Methods for preparing zeolites with surfactant-templated mesoporosity and tunable aluminum content

Patent metadata

Field	Value
Publication number	US-10626019-B2
Application number	US-201514983901-A
Country	US
Kind code	B2
Filing date	Dec 30, 2015
Priority date	Dec 30, 2014
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

Compositions and methods for preparing mesoporous and/or mesostructured materials from low SAR zeolites are provided herewith. In particular, methods are provided that involve: (a) providing a low SAR zeolite, (b) optionally subjecting the low SAR zeolite to an acid framework modification, and (c) subjecting the framework-modified zeolite to a mesopore formation treatment. The resulting mesoporous zeolites can have bi-modal mesoporosity and higher aluminum contents relative to existing mesoporous zeolites.

First claim

What is claimed is:

1. A method of forming a mesoporous zeolite comprising:
(a) modifying an initial zeolite to thereby yield a low SAR zeolite, wherein said low SAR zeolite has a silica to alumina molar ratio that is at least 20 percent lower than said initial zeolite, wherein said silica to alumina molar ratio of said low SAR zeolite is higher than the destabilizing SAR value of said initial zeolite;
(b) treating said low SAR zeolite with an acid to thereby yield an acid-treated zeolite;
(c) contacting at least a portion of said acid-treated zeolite with a pore forming agent to thereby form said mesoporous zeolite.

2. The method of claim 1 , wherein said modifying of step (a) comprises desilicating or aluminating said initial zeolite.

3. The method of claim 2 , wherein said desilicating comprises contacting said initial zeolite with a base.

4. The method of claim 3 , wherein the base can be selected from the group consisting of ammonium hydroxide, tetraalkyl ammonium hydroxides, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, amines, and mixtures of two or more thereof.

5. The method of claim 2 , wherein said desilicating occurs at a temperature in the range of 20 to 160° C. and over a time period of 0.5 to 48 hours.

6. The method of claim 1 , wherein said mesoporous zeolite has a dV/log(d) in the range of 0.3 to 100.

7. The method of claim 1 , wherein said low SAR zeolite has a mesopore ratio that is lower than the mesopore ratio of said initial zeolite.

8. The method of claim 1 , wherein said low SAR zeolite has a mesopore ratio that is at least 25 percent lower than the mesopore ratio of said initial zeolite.

9. The method of claim 1 , wherein said pore forming agent comprises a surfactant.

10. The method of claim 1 , wherein said initial zeolite comprises a ZSM-5, a mordenite, a faujasite, a BEA zeolite, a LTL zeolite, an FRE zeolite, or combinations thereof.

11. A method of forming a mesoporous zeolite comprising:
(a) providing a low SAR zeolite, wherein said low SAR zeolite is selected from the group consisting of a ZSM-5 having a silica to alumina molar ratio of 17 or less, a mordenite having a silica to alumina molar ratio of 10 or less, a faujasite having a silica to alumina molar ratio of 5 or less, a BEA zeolite having a silica to alumina molar ratio of 15 or less, a LTL zeolite having a silica to alumina molar ratio of 5 or less, an FRE zeolite having a silica to alumina molar ratio of 10 or less, and mixtures thereof, wherein said providing comprises desilicating an initial zeolite, wherein said desilicating comprises contacting said initial zeolite with a base at a temperature in the range of 20 to 160° C. and over a time period of 0.5 to 48 hours;
(b) treating said low SAR zeolite with an acid to thereby yield an acid-treated zeolite; and
(c) contacting at least a portion of said acid-treated zeolite with a pore forming agent to thereby form said mesoporous zeolite.

12. The method of claim 11 , wherein the base can be selected from the group consisting of ammonium hydroxide, tetraalkyl ammonium hydroxides, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, amines, and mixtures of two or more thereof.

13. The method of claim 11 , wherein said mesoporous zeolite has a dV/log(d) in the range of 0.3 to 100.

14. The method of claim 11 , wherein said mesoporous zeolite has a mesopore ratio that is at least 25 percent greater than the mesopore ratio of said low SAR zeolite.

15. The method of claim 11 , wherein said pore forming agent comprises a surfactant.

16. A method of forming a mesoporous zeolite comprising:
(a) subjecting an initial zeolite to a framework modification process to thereby produce a framework-modified zeolite, wherein said framework-modified zeolite has a silica to alumina molar ratio that is lower than said initial zeolite, wherein said framework modification process comprises desilicating said initial zeolite at a temperature in the range of 20 to 160° C. and over a time period of 0.5 to 48 hours to thereby form said framework-modified zeolite, wherein said desilicating comprises contacting said initial zeolite with a base;
(b) contacting at least a portion of said framework-modified zeolite with an acid to thereby form an acid-treated zeolite; and
(c) contacting at least a portion of said acid-treated zeolite with a pore forming agent to thereby form said mesoporous zeolite.

17. The method of claim 16 , wherein the base can be selected from the group consisting of ammonium hydroxide, tetraalkyl ammonium hydroxides, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, amines, and mixtures of two or more thereof.

18. The method of claim 16 , wherein said mesoporous zeolite has a peak dV/log(d) in the range of 0.3 to 100.

19. The method of claim 16 , wherein said framework-modified zeolite has a mesopore ratio that is at least 25 percent lower than the mesopore ratio of said initial zeolite.

20. The method of claim 16 , wherein said acid comprises hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (“EDTA”), tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures of two or more thereof.

21. The method of claim 16 , wherein said mesoporous zeolite has a mesopore ratio that is at least 25 percent greater than the mesopore ratio of said low SAR zeolite.

22. The method of claim 16 , wherein said pore forming agent comprises a surfactant.

Assignees

• Rive Tech Inc
• Grace W R & Co

Inventors

• Li Kunhao
• Garcia-Martinez Javier

Classifications

• C01B39/20

  Faujasite type, e.g. type X or Y · CPC title

• C01B39/26

  Mordenite type {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title

• C01B39/38

  Type ZSM-5 · CPC title

• C01B39/026 Primary

  After-treatment · CPC title

• C01B39/46

  Other types characterised by their X-ray diffraction pattern and their defined composition {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title