METHODS FOR UPGRADING OF CONTAMINATED HYDROCARBON STREAMS

• US 20140291199A1
• Filed: 04/07/2014
• Published: 10/02/2014
• Est. Priority Date: 03/26/2008
• Status: Abandoned Application

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Litz, Kyle E., Vreeland, Jennifer L., Rankin, Jonathan P., Rossetti, Mark N., Jordan, Tracey M., McCaskill, Trent A.
• Application Number:
  US14/246,508
• Publication Number:
  US 20140291199A1
• Time in Patent Office: Days
• US Class Current: 208/14
• CPC Class Codes: C10G 19/073 with solid alkaline material
• CPC Class Codes: C10G 19/08 Recovery of used refining agents
• CPC Class Codes: C10G 2300/201 Impurities
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 27/12 with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates plumbites or plumbates C10G19/06
• CPC Class Codes: C10G 53/12 including at least one alkaline treatment step
• CPC Class Codes: C10G 53/14 including at least one oxidation step

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 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, comprising:

reacting at least one of sulfones, sulfoxides, and mixtures thereof in the heteroatom-containing feed with at least one caustic and at least one selectivity promoter to produce an upgraded hydrocarbon.

2. The method of claim 1, wherein the upgraded hydrocarbon is substantially heteroatom-free.

3. The method of claim 1, wherein the upgraded hydrocarbon is substantially free of oxygen, sulfur, and nitrogen.

4. The method of claim 1, wherein a sulfate by-product is also produced.

5. The method of claim 1, wherein the step of reacting results in a conversion of 50% or greater the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

6. The method of claim 1, wherein the step of reacting results in a conversion of 93% or greater the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

7. The method of claim 1, wherein the step of reacting results in a conversion of 100% the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

8. The method of claim 1, wherein the step of reacting the at least one of sulfones, sulfoxides, and mixtures thereof results in a mole percent yield which is mostly biphenyl and ortho-phenylphenol.

9. The method of claim 1, wherein the step of reacting reduces a total acid number of the upgraded heteroatom.

10. The method of claim 1, wherein the step of reacting is done under a biphasic condition.

11. The method of claim 1, wherein the step of reacting increases an API gravity.

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

providing a hydrocarbon stream having heteroatom moieties;

providing at least one caustic and at least one selectivity promoter; and

selectively removing the heteroatom moieties with the at least one caustic and the at least one selectivity promoter.

13. The method of claim 12, wherein the step of selectively removing the heteroatom moieties has a percent conversion which is 50% or greater of the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

14. The method of claim 12, wherein the step of selectively removing results in a conversion of 93% or greater of the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

15. The method of claim 12, wherein the step of selectively removing results in a conversion of 100% of the at least one of sulfones, sulfoxides, and mixtures thereof to biphenyl and phenol.

16. The method of claim 12, wherein the step of selectively removing the heteroatom moieties results in a mole percent yield which is mostly biphenyl and ortho-phenylphenol.

17. The method of claim 12, wherein a reaction mechanism includes an alcoholysis reaction.

18. The method of claim 12, wherein the at least one selectivity promoter comprises an organic alcohol.

19. The method of claim 12, wherein the at least one caustic is in a molten phase during the step of reacting.

20. The method of claim 12, wherein the at least one caustic and the at least one selectivity promoter are at least one of same components and different components.

21. The method of claim 12, wherein the selectivity promoter has a pKa value, as measured in DMSO, in the range of from about 9 to about 32.

22. The method of claim 12, wherein the at least one selectivity promoter is at least one of ethylene glycol and propylene glycol.

23. The method of claim 12, wherein the at least one caustic is selected from the group consisting of inorganic oxides and sulfides from group IA and HA elements, inorganic hydroxides from group IA and HA elements, and/or mixtures thereof.

24. The method of claim 12, wherein a mole ratio of caustic:

selectivity promoter is in the range of from about 10;

1 to about 1;

10, and a 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.

25. The method of claim 12, wherein the at least one selectivity promoter is an amine and a reaction mechanism includes an aminolysis reaction.

26. The method of claim 12, wherein the selectivity promoter is selected from the group consisting of:

crown ethers, hydroxyl-functional organic compounds;

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

/or mixtures thereof.

27. The method of claim 26, wherein the hydroxyl-functional organic compounds are selected from the group consisting:

methanol, ethanol, isopropanol, ethylhexanol, cyclohexanol, ethanolamine, di-, and tri-ethanolamine, mono- and di-methylaminoethanol, ethylene glycol, propylene glycol, 1,3-propanediol, and 1,2-cyclohexanediol, glycerol, erythritol, xylitol, sorbitol, glucose, fructose, galactose, sucrose, lactose, and maltose, starch, cellulose, glycogen, chitan, wood chips and shavings, vinyl alcohol, and allyl alcohol, phenol, benzyl alcohol, naphthol, α

-tetralol, ammonium salts, choline hydroxide, and benzyltrimethylammonium hydroxide.

28. The method of claim 26, wherein the straight, branched, or cyclic amines having at least one H substituent are selected from the group consisting of methylamine, ethylamine, 2-ethylhexylamine, piperazine, 1,2-diaminoethane and/or mixtures thereof.

29. The method of claim 26, wherein the crown ethers are selected from the group consisting of:

18-crown-6,15-crown-5 and/or mixtures thereof.

30. A hydrocarbon product produced by the method of claim 12.

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

reacting at least one of sulfones, sulfoxides, and combinations thereof in the heteroatom-containing feed with at least one caustic and at least one selectivity promoter;

wherein reacting with at least one caustic and at least one selectivity promoter is at a temperature in a range from about 150°

C. to about 350°

C. and at a pressure in the range of from about 0 psig to about 2000 psig;

wherein the selectivity promoter is an organic alcohol.

32. The method of claim 31, wherein a reaction mechanism of the method includes an alcoholysis reaction.

33. The method of claim 31, wherein the organic alcohol is ROH, wherein R is a C₁-C₁₈ alkyl-, aryl-, alkenyl-, substituted alkyl-, or substituted aryl-group.

34. The method of claim 31, wherein the at least one caustic is in a molten phase during the step of reacting.

35. The method of claim 31, further comprising the step of separating the substantially heteroatom-free hydrocarbon product for fuel.

36. The method of claim 31, wherein the method produces less than about 20% oxygenated by-products in the treated stream.

37. A method for upgrading hydrocarbon comprising:

combining at least one of a sulfone and sulfoxide containing hydrocarbon with a caustic under biphasic conditions to form sulfates and biphenyls;

removing the sulfates; and

providing the biphenyls as fuel.

38. The method of claim 37, wherein the sulfone containing hydrocarbon comprises substituted and unsubstituted diphenylsulfones.

39. The method of claim 37, wherein the step of removing the sulfate comprises transferring the sulfates and biphenyls to a product separator and separating the sulfate from the biphenyl.

40. The method of claim 37, wherein the step of combining the sulfone containing hydrocarbon with the caustic under biphasic conditions is carried out at a temperature from about 150°

C. to 350°

C.