Beta molecular sieve, preparation method therefor and hydrogenation catalyst containing same

Patent metadata

Field	Value
Publication number	US-10112186-B2
Application number	US-201415036368-A
Country	US
Kind code	B2
Filing date	Oct 28, 2014
Priority date	Nov 26, 2013
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

Disclosed are a beta molecular sieve, a preparation method therefor, and a hydrogenation catalyst containing same. The properties of the beta molecular sieve are as follows: the molar ratio of SiO 2 /Al 2 O 3 is 30-150, the non-framework aluminum accounts for not more than 2% of the total aluminum, and the silicon atoms coordinated in a Si(OAl) structure account for not less than 95% of the silicon atoms in the framework structure. The preparation method comprises: contacting the raw material powder of the beta molecular sieve with normal pressure and dynamic water vapor, and then with ammonium fluosilicate. The beta molecular sieve of the present invention has the features of a uniform skeleton structure of silicon and aluminum, an appropriate acidity, and a reasonable pore structure, and is suitable as an acidic component of a hydro-upgrading catalyst and a hydro-cracking catalyst for diesel oil.

First claim

What is claimed is:

1. A β zeolite having a SiO 2 /Al 2 O 3 molar ratio of 30-150, non-skeleton aluminum of not more than 2% based on the total aluminum, Si(OAl)-coordinated silicon atom of not less than 95% based on silicon atom in a skeleton structure.

2. The β zeolite according to claim 1 , wherein the β zeolite has a SiO 2 /Al 2 O 3 molar ratio of 40-150, non-skeleton aluminum of not more than 1% based on the total aluminum, Si(OAl)-coordinated silicon atom of 96%-99% based on silicon atom in a skeleton structure.

3. The β zeolite according to claim 1 , wherein the β zeolite has a relative crystallinity of 100%-140%.

4. The β zeolite according to claim 1 , wherein the β zeolite has an IR acid in an amount of 0.1-0.5 mmol/g, and a medium strong acid in an acid amount of not less than 80% based on the total acid amount, as measured by NH 3 -TPD method.

5. The β zeolite according to claim 4 , wherein the β zeolite has an IR acid in an amount of 0.15-0.45 mmol/g, and a medium strong acid in an acid amount of 85-95% based on the total acid amount, as measured by NH 3 -TPD method.

6. The β zeolite according to claim 1 , wherein the β zeolite has a Na 2 O content of not more than 0.15 wt %.

7. The β zeolite according to claim 1 , wherein the β zeolite has a BET surface area of 400 m 2 /g-800 m 2 /g and a total pore volume of 0.30 mL/g-0.50 mL/g.

8. A preparation method of a β zeolite of claim 1 , comprising:
(1) contacting β zeolite raw material powder with water vapor at a temperature of 500-650° C. for 5-10 hours; and
(2) contacting the product from step (1) with ammonium hexafluorosilicate, then filtering, washing and drying to obtain the β zeolite.

9. The method according to claim 8 , wherein step (1) further comprises heating the raw material powder a heating rate of 50-150° C./h to 250-450° C. before introducing the water vapor, continuing heating to 500-650° C., and then maintaining the temperature for 5-10 h.

10. The method according to claim 8 , wherein in step (1), the water vapor passes through the β zeolite raw material powder at 50-100 L/h per kilogram of the β zeolite raw material powder.

11. The method according to claim 8 , wherein the β zeolite raw material powder in step (1) has a SiO 2 /Al 2 O 3 molar ratio of 22.5-28.5, and a Na 2 O content of 1.0 wt %-3.0 wt %.

12. The method according to claim 8 , wherein the ammonium hexafluorosilicate used in step (2) is in an aqueous solution having an ammonium hexafluorosilicate concentration of 10 g-60 g/100 mL, and a liquid-solid volume ratio of the aqueous solution of ammonium hexafluorosilicate and the β zeolite raw material is 3:1-15:1.

13. The method according to claim 8 , wherein step (2) is carried out at a temperature of 40-120° C. and for a duration of 0.5-8.0 h.

14. A hydrogenation catalyst containing a hydrogenation active metal component and a carrier, wherein the carrier contains a β zeolite of claim 1 .

15. The hydrogenation catalyst according to claim 14 , wherein based on a total weight of the carrier, the carrier comprises 5%-40% of the β zeolite and 60%-95% of alumina.

16. The hydrogenation catalyst according to claim 15 , wherein based on the total weight of the carrier, the carrier comprises 3%-20% of the β zeolite, 10%-70% of an amorphous silica-alumina, and 15%-70% of the alumina.

17. The hydrogenation catalyst according to claim 16 , wherein the amorphous silica-alumina has 5 wt %-40 wt % of SiO 2 , a pore volume of 0.6-1.1 mL/g, and a BET surface area of 300-500 m 2 /g.

18. The hydrogenation catalyst according to claim 15 , wherein based on the total weight of the carrier, the carrier has 5%-20% of the β zeolite, 10%-40% of Y zeolite, and 40%-85% of the alumina.

19. The hydrogenation catalyst according to claim 18 , wherein the Y zeolite has a BET surface area of 850 m 2 /g-950 m 2 /g, a total pore volume of 0.43 mL/g-0.55 mL/g, a SiO 2 /Al 2 O 3 molar ratio of 20-150, a cell parameter of 2.425-2.433 nm, and an IR acid in an amount of 0.1-0.4 mmol/g.

20. The hydrogenation catalyst according to claim 14 , wherein the hydrogenation active metal component comprises Group VIB metal of molybdenum and/or tungsten, and Group VIII metal of cobalt and/or nickel; and in the hydrogenation catalyst, based on a total amount of the catalyst, the catalyst comprises 10 wt %-30 wt % of the Group VIB metal oxide and 4 wt %-8 wt % of the Group VII metal oxide.

Assignees

• China Petroleum & Chem Corp
• Fushun Res Institute Of Petroleum And Petrochemicals Sinopec Corp

Inventors

• Liu Chang
• Wang Fenglai
• Wang Keqi
• Du Yanze
• Zhao Hong
• Guan Minghua

Classifications

• B01J2229/36

  Steaming · CPC title

• C10G47/16

  Crystalline alumino-silicate carriers · CPC title

• B01J2229/26

  to stabilize the total catalyst structure · 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

• B01J29/061

  containing metallic elements added to the zeolite · CPC title