Catalyst for epoxidation reactions

• US 6,884,743 B2
• Filed: 09/16/2002
• Issued: 04/26/2005
• Est. Priority Date: 09/16/2002
• Status: Expired due to Fees

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Krug, Georg, Teles, Joaquim Henrique, Rudolf, Peter, Müller, Ulrich, Göbbel, Hans-Georg, Bassler, Peter
• Primary Examiner(s): Ildebrando, Christina
• Application Number:
  US10/243,669
• Publication Number:
  US 20040053772A1
• Time in Patent Office: 953 Days
• Field of Search: 502/60, 502/64, 502/71, 502/77, 423/702, 423/704, 423/705, 423/707
• US Class Current: 502/64
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids

Abstract

The present invention relates to the manufacture of solid materials or shaped bodies containing at least one zeolite and being at least partly crystalline. Furthermore, the present invention relates to the solid materials or shaped bodies as such and to the use of these materials for reactions of compounds having at least one C—C double bond with at least one hydroperoxide. Specifically, the present invention relates to a process for the manufacture of a solid material containing at least one zeolite and being at least partly crystalline, wherein the synthesis of the said solid material involves at least one partial step of contacting at least one transition metal oxide source with at least one epoxide or hydrolysate thereof prior to or during the at least partial crystallization of said solid material.

Claims

1. Process for preparing a solid material containing at least one zeolite and being at least partly crystalline comprising a step (I), which step comprises at least partial crystallization of at least one solid material containing at least one zeolite out of a synthesis mixture, wherein said at least partial crystallization comprises contacting at least one transition metal oxide source with at least one epoxide or hydrolysate thereof prior to or during the at least partial crystallization.

2. Process according to claim 1, wherein step (I) comprises at least the following steps:

(Ia) mixing of at least one hydrolyzable silicon source with a mineralizing and/or structuring agent and water;

(Ib) mixing of at least one transition metal oxide source with an epoxide or a hydrolysate thereof;

(Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;

(Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;

(Ie) adding water to the bottom of (Id);

(If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature.

3. Process according to claim 2, wherein the hydrolyzable silicon source comprises at least one silicon oxide, the mineralizing and/or structuring agent comprises at least one tetraalkylammonium hydroxide, the transition metal oxide source comprises at least one titanate and the epoxide or hydrolysate thereof comprises at least the epoxide or the hydrolysate thereof of the reaction for which the solid material is ultimately employed as a catalyst.

4. Process according to claim 3, wherein the hydrolyzable silicon source comprises at least tetraethoxy silicate, the mineralizing and/or structuring agent comprises at least tetrapropylammonium hydroxide, the transition metal oxide source comprises at least tetrabutylorthotitanate and the epoxide or the hydrolysate thereof comprises at least propylene oxide or propylene glycol.

5. Process according to any of claim 1, wherein the at least one zeolite belongs to at least one of the following structure classes:

MFI, MEL, MWW, BEA and any mixed structures thereof.

6. Integrated process for the production of a solid material containing at least one zeolite, comprising at least the following steps:

(I) at least partial crystallization of at least one solid material containing at least one zeolite out of a synthesis mixture, resulting in mixture (I) containing at least said solid material and a mother liquor, said at least partial crystallization comprising at least the following steps;

(Ia) mixing of at least one hydrolyzable silicon source with a mineralizing and/or structuring agent and water;

(Ib) mixing of at least one transition metal oxide source with an epoxide or a hydrolysate thereof;

(Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;

(Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;

(Ie) adding water to the bottom of (Id);

(If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature;

(II) separating and/or concentrating of the solid material in mixture (I).

7. Integrated process according to claim 6, wherein, after step (II), at least one of the following two additional steps is performed:

(W) bringing the solid material from step (II) in contact with a composition containing water;

(III) agglomerating or granulating or agglomerating and granulating of the solid material from step (W) or from step (II).

8. Integrated process according to claim 7, wherein, after step (W), a repetition of step (II) is performed.

9. Integrated process according to claim 7, wherein after at least one of the steps (I), (W) or (III), a step (C) of calcining the solid material is performed.

10. Integrated process according to claim 6, wherein after step (II), a step (C) of calcining the solid material is performed.

11. Integrated process as claimed in claim 6, wherein the hydrolyzable silicon source comprises at least one silicon oxide, the mineralizing and/or structuring agent comprises at least one tetraalkylammonium hydroxide, the transition metal oxide source comprises at least one titanate and the epoxide or the hydrolysate thereof of the reaction for which the solid material is ultimately employed as a catalyst.

12. Integrated process as claimed in claim 11, wherein the hydrolyzable silicon source comprises at least tetraethoxy silicate, the mineralizing and/or structuring agent comprises at least tetrapropylammonium hydroxide, the transition metal oxide source comprises at least tetrabutylorthotitanate and the epoxide or the hydrolysate thereof comprises at least propylene oxide or propylene glycol.

13. Integrated process for the production of a shaped body containing at least one zeolite, comprising at least the following steps:

(I) at least partial crystallization of at least one solid material containing at least one zeolite out of a synthesis mixture, resulting in mixture (I) containing at least said solid material and a mother liquor, said at least partial crystallization at least the following steps;

(Ia) mixing of at least one hydrolyzable silicon source with a mineralizing and/or structuring agent and water;

(Ib) mixing of at least one transition metal oxide source with an epoxide or a hydrolysate thereof;

(Ic) mixing of the mixtures from (Ia) and (Ib) so that at least a part of the hydrolyzable compounds hydrolyzes;

(Id) distilling at least parts of the alcohol that has been formed as a result of the at least partial hydrolysation of at least part of the hydrolyzable compounds;

(Ie) adding water to the bottom of (Id);

(If) reacting of the synthesis mixture resulting from (Ie) at a temperature elevated with respect to room temperature;

(II) separating and/or concentrating of the solid material in mixture (I);

(III) agglomerating or granulating or agglomerating and granulating of the solid material;

(S) shaping of the solid material from step (II) or (III).

14. Integrated process according to claim 13, wherein the following step (W) is performed after step (II) or after step (S) or after step (II) and after step (S):

(W) bringing the solid material from step (II) or the shaped body from step (S) in contact with a composition containing water.

15. Integrated process as claimed in claim 14, wherein after at least one of the steps (II), (W), (III), or (S), a step (C) of calcining the solid material or the shaped body or the solid material and the shaped body is performed.

16. Integrated process according to claim 15, wherein said step of calcining is performed at temperatures higher than 400°

C.

17. Integrated process according to claim 13, wherein the at least one step of shaping the solid material is selected from the group consisting of pelletizing, pressing, extruding, sintering, roasting, and briquetting.

18. Integrated process according to claim 17, wherein before and during or before or during the step of (S) of shaping the solid material, a binding material is added to said solid material.

19. Integrated process as claimed in claim 13, wherein the hydrolyzable silicon source comprises at least one silicon oxide, the mineralizing and/or structuring agent comprises at least one tetraalkylammonium hydroxide, the transition metal oxide source comprises at least one titanate and the epoxide or hydrolysate thereof comprises at least the epoxide or the hydrolysate thereof of the reaction for which the solid material is ultimately employed as a catalyst.

20. Integrated process as claimed in claim 19, wherein the hydrolyzable silicon source comprises at least tetraethoxy silicate, the mineralizing and/or structuring agent comprises at least tetrapropylammonium hydroxide, the transition metal oxide source comprises at least tetrabutylorthotitanate and the epoxide or the hydrolysate thereof comprises at least propylene oxide or propylene glycol.

21. Integrated process as claimed in claim 13, wherein after at least one of the steps (II), (III), or (S), a step (C) of calcining the solid material or the shaped body or the solid material and the shaped body is performed.