Zeolites, the production thereof, and their uses for upgrading heavy oils

Patent metadata

Field	Value
Publication number	US-10407311-B2
Application number	US-201715821001-A
Country	US
Kind code	B2
Filing date	Nov 22, 2017
Priority date	May 17, 2017
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

According to one or more embodiments disclosed herein, a mesoporous zeolite may be made by a method comprising contacting an initial zeolite material with ammonium hexafluorosilicate to modify the framework of the initial zeolite material, and forming mesopores in the framework-modified zeolite material. The contacting may form a framework-modified zeolite material. The mesoporous zeolites may be incorporated into catalysts.

First claim

What is claimed is:

1. A method for making a mesoporous zeolite, the method comprising:
contacting an initial zeolite material with ammonium hexafluorosilicate in water to modify the framework of the initial zeolite material, forming a framework-modified zeolite material, the initial zeolite material comprising silica and alumina, and comprising an FAU framework type structure; and
forming mesopores in the framework-modified zeolite material.

2. The method of claim 1 , wherein the initial zeolite material comprises ammonium and sodium.

3. The method of claim 2 , wherein the initial zeolite material is formed by ion-exchanging a zeolite comprising sodium with ammonium.

4. The method of claim 1 , wherein forming the mesopores comprises:
combining the framework-modified zeolite material with one or more of a base or a surfactant cetrimonium bromide to form a mixture; and
heating the mixture to an elevated temperature for a heating time period to form the mesopores.

5. The method of any of claim 4 , wherein the elevated temperature is from 100° C. to 150° C. and the heating time period is from 1 to 5 days.

6. The method of any of claim 4 , wherein the base comprises an aqueous solution comprising one or more of NaO, KOH, or ammonium hydroxide.

7. The method of claim 1 , wherein the surfactant is cetrimonium bromide.

8. The method of claim 1 , wherein the separating comprises one or more of washing, drying, or calcining the nano-sized zeolite particles.

9. The method of claim 1 , wherein the ammonium hexafluorosilicate that contacts the initial zeolite is in an aqueous solution.

10. The method of claim 9 , wherein the ammonium hexafluorosilicate has a concentration of from 0.2M to 2.0M.

11. The method of claim 1 , further comprising separating the zeolite comprising mesopores from the other contents of the mixture.

12. The method of claim 1 , wherein the mesoporous zeolite has at least 90% crystallinity with respect to the initial zeolite.

13. A method of making a catalyst, the method comprising:
forming a mesoporous zeolite by a method comprising:
contacting an initial zeolite material with ammonium hexafluorosilicate in water to modify the framework of the initial zeolite material, forming a framework-modified zeolite material, the initial zeolite material comprising silica and alumina, and comprising an FAU framework type structure; and
forming mesopores in the framework-modified zeolite material to form a mesoporous zeolite; and

incorporating the mesoporous zeolite with a metal oxide support material and one or more metal catalyst materials to form the catalyst.

14. The method of claim 13 , wherein one or more of the metal catalyst materials comprise an oxide or sulfide of W, Mo, Ni, or Co.

15. The method of claim 13 , wherein the catalyst comprises an oxide or sulfide of W and an oxide or sulfide of Ni.

16. The method of claim 13 , wherein the catalyst comprises an oxide or sulfide of Mo and an oxide or sulfide of Ni.

17. The method of claim 13 , wherein the catalyst comprises:
from 20 wt. % to 26 wt. % of an oxide or sulfide of W;
from 4 wt. % to 6 wt. % of an oxide or sulfide of Ni;
from 10 wt. % to 60 wt. % of the mesoporous zeolite; and
from 10 wt. % to 70 wt. % of alumina.

18. The method of claim 13 , wherein the catalyst comprises:
from 14 wt. % to 16 wt. % of an oxide or sulfide of Mo;
from 4 wt. % to 6 wt. % of an oxide or sulfide of Ni;
from 10 wt. % to 60 wt. % of the mesoporous zeolite; and
from 20 wt. % to 80 wt. % of alumina.

19. The method of claim 13 , wherein the metal oxide support material comprises alumina.

20. The method of claim 13 , wherein the mesoporous zeolite has at least 90% crystallinity with respect to the initial zeolite.

Assignees

• Saudi Arabian Oil Co

Inventors

• Ding Lianhui
• Al-Sayed Essam
• Shaik Kareemuddin
• Bourane Abdennour

Classifications

• C10G47/16

  Crystalline alumino-silicate carriers · CPC title

• C10G45/12

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C10G47/20

  the catalyst containing other metals or compounds thereof · CPC title

• C10G45/04

  characterised by the catalyst used · CPC title