Oxidation silicalite

The separation layer may be dense (non-porous), such as Pd or Pd-alloy membranes for hydrogen separation and mixed (electronic, ionic) conducting oxide membranes for oxygen separation, or porous, such as metal oxides, silicalite, or zeolite membranes. Inorganic membranes are generally named for this separation layer, since it determines the properties and application of the membrane. The flux and selectivity of inorganic membranes are mainly determined by the quality of the separation layer, which is required to be defect-free and as thin as possible. 

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

In the 1980 s zeolites attracted a renewed attention. They were shown to be rather promising catalysts if, instead of O2, a chemically pre-modified oxygen entering the oxygen-containing molecules is used. The most known example is an excellent catalytic performance of titanium silicalites in the liquid phase oxidations with H2O2 [5]. A gas phase oxidation with nitrous oxide is another approach in this field being intensively developed in the last years [2],... 

The reaction is carried out using a titanium silicalite-1 (TS-1) zeolite catalyst [30, 122]. This type of catalyst is known to accelerate the selective oxidation of alcohols, epoxidation of alkenes and hydroxylation of aromatics. These reactions have importance for fine-chemical production. 

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). 

Many of these problems disappeared in 1983 when Taramasso, Perego, and Notari synthesized titanium silicalite-1 (TS-1),1 which greatly affected the use of zeolite catalysts for practical oxidation chemistry. This catalyst shows outstanding activity, selectivity, and stability below 100°C. 

TS-l and titanium silicalite-2 (TS-2) are microporous solid materials made of Si02 and Ti02 that have silicalite structures (TS-1 has the ZSM-5 structure and TS-2, the ZSM-11 structure) modified by isomorphous substitution of Si(IV) with Ti(IV). TS-1 and TS-2, the former being most studied, show similar properties in catalysis of H202 oxidations. 

Although the complete mechanism for each of the previously described reactions is not known, substantial details have been worked out. First, it is clear that Ti is incorporated into the framework of the silicalite structure. Too much Ti (more than about 2.5%) in the preparation steps forms nonframework TiOz crystallites, which decompose H202. Second, the rate enhancement due to methanol suggests a tight association at the Ti active site as shown in Fig. 6.8.37,38 This is supported by the fact that methanol oxidizes much more slowly than other alcohols.47 This tight coordination of methanol is proposed to increase the electrophilicity of the Ti-coordinated H202 and facilitate oxygen transfer to the alkene.31... 

Mn impregnated into MCM-4i, a silicalite containing uniform mesopores of approximately 22 A, catalyzes TBHP epoxidation of alkenes.88 Over Mn-MCM-41, both cis- and trans-stilbene yield trans-stilbene oxide, which the authors conclude signals a radical mechanism.88 In contrast, over Ti—MCM-41, trans-stilbene cannot be oxidized, only cis-stilbene is epoxidized to the cis-stilbene oxide, which suggest a radical-free mechanism.89 Finally, emphasizing the shape selectivity possibilities, only trans-stilbene (not cis-stilbene) can be epoxidized over Mn-ZSM-5, a zeolite with relatively small pores of 5.1 x 5.4 A (Fig. 6.14).88... 

Copper exchanged Silicalite-1 evidence of the location of copper oxide nanoclusters in the supermicropores of S-l... 

The increasing volume of chemical production, insufficient capacity and high price of olefins stimulate the rising trend in the innovation of current processes. High attention has been devoted to the direct ammoxidation of propane to acrylonitrile. A number of mixed oxide catalysts were investigated in propane ammoxidation [1]. However, up to now no catalytic system achieved reaction parameters suitable for commercial application. Nowadays the attention in the field of activation and conversion of paraffins is turned to catalytic systems where atomically dispersed metal ions are responsible for the activity of the catalysts. Ones of appropriate candidates are Fe-zeolites. Very recently, an activity of Fe-silicalite in the ammoxidation of propane was reported [2, 3]. This catalytic system exhibited relatively low yield (maximally 10% for propane to acrylonitrile). Despite the low performance, Fe-silicalites are one of the few zeolitic systems, which reveal some catalytic activity in propane ammoxidation, and therefore, we believe that it has a potential to be improved. Up to this day, investigation of Fe-silicalite and Fe-MFI catalysts in the propane ammoxidation were only reported in the literature. In this study, we compare the catalytic activity of Fe-silicalite and Fe-MTW zeolites in direct ammoxidation of propane to acrylonitrile. 

In the direct ammoxidation of propane over Fe-zeolite catalysts the product mixture consisted of propene, acrylonitrile (AN), acetonitrile (AcN), and carbon oxides. Traces of methane, ethane, ethene and HCN were also detected with selectivity not exceeding 3%. The catalytic performances of the investigated catalysts are summarized in the Table 1. It must be noted that catalytic activity of MTW and silicalite matrix without iron (Fe concentration is lower than 50 ppm) was negligible. The propane conversion was below 1.5 % and no nitriles were detected. It is clearly seen from the Table 1 that the activity and selectivity of catalysts are influenced not only by the content of iron, but also by the zeolite framework structure. Typically, the Fe-MTW zeolites exhibit higher selectivity to propene (even at higher propane conversion than in the case of Fe-silicalite) and substantially lower selectivity to nitriles (both acrylonitrile and acetonitrile). The Fe-silicalite catalyst exhibits acrylonitrile selectivity 31.5 %, whereas the Fe-MTW catalysts with Fe concentration 1400 and 18900 ppm exhibit, at similar propane conversion, the AN selectivity 19.2 and 15.2 %, respectively. On the other hand, Fe-MTW zeolites exhibit higher AN/AcN ratio in comparison with Fe-silicalite catalyst (see Table 1). Fe-MTW-11500 catalyst reveals rather rare behavior. The concentration of Fe ions in the sample is comparable to Fe-sil-12900 catalyst, as well as... 

In the present study isomorphic substitution of Al with Sn [11-13] in the silicalite framework was attempted in order to induce catalytic functionalities and these catalysts was studied for Baeyer-Villiger oxidation of 2-adamantanone and norboranone. 

The carbon templated tin incorporated mesoporous silicalite catalysts with MFI structure were successfully synthesized using microwave and well characterized using all the physico-chemical techniques. The catalytic activity of these catalysts was studied for liquid phase Baeyer-Villiger oxidation of various cyclic ketones using hydrogen peroxide. All the catalyst showed high conversion ( 100%) for bicyclic ketones with 100% selectivity to the corresponding lactone. 

Recently, based on such an oxidative system, the synthesis of nitrone (12) an inhibitor of 5a-reductase has been carried out (Scheme 2.7) (50). Oxidation of amines with H2O2 can be catalyzed with peroxotungstophosphate (PCWP) (51), Se02 (52-54), and titanium silicalite molecular sieves TS-1 and TS-2 (55, 56). 

The direct conversion of propene to its epoxide, in near quantitative yields, with aqueous H202 will be environmentally more benign. One of the unique features of TS-1 as a solid oxidation catalyst is its ability to utilize aqueous H202 as the oxidant for such conversions. This ability of TS-1 derives from the fact that silicalite-1 is hydrophobic, in contrast to the hydrophilic amorphous Ti-Si02. Consequently, hydrophobic reactants, such as alkenes, are preferentially adsorbed by TS-1, thus precluding the strong inhibition by H20 observed with amorphous Ti-Si02. 

The oxidative dehydrogenation of propane to give propene catalyzed by TS-1, Ti-beta, Ti-MCM-41, Ti02-silicalite-l, or others was investigated by Schuster et al (259). TS-1 was the best catalyst, with a selectivity of 82% for propene at a propane conversion of 11% (Fig. 42). Sulfation of TS-1 by H2S04 prior to the reaction increased the conversion to 17%, with a selectivity of about 74%. Although conversion of propane was higher on Ti-beta and Ti-MCM-41, selectivity for propene was much lower C02 was the main product. Lewis acid sites were considered to be the major active sites (259). 

With aqueous H202, catalyzed glycerol oxidation has also been examined [52], With Ti, V- and Fe-substituted silicalite (TS-1, VS-1, FeSl) low conversion was obtained from 70 °C on. Formate esters of glycerol were dominant (60-80% selectivity) (Scheme 11.13), along with some hydroxyethanoic acid. 

The titanium-silicalite composihon, TS-1, has achieved commercializahon in selective oxidation processes and iron-siUcalite in ethylbenzene synthesis. 

The most commonly employed crystalline materials for liquid adsorptive separations are zeolite-based structured materials. Depending on the specific components and their structural framework, crystalline materials can be zeoUtes (silica, alumina), silicalite (silica) or AlPO-based molecular sieves (alumina, phosphoms oxide). Faujasites (X, Y) and other zeolites (A, ZSM-5, beta, mordenite, etc.) are the most popular materials. This is due to their narrow pore size distribution and the ability to tune or adjust their physicochemical properties, particularly their acidic-basic properties, by the ion exchange of cations, changing the Si02/Al203 ratio and varying the water content. These techniques are described and discussed in Chapter 2. By adjusting the properties almost an infinite number of zeolite materials and desorbent combinations can be studied. 

Recently, the preparation of metallosilicates with MFI structure, which are composed of silicone oxide and metal oxide substituted isomorphously to aluminium oxide, has been studied actively [1,2]. It is expected that acid sites of different strength from those of aluminosilicate are generated when some tri-valent elements other than aluminium are introduced into the framework of silicalite. The Bronsted acid sites of metallosilicates must be Si(0H)Me, so the facility of heterogeneous rupture of the OH bond should be due to the properties of the metal element. Therefore, the acidity of metallosilicate could be controlled by choosing the metal element. Moreover, the transition-metal elements introduced into the zeolite framework play specific catalytic roles. For example, Ti-silicate with MFI structure has the high activity and selectivity for the hydroxylation of phenol to produce catechol and hydroquinon [3],... 

Oxidations of various organic substrates with aqueous hydrogen peroxide have been reported on titanium containing derivatives of silicalite-1, denoted as Titanium-Silicalite-1 or TS-1 [93-97]. Examples of reactions which are catalyzed by TS-1 with high H2O2 yields and product selectivities are listed in Table 6. The oxidations are generally carried out at atmospheric pressure and at temperatures ranging from 273 to 373 K. 

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