METHODS FOR UPGRADING OF CONTAMINATED HYDROCARBON STREAMS

• US 20110031164A1
• Filed: 10/14/2010
• Published: 02/10/2011
• Est. Priority Date: 03/26/2008
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Rankin, Jonathan P., Litz, Kyle E., Rossetti, Mark N., Vreeland, Jennifer L., Jordan, Tracey M.
• Granted Patent: US 8,241,490 B2
• Time in Patent Office: Days
• US Class Current: 208/266
• CPC Class Codes: C10G 19/067 with molten alkaline material
• 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 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/44 Solvents
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 27/06 in the presence of alkaline solutions
• 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 53/04 including at least one extraction step
• 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, the method comprising:

contacting the heteroatom-containing hydrocarbon feed with an oxidant;

contacting the oxidized heteroatom-containing hydrocarbon feed with at least one caustic and at least one selectivity promoter; and

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

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

3. The method of claim 1, wherein the at least one caustic is in the molten phase.

4. The method of claim 3, wherein the at least one caustic in the molten phase is a eutectic mixture of inorganic hydroxides having a melting point of less than about 350°

C.

5. The method of claim 4, wherein the eutectic mixture of inorganic hydroxides is a eutectic mixture of sodium hydroxide and potassium hydroxide.

6. The method of claim 1, wherein the at least one caustic is supported on an inert support.

7. The method of claim 6, wherein the inert support has a specific surface area in the range of from about 10 to about 1000 m²/g, a pore volume in the range of from about 0.1 to about 5 ml/g and a mean particle size in the range of from about 0.1 to about 10 cm.

8. The method of claim 1, wherein the hydrocarbon feed is contacted with the oxidant at a temperature in the range of about 20°

C. to about 90°

C. and a pressure in the range of about 0.5 atmospheres to about 10 atmospheres.

9. The method of claim 1, wherein the oxidant is selected from the group consisting of hydrogen peroxide, peracetic acid, benzyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, sodium hypochlorite, oxygen, air, and/or mixtures thereof.

10. The method of claim 1, wherein the oxidized heteroatom-containing hydrocarbon containing feed is extracted by solvent prior to contacting with the at least one caustic and the at least one selectivity promoter.

11. The method of claim 10, wherein the solvent used for extraction is selected from the group consisting of acetone, methanol, ethanol, ethyl lactate, N-methylpyrollidone, dimethylacetamide, dimethylformamide, gamma-butyrolactone, dimethyl sulfoxide, propylene carbonate, acetonitrile, acetic acid, sulfuric acid, liquid sulfur dioxide, and/or mixtures thereof.

12. The method of claim 1, wherein contacting with at least one caustic and at least one selectivity promoter is at a temperature in the 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.

13. The method of claim 1, wherein the selectivity promoter is an organic alcohol, ROH, wherein R is a C₁-C₁₈ alkyl-, aryl-, alkenyl-, substituted alkyl-, or substituted aryl-group.

14. The method of claim 1, wherein the oxidant is used in the presence of a catalyst.

15. The method of claim 14, wherein the catalyst comprises a metal compound represented by the general formula M_mO_m(OR)_n,

wherein M is a metal;

R is carbon group having at least 3 carbon atoms, where at each occurrence R is selected from the group consisting of a substituted alkyl group containing at least one OH group, a substituted cycloalkyl group containing at least one OH group, a substituted cycloalkylalkyl group containing at least one OH group, a substituted heterocyclyl group containing at least one OH group, and/or a heterocyclylalkyl containing at least one OH group; and

subscripts m and n are each independently integers between about 1 and about 8.

16. The method of claim 15, wherein the catalyst comprises bis(polyol)oxotitanium(IV).

17. The method of claim 15, wherein the catalyst comprises bis(glycerol)oxotitanium(IV).

18. The method of claim 14, wherein the catalyst is prepared by the reaction of Q-R-Q′

with a bis(polyol)oxotitanium(IV) catalyst, wherein Q and Q′

each independently comprise an isocyanate, anhydride, sulfonyl halide, benzyl halide, carboxylic acid halide, phosphoryl acid halide, silyl chloride, or any chemical functionality capable of reacting with the —

OH pendant group of the catalyst, and wherein R comprises a linking group.

19. 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 to oxidize at least a portion of the heteroatom contaminants to form a first intermediate stream;

contacting the first intermediate stream with at least one caustic and at least one selectivity promoter to form a second intermediate stream;

separating a substantially heteroatom-free hydrocarbon product from the second intermediate stream;

recovering the at least one caustic and at least one selectivity promoter from the second intermediate stream; and

recycling the recovered at least one caustic and at least one selectivity promoter.

20. A method of upgrading a heteroatom-containing hydrocarbon feed by removing heteroatom contaminants, the method comprising oxidizing dibenzothiophenes to sulfones, reacting the sulfones with caustic and a selectivity promoter, and separating a substantially heteroatom-free hydrocarbon product.