Organosulfur oxidation process

• US 20040178121A1
• Filed: 03/13/2003
• Published: 09/16/2004
• Est. Priority Date: 03/13/2003
• Status: Abandoned Application

• Current Assignee: Lyondell Chemical Technology LP (Lyondellbasell Industries NV)
• Original Assignee: Lyondell Chemical Technology LP (Lyondellbasell Industries NV)
• Inventors: Leyshon, David W., Carroll, Kevin M., Han, Yuan-Zhang, Karas, Lawrence J.
• Application Number:
  US10/387,849
• Publication Number:
  US 20040178121A1
• Time in Patent Office: Days
• US Class Current: 208/196
• CPC Class Codes: C10G 27/12 with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates plumbites or plumbates C10G19/06

Abstract

This invention is a method of oxidizing organosulfur impurites found in fuel streams. The method comprises reacting the organosulfur impurities with an organic hydroperoxide in the presence of a titanium-containing catalyst. The titanium-containing catalyst is obtained by impregnating a siliceous solid with a titanium halide in a hydrocarbon solvent, or a vapor stream of titanium tetrachloride, followed by calcination. The resulting sulfones are more readily removed from the fuel stream than the non-oxidized organosulfur impurities.

Claims

1. A process comprising contacting a fuel stream containing organosulfur impurities with an organic hydroperoxide in the presence of a catalyst obtained by a method comprising the steps of:

(a) impregnating an inorganic siliceous solid with a titanium source selected from the group consisting of;

(1) a solution of a titanium halide in a non-oxygenated hydrocarbon solvent; and

(2) a vapor stream of titanium tetrachloride;

(b) calcining the impregnated siliceous solid to form the catalyst; and

(c) optionally, heating the catalyst in the presence of water;

wherein a substantial portion of the organosulfur impurities are converted into sulfones.

2. The process of claim 1 wherein the titanium halide is titanium tetrachloride.

3. The process of claim 1 wherein impregnation step (a)(1) is accomplished by combining a solution of the titanium halide in the non-oxygenated hydrocarbon solvent with the inorganic siliceous solid and thereafter removing the hydrocarbon solvent.

4. The process of claim 1 wherein the inorganic siliceous solid is selected from the group consisting of silica and MCM-41.

5. The process of claim 1 wherein the non-oxygenated hydrocarbon solvent is selected from the group consisting of C₅-C₁₂ aliphatic hydrocarbons, C₆-C₁₂ aromatic hydrocarbons, C₁-C₁₀ halogenated aliphatic hydrocarbons, C₆-C₁₀ halogenated aromatic hydrocarbons, and mixtures thereof.

6. The process of claim 1 wherein water is substantially excluded until after step (b) is completed.

7. The process of claim 1 wherein the method of obtaining the catalyst comprises an additional step after step (c) of treating the catalyst with a silylating agent.

8. The process of claim 1 wherein calcination step (b) is performed at a temperature of at least 500°

C.

9. The process of claim 1 wherein step (b) is performed in a substantially oxygen-free atmosphere.

10. The process of claim 1 wherein the organic hydroperoxide is t-butyl hydroperoxide.

11. The process of claim 1 wherein the organic hydroperoxide is substantially free of alcohol.

12. A process comprising contacting a diesel fuel stream containing organosulfur impurities with t-butyl hydroperoxide in the presence of a catalyst obtained by a method comprising the steps of:

(a) impregnating an inorganic siliceous solid with a titanium source selected from the group consisting of;

(1) a solution of a titanium chloride in a non-oxygenated hydrocarbon solvent; and

(2) a vapor stream of titanium tetrachloride;

(b) calcining the impregnated siliceous solid to form the catalyst; and

(c) optionally, heating the catalyst in the presence of water;

wherein a substantial portion of the organosulfur impurities are converted into sulfones.

13. The process of claim 12 wherein impregnation step (a)(1) is accomplished by combining a solution of the titanium halide in the non-oxygenated hydrocarbon solvent with the inorganic siliceous solid and thereafter removing the hydrocarbon solvent.

14. The process of claim 12 wherein the inorganic siliceous solid is selected from the group consisting of silica and MCM-41.

15. The process of claim 12 wherein the non-oxygenated hydrocarbon solvent is selected from the group consisting of C₅-C₁₂ aliphatic hydrocarbons, C₆-C₁₂ aromatic hydrocarbons, C₁-C₁₀ halogenated aliphatic hydrocarbons, C₆-C₁₀ halogenated aromatic hydrocarbons, and mixtures thereof.

16. The process of claim 12 wherein water is substantially excluded until after step (b) is completed.

17. The process of claim 12 wherein the method of obtaining the catalyst comprises an additional step after step (c) of treating the catalyst with a silylating agent.

18. The process of claim 12 wherein calcination step (b) is performed at a temperature of at least 500°

C.

19. The process of claim 12 wherein step (b) is performed in a substantially oxygen-free atmosphere.

20. The process of claim 12 wherein the t-butyl hydroperoxide is substantially free of t-butyl alcohol.