Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – Zsm type
Patent
1995-05-24
1998-04-07
O'Sullivan, Peter
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
Zsm type
502 60, 502 62, 502 63, 502 64, 502 71, 502 73, 502 76, 502 87, 549531, 564267, 568385, 568311, B01J 2940
Patent
active
057364796
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/DE93/01117 filed 24 Nov. 1993.
BACKGROUND OF THE INVENTION
The invention relates to new oxidation catalysts, processes for the production thereof as well as the use of these catalysts for oxidation reactions under mild conditions, e.g. temperatures of 20.degree. to 120.degree. C. and pressures equal to or higher than atmospheric pressure.
Numerous oxidation catalysts are already known which are used for oxidation reactions with H.sub.2 O.sub.2 as an oxidizing agent. In DE-OS 3 309 669, for example, a catalyst is described made of zeolitic materials with foreign elements. Indicated as modifying foreign elements are Cr, Be, Ti, V, Mn, Fe, Ca, Zn, Rh, Ag, Sn, Sb and B.
In recent years, preferably crystalline titanium silicalites have been used as oxidation catalysts. The following applications are known, for example: the synthesis of glycol monomethyl ether (EP 100 118), the epoxidation of mono-olefins (EP 100 119), the epoxidation of di-olefins to monoepoxides (EP 190 609), the conversion of styrene to .beta.-phenylaldehyde (EP 102 097), the hydroxylation of aromatics (GB 2 116 974), the oxidation of alkanes into alcohols and ketones (Nature, 345 (1990) 240), the oxidation of alcohols to aldehydes and ketones respectively (EP 102 655) as well as the conversion of cyclohexanone with NH.sub.3 and H.sub.2 O.sub.2 to the oxime (EP 208 311 and 226 257).
The literature mentions various processes for the production of the crystalline titanium silicalites. In U.S. Pat. No. 4,410,501 two production processes are described. Both processes entail the production of a TiO.sub.2 --SiO.sub.2 -gel, which in the presence of tetrapropyl ammonium hydroxide (TPAOH) and water is converted under hydrothermal conditions into the crystalline titanium silicalite (TS-1). As starting products for the gel formation tetraethyl orthosilicate (TEOS) and tetraethyl orthotitanate (TEOT) or colloidal SiO.sub.2 and tetrapropyl ammonium peroxotitanate were used. The use of tetrabutyl orthotitanate as a source of TiO.sub.2 is described in J. Catal. 130 (1991), 1.
Furthermore, titanium silicalites could be produced by the high temperature treatment of H-ZSM 5 or silicalite-1 with TiCl.sub.4 (Catal. Lett. 13 (1992) 229). The EP 299 430 protects a production process of titanium silicalite according to which amorphous SiO.sub.2 is impregnated with a titanium compound and then crystallized in the presence of a template to the titanium silicalite.
The hydrothermal conversion of jointly precipitated TiO.sub.2 --SiO.sub.2 products in the presence of templates to titanium silicalite is protected in EP 311 933.
All these titanium silicalite catalysts known from the state of the art have the disadvantage that they are very costly, have a small particle size for batch processes and accordingly are difficult to handle. Furthermore, to ensure high activity and selectivity values an activation with H.sub.2 O.sub.2 and H.sub.2 SO.sub.4 is required prior to their use.
SUMMARY OF THE INVENTION
The object of the present invention was, therefore, to develop less costly oxidation catalysts, which in addition also display an improved activity and selectivity behaviour.
This object is achieved by a new catalytic system consisting of titanium silicalite with a MFI-structure crystallized in situ and carried on activated charcoal or on metal oxide.
The titanium silicalite content of the catalysts according to the invention lies within the limits of 1 to 90% by mass; preferably it is 10 to 90% by mass. For titanium silicalite carried on activated charcoal the preferred titanium silicalite content lies in the range of 40 to 60% by mass, whereas for titanium silicalite carried on metal oxide the preferred titanium silicalite content is 30 to 50% by mass.
The Si--Ti atomic ratio in the carried phase is 10 to 100.
As oxides onto which the titanium silicalites are crystallized Al.sub.2 O.sub.3, SiO.sub.2, TiO.sub.2, ZrO.sub.2 or Al.sub.2 O.sub.3. SiO.sub.2 are used. However, also any mixtures of the indicated oxides can be used.
DETAIL
REFERENCES:
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Nature -vol. 345 -"Oxyfunctionalization of alkanes with hydrogen peroxide on titanium silicalite" D.R.C. Huybrechts, L. De Bruycker & P.A. Jacobs; May 17, 1990.
Catalysis Letters 13 (1992). Titanium deposited from TiCl.sub.4 on amorphous silica and silicalite-1 as catalyst in aromatic hydroxylation reactions, by P.J. Kooyman et al., pp. 229-238.
Journal of Catalysis 131 (1991). Catalytic Properties of Crystalline Titanium Silicalites, by A. Thangaraj et al., pp. 394-400.
Journal of Catalysis 130 (1991). Catalytic Properties of Crystalline Titanium Silicalities, 1. Synthesis and Characterization of Titanium-Rich Zeolites with MFI Structure by A. Thangaru et al., pp. 1-8.
Birke Peter
Geyer Reinhard
Kraak Peter
Muller Willibald
Neubauer Hans-Dieter
Leuna-Katalysatoren GmbH
O'Sullivan Peter
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