Process for Oxidative Desulfurization and Sulfone Management by Gasification

• US 20120055849A1
• Filed: 09/07/2010
• Published: 03/08/2012
• Est. Priority Date: 09/07/2010
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Bourane, Abdennour, Koseoglu, Omer Refa, Kressmann, Stephane Cyrille
• Granted Patent: US 9,574,142 B2
• Time in Patent Office: Days
• US Class Current: 208/240
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/127 Catalytic desulfurisation
• CPC Class Codes: C01B 2203/84 Energy production
• CPC Class Codes: C01B 3/386 Catalytic partial combustion
• CPC Class Codes: C10G 21/12 Organic compounds only
• CPC Class Codes: C10G 2300/1037 Hydrocarbon fractions
• CPC Class Codes: C10G 2300/1055 Diesel having a boiling range of about 230 - 330 °C
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/207 Acid gases, e.g. H2S, COS, SO2, HCN
• CPC Class Codes: C10G 2300/44 Solvents
• 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 27/14 with ozone-containing gases
• CPC Class Codes: C10G 53/04 including at least one extraction step
• CPC Class Codes: C10G 53/14 including at least one oxidation step
• CPC Class Codes: C10J 2300/1665 to alcohols, e.g. methanol or ethanol
• CPC Class Codes: C10J 2300/1807 Recycle loops, e.g. gas, solids, heating medium, water

Abstract

A method and apparatus for upgrading a hydrocarbon feedstock is provided. The method includes the steps of (a) supplying a hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock is oxidized in the presence of a catalyst under conditions sufficient to selectively oxidize sulfur compounds present in the hydrocarbon feedstock; (c) separating the hydrocarbons and the oxidized sulfur compounds by solvent extraction; (d) collecting a residue stream that includes the oxidized sulfur compounds; and (e) supplying the residue stream to a gasifier to produce a syngas stream and a hydrogen sulfide stream.

Claims

1. A method of upgrading a hydrocarbon feedstock, the method comprising the steps of:

supplying the hydrocarbon feedstock to an oxidation reactor, the hydrocarbon feedstock comprising sulfur compounds;

contacting the hydrocarbon feedstock with an oxidant in the presence of a catalyst in the oxidation reactor under conditions sufficient to selectively oxidize sulfur compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream that comprises hydrocarbons and oxidized sulfur compounds;

separating the hydrocarbons and the oxidized sulfur compounds in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream comprising the polar solvent and the oxidized sulfur compounds, wherein the extracted hydrocarbon stream has a lower concentration of sulfur compounds than the hydrocarbon feedstock;

separating the mixed stream into a first recovered polar solvent stream and a first residue stream; and

supplying the first residue stream to a gasifier to produce a syngas stream and a hydrogen sulfide stream.

2. The method of claim 1, wherein the oxidant is selected from the group consisting of air, oxygen, ozone, nitrous oxide, peroxides, hydroperoxides, organic peracids, and combinations thereof.

3. The method of claim 1, wherein the oxidation reactor catalyst is a metal oxide having the formula M_xO_y, wherein M is an element selected from Groups IVB, VB, and VIB of the periodic table.

4. The method of claim 1, wherein the oxidation reactor is maintained at a temperature of between about 20 and 150°

C. and at a pressure of between about 1-10 bars.

5. The method of claim 1, wherein the ratio of the oxidant to sulfur compounds present in the hydrocarbon feedstock is between about 4:

1 and 10;

1.

6. The method of claim 1, wherein the polar solvent has a Hildebrandt value of greater than about 19.

7. The method of claim 1, wherein the polar solvent is selected from the group consisting of acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethlyformamide, acetonitrile, methanol and combinations of the same.

8. The method of claim 1, wherein the polar solvent is acetonitrile.

9. The method of claim 1, wherein the polar solvent is methanol.

10. The method of claim 1, wherein the solvent extraction is conducted at a temperature of between about 20°

C. and 60°

C. and at a pressure of between about 1-10 bars.

11. The method of claim 1, further comprising the step of supplying the extracted hydrocarbon stream to an adsorption column, the adsorption column being charged with an adsorbent suitable for the removal of oxidized compounds present in the extracted hydrocarbon stream, the adsorption column producing a high purity hydrocarbon product stream and a second residue stream, the second residue stream containing a portion of the oxidized compounds.

12. The method of claim 1, further comprising the step of supplying the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped oil stream.

13. The method of claim 12, further comprising the step of supplying stripped oil stream to an adsorption column, the adsorption column being charged with an adsorbent suitable for the removal of oxidized compounds present in the stripped oil stream, the adsorption column producing a high purity hydrocarbon product stream and a second residue stream, the second residue stream containing a portion of the oxidized compounds.

14. The method of claim 13, further comprising supplying the second residue stream to gasifier.

15. The method of claim 13, wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays, and combinations of the same.

16. The method of claim 13, wherein the adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, and activated carbon, and the polymer is selected from the group consisting of polysulfone, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane and combinations of the same.

17. A method of providing a desulfurized hydrocarbon stream, and a syngas stream, from a sulfur containing hydrocarbon feedstock, the method comprising the steps of:

supplying the hydrocarbon feedstock to an oxidation reactor, the hydrocarbon feedstock comprising sulfur compounds;

catalytically oxidizing the sulfur compounds present in the hydrocarbon feedstock in the oxidation reactor with an oxidant in the presence of a catalyst under conditions sufficient to selectively oxidize at least a portion of the sulfur compounds present in the hydrocarbon feedstock to sulfones and produce an oxidized hydrocarbon stream comprising hydrocarbons and sulfones;

selectively extracting the oxidized hydrocarbon stream with a polar organic solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream comprising the polar organic solvent and the sulfones, wherein the extracted hydrocarbon stream has a lower sulfur concentration than the hydrocarbon feedstock;

separating the mixed stream into a first recovered polar solvent stream and a first residue stream comprising the sulfones;

supplying the extracted hydrocarbon stream to a stripper, the stripper being operable to separate the extracted hydrocarbon stream into a stripped oil stream and a second recovered polar solvent stream;

supplying at least one of the first recovered polar solvent stream and second recovered polar solvent stream to the extraction step; and

supplying the residue stream comprising sulfones to a gasifier and oxidizing the residue stream with an oxidant to produce a syngas stream and a hydrogen sulfide stream.

18. The method of claim 17, the method further comprising the steps of:

supplying at least a portion of the syngas stream to a methanol production unit, wherein the syngas stream is catalytically converted into methanol;

supplying the methanol as the polar organic solvent for extraction of the oxidized hydrocarbon stream.

19. The method of claim 17, further comprising the steps of:

supplying the hydrogen sulfide stream to a Claus unit, wherein the hydrogen sulfide is contacted with a catalyst at elevated temperatures to produce a solid elemental sulfur product.

20. The method of claim 17 wherein the oxidant supplied to the oxidation reactor and the gasifier are oxygen.

21. The method of claim 17 wherein the polar solvent is acetonitrile.

22. The method of claim 17 wherein the polar solvent is methanol.

23. The method of claim 17, further comprising the step of supplying the extracted hydrocarbon stream to an adsorption column, the adsorption column being charged with an adsorbent suitable for the removal of oxidized compounds present in the extracted hydrocarbon stream, the adsorption column producing a high purity hydrocarbon product stream and a second residue stream, the second residue stream containing a portion of the oxidized compounds.

24. The method of claim 17, further comprising supplying the second residue stream to the gasifier.

25. A method of providing a desulfurized hydrocarbon stream, and a syngas stream, from a sulfur containing hydrocarbon feedstock, the method comprising the steps of:

supplying the sulfur containing hydrocarbon feedstock and an oxidant to an oxidation reactor, said oxidation reactor being charged with a catalyst;

catalytically oxidizing the sulfur compounds present in the hydrocarbon feedstock under conditions sufficient to selectively oxidize at least a portion of the sulfur compounds present in the hydrocarbon feedstock to sulfones and produce an oxidized hydrocarbon stream comprising hydrocarbons and sulfones;

selectively extracting the oxidized hydrocarbon stream with a polar organic solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream comprising the polar organic solvent and the sulfones, wherein the extracted hydrocarbon stream has a lower sulfur concentration than the hydrocarbon feedstock;

separating the mixed stream into a first recovered polar solvent stream and a first residue stream comprising the sulfones;

supplying the extracted hydrocarbon stream to a stripper, the stripper being operable to separate the extracted hydrocarbon stream into a stripped oil stream and a second recovered polar solvent stream;

supplying at least one of the first recovered polar solvent stream and second recovered polar solvent stream to the extraction step;

supplying the stripped oil stream to an adsorber charged with an adsorbent to produce a high purity hydrocarbon product stream and a second residue stream comprising a portion of the oxidized compounds, said adsorbent being suitable for the removal of oxidized compounds present in stripped oil stream;

supplying the residue stream comprising sulfones to a gasifier and oxidizing the residue stream with an oxidant to produce a syngas stream and a hydrogen sulfide stream; and

supplying the hydrogen sulfide to a catalytically charged Claus reactor to produce elemental sulfur.