Organotemplate-free synthetic process for the production of a zeolitic material

Patent metadata

Field	Value
Publication number	US-9011815-B2
Application number	US-201213654074-A
Country	US
Kind code	B2
Filing date	Oct 17, 2012
Priority date	Jun 18, 2009
Publication date	Apr 21, 2015
Grant date	Apr 21, 2015

Abstract

The present invention relates to an organotemplate-free synthetic process for the production of a zeolitic material having a BEA framework structure comprising YO 2 and optionally comprising X 2 O 3 , wherein said process comprises the steps of (1) preparing a mixture comprising seed crystals and at least one source for YO 2 ; and (2) crystallizing the mixture; wherein Y is a tetravalent element, and X is a trivalent element, wherein the zeolitic material optionally comprises at least one alkali metal M, wherein when the BEA framework additionally comprises X 2 O 3 , the mixture according to step (1) comprises at least one source for X 2 O 3 , and wherein the seed crystals comprise zeolitic material having a BEA framework structure, preferably zeolite Beta.

First claim

We claim:

1. An organotemplate-free synthetic process for the production of a zeolitic material having a BEA framework structure comprising YO 2 and X 2 O 3 , wherein said process comprises
(1) preparing a mixture comprising seed crystals, at least one source for YO 2 , and at least one source of X 2 O 3 ;
(2) crystallizing the mixture; and
(6) subjecting said zeolitic material having a BEA framework structure to an ion-exchange procedure,
wherein Y is a tetravalent element, and X is a trivalent element,
wherein the seed crystals comprise zeolitic material having a BEA framework structure, and
wherein in step (6) at least one ionic non-framework element contained in said zeolitic material having a BEA framework is ion-exchanged against Fe and/or Cu.

2. The process according to claim 1 , wherein Y is Si.

3. The process according to claim 1 , wherein the at least one source for YO 2 comprises at least one silicate.

4. The process according to claim 1 , wherein X is A 1 .

5. The process according to claim 1 , wherein the at least one source for X 2 O 3 comprises at least one aluminate salt.

6. The process according to claim 5 , wherein the at least one source for X 2 O 3 comprises sodium and/or potassium aluminate.

7. The process according to claim 1 , wherein the mixture according to step (1) further comprises a solvent.

8. The process according to claim 1 , wherein the mixture according to step (1) further comprises at least one source for OH − .

9. The process according to claim 1 , wherein the crystallization in step (2) involves heating of the mixture.

10. The process according to claim 1 further comprising at least one of the following
(3) isolating the zeolitic material having a BEA framework structure, and/or
(4) washing the zeolitic material having a BEA framework structure, and/or
(5) drying the zeolitic material having a BEA framework structure,
wherein the steps (3) and/or (4) and/or (5) and/or (6) can be conducted in any order.

11. The process according to claim 1 , wherein the zeolitic material having a BEA framework structure formed in step (2) comprises zeolite Beta.

12. The process according to claim 1 , wherein the seed crystals comprise a zeolitic material having a BEA framework structure as synthesized according to the process of claim 1 .

13. The process according to claim 1 , wherein the organotemplate-free synthesis does not comprise a calcination step.

14. An organotemplate-free zeolitic material having a BEA framework structure obtainable and/or obtained according to claim 1 .

15. An organotemplate-free zeolitic material having a BEA framework structure, having an X-ray diffraction pattern comprising at least the following reflections:

Intensity
Diffraction angle

(%)
2θ/° [Cu K(alpha 1)]

[12-32]
[21.07-21.27]

100
[22.12-22.32]

[14-34]
[25.01-25.21]

[12-32]
[26.78-26.98]

[14-34]
[28.39-28.59]

[28-48]
[29.24-29.44]

[10-30]
[30.00-30.20]

[11-31]
[32.86-33.26]

[13-33]
[42.90-43.30]

wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern,
wherein the BEA framework structure comprises YO 2 and optionally comprises X 2 O 3 ,
wherein Y is a tetravalent element, and X is a trivalent element,
wherein the zeolitic material comprises at least one alkali metal M, wherein at least a portion of said alkali metal atoms M is substituted by Fe and/or Cu.

16. The organotemplate-free zeolitic material according to claim 15 , wherein the X-ray diffraction pattern comprises the following reflection:

Intensity
Diffraction angle

(%)
2θ/° [Cu K(alpha 1)]

[11-31]
[25.53-25.73]

17. The organotemplate-free zeolitic material according to claim 15 , wherein Y is Si.

18. The organotemplate-free zeolitic material according to claim 15 , wherein X is A 1 .

19. The organotemplate-free zeolitic material according to claim 15 , wherein said material comprises at least sodium and/or potassium.

20. The organotemplate-free zeolitic material according to claim 15 , wherein said material comprises zeolite Beta.

21. A method of using an organotemplate-free zeolitic material according to claim 15 in a catalytic process.

22. The organotemplate-free zeolitic material according to claim 15 , wherein said zeolitic material has a BEA framework structure comprising YO 2 and X 2 O 3 and is obtainable and/or obtained by a process comprising
(1) preparing a mixture comprising seed crystals, at least one source for YO 2 and at least one source of X 2 O 3 ;
(2) crystallizing the mixture; and
(6) subjecting said zeolitic material having a BEA framework structure to an ion-exchange procedure,
wherein Y is a tetravalent element, and X is a trivalent element,
wherein the seed crystals comprise zeolitic material having a BEA framework structure, and
wherein in step (6) at least one ionic non-framework element contained in said zeolitic material having a BEA framework is ion-exchanged against Fe and/or Cu.

Assignees

• Xiao Feng-Shou
• Xie Bin
• Mueller Ulrich
• Yilmaz Bilge
• Basf Se

Inventors

• Xiao Feng-Shou
• Xie Bin
• Mueller Ulrich
• Yilmaz Bilge

Classifications

• B01J2235/05

  Nuclear magnetic resonance [NMR] · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/56

  Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths · CPC title