Process for the preparation of a titanium zeolite catalyst

Patent metadata

Field	Value
Publication number	US-9302257-B2
Application number	US-95480210-A
Country	US
Kind code	B2
Filing date	Nov 26, 2010
Priority date	Nov 27, 2009
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

A process for the preparation of a catalyst for the use in a hydrocarbon conversion reaction, said catalyst containing a titanium zeolite and carbonaceous material, the catalyst containing said carbonaceous material in an amount of from 0.01 to 0.5% by weight based on the total weight of titanium zeolite contained in the catalyst, the process comprising (i) preparing a catalyst containing the titanium zeolite and (ii) depositing carbonaceous material on the catalyst according to (i) in an amount of from 0.01 to 0.5% by weight based on the total weight of titanium zeolite contained in the catalyst by contacting said catalyst, prior to using the catalyst in said hydrocarbon conversion reaction, with a fluid containing at least one hydrocarbon in an inert atmosphere, to obtain the carbonaceous material containing catalyst, wherein in (ii), the catalyst is not contacted with an oxygen containing gas.

First claim

The invention claimed is:

1. A process for the preparation of a catalyst for the use in a hydrocarbon conversion reaction,
the catalyst comprising:
a titanium zeolite; and
a carbonaceous material in an amount of from 0.01 to 0.5% by weight based on a total weight of the titanium zeolite in the catalyst;
the process comprising:
(i) preparing a catalyst containing the titanium zeolite;
(ii) treating the catalyst with an inert gas to place the catalyst in an inert atmosphere;
(iii) elevating the temperature of the catalyst in the inert atmosphere to a temperature above 300° C.; and
(iv) contacting the catalyst with a fluid comprising a hydrocarbon in the inert atmosphere to deposit a carbonaceous material on the catalyst at the temperature above 300° C. in an amount of from 0.01 to 0.5% by weight based on the total weight of titanium zeolite to obtain the prepared catalyst;
wherein in (ii-iv), the catalyst is not contacted with an oxygen containing gas; and after the deposition of the carbonaceous material (iv), the catalyst is not subjected to an additional heat treating step.

2. The process of claim 1 , wherein the fluid comprising a hydrocarbon is a gas stream.

3. The process of claim 1 , wherein the inert gas is nitrogen.

4. The process of claim 1 , wherein in (iv), the fluid comprising a hydrocarbon is a gas stream further comprising an inert gas or a mixture of inert gases, wherein in the gas stream, a volume ratio of hydrocarbon to inert gas or inert gases is in the range of from 1:50 to 1:5.

5. The process of claim 1 , wherein the hydrocarbon contacting the catalyst is the hydrocarbon being converted in the hydrocarbon conversion process.

6. The process of claim 1 , wherein the hydrocarbon contacting the catalyst is an olefin.

7. The process of claim 1 , wherein the hydrocarbon contacting the catalyst is propylene.

8. The process of claim 1 , wherein the temperature of contacting the catalyst with the fluid comprising a hydrocarbon is from 400 to 500° C.

9. The process of claim 1 , wherein a time of contacting the catalyst with the hydrocarbon is from 12 to 48 h.

10. The process of claim 1 , wherein the titanium zeolite has an MFI, MEL, MWW, BEA or FER structure or a mixed structure of two or more thereof.

11. The process of claim 1 , wherein the titanium zeolite has an MFI structure.

12. The process of claim 1 , wherein the catalyst is not subject to a silylation treatment.

13. The process of claim 1 , further comprising hydrothermal treatment of the catalyst containing the titanium zeolite prior to placing the catalyst in an inert atmosphere.

14. The process of claim 1 , wherein preparing the catalyst containing the titanium zeolite comprises shaping the catalyst to obtain a molding comprising the titanium zeolite.

15. The process of claim 1 , wherein preparing the catalyst containing the titanium zeolite comprises a silica binder and shaping the catalyst to obtain a molding comprising the titanium zeolite and a silica binder.

16. The process of claim 1 , wherein the prepared catalyst contains the carbonaceous material in the amount deposited on the catalyst during the contacting of the catalyst with the hydrocarbon in the inert atmosphere.

17. A catalyst obtained by the process of claim 1 , comprising a titanium zeolite and carbonaceous material, wherein an amount of the carbonaceous material is from 0.01 to 0.5%, based on the total weight of titanium zeolite in the catalyst, and wherein the titanium zeolite has an MFI, MEL, MWW, BEA or FER structure or a mixed structure of two or more thereof.

18. The catalyst of claim 17 , wherein the titanium zeolite has an MFI structure.

19. The catalyst of claim 17 , wherein in (i), the catalyst is a shaped molding comprising the titanium zeolite, and and further comprising micropores and mesopores.

20. The catalyst of claim 19 , wherein the molding further comprises a silica binder and wherein an amount of the titanium zeolite and the carbonaceous material is from 70 to 80% by weight, and an amount of the silica binder is from 20 to 30% by weight, in each case based on the total weight of the molding.

21. The catalyst of claim 19 , wherein a crush strength of the molding is at least 22 N, determined using an apparatus from Zwick, type BZ2.5/TS1S.

22. A method for converting a hydrocarbon comprising contacting the hydrocarbon to be converted with the catalyst to of claim 17 .

23. The method of claim 22 , wherein the process for the conversion of a hydrocarbon is a process for the preparation of propylene oxide, and the process comprises
contacting the catalyst with a reaction mixture comprising propylene, hydroperoxide, and at least one solvent.

24. The method of claim 23 , wherein the catalyst is a titanium silicalite-1 catalyst, the hydroperoxide is hydrogen peroxide and the solvent is methanol.

25. The method of claim 23 , wherein the prepared catalyst contains the carbonaceous material in the amount deposited on the catalyst during the contacting of the catalyst with the hydrocarbon in the inert atmosphere.

26. The method of claim 22 , wherein said hydrocarbon is propylene and the conversion is into propylene oxide.

27. A process for the preparation of a catalyst for the use in a hydrocarbon conversion reaction, the catalyst comprising:
a titanium zeolite; and
a carbonaceous material in an amount of from 0.01 to 0.5% by weight based on a total weight of the titanium zeolite in the catalyst;
the process comprising:
(i) preparing a catalyst containing the titanium zeolite;
(ii) treating the catalyst with an inert gas to place the catalyst in an inert atmosphere;
(iii) elevating the temperature of the catalyst in the inert atmosphere to a temperature above 300° C.; and
(iv) contacting the catalyst with a fluid containing a hydrocarbon in the inert atmosphere to deposit a carbonaceous material on the catalyst at the temperature above 300° C. in an amount of from 0.01 to 0.5% by weight based on the total weight of titanium zeolite to obtain the prepared catalyst;
wherein in (ii-iv), the catalyst is not contacted with an oxygen containing gas; and after the deposition of the carbonaceous material (iv), the catalyst is not subjected to an additional heat treating step, and
wherein the catalyst shows improved catalytic properties in the hydrocarbon conversion processes compared to a catalyst of the same composition which has not been contacted with a hydrocarbon in accordance with (ii-iv).

28. The method of claim 27 , wherein said improved catalytic properties result in a longer life time and/or higher selectivity concerning a valuable product and/or lower selectivities concerning a by-product and/or secondary product and/or improved activity.

29. The method of claim 28 , wherein said carbonaceous material is deposited on said catalyst in an amount of from 0.01 to 0.06 wt.-%.

30. A catalyst obtained by the method of claim 29 .

31. The catalyst of claim 30 , which exhibits improved selectivity for propylene oxide in the epoxidation reaction of propylene with hydrogen peroxide in the presence of methanol or a methanol/water mixture as solvent.

Assignees

• Müller Ulrich
• Rudolf Peter
• Krug Georg
• Senk Rainer
• Basf Se
• Dow Chemical Co

Inventors

• Müller Ulrich
• Rudolf Peter
• Krug Georg
• Senk Rainer

Classifications

• B01J29/89 Primary

  Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)} · CPC title

• B01J37/0018 Primary

  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 title

• C07D301/12

  with hydrogen peroxide or inorganic peroxides or peracids · CPC title

• B01J2229/42

  Addition of matrix or binder particles · CPC title

• B01J37/084

  Decomposition of carbon-containing compounds into carbon · CPC title