Synthesis of zeolitic materials using N,N-dimethyl organotemplates

Patent metadata

Field	Value
Publication number	US-9670415-B2
Application number	US-201213605701-A
Country	US
Kind code	B2
Filing date	Sep 6, 2012
Priority date	Sep 6, 2011
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

The present invention relates to a process for the preparation of a zeolitic material having a structure comprising YO 2 and optionally comprising X 2 O 3 , preferably comprising YO 2 and X 2 O 3 , wherein said process comprises the steps of
(1) providing a mixture comprising one or more ammonium compounds of which the ammonium cation has the formula (I):

[R 1 R 2 NR 3 R 4 ] +   (I)
and further comprising one or more sources for YO 2 and one or more sources for X 2 O 3 ;
(2) crystallizing the mixture provided in (1);

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

wherein in formula (I)

R 1 and R 2 are independently from one another derivatized or underivatized methyl, and

R 3 and R 4 are independently from one another derivatized or underivatized (C 3 -C 5 )alkyl, and

wherein the molar ratio of ammonium cation having the formula (I) to Y in the mixture provided in step (1) and crystallized in step (2) is equal to or greater than 0.25.

First claim

What is claimed is:

1. A process for the preparation of a zeolitic material having a CHA framework structure wherein said process comprises
(1) providing a mixture comprising
N,N-dimethylpiperidinium hydroxide, and
one of more sources for YO 2 and one or more sources for X 2 O 3 ;

(2) crystallizing the mixture provided in (1);
wherein Y is a tetravalent element, and X is a trivalent element, and
wherein the molar ratio of ammonium cation having the formula (I) to Y in the mixture provided in (1) and crystallized in (2) is equal to or greater than 0.25;
wherein the zeolitic material comprises YO 2 and X 2 O 3 wherein Y is a tetravalent element, and X is a trivalent element, and
wherein the zeolitic material displays a Y:X molar ratio in the range of from 1.5 to 10.5,
wherein the zeolitic material optionally further comprises Z 2 O 5 in addition to YO 2 and X 2 O 3 , wherein Z is a pentavalent element, and
wherein the zeolitic material then displays a Y:nX:pZ molar ratio, the value for the ratio (1+2p):(n−p) is in the range of from 1 to 5.5.

2. 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.

3. The process of claim 1 , wherein the one or more sources for YO 2 comprises one or more compounds selected from the group consisting of silicas, fumed silicas, silicates, and mixtures of two or more thereof.

4. 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.

5. The process of claim 1 , wherein the one or more sources for X 2 O 3 comprises one or more compounds selected from the group consisting of aluminas, aluminates, and mixtures of two or more thereof.

6. The process of claim 1 , wherein the structure of the zeolitic material further comprises Z 2 O 5 in addition to YO 2 and X 2 O 3 , and wherein the mixture provided in (1) further comprises one or more sources for Z 2 O 5 , wherein Z is a pentavalent element.

7. The process of claim 6 , wherein Z is selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta, and mixtures of two or more thereof.

8. The process of claim 1 , wherein the mixture provided in step (1) further comprises a solvent.

9. The process of claim 8 , wherein the solvent comprises water, and wherein the H 2 O:YO 2 molar ratio of the mixture provided in (1) ranges from 1 to 150 and
wherein the H 2 O:X 2 O 3 molar ratio of the mixture provided in (1) ranges from 100 to 8,000.

10. The process of claim 8 , wherein the solvent comprises water, and wherein the pH of the mixture provided in (1) is in the range of from 8 to 14.

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

12. The process of claim 11 , wherein the heating in step (2) is conducted under solvothermal conditions.

13. The process of claim 11 , wherein the crystallization in (2) involves heating of the mixture for a period ranging from 0.1 to 20 d.

14. The process of claim 1 , further comprising one or more of
(3) isolating the zeolitic material, preferably by filtration,
and/or
(4) washing the zeolitic material,
and/or
(5) drying the zeolitic material.

15. The process of claim 14 , further comprising one or more of
(6) calcining the zeolitic material obtained according to (2) or (3) or (4) or (5),
wherein the steps (3) and/or (4) and/or (5) and/or (6) can be conducted in any order.

16. A synthetic zeolitic material having a CHA framework structure, said zeolitic material being optionally obtainable and/or obtained by a process comprising
(1) providing a mixture comprising N,N-dimethylpiperidinium hydroxide
and one or more sources for YO 2 and one or more sources for X 2 O 3 ;
(2) crystallizing the mixture provided in (1);
wherein Y is a tetravalent element, and X is a trivalent element,
wherein the molar ratio of ammonium cation having the formula (I) to Y in the mixture provided in (1) and crystallized in (2) is equal to or greater than 0.25,
wherein the zeolitic material comprises YO 2 and X 2 O 3 , wherein Y is a tetravalent element and X is a trivalent element, and
wherein the zeolitic material displays a Y:X molar ratio comprised in the range of from 1.5 to 10.5,
wherein when the zeolitic material optionally further comprises Z 2 O 5 in addition to YO 2 and X 2 O 3 , wherein Z is a pentavalent element, and
wherein the zeolitic material then displays a Y:nX:pZ molar ratio, the value for the ratio (1+2p):(n−p) is in the range of from 1 to 5.5.

17. The synthetic zeolitic material of claim 16 , wherein the material comprises one or more zeolites selected from the group consisting of (Ni(deta) 2 )-UT-6, Chabazite, |Li—Na|[Al—Si—O]-CHA, DAF-5, Dehyd. Na-Chabazite, K-Chabazite (Iran), LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ-62, UiO-21, Willhendersonite, ZK-14, ZYT-6, and combinations of two or more thereof.

18. The material of claim 16 , wherein Z is selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta, and mixtures of two or more thereof.

19. The material of claim 16 , wherein the framework structure does not contain a pentavalent element Z in addition to YO 2 and X 2 O 3 .

20. The material of claim 16 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

21. The material of claim 16 , wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

Assignees

• Yilmaz Bilge
• Berens Ulrich
• Swaminathan Vijay Narayanan
• Müller Ulrich
• Iffland Gabriele
• Szarvas Laszlo
• Basf Se

Inventors

• Yilmaz Bilge
• Berens Ulrich
• Swaminathan Vijay Narayanan
• Müller Ulrich
• Iffland Gabriele
• Szarvas Laszlo

Classifications

• B01D2255/50

  Zeolites · CPC title

• B01D53/9436

  Ammonia · CPC title

• B01J29/7015

  CHA-type, e.g. Chabazite, LZ-218 · CPC title

• C10G2300/405

  Limiting CO, NOx or SOx emissions · CPC title

• C07C11/02

  Alkenes · CPC title