Additives for gas phase oxidative desulfurization catalysts

Patent metadata

Field	Value
Publication number	US-10384197-B2
Application number	US-201615219749-A
Country	US
Kind code	B2
Filing date	Jul 26, 2016
Priority date	Jul 26, 2016
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

A composition useful in oxidative desulfurization of gaseous hydrocarbons is described. It comprises a CuZnAl—O mixed oxide, and an H form of a zeolite. The mixed oxide can contain one or more metal oxide promoters. The H form of the zeolite can be desilicated, and can also contain one or more transition metals.

First claim

We claim:

1. A method for oxidatively reducing sulfur content in a gaseous hydrocarbon feedstock comprising: contacting said gaseous hydrocarbon feedstock with a mixed oxide catalytic composition prepared by precipitation method, wherein said mixed oxide catalytic composition contains (i) copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt %, (ii) zinc oxide in an amount ranging from 5 wt % to less than 20 wt %, (iii) aluminum oxide in an amount ranging from 20 wt % to 70 wt %, and (iv) a boron oxide promoter, wherein said mixed oxide catalytic composition (a) has a spinel oxide phase with formula Cu x Zn 1-x Al 2 O 4 wherein x ranges from O to 1, (b) contains dispersed ZnO and CuO, and adding at least one zeolite in H form selected from the group consisting of: HZSM-5, HY, HX, H-mordenite, MFI, FAU, BEA, MOR, and FER to said mixed oxide catalytic composition, said zeolite in H form containing at least one transition metal additive, wherein oxidative reduction of sulfur is carried out at a temperature of from 240° C. to 440° C., to oxidatively desulfurize said gaseous hydrocarbon feedstock.

2. The method of claim 1 , wherein said mixed oxide catalytic composition is in granular form.

3. The method of claim 1 , wherein said mixed oxide catalytic composition is formed as a cylinder, a sphere, a trilobe, or a quatrolobe.

4. The method of claim 2 , wherein granules of said mixed oxide catalytic composition has a diameter of from 1 mm to 4 mm.

5. The method of claim 1 , wherein said mixed oxide catalytic composition has a surface area of from 10 m 2 /g to 100 m 2 /g.

6. The method of claim 5 , wherein said mixed oxide catalytic composition has a surface area of from 50 m 2 /g to 100 m 2 /g.

7. The method of claim 1 , wherein the total pore volume of said mixed oxide catalytic composition is from about 0.1 cm 3 /g to about 0.5 cm 3 /g.

8. The method of claim 1 , wherein said mixed oxide catalytic composition comprises from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % of Al 2 O 3 .

9. The method of claim 8 , wherein said mixed oxide catalytic composition comprises from 30 wt % to 45 wt % CuO, from 12 wt % to less than 20 wt % ZnO, and from 20 wt % to 40 wt % Al 2 O 3 .

10. The method of claim 1 , wherein X is from 0.1 to 0.6.

11. The method of claim 10 , wherein X is from 0.2 to 0.5.

12. The method of claim 1 , wherein said mixed oxide catalytic composition further comprises an oxide promoter which is an oxide of Mo, W, Si, or P.

13. The method of claim 1 , wherein said at least one zeolite in H-form is desilicated.

14. The method of claim 1 , wherein said transition metal additive is La or Y.

15. The method of claim 1 , wherein said at least one zeolite in H-form comprises from about 5 to about 50 percent by weight of said mixed oxide catalytic composition.

16. The method of claim 1 , wherein said at least one zeolite in H-form has a silicate module (silicon to aluminum atomic ratio) of from 2 to 90.

17. The method of claim 1 , wherein said at least one zeolite in H-form has an amorphous or crystalline structure.

18. The method of claim 1 , wherein said mixed oxide catalytic composition further comprises a Mo oxide.

Assignees

• Saudi Arabian Oil Co
• Boreskova Inst Kataliza Sibir

Inventors

• Koseoglu Omer Refa
• Jin Yaming
• Ismagilov Zinfer
• Yashnik Svetlana
• Kerzhentsev Mikhail
• Parmon Valentin

Classifications

• B01D53/8603

  Removing sulfur compounds · CPC title

• B01J23/005 Primary

  Spinels · CPC title

• B01D2255/50

  Zeolites · CPC title

• B01D2255/9207

  Specific surface · CPC title

• B01J23/28

  Molybdenum · CPC title