Methods for upgrading of contaminated hydrocarbon streams

• US 8,197,671 B2
• Filed: 12/23/2010
• Issued: 06/12/2012
• Est. Priority Date: 03/26/2008
• Status: Active Grant

• Current Assignee: Auterra, Inc.
• Original Assignee: Auterra, Inc.
• Inventors: Rankin, Jonathan P., Vreeland, Jennifer L., Litz, Kyle E., Jordan, Tracey M., Rossetti, Mark N., Burnett, Eric H.
• Primary Examiner(s): Nguyen, Tam M
• Application Number:
  US12/977,639
• Publication Number:
  US 20110108464A1
• Time in Patent Office: 537 Days
• Field of Search: None
• US Class Current: 208/208.R
• 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 2300/44 Solvents
• CPC Class Codes: C10G 2300/80 Additives
• 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;

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

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; and

wherein the selectivity promoter is an organic alcohol, ROH, wherein R is a C₁-C₁₈ alkyl-, aryl-, alkenyl-, substituted alkyl-, or substituted aryl-group.

2. The method of claim 1, wherein the immiscible acid is selected from the group consisting of carboxylic acids, sulfuric acid, hydrochloric acid, and/or mixtures thereof.

3. The method of claim 2, wherein the carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, lactic acid, benzoic acid, and/or mixtures thereof.

4. 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.

5. The method of claim 1, wherein the at least one caustic is in the molten phase, further wherein at least one caustic is supported on an inert support.

6. The method of claim 5, 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.

7. The method of claim 6, wherein the eutectic mixture of inorganic hydroxides is a eutectic mixture of sodium hydroxide and potassium hydroxide.

8. The method of claim 5, 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.

9. 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.

10. 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.

11. 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.

12. The method of claim 11, 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.

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

14. The method of claim 13, 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.

15. The method of claim 14, wherein the catalyst comprises at least one of bis(polyol)oxotitanium(IV) and bis(glycerol)oxotitanium(IV).

16. The method of claim 15, 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.

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

contacting the heteroatom-containing hydrocarbon feed with at least one 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 oxidant and at least one immiscible acid to oxide at least a portion of any remaining heteroatom contaminants to form a second intermediate stream;

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

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

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

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

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; and

wherein the selectivity promoter is an organic alcohol, ROH, wherein R is a C1-C18 alkyl-, aryl-, alkenyl-, substituted alkyl-, or substituted aryl-group.

18. 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;

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; and

wherein the selectivity promoter is an organic alcohol, ROH, wherein R is a C1-C18 alkyl-, aryl-, alkenyl-, substituted alkyl-, or substituted aryl-group.