Process for oxidative desulfurization and sulfone disposal using solvent deasphalting

Patent metadata

Field	Value
Publication number	US-9598647-B2
Application number	US-87663610-A
Country	US
Kind code	B2
Filing date	Sep 7, 2010
Priority date	Sep 7, 2010
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

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 deasphalting unit.

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 containing 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 containing compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream that comprises hydrocarbons and oxidized sulfur containing 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 containing compounds, wherein the extracted hydrocarbon stream has a lower concentration of sulfur 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; and
supplying the first residue stream to a deasphalting unit to produce a deasphalted oil stream and a pitch stream, wherein said pitch stream includes a substantial portion of the oxidized sulfur containing compounds removed from the hydrocarbon feedstock,
wherein the hydrocarbon feedstock further comprises nitrogen containing compounds, such that the step of contacting the hydrocarbon feedstock with the oxidant in the presence the catalyst oxidizes at least a portion of the nitrogen containing compounds, wherein the first residue stream supplied to the deasphalting unit includes the oxidized nitrogen containing compounds, and wherein said pitch stream further includes a substantial portion of the oxidized nitrogen containing compounds removed from the hydrocarbon feedstock,
the method further comprising the steps of
supplying the extracted hydrocarbon stream to a stripper to produce a second recovered non-acidic polar organic solvent stream and a stripped hydrocarbon stream; and
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.

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

3. The method of claim 1 , wherein the 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.

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 containing compounds present in the hydrocarbon feedstock is between about 4:1 and 10:1.

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

7. 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.

8. 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 sulfur containing compounds and oxidized nitrogen containing compounds.

9. The method of claim 8 , further comprising supplying the second residue stream to the deasphalting unit.

10. The method of claim 8 , wherein the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays and combinations of the same.

11. The method of claim 8 , 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.

12. The method of claim 1 , wherein the step of supplying the first residue stream to the deasphalting unit further comprises supplying a deasphalting solvent selected from a paraffinic solvent having between 3 and 7 carbon atoms to the deasphalting unit and extracting the first residue stream with the deasphalting solvent at a temperature and pressure at or below the critical temperature and pressure of the paraffinic solvent, wherein the deasphalted oil stream includes a major fraction of the paraffinic solvent.

13. 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 containing compounds;
catalytically oxidizing the sulfur containing compounds in the hydrocarbon feedstock in the oxidation reactor with an oxidant in the presence of a catalyst under conditions sufficient to selectively oxidize the sulfur containing compounds present in the hydrocarbon feedstock to sulfones and produce a treated hydrocarbon stream comprising hydrocarbons and sulfones;
extracting the treated 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 sulfones;
supplying the extracted hydrocarbon stream to a stripper, the stripper operable to separate the extracted hydrocarbon stream into a stripped oil stream and a second recovered non-acidic polar organic solvent stream;
recycling the first recovered non-acidic polar organic solvent stream and second recovered non-acidic polar organic solvent stream to the extraction step; and
supplying the residue stream comprising sulfones to a deasphalting unit and extracting the residue stream with a paraffinic solvent having between 3 and 7 carbon atoms to produce a deasphalted oil stream and a pitch stream, wherein said extraction of the residue stream is conducted a temperature and pressure that is at or below the supercritical temperature and pressure of the paraffinic solvent,
wherein the hydrocarbon feedstock further comprises nitrogen containing compounds, such that the step of catalytically oxidizing further comprises catalytically oxidizing the nitrogen containing compounds in the hydrocarbon feedstock with the oxidant in the presence of the catalyst, and wherein the residue stream supplied to the deasphalting unit includes the oxidized nitrogen containing compounds.

14. The method of claim 13 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 and the solvent extract

Assignees

• Bourane Abdennour
• Koseoglu Omer Refa
• Kressmann Stephane Cyrille
• Saudi Arabian Oil Co

Inventors

• Bourane Abdennour
• Koseoglu Omer Refa
• Kressmann Stephane Cyrille

Classifications

• C10G21/16

  Oxygen-containing compounds · CPC title

• C10G27/04 Primary

  with oxygen or compounds generating oxygen · CPC title

• C10G21/28

  Recovery of used solvent · CPC title

• C10G53/14

  including at least one oxidation step · CPC title

• C10G21/22

  Compounds containing sulfur, selenium, or tellurium · CPC title