Alkali-free synthesis of zeolitic materials of the LEV-type structure

Patent metadata

Field	Value
Publication number	US-9334171-B2
Application number	US-201113163377-A
Country	US
Kind code	B2
Filing date	Jun 17, 2011
Priority date	Jun 18, 2010
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

A process for the production of a zeolitic material having an LEV-type framework structure comprising YO2 and optionally comprising X203, wherein said process comprises preparing a mixture comprising one or more sources for YO2, one or more solvents, and optionally comprising seed crystals; and crystallizing the mixture; wherein Y is a tetravalent element, and X is a trivalent element, and wherein the crystallized mixture contains 0.1 wt.-% or less, more preferably 0.01 wt.-% or less of one or more metals M based on 100 wt.-% of YO2, wherein even more preferably the crystallized mixture contains no metal M, wherein M stands for sodium and/or potassium, wherein preferably M stands for the group of alkali and alkaline earth metals.

First claim

The invention claimed is:

1. A process for the production of a zeolitic material having an LEV-type framework structure comprising YO 2 and optionally comprising X 2 O 3 , wherein said process comprises:
(1) preparing a mixture comprising one or more sources for YO 2 , one or more solvents, one or more tetraalkylammonium compounds, and optionally comprising seed crystals; and
(2) crystallizing the mixture obtained in step (1);
wherein Y is a tetravalent element, and X is a trivalent element, and
wherein the mixture obtained in step (1) and to be crystallized in step (2) contains less than 0.01 wt. % of sodium and potassium based on 100 wt % of YO 2 .

2. The process of claim 1 , wherein the molar ratio of the total amount of the one or more solvents to YO 2 of the mixture obtained in step (1) is 50 or less.

3. The process of claim 1 , wherein the one or more solvents comprise one or more polar solvents.

4. The process of claim 1 , wherein the molar ratio of the total amount of the one or more tetraalkylammonium compounds to YO 2 of the mixture obtained in step (1) ranges from 0.01 to 2.

5. The process of claim 1 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

6. The process of claim 1 , wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

7. The process of claim 1 , wherein the one or more sources for YO 2 comprises silica.

8. The process of claim 1 , wherein the mixture in step (1) further comprises one or more sources for X 2 O 3 .

9. The process of claim 8 , wherein the one or more sources for X 2 O 3 comprises one or more aluminum compounds.

10. The process of claim 8 , wherein the YO 2 :X 2 O 3 molar ratio of the mixture obtained in step (1) ranges from 2 to 200.

11. The process of claim 1 , wherein the mixture according to step (1) further comprises one or more sources for OH − .

12. The process of claim 11 , wherein the OH − :YO 2 molar ratio of the mixture obtained in step (1) ranges from 0.01 to 5.

13. The process of claim 1 , wherein the mixture according to step (1) further comprises one or more sources of one or more elements suitable for isomorphous substitution of at least a portion of the Y atoms and/or of the X atoms in the LEV-type framework structure.

14. The process of claim 13 , wherein the molar ratio of YO 2 to the total amount of the one or more elements suitable for isomorphous substitution of at least a portion of the Y atoms and/or of the X atoms in the LEV-type framework structure ranges from 3 to 300.

15. The process of claim 1 , wherein the mixture in step (1) further comprises one or more sources for X 2 O 3 , and wherein the molar ratio of YO 2 to X 2 O 3 to the total amount of the one or more tetraalkylammonium compounds of the mixture obtained in step (1) ranges from 1:(0.005-1):(0.05-10).

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

17. The process of claim 1 , wherein the crystallization in step (2) is conducted under solvothermal conditions.

18. The process of claim 16 , wherein the crystallization in step (2) involves heating of the mixture for at least 0.1 d.

19. The process of claim 1 , wherein the crystallization in step (2) involves agitating the mixture.

20. The process of claim 1 , further comprising one or more of the following:
(3) isolating the zeolitic material having an LEV-type framework structure, and/or
(4) washing the zeolitic material having an LEV-type framework structure, and/or
(5) drying and/or calcining the zeolitic material having an LEV-type framework structure, and/or
(6) subjecting the zeolitic material having an LEV-type framework structure to an ion-exchange procedure,
wherein the steps (3) and/or (4) and/or (5) and/or (6) can be conducted in any order.

21. The process of claim 20 , wherein the calcination in step (5) is conducted at a temperature in the range of from 300 to 900° C.

22. The process of claim 20 , wherein after step (2) and prior to step (3) the pH of the crystallization product is adjusted to a pH in the range of from 5 to 12.

23. The process of claim 20 , wherein in step (6) the zeolitic material having an LEV-type framework is ion-exchanged with at least one cation and/or cationic element.

24. The process of claim 1 , wherein the zeolitic material having an LEV-type framework structure formed in step (2) comprises one or more zeolites selected from the group consisting of Levyne, LZ-132, NU-3, RUB-1, ZK-20, ZSM-45, RUB-50, and mixtures of two or more thereof.

25. The process of claim 1 , wherein the seed crystals at least partially comprise zeolitic material not having an LEV-type framework structure.

26. The process of claim 25 , wherein the zeolitic material not having an LEV-type framework structure contained in the seed crystals comprises zeolitic material having a CHA-type framework structure.

27. The process of claim 1 , wherein the seed crystals at least partially comprise zeolitic material having an LEV-type framework structure.

28. The process of claim 27 , wherein the zeolitic material having an LEV-type framework structure contained in the seed crystals comprises one or more zeolites selected from the group consisting of Levyne, LZ-132, NU-3, RUB-1, ZK-20, ZSM-45, RUB-50.

29. The process of claim 1 , wherein the amount of seed crystals in the mixture according to step (1) ranges from 0.01 to 30 wt.-% based on 100 wt.-% of YO 2 in the at least one source for YO 2 .

30. The process of claim 1 , wherein the mixture according to step (1) contains 5 wt.-% or less of seed crystals based on 100 wt.-% of YO 2 .

31. A zeolitic material having an LEV-type framework structure obtainable according to the process of claim 1 .

32. A non-ion-exchanged zeolitic material, said zeolitic material having an LEV-type framework structure comprising YO 2 and comprising X 2 O 3 , wherein Y is a tetravalent element, and X is a trivalent element, wherein the non-ion-exchanged zeolitic material contains less than 0.1 wt. % of sodium and potassium based on 100 wt. % of X, and wherein the BET surface area of the calcined zeolitic material determined according to DIN 66131 ranges from 650 to 1,100 m 2 /g.

33. The zeolitic material of claim 32 , wherein the LEV-type framework structure comprises X 2 O 3 , and wherein the zeolitic material displays an Y:X atomic ratio of from 1 to 200.

34. The zeolitic material of claim 32 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

35. The zeolitic material of claim 32 , wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

36. The zeolitic material of claim 32 , said material having an X-ray diffraction pattern comprising at least the following reflections:

Intensity
Diffraction angle 2θ/°

(%)
[Cu K(alpha 1)]

Assignees

• Yilmaz Bilge
• Müller Ulrich
• Pfaff Meike
• Gies Hermann
• Xiao Feng-Shou
• Tatsumi Takashi
• Bao Xinhe
• Zhang Weiping
• De Vos Dirk
• Imai Hiroyuki
• Xie Bin
• Zhang Haiyan
• Basf Se
• Tokyo Inst Tech

Inventors

• Yilmaz Bilge
• Müller Ulrich
• Pfaff Meike
• Gies Hermann
• Xiao Feng-Shou
• Tatsumi Takashi
• Bao Xinhe
• Zhang Weiping
• De Vos Dirk
• Imai Hiroyuki
• Xie Bin
• Zhang Haiyan

Classifications

• B01D2255/9207

  Specific surface · CPC title

• C10G11/18

  according to the "fluidised-bed" technique · CPC title

• B01D2253/108

  Zeolites · CPC title

• C01B39/48

  using at least one organic template directing agent · CPC title

• B01D2251/2067

  Urea · CPC title