Process for the extractive oxidation of contaminants from raw hydrocarbon streams

• US 20040222134A1
• Filed: 05/06/2003
• Published: 11/11/2004
• Est. Priority Date: 05/06/2003
• Status: Active Grant

• Current Assignee: Petrã“Leo Brasileiro SA - Petrobras (Presidãªncia Da Repãºblica)
• Original Assignee: Petrã“Leo Brasileiro SA - Petrobras (Presidãªncia Da Repãºblica)
• Inventors: de Souza, Wladmir Ferraz
• Granted Patent: US 7,175,755 B2
• Time in Patent Office: Days
• US Class Current: 208/237
• 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 67/08 including acid treatment as the refining step in the absence of hydrogen
• CPC Class Codes: C10G 67/12 including oxidation as the refining step in the absence of hydrogen
• CPC Class Codes: C10G 69/04 including at least one step of catalytic cracking in the absence of hydrogen

Abstract

A process for the extractive oxidation of contaminants from raw hydrocarbon streams rich in heteroatomic polar compounds is described, the said process involving the extractive oxidation of sulfur and nitrogen compounds from said streams, the said process comprising treating said streams with a peroxide solution/organic acid couple, the weight percent of the peroxide solution and organic acid based on raw hydrocarbon being at least 3 for both the peroxide and organic acid solution, under an acidic pH, atmospheric or higher pressure and ambient or higher temperature. As a result of the reaction, the oxidized heteroatomic compounds, having strong affinity for the aqueous phase, are extracted into said aqueous phase, while the oxidized hydrocarbon is neutralized, water washed and dried, the resulting end product being a hydrocarbon stream from which have been removed 88.1 wt % or more of total nitrogen compounds and basic nitrogen up to 99.1 wt %, both calculated as mass contents, total Sulfur 23.3% removal, and removal of total olefins is limited to 6.5 weight %. The treated product is further directed to any refining process.

Claims

1. A process for the extractive oxidation of contaminants from raw hydrocarbon streams by oxidation and/or inertization of sulfur and nitrogen compounds from raw hydrocarbon streams rich in heteroatomic polar compounds in the presence of a peroxide solution/organic acid at atmospheric or higher pressure, under equal or higher than ambient temperature, wherein said process comprises the following steps:

a) Oxidizing sulfur and nitrogen compounds present in said raw hydrocarbon streams by admixing, under agitation, said organic acid and said peroxide solution, the weight percent of the peroxide solution and organic acid based on raw hydrocarbon being at least 3 for both the peroxide solution and the organic acid, then adding to said oxidant solution said raw hydrocarbon stream containing sulfur and nitrogen compounds, at a pH between 1.0 and 6.0, the reaction being carried out under reflux of vaporized hydrocarbon obtained by external heating, for the period of time required to effect the extractive oxidation and obtaining a hydrocarbon stream wherefrom the sulfur and nitrogen compounds have been partially oxidized and simultaneously extracted by the aqueous oxidant, yielding a lower aqueous phase and an upper oxidized hydrocarbon phase;

b) After the end of said extractive oxidation, separating the upper oxidized hydrocarbon phase, neutralizing and water washing same, filtering and drying;

c) Recovering said treated, odorless, clear yellowish and stable hydrocarbon phase wherefrom the total nitrogen compounds have been removed up to 88.1% by weight, basic nitrogen compounds have been removed up to 99.1% by weight, and sulfur compounds have been removed up to 23% by weight, followed by olefin removal limited to 6.5 weight %, all percentages being based on the original feedstock content.

2. A process according to claim 1, wherein the treated hydrocarbon phase is further directed to any refining process.

3. A process according to claim 2, wherein the refining process is a hydrotreating process.

4. A process according to claim 1, wherein alternatively the so-prepared oxidant solution is added to the raw hydrocarbon.

5. A process according to claim 1, wherein the raw hydrocarbon feed is any raw light and middle distillate.

6. A process according to claim 5, wherein the raw hydrocarbon feed includes raw naphthas from thermal processes such as delayed coking.

7. A process according to claim 5, wherein the raw hydrocarbon feed includes raw naphthas from fluid catalytic cracking.

8. A process according to claim 5, wherein the raw hydrocarbon feed includes raw naphthas from shale oil retorting processes or other chemical processes.

9. A process according to claims 5, 6, 7 and 8, wherein the raw hydrocarbon feed is raw naphtha of boiling range of from 30°

C. to 300°

C.

10. A process according to claim 6, wherein the raw naphtha is obtained from oil shale retorting.

11. A process according to claim 1, wherein the peroxide is added as such or in solution.

12. A process according to claim 11, wherein the peroxide is hydrogen peroxide at a concentration of at least 30 weight %.

13. A process according to claim 11, wherein the hydrogen peroxide concentration is 50 weight %.

14. A process according to claim 11, wherein the hydrogen peroxide concentration is 60 weight %.

15. A process according to claim 1, wherein the extractive oxidation of heteroatomic polar compounds from the said raw hydrocarbon streams comprises said oxidized compounds, as a result of the strong affinity of same for the aqueous phase, being extracted into said phase by the aqueous oxidant itself.

16. A process according to claim 1, wherein the organic acid is formic acid.

17. A process according to claim 1, wherein the organic acid is acetic acid.

18. A process according to claim 1, wherein the weight percent of the peroxide solution and organic acid based on the raw hydrocarbon is of from 6 to 15 for both the peroxide and the organic acid.

19. A process according to claim 18, wherein there is a difference in weight percents between the peroxide solution and organic acid solution.

20. A process according to claim 1, wherein the peroxide/organic acid molar ratio is in the range of from 0.5 to 1.2.

21. A process according to claim 20, wherein said molar ratio is in the range of from 0.9 to 1.1.

22. A process according to claim 21, wherein said molar ratio is in the range of from 0.95 to 1.

23. A process according to claim 1, wherein the waste aqueous phase, waste alkaline neutralizing and wastewater solutions are completely purged.

24. A process according to claim 1, wherein alternatively the waste aqueous phase and waste alkaline neutralizing solutions are partially recycled.

25. A process according to claim 1, wherein alternatively the organic acid-rich waste aqueous phase is concentrated and recycled to the reaction tank.