Method of desulfurization of hydrocarbons

• US 6,160,193 A
• Filed: 11/23/1998
• Issued: 12/12/2000
• Est. Priority Date: 11/20/1997
• Status: Expired due to Fees

• Current Assignee: Petro Star Inc. (Arctic Slope Regional Corporation)
• Original Assignee: Petro Star Inc. (Arctic Slope Regional Corporation)
• Inventors: Gore, Walter
• Primary Examiner(s): Griffin, Walter D.
• Assistant Examiner(s): Nguyen, Tam M.
• Application Number:
  US09/199,709
• Time in Patent Office: 750 Days
• Field of Search: 208/208 R, 208/219, 208/240, 208/254 R, 585/833
• US Class Current: 585/833
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen

Abstract

A method for the removal of sulfur and nitrogen containing compounds from petroleum distillates. Sulfur- and nitrogen-containing compounds are oxidized using a selective oxidant to create compounds that can be preferentially extracted from a petroleum distillate due to their increased relative polarity. Oxidation is accomplished by contacting an oxidant with a distillate under optimum conditions for that distillate and continuing the reaction until oxidized sulfur- and nitrogen-containing compounds are confirmed. Extraction is accomplished by contacting oxidized distillate with a non-miscible solvent that is selective for the relatively polar oxidized sulfur- and nitrogen-containing compounds. The oxidized compounds and solvent are separated from the distillate by gravity separation or centrifugation. The distillate is water washed and polished using clay filtration. The extraction solvent is separated from the solvent/oxidized compound mixture by a simple distillation for recycling. The high sulfur/high nitrogen fraction can be recovered using any number of treatments.

Claims

1. A method for removing sulfur- and nitrogen-containing compounds from a liquid fuel that includes, hydrocarbon fuel compounds, comprising the steps of:

a) oxidizing a liquid fuel with an oxidant to form oxidized sulfur- and nitrogen-containing compounds;

b) monitoring the oxidizing of said liquid fuel;

c) stopping said oxidizing when greater than about 90 percent of the sulfur- and nitrogen-containing compounds have been oxidized, but before any of the hydrocarbon fuel compounds have been oxidized;

d) separating the liquid fuel containing oxidized sulfur- and nitrogen-containing compounds from depleted oxidant; and

e) extracting said oxidized sulfur- and nitrogen-containing compounds from the liquid fuel by contacting said liquid fuel with a solvent that is selective for the oxidized sulfur- and nitrogen-containing compounds.

2. The method of claim 1 further comprising the step of separating the oxidized sulfur- and nitrogen-containing compounds from said solvent by gravity separation.

3. The method of claim 1 further comprising the step of separating the oxidized sulfur- and nitrogen-containing compounds from said solvent by gravity separation.

4. The method of claim 1 further comprising the step of:

a) washing the oxidized sulfur- and nitrogen-containing compounds with water; and

b) polishing the oxidized sulfur- and nitrogen-containing compounds using clay filtration.

5. The method of claim 1 wherein the oxidant is selected from the group of perboric acid, persulfuric acid, peracetic acid, direct ozone and dioxirane.

6. The method of claim 1 wherein the solvent is selected from the group of dimethyl sulfoxide, methanol, sulfolane, triethanolamine, and acetonitrile.

7. The method of claim 1 wherein the oxidizing step is confirmed by use of gas chromatography.

8. The method of claim 1 wherein the oxidizing step is confirmed by use of an infrared spectrometer.

9. The process of claim 1 wherein the oxidizing is stopped when oxidation of the sulfur-containing compounds has reached between about 95 to 98 percent.

10. The process of claim 1 wherein the step of stopping of the oxidizing includes the step of cooling the reaction to a point between about 20 to 30 degrees C. lower than the reaction temperature.

11. The process of claim 10 wherein the step of stopping of the oxidizing further includes the step of adding a reducing agent during the step of cooling the reaction.

12. The process of claim 11 wherein the reducing agent is selected from the group of sodium thiosulfate and sodium bisulfite.

13. The process of claim 11 wherein the reducing agent is injected into the reaction in a dilute aqueous solutions containing between about 1 to 5 weight percent of the reducing agent.

14. The process of claim 1 wherein the temperature of the oxidizing step is between about 30 to 110 degrees Celsius.

15. The process of claim 1 wherein the temperature of the oxidizing step is between about 60 and 95 degrees Celsius.

16. The process of claim 1 wherein the oxidizing step pressure is less than 150 pounds per square inch gauge.

17. A method for removing sulfur- and nitrogen-containing compounds from a liquid fuel, comprising:

(a) treating a liquid fuel that includes, hydrocarbon fuel compounds, and sulfur- and nitrogen-containing compounds with an oxidant to provide a liquid fuel that includes oxidized sulfur- and nitrogen-containing compound and depleted oxidant, wherein the oxidant converts greater than about 90 percent of the sulfur- and nitrogen-containing compounds, to oxidized sulfur- and nitrogen-containing compounds, but wherein said treatment is stopped before any of the hydrocarbon fuel compounds have been oxidized;

(b) monitoring the conversion of the sulfur- and nitrogen-containing compounds to oxidized sulfur- and nitrogen-containing compounds; and

(c) extracting the oxidized sulfur- and nitrogen-containing compounds from the liquid fuel by contacting the liquid fuel that includes the oxidized sulfur- and nitrogen-containing compounds with a solvent selective for the sulfur- and nitrogen-containing compounds.

18. The method of claim 17, further comprising separating the liquid fuel that includes oxidized sulfur- and nitrogen-containing compounds from the depleted oxidant, prior to extracting said oxidized sulfur- and nitrogen-containing compounds from said liquid fuel.

19. The method of claim 17, wherein the oxidant comprises peroxyacetic acid.

20. The method of claim 17, wherein the solvent comprises dimethylsulfoxide.

21. The method of claim 17, wherein the oxidant converts greater than about 95 percent of the sulfur- and nitrogen-containing compounds to oxidized sulfur- and nitrogen-containing compounds.

22. The method of claim 17, wherein the oxidant converts greater than about 98 percent of the sulfur- and nitrogen-containing compounds to oxidized sulfur-containing and nitrogen-containing compounds.