Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds

• US 10,266,417 B2
• Filed: 09/13/2016
• Issued: 04/23/2019
• Est. Priority Date: 04/24/2012
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Feyen, Mathias, Muller, Ulrich, Parvulescu, Andrei-Nicolae, Schaack, Bernd Bastian, Ahrens, Sebastian, Gerhard, Dirk, Son, Sunghee, Iffland, Gabriele, Seelig, Bianca
• Primary Examiner(s): Brunsman, David M
• Application Number:
  US15/264,314
• Publication Number:
  US 20170001874A1
• Time in Patent Office: 952 Days
• CPC Class Codes: B01J 20/18 Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/186 Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 2229/183 in framework positions
• CPC Class Codes: B01J 2229/186 not in framework positions
• CPC Class Codes: B01J 29/00 Catalysts comprising molecular sieves molecular sieves per se C01B
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• 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: B01J 37/009 Preparation by separation, e.g. by filtration, decantation, screening
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/30 Ion-exchange
• CPC Class Codes: C01B 37/005 Silicates, i.e. so-called metallosilicalites or metallozeosilites
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/04 : using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• CPC Class Codes: C01B 39/065 : Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
• CPC Class Codes: C01B 39/085 : Group IVB- metallosilicates
• CPC Class Codes: C01B 39/40 : using at least one organic template directing agent
• CPC Class Codes: C01B 39/48 : using at least one organic template directing agent
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2006/12 : Surface area

Abstract

The present invention relates to a process for the preparation of a zeolitic material comprising the steps of:

• (1) providing a mixture comprising one or more sources for YO₂ and one or more alkenyltrialkylammonium cation R¹R²R³R⁴N⁺-containing compounds as structure directing agent; and
• (2) crystallizing the mixture obtained in step (1) to obtain a zeolitic material;
  wherein Y is a tetravalent element, and wherein
• R¹, R², and R³ independently from one another stand for alkyl; and
• R⁴ stands for alkenyl, as well as to zeolitic materials which may be obtained according to the inventive process and to their use.

Claims

1. A synthetic zeolitic material having an MFI-type framework structure obtained by a process comprising:

(1) providing a mixture comprising one or more sources for YO₂ and one or more alkenyltrialkylammonium cation R¹R²R³R⁴N⁺-containing compounds as structure directing agent; and

(2) crystallizing the mixture obtained in (1) to obtain a zeolitic material;

wherein Y is a tetravalent element, and

wherein R¹, R², and R³ are each a propyl group; and

R⁴ is a 2-propen-1-yl or 1-propen-1-yl group.

2. The synthetic zeolitic material of claim 1 comprising YO₂, wherein Y is a tetravalent element, and X is a trivalent element, said material having an X-ray diffraction pattern comprising at least the following reflections:

3. The zeolitic material of claim 2, wherein the ²⁹Si MAS NMR of the zeolitic material comprises:

a first peak (P″

1) in the range of from −

110.4 to −

114.0 ppm; and

a second peak (P″

2) in the range of from −

100.2 to −

104.2 ppm.

4. The synthetic zeolitic material of claim 1 comprising YO₂ and optionally comprising X₂O₃,

wherein Y is a tetravalent element, and X is a trivalent element,

said material having an X-ray diffraction pattern comprising at least the following reflections:

5. The zeolitic material of claim 4, wherein the ²⁹Si MAS NMR of the zeolitic material comprises:

a first peak (P1) in the range of from −

110.4 to −

114.0 ppm.

6. The zeolitic material of claim 5, wherein the deconvoluted ²⁹Si MAS NMR spectrum comprises one additional peak comprised in the range of from −

113.2 to −

115.2 ppm.

7. The zeolitic material of claim 5, wherein at least a portion of the Y atoms and/or of the X atoms in the MFI-type framework structure is isomorphously substituted by one or more elements, wherein the one or more elements are selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, Be, and mixtures of two or more thereof.

8. The zeolitic material of claim 7, wherein a molar ratio of YO₂ to the one or more element ranges from 5 to 100.

9. The zeolitic material of claim 4, wherein the ²⁷AI MAS NMR of the zeolitic material comprises:

a first peak (P′

1) in the range of from 50.00 to 53.50 ppm; and

a second peak (P′

2) in the range of from −

0.50 to −

2.00 ppm;

wherein the integration of the first and second peaks in the ²⁷AI MAS NMR of the zeolitic material offers a ratio of the integration values P′

1;

P′

2 of 1;

(0.5-1.2).

10. The zeolitic material of claim 4, wherein the YO₂:

X₂O₃ molar ratio ranges from 2 to 200.

11. The zeolitic material of claim 4, wherein the MFI-type framework structure of the zeolitic material does not contain X₂O₃.

12. The zeolitic material of claim 4, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

13. The zeolitic material of claim 4, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

14. The zeolitic material of claim 4, wherein the zeolitic material comprises one or more cation and/or cationic elements as ionic non-framework elements.

15. The zeolitic material of claim 4, wherein the BET surface area of the zeolitic material determined according to DIN 66135 ranges from 50 to 700 m²/g.

16. The zeolitic material of claim 1, wherein the zeolitic material is effective in converting at least 80% isopropanol in catalytic decomposition at 200°

C.

20. The process of claim 10, wherein a molar ratio of 2-propen-1-yl to 1-propen-1-yl is from 25:

75 to 99;

1.

17. A process for the preparation of a zeolitic material comprising:

(1) providing a mixture comprising one or more sources for YO₂ and one or more alkenyltrialkylammonium cation R¹R²R³R⁴N⁺-containing compounds as structure directing agent; and

(2) crystallizing the mixture obtained in (1) to obtain a zeolitic material;

wherein Y is a tetravalent element, and

wherein R¹, R², and R³ are each a propyl group; and

R⁴ is a 2-propen-1-yl or 1-propen-1-yl group.

18. The process of claim 17, wherein the structure directing agent comprises a hydroxide anion.

19. The process of claim 17, wherein the mixture provided in (1) comprises two R¹R²R³R⁴N⁺-containing compounds, wherein R⁴ of the first compound is a 2-propen-1-yl group and R⁴ of the second compound is a 1-propen-1-yl group.

21. The process of claim 17, wherein Y is at least one selected from the group consisting of Si, Sn, Ti, Zr and Ge.

22. The process of claim 17, wherein the one or more sources for YO₂ comprises one or more compounds selected from the group consisting of fumed silica, silica hydrosols, reactive amorphous solid silicas, silica gel, silicic acid, water glass, sodium metasilicate hydrate, sesquisilicate, disilicate, colloidal silica, pyrogenic silica, silicic acid esters, and mixtures of two or more thereof.

23. The process of claim 17, wherein the mixture provided in (1) further comprises one or more sources for X₂O₃, wherein X is a trivalent element.

24. The process of claim 23, wherein X is at least one selected from the group consisting of Al, B, In and Ga.

25. The process of claim 23 or 24, wherein the one or more sources for X₂O₃ comprises one or more compounds selected from the group consisting of aluminum, aluminum alkoxides and alumina.

26. The process of claim 23, wherein the YO₂:

X₂O₃ molar ratio of the mixture according to (1) is from 0.5 to 500.

27. The process of claim 23, wherein the mixture of (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 zeolite framework structure.

28. The process of claim 27, wherein the one or more sources for isomorphous substitution comprises one or more titania precursor compounds.

29. The process of claim 27 or 28, wherein the molar ratio of YO₂ to 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 zeolite framework structure is from 1 to 300.

30. The process of claim 17, wherein the mixture provided in (1) does not comprise a source for X₂O₃, wherein X is a trivalent element.

31. The process of claim 17, wherein the mixture according to (1) further comprises one or more solvents, wherein said one or more solvents comprises water.

32. The process of claim 31, wherein a H₂O:

YO₂ molar ratio of the mixture is from 3 to 100.

33. The process of claim 17, wherein a molar ratio of the one or more alkenyltrialkylammonium cations R¹R²R³R⁴N³⁰ :

YO₂ in the mixture is from 0.01 to 5.

34. The process of claim 17, wherein the crystallization in (2) comprises heating of the mixture at a temperature of from 90 to 210°

C.

35. The process of claim 34, wherein the crystallization in (2) is conducted under solvothermal conditions.

36. The process of claim 34, wherein the crystallization in (2) comprises heating the mixture for a period of time of from 5 to 120 h.

37. The process of claim 17, wherein the crystallization in (2) comprises agitating the mixture.

38. The process of claim 17 further comprising one or more of the following:

(3) isolating the zeolitic material, by filtration,

(4) washing the zeolitic material,

(5) drying the zeolitic material,

6) subjecting the zeolitic material to an ion-exchange procedure,

wherein the isolating, washing, drying and ion exchange can be conducted in any order.

39. The process of claim 38, comprising (6) wherein one or more ionic non-framework elements contained in the zeolite framework is ion-exchanged.

40. The process of claim 17, wherein the zeolitic material formed in (2) comprises one or more zeolites having the MFI-type framework structure.