Process for oxidative desulfurization and sulfone management by gasification

Patent metadata

Field	Value
Publication number	US-10035960-B2
Application number	US-201715413665-A
Country	US
Kind code	B2
Filing date	Jan 24, 2017
Priority date	Sep 7, 2010
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

Embodiments provide a method including: supplying the hydrocarbon feedstock to an oxidation reactor, where the hydrocarbon feedstock is oxidized in the presence of a catalyst to selectively oxidize sulfur compounds present in the hydrocarbon feedstock; separating the hydrocarbons and the oxidized sulfur compounds by solvent extraction; collecting a residue stream that includes oxidized sulfur compounds; supplying the residue stream to a gasifier to produce a syngas stream and a hydrogen sulfide stream; supplying the extracted hydrocarbon stream to a stripper to produce a stripped oil stream, which is then supplied to an adsorption column, such that the adsorption column can produce a high purity hydrocarbon product stream, a second residue stream, and a spent adsorbent stream, the spent adsorbent stream containing another portion of the oxidized compounds; and supplying the spent adsorbent stream to the gasifier to produce additional syngas for the syngas stream, thereby disposing of the adsorbent.

First claim

That which is claimed is:

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 non-acidic polar organic solvent, the non-acidic polar organic solvent being dimethylformamide, to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream comprising the non-acidic polar organic 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 using a distillation column into a first recovered non-acidic polar organic solvent stream and a first residue stream;
supplying the first residue stream to a gasifier to produce a syngas stream and a hydrogen sulfide stream;
supplying the extracted hydrocarbon stream to a stripper to produce a second recovered non-acidic polar organic solvent stream and a stripped oil stream;
recycling the first recovered non-acidic polar organic solvent stream and the second non-acidic polar organic solvent stream to an extraction vessel for the step of separating the hydrocarbons and the oxidized sulfur compounds in the oxidized hydrocarbon stream;
supplying the 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 a second residue stream, the second residue stream containing a portion of the oxidized compounds, and a spent adsorbent stream, the spent adsorbent stream containing another portion of the oxidized compounds; and
supplying the spent adsorbent stream to the gasifier to produce additional syngas for the syngas stream, thereby disposing of the adsorbent.

2. The method of claim 1 , wherein the spent adsorbent stream is one of continuously or intermittently supplied to the gasifier.

3. The method of claim 1 , wherein the adsorbent comprises one of a carbon-based adsorbent or a non-carbon based adsorbent.

4. The method of claim 3 , wherein, when the adsorbent is the carbon-based adsorbent, the gasification of the spent adsorbent stream produces syngas with no ash.

5. The method of claim 3 , wherein, when the adsorbent is the non-carbon-based adsorbent, the spent adsorbent acts as a slag material to cool reactor walls of the gasifier and the gasification of the spent adsorbent produces syngas with ash.

6. 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.

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

8. 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.

9. 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.

10. The method of claim 1 , wherein the non-acidic polar organic solvent has a Hildebrandt value of greater than about 19.

11. 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.

12. The method of claim 1 , further comprising supplying the second residue stream to the gasifier.

13. The method of claim 1 , wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays, and combinations of the same.

14. The method of claim 1 , 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.

15. 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 non-acidic polar organic solvent, the non-acidic polar organic solvent being dimethylformamide, to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream comprising the non-acidic polar organic solvent and the sulfones, wherein the extracted hydrocarbon stream has a lower sulfur concentration than the hydrocarbon feedstock;
separating the mixed stream using a distillation column into a first recovered non-acidic polar organic 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 non-acidic polar organic solvent stream;
recycling at least one of the first recovered non-acidic polar organic solvent stream and the second recovered non-acidic polar organic solvent stream to the extraction step for the step of separating the hydrocarbons and the oxidized sulfur compounds in the oxidized hydrocarbon 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;
supplying the 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 a second residue stream, the second residue stream containing a portion of the oxidized compounds, and a spent adsorbent stream, the spent adsorbent stream containing another portion of the oxidized compounds; and
supplying the spent adsorbent stream to the gasifier to produce additional syngas for the syngas stream, thereby disposing of the adsorbent.

16. The method of claim 15 , further comprising:
supplying at least a portion of the syngas stream to a methanol production unit, wherein the syngas stream is catalytically converted into methanol; and
supplying the methanol to the dimethylformamide non-acidic polar organic solvent for extraction of the oxidized hydrocarbon stream.

17. The method of claim 15 , further comprising:
supplying the hydrogen sulfi

Assignees

• Saudi Arabian Oil Co

Inventors

• Koseoglu Omer Refa
• Bourane Abdennour
• Kressmann Stephane

Classifications

• C01B2203/0261

  containing a catalytic partial oxidation step [CPO] · CPC title

• C10J2300/1665

  to alcohols, e.g. methanol or ethanol · CPC title

• C10G27/12

  with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates (plumbites or plumbates C10G19/06) · CPC title

• C01B2203/127

  Catalytic desulfurisation · CPC title

• C10G2300/1037

  Hydrocarbon fractions · CPC title