Zeolites

A promising and cleaner route was opened by the discovery of titanium silica-lite-1 (TS-1) [1,2]. Its successful application in the hydroxylation of phenol started a surge of studies on related catalysts. Since then, and mostly in recent years, the preparation of several other zeolites, with different transition metals in their lattice and of different structure, has been claimed [3]. Few of them have been tested for the hydroxylation of benzene and substituted benzenes with hydrogen peroxide. Ongoing research on suppoi ted metals and metal oxides has continued simultaneously. As a result, knowledge in the field of aromatic hydroxylation has experienced major advances in recent years. For the sake of simplicity, the subject matter will be ordered according to four classes of catalyst medium-pore titanium zeolites, large-pore titanium zeolites, other transition metal-substituted molecular sieves, and supported metals and mixed oxides. 

Then, it would be of great interest to obtain large-pore titanium zeolites which would allow the diffusion of bulkier organic molecules to the internal Ti sites, thus broadening the possibilities of these materials. 

The authors suggest that the new method could be of some value for titanium containing zeolites with structures different from silicalite, for instance large pore zeolites which could be useful in the oxidation of large molecules which cannot be oxidized with TS-1. 

Since the first synthesis of TS-1 in 1983 [1], considerable efforts have been devoted to the synthesis of titanium-containing zeolites [2, 3]. Recently, Ti-beta, a large-pore molecular sieve, has been extensively studied [4, 5]. Owing to its unique large-pore channel system, Ti-beta seems to be more active than the medium-pore TS-1 catalyst for the oxidation of cyclic and branched alkenes with aqueous hydrogen peroxide. Under the usual synthesis conditions, however, Ti-beta crystallizes with some Al as a framework constituent [4], This leads to the presence of acid centers, which may have a detrimental effect on the activity or selectivity of this type of catalyst. Since 1992, the discovery of a new family of mesoporous molecular sieves has received much attention [6,7], Because of their mesoporous nature (20-100A), the Ti-MCM-41 zeolites may be useful as oxidation catalysts for larger molecules [8], In this... 

Octahedral coordination of Tiiv is also present in the titanium silicates ETS-4 and ETS-10. The structure of these materials is reported to be similar to that of zorite, and they can be described as microporous crystals with uniform pores similar in dimensions to classical small- and large-pore zeolites. In ETS-4 and ETS-10, there are two monovalent cations or one divalent cation for each Tilv ion (Kuznicki, 1989, 1990 Kuznicki et al., 1991a, 1991b, 1991c, 1993 Deeba et al., 1994). A recent report of the synthesis of ETS-10 with tetramethyl-ammonium chloride indicates a ratio of monovalent cations to Tilv of 1.6 (Valtchev et al., 1994). The acidic properties of these materials have not been reported. A material modified by the addition of Al3+ has been obtained, ETAS-10, which, after exchange with NH4 salts, exhibits acidic properties but these are due to the presence of Al3+ and not to the Tilv (Deeba et al., 1994). 

Unfortunately, the use of TS1 (as well as TS2 discovered in 1990 by the group of Ratnasamy (27)) in catalytic oxidations is restricted to the relatively small substrates able to enter the pores of these zeolites (apertures 0.55 nm). Therefore, many research groups attempted to incorporate titanium in large pore molecular sieves BEA zeolites, mesoporous molecular sieves MCM41 and MCM48. Other transition metal zeolites were also synthesized and tested in oxidation one of the main problems of these systems is the release of redox cations in liquid phase (24). Progress remains to be made to develop molecular sieves catalyzing the oxidation... 

Kuznicki S. M., Large-pored crystalline titanium molecular sieve zeolites, US Patent 4853202(1999). 

Titanium-containing zeolites, such as Ti-BEA, Ti-FAU, and TS-1 have been tested as catalysts for the Ruff oxidative degradation of calcium D-gluconate 72 to D-arabinose 55 using diluted hydrogen peroxide as the oxidant. Only large-pore zeolites Ti-BEA and Ti-FAU were found to be active. It was shown, in particular, that a very rapid leaching of titanium occurred and that the titanium species present in the solution were responsible for the catalytic activity observed [67,68]. 

W. Adam, A. Corma, H. Garcia, O. Weichold, Titanium-catalyzed heterogeneous oxidations of silanes, chiral allylic alcohols, 3-alkylcyclohexanes, and thianthrene 5-oxide A comparison of the reactivities and selectivites for the large-pore zeolite Ti-p, the mesoporous Ti-MCM-41, and the layered alumosilicate Ti-lTQ-2, /. Catal. 196 (2000) 339. 

UTD-1 may have catalytic properties such as those observed with the commercially sucsessfiil titanium silicahte TS-1 catalyst which is effective for alkane and alkene o ddation as well as phenol hydroxylation in the presence of hydrogen peroxide [8]. The large pore nature of Ti-UTD-1 should allow the reaction of large substrates such as 2,6-di-tert-butylphenol as well as the use of oxidants such as tert-butylhydroperoxide (t-BHP) which are too large for the medium pore TS-1 zeolite. Ti-UTD-1 offers an opportunity to examine reactivity in pore space greater than Ti-beta but less than the mesoporous Ti-MCM-41 type molecular sieves. In the present study results for the peroxide based oxidation of cyclohexane, cyclohexene and 2,6-di-tert-butylphenol will be presented. 

The novel zeolite UTD-1 with titanium in the framework (up to 3.5% by weight) is an effective catalyst for the oxidation of cyclohexane, cyclohexene and 2,6-di-tert-butyl phenol. The catalytic behavior is similar to that of other large pore zeolites and mesoporous molecular sieves modified with titanium which includes solvents effects. Additionally, Ti-UTD-1 allows the use of oxidants and substrates too large for the commercial TS-1 catalyst. We are currently evaluating further the role of solvent and oxidant in an effort to improve selectivity as well as expand the utility of this material in oxidation catalysis. 

There is still another wide space for research activities related to titanium containing zeolites the synthesis of large pores Tl-zeolites, the activation of TS-1 with oxidants different from HjOj, the comprehension of the mechanism of reactions catalyzed by TS-... 

Although titanium silicalite was discovered over a decade ago, studies on other redox zeolites are just beginning. This is a field in which the most promising results are anticipated. The synthesis of large pore zeolites, containing Ti or other redox metal atoms, can open entirely new routes to catal)4ic oxidations and new products. 

Many oxidation reactions have been carried out using hydrogen peroxide and the titanosilicate, TS-1. However, this catalyst has relatively small pores and is therefore not an efficient catalyst for the oxidation of large molecules. This problem has been solved by the successful generation of a medium-pore titanium zeolite Beta-Ti [136]. Cyclododecane and cyclohexane are both oxidised selectively by H2O2 in the presence of the new titanium zeolite, favouring the ketone product. 

Figure 4.7. Possibilities for the synthesis of Vitamin K3. The small pore titaninm zeolite TS-1 cannot fit the large naphthalene molecule into its pore system, and thus is effective in this transformation. The larger titanium MTS material is capable of interacting with the molecule, and the desired transformation can take place.

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