Production of a titanium silicalite shaped article

• US 20030130116A1
• Filed: 10/15/2002
• Published: 07/10/2003
• Est. Priority Date: 03/29/2000
• Status: Active Grant

• Current Assignee: Evonik Operations GmbH (Rag-Stiftung)
• Original Assignee: Evonik Degussa GmbH (Rag-Stiftung)
• Inventors: Jantke, Ralf, Hasenzahl, Steffen
• Granted Patent: US 8,449,812 B2
• Time in Patent Office: Days
• US Class Current: 502/242
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: C07C 249/04 of oximes
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids

Abstract

The present invention relates to a process for the production of a titanium silicalite shaped article by:a) preparation of a synthesis gel containing a Si₂ source, a Ti₂ source, a template compound and water,b) crystallisation of the synthesis gel under hydrothermal conditions,c) drying of the titanium silicalite from step b) at a temperature below the decomposition temperature of the template compound,d) preparation of a formable mass containing the product from step c), a binder and a paste-forming agent,e) forming of the mass from step d) into a green shaped article,f) optionally drying, andg) calcination of the green shaped article, as well asa titanium silicalite shaped article obtainable according to this process, and the use of this shaped article as a catalyst in epoxidation or ammoximation reactions.

Claims

1. Process for the production of a titanium silicalite shaped article by:

a) preparation of a synthesis gel containing a SiO₂ source, a TiO₂ source, a template compound and water,

b) crystallisation of the synthesis gel under hydrothermal conditions,

c) drying of the titanium silicalite from step b) at a temperature below the decomposition temperature of the template compound,

d) preparation of a formable mass containing the product from step c), a binder and a paste-forming agent,

e) forming of the mass from step d) into a green shaped article,

f) optionally drying, and

g) calcination of the green shaped article,

characterised in that the template compound is chosen in a way that the titanium silicalite obtained by step b) exhibits MFI, MEL or BEA structure and the calcination step takes place after the formation of the green shaped article.

2. Process according to claim 1, wherein the crystal suspension from step b) is optionally neutralised, the solid material is separated using a solid-liquid separation process, and the said material is then dried according to step c).

3. Process according to claim 1, wherein the crystal suspension from step b) is dried directly according to step c) without prior separation of the solid material.

4. Process according to claim 3, wherein the titanium silicalite suspension from step b) is concentrated by distilling off volatile constituents and/or by adding uncalcined titanium silicalite.

5. Process according to claim 4, wherein the solids content of the titanium silicalite suspension before the drying step c) is at least 50 wt. %.

6. Process according to any of the preceding claims, wherein an aqueous medium that optionally contains a water-miscible organic solvent is used as paste-forming agent.

7. Process according to any of the preceding claims, wherein the drying temperature in step c) is within the range of 50°

to less than 400°

C.

10. Process according to any of the preceding claims, wherein compounds of silicon, aluminium, boron, phosphorus, zirconium and/or titanium are used as binder.

11. Process according to claim 10, wherein the binder is selected from aluminium oxide, silicon oxide, hydrolysable silicon compounds and partial or total hydrolysates thereof, boron compounds, phosphorus compounds, clay minerals and mixtures thereof.

12. Process according to any of the preceding claims, wherein the green shaped article is calcined at a temperature from 400°

C. to 1000°

C., preferably from 500°

C. to 750°

C.

13. Titanium silicalite shaped article obtainable by a process according to any of the preceding claims.

14. Process for the epoxidation of olefins with aqueous hydrogen peroxide in the presence of titanium silicalite shaped articles according to claim 13.

15. Process for the ammoximation of ketones with aqueous hydrogen peroxide and ammonia in the presence of titanium silicalite shaped articles according to claim 13.

8. Process for the production of a titanium silicalite shaped article by:

a) preparation of a synthesis gel containing a SiO₂ source, a TiO₂ source, a template compound and water,

b) crystallisation of the synthesis gel under hydrothermal conditions,

c) concentration of the crystal suspension from step b),

d) preparation of a formable mass containing the product from step c) and a binder,

e) forming of the mass from step d) into a green shaped article,

f) possible drying, and

g) calcination of the green shaped article,

characterised in that the template compound is chosen in a way that the titanium silicalite obtained by step b) exhibits MFI, MEL or DEA structure and the calcination step takes place after the formation of the green shaped article.

9. Process according to claim 8, wherein the solids content of the titanium silicalite suspension after the concentration in step c) is 10-50 wt. %.