CATALYTIC COMPOSITIONS USEFUL IN REMOVAL OF SULFUR COMPOUNDS FROM GASEOUS HYDROCARBONS, PROCESSES FOR MAKING THESE AND USES THEREOF

• US 20130028822A1
• Filed: 06/08/2012
• Published: 01/31/2013
• Est. Priority Date: 07/27/2011
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia), Boreskov Institute Of Catalysis (Russian Academy of Sciences)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Bourane, Abdennour, Koseoglu, Omer Refa, Ismagilov, Zinfer, Yashnik, Svetlana, Kerzhentsev, Mikhail, Parmon, Valentin
• Granted Patent: US 9,663,725 B2
• Time in Patent Office: Days
• US Class Current: 423/244.06
• CPC Class Codes: B01J 23/005 Spinels
• CPC Class Codes: B01J 23/80 with zinc, cadmium or mercury
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 23/94 of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 29/16 Metal oxides

Abstract

A catalytic composition is disclosed, which exhibits an X-ray amorphous oxide, with a spinel formula and highly dispersed crystals of ZnO, CuO, and optionally CeO₂. The composition is useful in oxidative and adsorptive processes for removing sulfur from gaseous hydrocarbons.

Claims

1. A catalytic composition useful in oxidative desulfurization of gaseous, sulfur containing hydrocarbons, comprising copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt %, zinc oxide in an amount ranging from 5 wt % to less than 20 wt %, and aluminum oxide in an amount ranging from 20 wt % to 70 wt %, wherein said catalytic composition has an X-ray amorphous oxide phase, and a formula Cu_xZn_1-xAl₂O₄ wherein x ranges from 0 to 1, highly dispersed crystalline ZnO and CuO.

2. The catalytic composition of claim 1, further comprising CeO₂ in the form of particles ranging in diameter from 5 nm to 10 nm, in an amount ranging from 0.1 wt % to 10 wt % of said catalytic composition.

3. The catalytic composition of claim 1, in granular form.

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

5. The catalytic composition of claim 1, wherein granules of said composition have a diameter of from 1 mm to 4 mm.

6. The catalytic composition of claim 1, having a specific surface area of from 10 m²/g to 100 m²/g.

7. The catalytic composition of claim 1, wherein pores of the granules of said composition have a diameter of from 8 nm to 12 nm.

8. The catalytic composition of claim 1, wherein pores of the granules of said composition have a volume of from about 0.1 cm³/g to about 0.5 cm³/g

9. The catalytic composition of claim 1, comprising from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % of Al₂O₃.

10. The catalytic composition of claim 9, comprising from 30 wt % to 45 wt % CuO, from 12 wt % to less than 20 wt % ZnO, and from 20 wt % to 40 wt % Al₂O₃.

11. The catalytic composition of claim 6, having a specific surface area of from 50 m²/g to 100 m²/g.

12. The catalytic composition of claim 7, said pores having a diameter of from 8 nm to 10 nm.

13. The catalytic composition of claim 1, wherein X is from 0.1 to 0.6.

14. The catalytic composition of claim 13, wherein X is from 0.2 to 0.5.

15. A method for removing a portion of sulfur contained in a hydrocarbon, comprising contacting said sulfur containing hydrocarbon in gaseous form to the catalytic composition of claim 1, in the presence of an oxygen containing gas to remove a portion of sulfur therefrom.

16. The method of claim 15, comprising oxidizing sulfur in said sulfur containing hydrocarbon.

17. The method of claim 15, comprising adsorbing a sulfur containing compound into said catalyst.

18. The method of claim 17, further comprising regenerating said catalyst.

19. A process for making the catalytic composition of claim 1, comprising:

(i) combining an aqueous solution containing each of copper nitrate, zinc nitrate, and aluminum nitrate with an alkaline solution containing NaOH and/or at least one of (NH₄)₂CO₃, Na₂CO₃ and NH₄HCO₃, at a temperature of from about 50°

C. to about 65°

C., and a pH of from about 6.5 to about 14, to form a precipitate containing at least one of (a) carbonates containing Cu, Zn, and Al, (b) hydroxides containing Cu, Zn, and Al, and (c) hydroxycarbonates containing of Cu, Zn, and Al;

(ii) aging said precipitate;

(iii) filtering and washing said precipitate;

(iv) drying said precipitate for at least 10 hours, at a temperature of at least 100°

C.; and

(v) calcinating said precipitate for from about 2 to about 4 hours, at a temperature of at least about 450-500°

C.

20. The process of claim 19, wherein said aqueous solution further comprises cerium nitrate, and said carbonates, hydroxides and hydroycarbonates contain Ce.

21. The process of claim 20, further comprising combining the precipitate of (i) with a binder selected from the group consisting of poly-ethylene oxide, polyvinyl alcohol, a sol of aluminum pseudoboehmite, silica gel and mixtures thereof, said binder being added in amount ranging from 1 to 10 weight % of said precipitate, to from an extrudable mixture, extruding said mixture through a die to form an extrudate, drying said extrudate for 24 hours at room temperature, followed by drying at 100°

C. for from 2-4 hours, and raising temperature to 500°

C., at a rate of from 2-5°

C./minute, to calcine said extrudate for from 2-4 hours.

22. The process of claim 19, wherein said precipitate comprises hydroxides, said process further comprising combining said precipitate with a binder selected from the group consisting of polyethylene oxide, polyvinyl alcohol, a sol of aluminum pseudoboehmite, silica gel, and mixtures thereof, said binder being added in an amount ranging from 3 to 20 weight percent of said precipitate, to from an extrudable mixture, extruding said mixture through a die to form an extrudate, drying said extrudate for 24 hours at room temperature, followed by drying at 100°

C. for from 2-4 hours, and raising temperature to 500°

C., at a rate of from 2-5°

C./minute, to calcine said extrudate for from 2-4 hours.