INTEGRATED SYSTEM AND PROCESS FOR IN-SITU ORGANIC PEROXIDE PRODUCTION AND OXIDATIVE HETEROATOM CONVERSION

• US 20130026062A1
• Filed: 07/27/2011
• Published: 01/31/2013
• Est. Priority Date: 07/27/2011
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: KOSEOGLU, Omer Refa, BOURANE, Abdennour, AL-SHAHRANI, Farhan M.
• Granted Patent: US 9,005,433 B2
• Time in Patent Office: Days
• US Class Current: 208/3
• CPC Class Codes: B01J 19/2445 placed in parallel
• CPC Class Codes: B01J 19/245 placed in series
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: C10G 2300/1096 Aromatics or polyaromatics
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/301 Boiling range
• CPC Class Codes: C10G 2300/4037 In-situ processes
• 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 53/04 including at least one extraction step
• CPC Class Codes: C10G 53/14 including at least one oxidation step
• CPC Class Codes: C10G 67/00 Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
• CPC Class Codes: C10G 67/0418 The hydrotreatment being a hydrorefining
• CPC Class Codes: C10G 67/12 including oxidation as the refining step in the absence of hydrogen
• CPC Class Codes: C10G 67/16 plural parallel stages only

Abstract

An oxidative treatment process, e.g., oxidative desulfurization or denitrification, is provided in which the oxidant is produced in-situ using an aromatic-rich portion of the original liquid hydrocarbon feedstock. The process reduces or replaces the need for the separate introduction of liquid oxidants such as hydrogen peroxide, organic peroxide and organic hydroperoxide in an oxidative treatment process.

Claims

1. A process for conversion of heteroatom-containing compounds in a hydrocarbon feedstock to their oxidation products comprising:

separating the hydrocarbon feedstock into an aromatic-lean fraction and an aromatic-rich fraction;

contacting the aromatic-rich fraction with an effective amount of gaseous oxidant under conditions effective for organic peroxide generation and to produce a mixture containing organic peroxide and heteroatom-containing hydrocarbons;

contacting the mixture containing produced organic peroxide and heteroatom-containing hydrocarbons with the aromatic-lean fraction under conditions effective for oxidative conversion of heteroatom-containing hydrocarbons in the mixture and in the aromatic-lean fraction into oxidation products of heteroatom-containing hydrocarbons.

2. The process as in claim 1, further comprising

separating the hydrocarbon feedstock into a first and second portion;

and

subjecting only the first portion to separation into the aromatic-lean fraction and the aromatic-rich fraction;

wherein contacting under conditions effective for conversion of heteroatom-containing hydrocarbons further comprises contacting the second portion for conversion of heteroatom-containing hydrocarbons in the second portion into oxidation products of those heteroatom-containing hydrocarbons.

5. The process as in either of claim 2 or 4, wherein separating the hydrocarbon feedstock or the aromatic-rich fraction into a first and second portion is with a diverter.

6. The process as in claim 5, wherein the first portion is about 1 V % to about 90 V % of the hydrocarbon feedstock.

7. The process as in claim 5, wherein the first portion is about 1 V % to about 50 V % of the hydrocarbon feedstock.

8. The process as in claim 5, wherein the first portion is about 1 V % to about 30 V % of the hydrocarbon feedstock.

9. The process as in either of claim 2 or 4, wherein separating the hydrocarbon feedstock or the aromatic-rich fraction into a first and second portion is with a flash separation apparatus or a distillation unit to produce the first portion having an initial boiling point in the range of about 300°

C. to about 360°

C.

10. The process as in claim 9, wherein the first portion is about 1 V % to about 50 V % of the hydrocarbon feedstock.

11. The process as in claim 9, wherein the first portion is about 1 V % to about 30 V % of the hydrocarbon feedstock.

12. The process as in claim 9, wherein the fast portion is about 1 V % to about 5 V % of the hydrocarbon feedstock.

13. The process as in either of claim 1 or 3, wherein contacting under conditions effective for organic peroxide generation and contacting under conditions effective for oxidative conversion of heteroatom-containing hydrocarbons into oxidation products of the heteroatom-containing hydrocarbons occur in separate vessels.

14. The process as in claim 13 wherein contacting under conditions effective for organic peroxide generation occurs in an organic peroxide generation apparatus.

15. The process as in claim 14 wherein reactions in the organic peroxide generation apparatus occur in the presence of catalyst.

16. The process as in claim 15 wherein the catalyst is a heterogeneous catalyst.

17. The process as in claim 16 wherein the heterogeneous catalyst is a compound having the general formula M_xO_y, where x=1 or 2, and y=2 or 5, and where M is an element that is selected from the group consisting of the elements of groups IVB, VB and VIB of the Periodic Table.

18. The process as in claim 16 wherein the heterogeneous catalyst is Co(Salophen) or complexes of Co(Salophen).

19. The process as in claim 15 wherein the catalyst is a homogeneous catalyst.

20. The process as in claim 19 herein the homogeneous catalyst is a transition metal complex.

21. The process as in claim 13 wherein contacting under conditions effective for oxidative conversion of heteroatom-containing hydrocarbons into oxidation products of the heteroatom-containing hydrocarbons occurs in an oxidative reaction apparatus.

22. The process as in claim 21 wherein reactions in the oxidative reaction apparatus occur in the presence of catalyst.

23. The process as in claim 15 wherein the catalyst includes one or more transition metal oxides.

24. The process as in either of claim 1 or 3, wherein contacting under conditions effective for organic peroxide generation and contacting under conditions effective for oxidative conversion of heteroatom-containing hydrocarbons into oxidation products of the heteroatom-containing hydrocarbons occur in a common vessel.

25. The process as in claim 24 wherein reactions in the common vessel occur in the presence of a bi-functional catalyst.

26. The process as in either of claim 1 or 3, further comprising removing oxidation products of sulfur-containing and nitrogen-containing hydrocarbon compounds from a hydrocarbon product stream.

27. The process as in claim 26, wherein removing oxidation products is by one or more of polishing, extraction, adsorption or decantation.

3. A process for conversion of heteroatom-containing compounds in a hydrocarbon feedstock to their oxidation products comprising:

separating the hydrocarbon feedstock into an aromatic-lean fraction and an aromatic-rich fraction;

contacting the aromatic-rich fraction with an effective amount of gaseous oxidant under conditions effective for organic peroxide generation and to produce a mixture containing organic peroxide and heteroatom-containing hydrocarbons;

hydrotreating all or a portion of the aromatic-lean fraction;

retaining the mixture containing produced organic peroxide and heteroatom-containing hydrocarbons under conditions effective for oxidative conversion of heteroatom-containing hydrocarbons into oxidation products of the heteroatom-containing hydrocarbons.

4. The process as in claim 3, further comprising

separating the aromatic-rich fraction hydrocarbon feedstock into a first and second portion;

and

subjecting only the first portion to contacting with an effective amount of gaseous oxidant under conditions effective for reaction into organic peroxide compounds;

wherein contacting under conditions effective for conversion of heteroatom-containing hydrocarbons further comprises contacting the second portion for conversion of heteroatom-containing hydrocarbons in the second portion into oxidation products of those heteroatom-containing hydrocarbons.

28. An apparatus for conversion of sulfur-containing and nitrogen-containing hydrocarbon compounds in a hydrocarbon feedstock to their respective oxidation products comprising:

an aromatic separation apparatus operable to extract aromatic compounds from the hydrocarbon feed, the aromatic separation zone including an inlet for receiving the hydrocarbon feedstock, an aromatic-rich outlet and an aromatic-lean outlet;

an organic peroxide generation apparatus in fluid communication with the aromatic-rich outlet and a source of gaseous oxidant and having an outlet for discharging a mixture containing organic peroxide and heteroatom-containing hydrocarbons, the organic peroxide generation apparatus operating under conditions effective to promote organic peroxide production by reaction of hydrocarbons in the aromatic-rich fraction and gaseous oxidant; and

an oxidative reaction apparatus in fluid communication with the organic peroxide generation apparatus outlet and the aromatic-lean outlet, and having an outlet for discharging a mixture containing oxidation products of heteroatom-containing hydrocarbons, the oxidative reaction apparatus operating under conditions effective to promote oxidation of heteroatom-containing hydrocarbons by reaction of heteroatom-containing hydrocarbons and the produced organic peroxide.

29. An apparatus for conversion of sulfur-containing and nitrogen-containing hydrocarbon compounds in a hydrocarbon feedstock to their respective oxidation products comprising:

a separation apparatus operable to separate the hydrocarbon feedstock into a first portion and a second portion and including an inlet for receiving the hydrocarbon feedstock, a first portion outlet and a second portion outlet;

an aromatic separation apparatus operable to extract aromatic compounds from the second portion, the aromatic separation zone including an inlet in fluid communication with the first portion outlet, an aromatic-rich outlet and an aromatic-lean outlet;

an organic peroxide generation apparatus in fluid communication with the aromatic-rich outlet and a source of gaseous oxidant and having an outlet for discharging a mixture containing organic peroxide and heteroatom-containing hydrocarbons, the organic peroxide generation apparatus operating under conditions effective to promote organic peroxide production by reaction of hydrocarbons in the aromatic-rich fraction and gaseous oxidant; and

an oxidative reaction apparatus in fluid communication with the organic peroxide generation apparatus outlet, the aromatic-lean outlet and the second portion outlet, and having an outlet for discharging a mixture containing oxidation products of heteroatom-containing hydrocarbons, the oxidative reaction apparatus operating under conditions effective to promote oxidation of heteroatom-containing hydrocarbons by reaction of heteroatom-containing hydrocarbons and the produced organic peroxide.

30. An apparatus for conversion of sulfur-containing and nitrogen-containing hydrocarbon compounds in a hydrocarbon feedstock to their respective oxidation products comprising:

an aromatic separation apparatus operable to extract aromatic compounds from the hydrocarbon feed, the aromatic separation zone including an inlet for receiving the hydrocarbon feedstock, an aromatic-rich outlet and an aromatic-lean outlet;

an organic peroxide generation apparatus in fluid communication with the aromatic-rich outlet and a source of gaseous oxidant and having an outlet for discharging a mixture containing organic peroxide and heteroatom-containing hydrocarbons, the organic peroxide generation apparatus operating under conditions effective to promote organic peroxide production by reaction of hydrocarbons in the aromatic-rich fraction and gaseous oxidant;

a hydrotreating apparatus in fluid communication with the aromatic-lean outlet and having a treated product outlet; and

an oxidative reaction apparatus in fluid communication with the organic peroxide generation apparatus outlet, and having an outlet for discharging a mixture containing oxidation products of heteroatom-containing hydrocarbons, the oxidative reaction apparatus operating under conditions effective to promote oxidation of heteroatom-containing hydrocarbons by reaction of heteroatom-containing hydrocarbons and the produced organic peroxide.

31. An apparatus for conversion of sulfur-containing and nitrogen-containing hydrocarbon compounds in a hydrocarbon feedstock to their respective oxidation products comprising:

an aromatic separation apparatus operable to extract aromatic compounds from the hydrocarbon feed, the aromatic separation zone including an inlet for receiving the hydrocarbon feedstock, an aromatic-rich outlet and an aromatic-lean outlet;

a vessel in fluid communication with the aromatic-rich outlet and a source of gaseous oxidant and having an outlet for discharging a mixture containing oxidation products of heteroatom-containing hydrocarbons, the vessel operating under conditions effective to promote organic peroxide production by reaction of hydrocarbons in the aromatic-rich fraction and gaseous oxidant, and to promote oxidation of heteroatom-containing hydrocarbons by reaction of heteroatom-containing hydrocarbons and the produced organic peroxide; and

a hydrotreating apparatus in fluid communication with the aromatic-lean outlet and having a treated product outlet.