Zeolitic materials and methods for their preparation using alkenyltrialkylammonium compounds

Patent metadata

Field	Value
Publication number	US-9475041-B2
Application number	US-201313869418-A
Country	US
Kind code	B2
Filing date	Apr 24, 2013
Priority date	Apr 24, 2012
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

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 YO 2 and one or more alkenyltrialkylammonium cation R 1 R 2 R 3 R 4 N + -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 R 1 , R 2 , and R 3 independently from one another stand for alkyl; and R 4 stands for alkenyl, as well as to zeolitic materials which may be obtained according to the inventive process and to their use.

First claim

The invention claimed is:

1. A synthetic zeolitic material having an MFI-type framework structure obtained by a process, comprising:
crystallizing a mixture comprising a YO 2 source and a structure directing agent comprising an alkenyltrialkylammonium cation R 1 R 2 R 3 R 4 N + -comprising compound, to obtain a zeolitic material;
wherein Y is a tetravalent element,
R 1 , R 2 , and R 3 are each independently an alkyl; and
R 4 is an alkenyl;
and wherein
a BET surface area of the synthetic zeolitic material determined according to DIN 66135 is from 50 to 700 m 2 /g, and
a maximum water absorption of the synthetic zeolitic material is from 2.9 wt % to 8.7 wt %.

2. A synthetic zeolitic material having an MFI-type framework structure comprising YO 2 and optionally comprising X 2 O 3 ,
wherein Y is a tetravalent element, and X is a trivalent element,
the synthetic zeolite material has an X-ray diffraction pattern comprising the following reflections:

Intensity (%)
Diffraction angle 2θ/° [Cu K(alpha 1)]

 55-100
7.66-8.20

40-75
8.58-9.05

 92-100
22.81-23.34

49-58
23.64-24.18

16-24
29.64-30.21

14-25
44.80-45.25

16-24
45.26-45.67

wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and wherein
a BET surface area of the synthetic zeolitic material determined according to DIN 66135 is from 50 to 700 m 2 /g, and
a maximum water absorption of the synthetic zeolitic material is from 2.9 wt % to 8.7 wt %.

3. The zeolitic material of claim 2 , wherein e 29 Si 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. A synthetic zeolitic material having an MFI-type framework structure comprising YO 2 and optionally comprising X 2 O 3 ,
wherein Y is a tetravalent element, and X is a trivalent element,
the synthetic zeolite material has an X-ray diffraction pattern comprising the following reflections:

Intensity (%)
Diffraction angle 2θ/° [Cu K(alpha

15-55
7.88-8.16

11-35
8.83-9.13

100
23.04-23.46

27-40
23.68-23.89

21-66
23.90-24.23

22-44
24.29-24.71

wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and wherein
a BET surface area of the synthetic zeolitic material determined according to DIN 66135 is from 50 to 700 m 2 /g, and
a maximum water absorption of the synthetic zeolitic material is from 2.9 wt % to 8.7 wt %.

5. The zeolitic material of claim 4 , wherein the 29 Si MAS NMR of the zeolitic material comprises:
a first peak (P1) in the range of from −110.4 to −114.0; and
a second peak (P2) in the range of from −101.4 to −106.8 ppm.

6. The zeolitic material of claim 5 , wherein the deconvoluted 29 Si MAS NMR spectrum further comprises an 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 selected from the group consisting of B, Fe, Ti, Sn, Ga, Ge, Zr, V, Nb, Cu, Zn, Li, and Be.

8. The zeolitic material of claim 7 , wherein molar ratio of YO 2 to the one or more element ranges from 5 to 100.

9. The zeolitic material of claim 4 , wherein the 22 Al MAS NMR of the zeolitic material comprises:
a first peak (P′1) in the range of from 50.00 to 53.50 pp; 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 27 Al MAS NMR of the zeolitic material provides 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 YO 2 : X 2 O 3 molar ratio ranges from 2 to 200.

11. The zeolitic material of claim 4 , wherein MFI-type framework structure of the zeolitic material does not comprise X 2 O 3 .

12. The zeolitic material of claim 4 , wherein Y is Si, Sn, Ti Zr, Ge, or any mixture thereof.

13. The zeolitic material of claim 4 , wherein X is Al, B, In, Ga or any mixture thereof.

14. The zeolitic material of claim 4 , wherein the zeolitic material farther comprises a cation and/or cationic element as ionic non-framework element.

Assignees

• Basf Se

Inventors

• Feyen Mathias
• Mueller Ulrich
• Parvulescu Andrei-Nicolae
• Schaack Bernd Bastian
• Ahrens Sebastian
• Gerhard Dirk
• Son Sunghee
• Iffland Gabriele
• Seelig Bianca

Classifications

• B01J20/28057

  Surface area, e.g. B.E.T specific surface area · CPC title

• B01J29/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• B01J20/186

  Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity · CPC title

• B01J29/00

  Catalysts comprising molecular sieves {(molecular sieves per se C01B)} · CPC title

• C01B39/04

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title