Additives for gas phase oxidative desulfurization catalysts

Patent metadata

Field	Value
Publication number	US-10589259-B2
Application number	US-201815878800-A
Country	US
Kind code	B2
Filing date	Jan 24, 2018
Priority date	Jul 26, 2016
Publication date	Mar 17, 2020
Grant date	Mar 17, 2020

Abstract

A composition useful in oxidative desulphurization 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 catalytic composition useful in oxidative desulfurization of gaseous, sulfur containing hydrocarbons, said catalytic composition comprising: (i) a CuZnAl—O mixed oxide component comprising copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt % of said CuZnAl—O mixed oxide component, zinc oxide in an amount ranging from 5 wt % to less than 20 wt % of said CuZnAl—O mixed oxide component, and aluminum oxide in an amount ranging from 20 wt % to 70 wt % of said CuZnAl—O mixed oxide component, wherein said catalytic composition has a spinel oxide phase with formula Cu x Zn 1-x Al 2 O 4 wherein x ranges from 0 to 1, dispersed crystalline ZnO and CuO, (ii) at least one zeolite in desilicated H form, selected from the group consisting of HZSM-5, HY, H-mordenite, a desilicated form of MFI, a desilicated form of BEA, a desilicated form of MOR, and a desilicated form of FER, and (iii) one or more oxide promoters.

2. The catalytic composition of claim 1 , wherein said CuZnAl—O mixed oxide component is in granular form.

3. The catalytic composition of claim 2 , wherein said granular form of said CuZnAl—O mixed oxide component comprises granules having a diameter of from 1 mm to 4 mm.

4. The catalytic composition of claim 1 , wherein said composition is formed as a cylinder, a sphere, a trilobe, or a quatrolobe.

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

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

7. The catalytic composition of claim 1 , wherein said CuZnAl—O mixed oxide component has a total pore volume of from about 0.1 cm 3 /g to about 0.5 cm 3 /g.

8. The catalytic composition of claim 1 , wherein said CuZnAl—O mixed oxide component 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 catalytic composition of claim 8 , wherein said CuZnAl—O mixed oxide component 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 catalytic composition of claim 1 , wherein x is from 0.1 to 0.6.

11. The catalytic composition of claim 10 , wherein x is from 0.2 to 0.5.

12. The catalytic composition of claim 1 , wherein said oxide promoter is a mixture of two or more oxides of Mo, W, Si, B or P.

13. The catalytic composition of claim 1 , wherein said zeolite in desilicated H form comprises a transition metal.

14. The catalytic composition of claim 13 , wherein said transition metal is La or Y.

15. The catalytic composition of claim 1 , wherein said zeolite in desilicated H form comprises from about 5 to about 50 percent by weight of said catalytic composition.

16. The catalytic composition of claim 1 , wherein said zeolite in desilicated H form has a silicate module (silicon to aluminum atomic ratio) of from 2 to 90.

17. The catalytic composition of claim 16 , wherein said silicate module is 30, said zeolite in H desilicated form is HZSM-5, and said HZSM-5 form further comprises one or both of La and Y.

18. The catalytic composition of claim 17 , further comprising oxides of B and Mo.

19. The catalytic composition of claim 17 , wherein said catalytic composition comprises La and oxides of B and Mo.

20. The catalytic composition of claim 17 , further comprising La, Y, and oxides of B and Mo.

21. The catalytic composition of claim 1 , wherein said zeolite in desilicated H form has an amorphous or crystalline structure.

22. The catalytic composition of claim 1 , wherein said zeolite in desilicated H form is HY and said oxide promoter is a mixture of oxides of Mo and B.

Assignees

• Saudi Arabian Oil Co
• Boreskova Inst Kataliza Sibir

Inventors

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

Classifications

• B01J29/405 Primary

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• B01D2255/504

  ZSM 5 zeolites · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01D2253/1124

  Metal oxides · CPC title

• B01J2523/17

  Copper · CPC title