PROCESS FOR OXIDATIVE DESULFURIZATION WITH INTEGRATED SULFONE DECOMPOSITION

• US 20130030236A1
• Filed: 07/25/2012
• Published: 01/31/2013
• Est. Priority Date: 07/31/2011
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: KOSEOGLU, Omer Refa, BOURANE, Abdennour
• Granted Patent: US 9,555,396 B2
• Time in Patent Office: Days
• US Class Current: 585/852
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/007 Mixed salts
• CPC Class Codes: B01J 23/06 of zinc, cadmium or mercury
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C10G 29/04 Metals, or metals deposited on a carrier
• CPC Class Codes: C10G 29/16 Metal oxides

Abstract

The process provided herein is concerned with disposal of oxidized sulfur compounds formed by oxidative desulfurization. The process uses solid base catalyst in the presence of a caustic solution or solid base catalyst pretreated with a base and eliminates the need to separate the sulfones from the hydrocarbon streams and recover the hydrocarbons.

Claims

1. A process for reducing the concentration of oxidized sulfur compounds from a mixture of liquid hydrocarbons and the oxidized sulfur compounds, the process comprising:

a. contacting the mixture of hydrocarbons and oxidized sulfur compounds with an effective amount of solid base catalyst composition in the presence of a caustic solution,

the solid base catalyst composition comprising separate components or a mixture of zinc oxide, aluminum oxide, zinc aluminates, layered double hydroxides, and magnesium/aluminum layered double hydroxide,

the contacting occurring under conditions effective to promote catalytic decomposition of a portion of the oxidized sulfur compounds into SO_x compounds;

b. removing SO_x compounds from the hydrocarbon mixture; and

c. recovering a hydrocarbon product having a reduced concentration of oxidized sulfur compounds.

2. The process as in claim 1, wherein the solid base catalyst composition includes an effective proportion of layered double hydroxide of the general formula (I)

ZnAl₂O₄

x(ZnO)

y(Al₂O₃)  

 

(I)

wherein x and y are independently between 0 and 2, and

wherein the total proportion of ZnAl₂O₄ in the formula (I) is at least 10 percent by weight.

3. The process as in claim 2, wherein the effective proportion of layered double hydroxide comprises at least 100% by weight of the total composition.

4. The process as in claim 2, wherein the effective proportion of layered double hydroxide comprises at least 50% by weight of the total composition.

5. The process as in claim 2, wherein the effective proportion of layered double hydroxide comprises at least 1% by weight of the total composition.

6. The process as in claim 1, wherein the solid base catalyst is a porous material in the form of powder, extrudates or spheres.

7. The process as in claim 1, wherein the solid base catalyst has a surface area in the range of from 10 m²/g to 600 m²/g.

8. The process as in claim 1, wherein the solid base catalyst has a surface area in the range of from 50 m²/g to 600 m²/g.

9. The process as in claim 1, wherein the solid base catalyst has a pore volume in the range of from 0.1 cm³/g to 0.5 cm³/g.

10. The process as in claim 1, wherein the solid base catalyst has a pore volume in the range of from 0.3 cm³/g to 0.5 cm³/g.

11. The process as in claim 1, wherein the solid base catalyst has a pore distribution of 0.001 microns to 0.1 microns.

12. The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 200°

C. to 600°

C.

13. The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300°

C. to 400°

C.

14. The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300°

C. to 350°

C.

15. The process of claim 1, the mixture of hydrocarbons and oxidized sulfur compounds being contacted with an effective amount of solid base catalyst in the presence of a caustic solution, wherein the base is dissolved in the mixture of hydrocarbons and oxidized sulfur compounds.

16. The process of claim 15, wherein the amount of the caustic solution is in the range of from 0.05 to 30 percent by weight based on the total quantity of solid base catalyst.

17. A process for manufacturing a solid base catalyst comprising providing solid base catalyst composition including

a layered double hydroxide of the general formula (I)

ZnAl₂O₄

x(ZnO)

y(Al₂O₃)  

 

(I)

wherein x and y are independently between 0 and 2, and

wherein the total proportion of ZnAl₂O₄ in the formula (I) is at least 10 percent by weight;

loading the solid base catalyst composition in a reactor;

heating the reactor to an effective temperature; and

passing a liquid caustic solution over the solid base catalyst in the reactor for a period of time sufficient to impart alkaline quality to the solid base catalyst.

18. The process as in claim 17, wherein the effective temperature is in the range of from about 250°

C. to about 350°

C.

19. The process as in claim 17, wherein the liquid caustic solution is sodium hydroxide having a concentration in the range of from about 0.25 to about 7 moles/liters of solid base catalyst.

20. The process as in claim 17, wherein the liquid caustic solution is passed over the solid base catalyst composition at a liquid hourly space velocity in the range of from 0.1 h^{31 1} to 10 h⁻

1.

21. The process as in claim 17, wherein the liquid caustic solution is passed over the solid base catalyst composition at a liquid hourly space velocity in the range of from 0.5 h⁻

1 to 2 h<sup>−

1</sup>.

22. A process for reducing the concentration of oxidized sulfur compounds from a mixture of liquid hydrocarbons and the oxidized sulfur compounds, the process comprising:

a. contacting the mixture of hydrocarbons and oxidized sulfur compounds with an effective amount of solid base catalyst composition pretreated with a caustic solution,

the solid base catalyst composition comprising separate components or a mixture of zinc oxide, aluminum oxide, zinc aluminates, layered double hydroxides, and magnesium/aluminum layered double hydroxide,

the contacting occurring under conditions effective to promote catalytic decomposition of a portion of the oxidized sulfur compounds into SO_x compounds;

b. removing SO_x from the hydrocarbon mixture; and

c. recovering a hydrocarbon product having a reduced concentration of oxidized sulfur compounds.

23. The process of claim 22, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 200°

C. to 600°

C.

24. The process of claim 22, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300°

C. to 400°

C.

25. The process of claim 22, the mixture of hydrocarbons and oxidized sulfur compounds being contacted at a temperature in the range of from 300°

C. to 350°

C.

26. A solid base catalyst composition comprising

a layered double hydroxide of the general formula (I)

ZnAl₂O₄

x(ZnO)

y(Al₂O₃)  

 

(I)

wherein x and y are independently between 0 and 2, and

wherein the total proportion of ZnAl₂O₄ in the formula (I) is at least 10 percent by weight;

wherein the layered double hydroxide has been alkaline treated by a liquid caustic solution.