Process for sulfur removal from hydrocarbon liquids

• US 6,558,533 B2
• Filed: 04/13/2001
• Issued: 05/06/2003
• Est. Priority Date: 04/13/2001
• Status: Expired due to Fees

• Current Assignee: W R Grace & Company - CONN (Standard Industries Holdings, Inc.)
• Original Assignee: W R Grace & Company - CONN (Standard Industries Holdings, Inc.)
• Inventors: Wormsbecher, Richard Franklin, Schmidt, Stephen Raymond, Harding, Robert Hibbard
• Primary Examiner(s): Griffin, Walter D.
• Assistant Examiner(s): Nguyen, Tam M.
• Application Number:
  US09/833,602
• Publication Number:
  US 20030019794A1
• Time in Patent Office: 753 Days
• Field of Search: 502/25, 502/28, 502/33, 502/517, 585/274, 585/276, 585/900, 585/904, 208/244, 208/208.R
• US Class Current: 208/244
• CPC Class Codes: B01J 25/02 Raney nickel
• CPC Class Codes: B01J 25/04 Regeneration or reactivation
• CPC Class Codes: C10G 29/04 Metals, or metals deposited on a carrier
• CPC Class Codes: Y10S 502/517 Sulfur or sulfur compound removal
• CPC Class Codes: Y10S 585/90 Rehabilitation of H acceptor
• CPC Class Codes: Y10S 585/904 Catalyst rehabilitation by reversion from different compound

Abstract

The present invention is directed to a method of desulfurization of a sulfur laden hydrocarbon liquids that comprises contacting the liquid with a sponge nickel metal alloy, removing the sulfur free liquid, regeneration of the alloy by contact with an aqueous solution of an oxidant and reusing the alloy for further desulfurization of additional sulfur laden liquid.

Claims

1. A process for desulfurization of a hydrocarbon liquid comprising

a) contacting sulfur-laden hydrocarbon liquid with a packed bed catalyst composition composed of sponge nickel metal alloy to produce a hydrocarbon liquid having a reduced sulfur content;

b) separating from the packed bed catalyst composition and recovering the hydrocarbon liquid having a reduced sulfur content;

c) regenerating the packed bed catalyst composition by treating it with an aqueous solution of at least one oxidant selected from the group consisting of hydrogen peroxide, an alkali metal hypochorite, an alkali metal nitrate, an organic peroxy acid or mixtures thereof, to remove sulfur contained therein;

d) contacting the regenerated packed bed catalyst composition of step c), alone or with additional packed bed catalyst composition, with additional sulfur-laden hydrocarbon liquid to remove sulfur therefrom; and

e) cyclically repeating steps b), c) and d).

2. The process of claim 1 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 150°

C. and at about one atmosphere pressure.

3. The process of claim 1 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 150°

C. and at a pressure of from ambient to about 1 MPa.

4. The process of claim 1, 2 or 3 wherein step c) is conducted at a temperature of from about 50°

C. to the boiling point of the aqueous oxidant solution.

5. The process of claim 4 wherein the oxidant is sodium hypochlorite, sodium nitrite or sodium nitrate.

6. The process of claim 4 wherein the oxidant is peroxyacetic acid.

7. The process of claim 1 wherein the step c) further includes washing the catalyst with water or with an alkaline solution.

8. The process of claim 1, 2, 3 or 7 wherein the steps a), b) and d) are each conducted in a first reaction zone and step c) is conducted in a second reaction zone.

23. The process of claim 1, 2, 3 or 7 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

24. The process of claim 4 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

25. The process of claim 5 the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

26. The process of claim 6 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

9. A process for desulfurization of a hydrocarbon liquid comprising

a) contacting sulfur-laden hydrocarbon liquid with a packed bed catalyst composition composed of sponge nickel metal alloy to produce a hydrocarbon liquid having a reduced sulfur content;

b) separating from the packed bed catalyst composition and recovering the hydrocarbon liquid having a reduced sulfur content;

c) regenerating the packed bed catalyst composition by treating it with hydrogen gas at elevated temperature of from about 100°

to 500°

C., to remove sulfur contained therein;

d) contacting the regenerated packed bed catalyst composition of step c), alone or with additional packed bed catalyst composition, with additional sulfur-laden hydrocarbon liquid to remove sulfur therefrom; and

e) cyclically repeating steps b), c) and d).

10. The process of claim 9 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 150°

C. and at about one atmosphere pressure.

11. The process of claim 9 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 70°

C. and at a pressure of from ambient to about 1 mPa.

12. The process of claim 9, 10 or 11 wherein step c) is carried out at from about 100°

C. to about 500°

C.

13. The process of claim 9, 10 or 11 wherein step c) is carried out at from about 200°

C. to about 400°

C.

14. The process of claim 9, 10 or 11 wherein step c) further comprises first washing the spent catalyst with a liquid selected from an aldehyde, ketone or an alkanol.

15. The process of claim 14 wherein the liquid is selected from acetone or a C₁-C₃ alkanol.

16. The process of claim 9, 10, or 11 wherein the steps a), b) and d) are each conducted in a first reaction zone and step c) is conducted in a second reaction zone.

27. The process of claims 9, 10 or 11 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

28. The process of claim 14 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

17. A process for desulfurization of a hydrocarbon liquid comprising

a) contacting, in a first reaction zone, sulfur-laden hydrocarbon liquid with a packed bed catalyst composition composed of sponge nickel metal alloy to produce a hydrocarbon liquid having a reduced sulfur content;

b) separating from the packed bed catalyst composition and recovering the hydrocarbon liquid having a reduced sulfur content;

c) regenerating the packed bed catalyst composition by contacting it in a second reaction zone with an aqueous solution of at least one oxidant selected from hydrogen peroxide, an alkali metal hypochorite, an alkali metal nitrate, an organic peroxy acid or mixtures thereof, to remove sulfur contained therein;

d) treating the packed bed catalyst composition of step c) with hydrogen gas at an elevated temperature of from about 100 to 500°

C.;

e) returning the catalyst composition of step d) to the first reaction zone and therein contacting the regenerated packed bed catalyst composition, alone or with additional packed bed catalyst composition, with additional sulfur-laden hydrocarbon liquid to remove sulfur therefrom; and

f) cyclically repeating steps b), c), and d).

18. The process of claim 17 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 150°

C. and at about one atmosphere pressure.

19. The process of claim 17 wherein the sulfur-laden hydrocarbon liquid is contacted with packed bed catalyst composition at temperatures of from about 20°

C. to 150°

C. and at a pressure of from ambient to about 1 MPa.

20. The process of claim, 17, 18 or 19 wherein step c) is carried out at a temperature of from about 50°

C. to the boiling point of the aqueous oxidant solution.

21. The process of claim 20 wherein step d) is carried out at from about 100°

C. to 500°

C.

22. The process of claim 17, 18 or 19 wherein the steps a), b) and d) are each conducted in a first reaction zone and step c) is conducted in a second reaction zone.

29. The process of claim 17, 18 or 19 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.

30. The process of claim 20 wherein the sulfur-laden hydrocarbon liquid is a petroleum feedstream containing elemental sulfur, sulfur-containing compounds or mixtures thereof in an amount sufficient to provide sulfur analysis of at least about 0.05 weight percent.