METHODS FOR UPGRADING OF CONTAMINATED HYDROCARBON STREAMS

• US 20120285864A1
• Filed: 06/11/2012
• Published: 11/15/2012
• Est. Priority Date: 03/26/2008
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Vreeland, Jennifer L., Litz, Kyle E., Jordan, Tracey M., Rossetti, Mark N., Burnett, Eric H., Rankin, Jonathan P., McCaskill, Trent A.
• Granted Patent: US 8,894,843 B2
• Time in Patent Office: Days
• US Class Current: 208/220
• CPC Class Codes: C10G 17/04 Liquid-liquid treatment forming two immiscible phases
• CPC Class Codes: C10G 17/07 using halogen acids or oxyacids of halogen acids generating halogen C10G27/02
• CPC Class Codes: C10G 21/00 Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents C10G17/00, C10G19/00 take precedence
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API
• CPC Class Codes: C10G 2300/44 Solvents
• CPC Class Codes: C10G 2300/80 Additives
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 27/00 Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
• CPC Class Codes: C10G 7/00 Distillation of hydrocarbon oils

Abstract

A method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants is disclosed. The method includes contacting the heteroatom-containing hydrocarbon feed with an oxidant and an immiscible acid to oxidize the heteroatoms, contacting the oxidized- heteroatom-containing hydrocarbon feed with caustic and a selectivity promoter, and removing the heteroatom contaminants from the heteroatom-containing hydrocarbon feed. The oxidant may be used in the presence of a catalyst.

Claims

1. A method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising:

contacting the heteroatom-containing hydrocarbon feed with an oxidant and an immiscible acid;

contacting the oxidized heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter, said at least one selectivity promoter comprising an organic compound having at least one acidic proton; and

removing the heteroatom contaminants from the heteroatom-containing hydrocarbon feed.

2. The method of claim 1, wherein the at least one caustic and the at least one selectivity promoter are different components.

3. The method of claim 1, wherein the selectivity promoter has a pKa value, as measured in DMSO, in the range of from about 9 to about 32.

4. The method of claim 1, wherein the at least one selectivity promoter further comprises a crown ether.

5. The method of claim 1, wherein the at least one selectivity promoter is selected from the group consisting of a hydroxyl- functional organic compound;

straight, branched, or cyclic amines having at least one H substituent; and

/or mixtures thereof.

6. The method of claim 5, wherein the at least one selectivity promoter is a hydroxyl-functional organic compound.

7. The method of claim 6, wherein the hydroxyl-functional organic compound is selected from the group consisting of ethylene glycol, propylene glycol, triethanolamine, and/or mixtures thereof.

8. The method of claim 7, wherein the hydroxyl-functional organic compound is ethylene glycol.

9. The method of claim 1, wherein the at least one caustic is selected from the group consisting of inorganic oxides and sulfides from group IA and IIA elements, inorganic hydroxides from group IA and IIA elements, and/or mixtures thereof.

10. The method of claim 9, wherein the at least one caustic is selected from the group consisting of NaOH, KOH, Na₂S, and or mixtures thereof.

11. The method of claim 1, wherein the at least one caustic and the at least one selectivity promoter are the same component.

12. The method of claim 11, wherein the same component is formed in situ.

13. The method of claim 11, wherein the at least one caustic is a Group IA or IIA hydroxide and the at least one selectivity promoter is ethylene glycol.

14. The method of claim 11, wherein the same component is formed prior to contacting the oxidized heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter.

15. The method of claim 1, wherein the removal of the heteroatom contaminants from the heteroatom-containing hydrocarbon feed is by gravity.

16. The method of claim 1, wherein the removal of the heteroatom contaminants from the heteroatom-containing hydrocarbon feed is by solvent extraction with water.

17. The method of claim 1, wherein the mole ratio of caustic:

selectivity promoter is in the range of from about 10;

1 to about 1;

10.

18. The method of claim 1, wherein the mole ratio of caustic and selectivity promoter:

heteroatom in the heteroatom-containing hydrocarbon feed is in the range of from about 100;

1 to about 1;

1.

19. A method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising oxidizing dibenzothiophenes in the heteroatom-containing feed to sulfones, contacting the sulfones under oxidizing biphasic conditions with an immiscible acid and an oxidant to remove at least a portion of the heteroatom contaminants, then reacting the sulfones with caustic and a selectivity promoter, and separating a substantially heteroatom-free hydrocarbon product for fuel.

20. The method of claim 19, wherein the heteroatom-free hydrocarbon product has a density in the range of from about 0.7 to about 1.1 g/mL