Claims
- 1. A method for the hydroxylation of aromatic hydrocarbons which comprises reacting a hydrocarbon with hydrogen peroxide in the presence of a catalyst said catalyst in the form of microspheres and comprising oligomeric silica and crystals of titanium-silicalite with an oligomeric silica/titanium-silicalite molar ratio in the rang of from 0.05 to 0.11, wherein said crystals of titanium silicalite are encaged with each other by means of Si-O-Si bridges.
- 2. A method according to claim 1, wherein said microspheres have a diameter of from 5 to 1000 .mu.m.
- 3. A method according to claim 1, wherein said hydroxylation is carried out at a temperature within the range of from 80.degree. to 120.degree. C.
- 4. A method according to claim 1, wherein said aromatic hydrocarbons are selected from the group consisting of phenol, anisole, toluene, benzene, acetanilide, chlorobenzene and nitrogenzene.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 20457 A/85 |
Apr 1985 |
ITX |
|
Parent Case Info
This application is a divisional of copending application Ser. No. 07/075,688, filed on July 20, 1987, now U.S. Pat. No. 4,859,785, which is a divisional of Ser. No. 06/854,890, filed on Apr. 23,1986, now U.S. Pat. No. 4,701,428.
The present invention relates to a catalyst on the basis of silicon and titanium, having a high mechanical strength, formed by microspheres and constituted by oligomeric silica and crystals of titanium-silicalite.
In the U.S. Pat. No. 4,410,501 and patent applications U.S. Ser. No. 480,947 and U.S. Ser. No. 513,807 the preparation of titanium-silicalite, its use as catalyst in the process of introducing hydroxy groups into aromatic hydrocarbons by hydrogen peroxide and its use as a catalyst in the process of epoxidation of olefinic compounds by hydrogen peroxide respectively are disclosed. The practical use of the so disclosed catalyst poses some problems relating to the separation and recovery of the same from the reaction mixture; in fact, the very small sizes of the individual crystals, smaller than 5 .mu.m, render with extreme difficulty their separation from a liquid medium. On the other hand, small sizes of the crystallites of zeolite are essential in liquid phase reactions in order to favor the diffusion of the reactants and the reaction products, and hence obtain the highest performance. Due to such a reason, the crystallization conditions are controlled for the purpose of obtaining the zeolite in crystals having dimensions as small as possible.
The difficulties inherent in the separation of the catalyst from the reaction medium and the need for recovering the catalyst to the greatest extent can seriously jeopardize the possibility of the use of the catalyst in an industrial process. In fact, due to the high cost of the raw products and to the complexity of the zeolite (titanium-silicalite) production process, the cost of recovery is very high, and its incidence on the production cost of organic substrates is considerable, so that the recovery and recycling of the zeolite must be secured to the greatest extent.
It has been surprisingly found that the small crystals of titanium-silicalite produced according to the prior art can be agglomerated with each other, giving rise to a catalyst which is more active and more selective than the single original crystals.
The catalyst, according to the present invention, on the basis of silicon and titanium, is formed by microspheres having a diameter preferably within the range of from about 5 to 1000.mu.m, and are constituted by oligomeric silica and crystals of titanium-silicalite with an oligomeric silica/ titanium-silicalite molar ratio within the range of from about 0.05 to 0.11, wherein the crystals of titanium-silicalite are encaged by means of Si-O-Si bridges.
The process for the preparation of the catalyst is based on the use of an aqueous solution of silica and tetraalkyl-ammonium hydroxide obtained by hydrolyzing a tetraalkyl-silicate, preferably tetraethyl-orthosilicate, in an aqueous solution of tetraalkyl-ammonium hydroxide.
The alkyl groups contained in the tetraalkyl-ammonium ion have a number of carbon atoms within the range of from about 1 to 5.
The hydrolysis is carried out in the liquid phase at a temperature within the range of from about room temperature to 200.degree. C., preferably 40.degree. C. to 100.degree. C., and more preferably within a time of from 0.2 to 10 hours.
In such a solution, the silica is present in an oligomeric form and at a high enough pH, i.e., at pH.gtoreq.10.
When the crystalline titanium-silicalite formed by very small crystals in dispersed in this solution, the surface of the crystals is partly attacked by the alkalinity of the medium: such a situation favors the formation of stable chemical bonds between the surface of the crystals and the oligomeric silicates in solution. By submitting this dispersion to rapid drying, by means of a spray-dryer, water is eliminated and at the same time the crosslinking of the oligomers occur, leading to the obtainment of microspheres formed by a tridimensional lattice wherein the crystallites of zeolite are closely encaged by Si-O-Si bridges.
Before being used, the microspheres are calcined first under an inert atmosphere (N.sub.2, H.sub.2, and so forth), and then under an oxidizer atmosphere at a temperature within the range of from about 150.degree. to 700.degree. C., preferably of from about 500.degree. to 600.degree. C.
Such a particular shape on the one hand guarantees an optimum mechanical strength of the agglomerates, and on the other hand improves the catalytic activity. This is probably due to the induction on the crystals of surface lattice defects, which constitute active centers in the reactions of activation of organic substrates and/or of H.sub.2 O.sub.2 in reactions involving such systems.
Upon decreasing the percentage of the crystalline phase in the agglomerate, the catalytic performance worsens, without great improvements in mechanical strengths being obtained. Tests have been carried out by dispersing into equimolar amounts of different silica sources, such as colloidal silica and sodium silicate, the same amounts of titanium-silicalite and operating as described above, but the products obtained had clearly lower characteristics than the novel catalyst.
The optimum concentration in total solids (SiO.sub.2, titanium-silicalite, TAA-OH) of the suspension to be atomized is of from 10 to 40% by weight. By varying the concentration of the solids in the suspension, or the dimensions of the atomizer, the average diameter of the particles obtained can be varied. The diameter of the microspheres of the catalyst can thus be varied within the range of from 5 to 100 .mu.m. Thus the most suitable size for the desired application is selected.
The catalyst obtained as hereinabove disclosed can be used in the introduction of hydroxy groups into aromatic substrates by H.sub.2 O.sub.2 and in the epoxidation of olefins by H.sub.2 O.sub.2.
The aromatic substrates which can be hydroxylated are e.g. phenol, anisole, toluene, benzene, acetanilide, chlorobenzene, nitrobenzene.
The hydroxylating reaction is carried out at temperatures within the range of from about 80.degree. C. to 120.degree. C. under room pressure in suitable solvents selected among: methanol, acetone, methylisobutylketone, tert.-butyl alcohol or any solvent miscible, or partially miscible, with water; or at higher temperatures by operating under pressure.
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2437648 |
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Divisions (2)
|
Number |
Date |
Country |
| Parent |
75688 |
Jul 1987 |
|
| Parent |
854890 |
Apr 1986 |
|
Patent Grant
4954653
