Selective liquid-liquid extraction of oxidative desulfurization reaction products

Patent metadata

Field	Value
Publication number	US-10947461-B2
Application number	US-201916366237-A
Country	US
Kind code	B2
Filing date	Mar 27, 2019
Priority date	Sep 27, 2011
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

The present invention provides selective extraction of sulfoxides, or sulfoxides in combination with sulfones, from hydrocarbon mixtures containing these compounds. A significant advantage of the invention is that oxidation products resulting from oxidative desulfurization of hydrocarbon feedstocks are selectively extracted with minimum co-extraction of non-oxidized products such as valuable hydrocarbon fuel components.

First claim

We claim:

1. An oxidative desulfurization process comprising:
reactively sulfoxidating a hydrocarbon fraction containing organosulfur compounds to produce a hydrocarbon mixture containing product components, and by-product sulfoxides or a combination of sulfoxides and sulfones;
contacting the mixture with a selective solvent formulation at a temperature in the range of about 0° C. to about 40° C.; and
recovering a hydrocarbon product of reduced sulfur content,

wherein the selective solvent formulation is determined by
qualitatively analyzing the hydrocarbon mixture to determine the composition including the type of sulfoxidation reaction products, the type of aromatic hydrocarbons and the type of non-aromatic hydrocarbons;
selecting as target sulfoxidation reaction products one or more sulfoxides or a combination of one or more sulfoxides and one or more sulfones;
determining the activity coefficient γ of a range of extraction solvent compositions for the target sulfoxidation reaction products and at least one type of aromatic or non-aromatic hydrocarbon in the hydrocarbon fraction, the extraction solvent compositions within the range of extraction solvent compositions comprising an aqueous solution having a concentration of about 2.5 weight % to about 70 weight % by weight polar organic solvent in water, the polar organic solvent selected from the group consisting of acetic acid, formic acid and combinations comprising acetic acid or formic acid; and
selecting, as the selective solvent formulation, an extraction solvent composition having an activity coefficient of less than about 16.5 for the target sulfoxidation reaction products that maximizes extraction of the target sulfoxidation reaction product, and an activity coefficient equal to or greater than about 16.5 for the at least one type of aromatic or non-aromatic hydrocarbon that minimizes co-extraction of the at least one type of aromatic or non-aromatic hydrocarbon.

2. The process as in claim 1 , wherein the concentration of the aqueous solution is about 2.5 weight % to about 20 weight % of acetic acid, and wherein the target compounds for extraction are non-bulky sulfoxide products.

3. The process as in claim 1 , wherein the concentration of the aqueous solution is about 20 weight % to about 40 weight % of acetic acid, and wherein the target compounds for extraction are bulky sulfoxide products.

4. The process as in claim 1 , wherein the concentration of the aqueous solution is about 5 weight % to about 20 weight % of formic acid, and wherein the target compounds for extraction are non-bulky sulfoxide products.

5. The process as in claim 1 , wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetonitrile and about 5 weight % to about 30 weight % of formic acid.

6. The process as in claim 1 , wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetic acid and about 5 weight % to about 30 weight % of acetone.

7. The process as in claim 1 , wherein the concentration of the aqueous solution is about 20 weight % to about 40 weight % of formic acid, and wherein the target compounds for extraction include 4,6-dimethyldibenzothiophene oxide.

8. The process as in claim 1 , wherein the concentration of the aqueous solution is about 10 weight % to about 30 weight % of acetic acid, and wherein the target compounds for extraction include thiophene sulfide and thiophene sulfone.

9. The process as in claim 1 , wherein the concentration of the aqueous solution is about 30 weight % to about 40 weight % of formic acid, and wherein the target compounds for extraction include thiophene sulfide and thiophene sulfone.

10. The process as in claim 1 , wherein reactively sulfoxidating a hydrocarbon fraction is effected by an oxidation process selected from the group consisting of photooxidation, photochemical oxidation, ozonation, ionic liquid oxidation, electro chemical oxidation, bio-desulfurization, oxidation by hydrogen peroxide, oxidation by organic peracid, oxidation by peroxomonophosphoric acid, oxidation by nitrogen oxides, oxidation by nitric acid, and a combination of any of the foregoing oxidation processes.

11. An oxidative desulfurization process comprising:
reactively sulfoxidating a hydrocarbon fraction containing organosulfur compounds to produce a hydrocarbon mixture containing product components, and by-product sulfoxides or a combination of sulfoxides and sulfones;
contacting the mixture with a selective solvent formulation at a temperature in the range of about 0° C. to about 40° C.; and
recovering a hydrocarbon product of reduced sulfur content,
wherein the selective solvent formulation is an aqueous solution determined by selecting as target sulfoxidation reaction products one or more sulfoxides or a combination of one or more sulfoxides and one or more sulfones, and wherein the aqueous solution is selected from the group consisting of
about 2.5 weight % to about 20 weight % of acetic acid and wherein the target compounds for extraction are non-bulky sulfoxide products,
about 20 weight % to about 40 weight % of acetic acid and wherein the target compounds for extraction are bulky sulfoxide products,
about 5 weight % to about 20 weight % of formic acid, and wherein the target compounds for extraction are non-bulky sulfoxide products,
about 5 weight % to about 30 weight % of acetonitrile and about 5 weight % to about 30 weight % of formic acid and wherein the target compounds for extraction are a combination of 1 or more sulfoxides and 1 or more sulfones,
about 5 weight % to about 30 weight % of acetic acid and about 5 weight % to about 30 weight % of acetone and wherein the target compounds for extraction are a combination of 1 or more sulfoxides and 1 or more sulfones,
about 20 weight % to about 40 weight % of formic acid and wherein the target compounds for extraction include 4,6-dimethyldibenzothiophene oxide,
about 10 weight % to about 30 weight % of acetic acid and wherein the target compounds for extraction include thiophene sulfide and thiophene sulfone, and
about 30 weight % to about 40 weight % of formic acid and wherein the target compounds for extraction include thiophene sulfide and thiophene sulfone.

Assignees

• Saudi Arabian Oil Co

Inventors

• Al-Shafei Emad Naji
• Hamad Esam Zaki

Classifications

• C10G53/14 Primary

  including at least one oxidation step · CPC title

• G01N33/287

  Sulfur content · CPC title

• C10G53/04

  including at least one extraction step · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• C10G27/00

  Refining of hydrocarbon oils in the absence of hydrogen, by oxidation · CPC title