Hydrogen peroxide titanium silicalite catalysts

The advantage of the above two methods are high yields of epoxides, and the titanium silicalite catalyst is not deactivated or poisoned by the contaminants in the crude oxidation mixture. Hence, the processes are commercially attractive. The in situ hydrogen peroxide generation based on the AO process from either the anthraquinone/anthrahydroquinone or ketone/alcohol redox couples has also been used for the following synthetic reactions ... 

G. F. Tliiele, E. Roland, Propylene epoxidation with hydrogen peroxide and titanium silicalite catalyst Activitv, deactivation, and regeneration of the catalyst, /. Mol. Catal. A Chem. 117(1997)351. 

Hydroxylamine can be prepared from ammonia and hydrogen peroxide using a titanium silicalite catalyst in 83% yield.68 The by-product acetic acid could be recycled to acetic anhydride by pyrolyzing part of it to ketene. 

Solid catalysts may also be used for reactions implying oxidants differ by dioxygen. The most popular case is that of titanium-silicalite catalysts for oxidation with hydrogen peroxide. The active species in the presence of water has been characterised to be a side-on peroxo complex characterised by a Raman-detected 0-0 stretching at 618 cm Upon drying, this species converts into a hydroperoxo species characterised using IR by an 0-0 stretching at 837 cm and a broad OH band at 3400 cm ... 

Tetrahedrally-coordinated cations are also encountered in the lattice of zeolites (Figure 3.8). The well-defined nature of the lattice, the variety of microchannel dimensions, and the many possibilities for isomorphous substitution make them ideal catalysts for the production of fine chemicals. A recent application is the oxidation of phenol to catechol by hydrogen peroxide using a titanium-silicalite catalyst with Ti ions in tetrahedral sites. 

An extremely versatile catalyst for a variety of synthetically useful oxidations with aqueous hydrogen peroxide is obtained by isomorphous substitution of Si by Ti in molecular sieve materials such as silicalite (the all-silica analogue of zeolite ZSM-5) and zeolite beta. Titanium(IV) silicalite (TS-1), developed by Enichem (Notari, 1988), was the progenitor of this class of materials, which have become known as redox molecular sieves (Arends et al., 1997). 

In the present work the synthesis of highly dispersed niobium or titanium containing mesoporous molecular sieves catalyst by direct grafting of different niobium and titanium compounds is reported. Grafting is achieved by anchoring the desired compounds on the surface hydroxyl groups located on the inner and outer surface of siliceous MCM-41 and MCM-48 mesoporous molecular sieves. Catalytic activity was evaluated in the liquid phase epoxidation of a-pinene with hydrogen peroxide as oxidant and the results are compared with widely studied titanium silicalites. The emphasis is directed mainly on catalytic applications of niobium or titanium anchored material to add a more detailed view on their structural physicochemical properties. 

In classical processes cyclohexanone is converted to the corresponding oxime by reaction with hydroxylamine (see Fig. 2.27). The oxime subsequently affords caprolactam via the Beckmann rearrangement with sulphuric or phosphoric acid. Alternatively, in a more recent development, not yet commercialized, a mixture of cyclohexanone, ammonia and hydrogen peroxide is directly converted to cyclohexanone oxime over a titanium(IV)-silicalite (TS-1) catalyst. This route is more direct than the classical route and reduces the amount of salt formation but it involves the use of a more expensive oxidant (H2O2 rather than O2). 

The discovery of titanium silicalite-1 (TS1) by Enichem scientists (20-22) and its commercial use as a catalyst for a variety of selective oxidations with aqueous hydrogen peroxide under mild conditions (Figure 1.3) constituted a major breakthrough in oxidation catalysis. 

More promising from an industrial perspective, however, is the separation of the oxidation zone from the aqueous one effected by the catalytic material itself, through the selective adsorption of the reagents. The introduction of Titanium Silicalite-1 (TS-1), in which the hydrophobic properties of the pores protect the active sites from the inhibition of the external aqueous medium, was a demonstration of the concept. The catalyst, the substrate and the aqueous soluhon of hydrogen peroxide can, in this case, be mixed together, with a great simplification of the process and also a reduction of the hazards. Three commercial processes. 

The discovery in the early 80 s of titanium silicalites [62-64] opened the new application perspective of zeolitic materials as oxidation catalysts. Several reactions of partial oxidation of organic reactants using dilute solutions of hydrogen peroxide could for the first time be performed selectively in very mild conditions. Other elements inserted in the lattice of silicalites have since been shown to have similarly interesting catalytic properties including, vanadium, zirconium, chromium and more recently tin and arsenic [65]. Titanium silicalites with both MFI (TS-1) and MEL (TS-2) structures have however been the object of more attention and they still seem to display unmatched properties. Indeed some of these reactions like the oxyfunctionalization of alkanes [66-69] by H2O2 are not activated by other Ti containing catalysts (with the exception of Ti-Al-Beta [70]). The same situation... 

The primary use for the titanium silicalites is as shape selective catalysts for hydrogen peroxide oxidations. " Propylene is converted to propylene oxide at greater than 98% selectivity and 99% peroxide conversion at 50°C over TS-1. 2,97 Butadiene is oxidized to the monoepoxide (Eqn. 10.26), also in high selectivity, and primary alcohols are oxidized to the aldehydes in all cases with selectivites greater than 80%.97... 

The Oxirane process is a mature technology that has stood the test of time. Both ARCO and Shell have been successfully operating for more than two decades. More recently a heterogeneous titanium-substituted silicalite (TS-1) catalyst was developed by Enichem [43, 44]. In contrast to the Shell Ti /Si02 catalyst, TS-1 has a hydrophobic surface and is a remarkably effective catalyst for a variety of liquid-phase oxidations with 30 % aqueous hydrogen peroxide, including epoxidation [44]. It has been commercialized for the hydroxylation of phenol to... 

Key Words Lewis acid adducts, Radical oxidations, Epoxidation, Hydrogen peroxide, Bond dissociation energy, Catalyst durability, Methyltrioxorhenium, Cross-bridged cyclam, Mn(IV), Late transition metal. Propylene oxide. Titanium silicalite (TS-1) catalyst, Ethylanthrahydroquinone/H2 process, Polyoxometallates, Mn(IV) catalyst. Hydrogen abstraction. Rebound mechanism, Isotopic label, t-BuOOH, Peroxide adduct. 2008 Elsevier B.v. 

Key Words Direct propylene epoxidation. Propylene oxide, Gold, Titanium, Propene, Au/Ti catalysts. Catalysis by gold. Titanium silicalite, TS-1, Gold/TS-1, Hydrogen peroxide, Kinetics, Design of experiments, Deposition-precipitation, Ammonium nitrate, Selective oxidation, Alkene epoxidation, Density functional theory, DFT calculations, QM/MM calculations. 2008 Elsevier B.v. 

Up until the late seventies attempts to develop redox molecular sieves were mainly limited to the ion-exchange approach (see later). This situation changed dramatically with the discovery, by Enichem scientists in 1983 [6,7], of the unique activity of titanium silicalite-1 (TS-1) as a catalyst for oxidations with 30% aqueous hydrogen peroxide. Following the success of TS-1, interest in the development, and application in organic synthesis, of redox molecular sieves has increased exponentially and has been the subject of several recent reviews [8-11]. It has even provoked a revival of interest in another approach to producing redox molecular sieves the so-called ship-in-a-bottle method [12-15]. 

Titanium silicalite has been reeognized as an efficient redox catalyst in a number of industrial processes. Enichem has a process in which Ti silicalite catalyzed the conversion of eyelohexanone by ammonia and hydrogen peroxide to cyclohexnone oxime . The meehanism appears to involve the Ti 0x0 species. A number of proeedures are available from literature to make the Ti silicalite catalyst and it will be easy to incorporate eleetron mediators such as Ru or Pd into the silicalite matrix. The performance of such composite... 

Numerous other large-volume compounds can be made from ethylene and propylene by standard petrochemical methods. Ethylene can be oxidized to ethylene oxide using oxygen with a silver catalyst (12.4). Propylene can be oxidized to propylene oxide with hydrogen peroxide and titanium silicalite (see Chap. 4). Vinyl chloride (a carcinogen) is produced by adding chlorine to ethylene, followed by... 

Titanium silicalite (TS-1) is a porous crystalline titanium silicalite with the MFI structure, analogous to ZSM-5 [1], Catalytic centers are isolated Ti sites in a silica framework [4]. Unlike Ti02/Si02 with a similar elemental composition but an amorphous structure, TS-1 is an effective catalyst for the selective oxidation of different functional groups with dilute aqueous hydrogen peroxide [2]. The structural properties of lattice Ti sites, the hydrophobicity, and the size of the tridimensional channel system (ca 0.55 nm) are thought to be critical factors in determining the unusual catalytic properties of TS-1. 

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