Process for the upgrading of raw hydrocarbon streams

• US 7,153,414 B2
• Filed: 12/10/2002
• Issued: 12/26/2006
• Est. Priority Date: 12/10/2002
• Status: Expired due to Term

• Current Assignee: Petroleo Brasileiro SA - Petrobras
• Original Assignee: Petroleo Brasileiro SA - Petrobras
• Inventors: De Souza, Wladmir Ferraz
• Primary Examiner(s): Caldarola, Glenn
• Assistant Examiner(s): Singh, Prem C.
• Application Number:
  US10/314,963
• Publication Number:
  US 20040108252A1
• Time in Patent Office: 1,477 Days
• Field of Search: 208/208, 208/219, 208/222, 208/236, 208/244, 208/254, 208/255, 208/256, 208/295, 208/299, 208/208.R, 208/254.R
• US Class Current: 208/208.00R
• CPC Class Codes: C10G 27/00 Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
• 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 53/14 including at least one oxidation step

Abstract

A process for the upgrading of raw hydrocarbon streams rich in heteroatomic polar compounds and/or unsaturated moieties involving the extractive oxidation of sulfur, nitrogen, conjugated dienes and other unsaturated compounds from said streams, the said process comprising treating said streams with a peroxide solution/organic acid couple and an iron oxide catalyst which is a limonite ore, under an acidic pH, atmospheric pressure and ambient or higher temperature. As a result of the reaction, the oxidized heteroatomic compounds, having strong affinity for the aqueous slurry phase, are extracted into said aqueous phase, while the oxidized hydrocarbon is separated from catalyst by decanting, neutralizing, water washing and drying, the resulting end product being a hydrocarbon stream from which have been removed 90% or more of total nitrogen compounds and basic nitrogen up to 99.7%, both calculated as mass contents.

Claims

1. A process for the upgrading of raw hydrocarbon streams by oxidation and/or inertization of sulfur, nitrogen, conjugated dienes and other unsaturated compounds from raw hydrocarbon streams rich in heteroatomic polar compounds and/or unsaturated moieties in the presence of a peroxide solution/organic acid couple and a pulverized raw iron oxide catalyst at atmospheric pressure, under equal or higher than ambient temperature, wherein said process comprises the following steps:

a) oxidizing sulfur, nitrogen, conjugated dienes and unsaturated compounds present in said raw hydrocarbon streams by admixing, under agitation, said organic acid and said peroxide, the weight percent of the peroxide solution and organic acid based on raw hydrocarbon being at least 3 and 4 respectively, then adding said raw hydrocarbon stream containing sulfur, nitrogen, conjugated dienes and unsaturated compounds and then the raw iron oxide catalyst, pulverized and dried to a granulometry lower than 0.177 mm, in an amount of from 0.01 to 5.0 weight % based on the weight of raw hydrocarbon, at a pH between 1.0 and 6.0, the reaction being carried out under reflux of vaporized hydrocarbon, for the period of time required to effect the extractive oxidation and obtaining a hydrocarbon stream wherefrom the sulfur, nitrogen, conjugated dienes and unsaturated compounds have been partially oxidized and simultaneously extracted by the aqueous oxidant slurry, yielding a lower aqueous slurry phase and an upper oxidized hydrocarbon phase;

b) after the end of said extractive oxidation, separating the upper 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 90% by weight, basic nitrogen compounds have been removed up to 99.7% by weight, conjugated diene compounds have been removed up to 22% by weight, and sulfur compounds have been removed up to 13% by weight, followed by olefin removal ranging from 4% to 16 weight %, all percentages being based on the original feedstock content.

2. A process according to claim 1, wherein alternatively, the pulverized and dried raw iron oxide catalyst is added in the first place to the hydrocarbon stream containing sulfur, nitrogen and conjugated diene and other unsaturated compounds.

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

4. A process according to claim 1, wherein the raw hydrocarbon feed is raw naphtha of boiling range between 30 and 300°

C.

5. A process according to claim 4, wherein the raw naphtha is obtained from oil shale retorting.

6. A process according to claim 1, wherein the iron oxide catalyst comprises iron oxyhydroxide of formula FeOOH, hydrated iron oxyhydroxide of formula FeOOH._nH₂O and crystalline forms such as α

-FeOOH (Goethite), γ

-FeOOH (Lepidocrocite), β

-FeOOH (Akaganeite), and δ

′

-FeOOH (Ferroxyhite).

7. A process according to claim 6, wherein the amount of iron oxide catalyst is of from 0.5 to 3.0 weight % based on the weight of raw hydrocarbon submitted to the process.

8. A process according to claim 6, wherein the granulometry of the iron oxide catalyst is 0.105 mm (150 mesh Tyler) or less.

9. A process according to claim 6, wherein the granulometry of the iron oxide catalyst is 0.149 mm (100 mesh Tyler).

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

11. A process according to claim 10, wherein the peroxide is hydrogen peroxide at a concentration of at least 30 weight %.

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

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

14. 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 slurry phase, being extracted into said phase by the aqueous oxidant itself.

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

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

17. A process according to claim 1, wherein the weight percent of the peroxide solution and organic acid based on the raw hydrocarbon is 6 to 15 and 8 to 20, respectively.

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

19. A process according to claim 18, wherein said molar ratio is in the range of from 0.9 to 1.1.

20. A process according to claim 19, wherein said molar ratio is in the range of from 0.95 to 1.

21. A process according to claim 1, wherein the waste water and waste alkaline neutralizing solutions from the neutralized and washed hydrocarbon are completely purged.

22. A process according to claim 21, wherein the waste water and waste alkaline neutralizing solutions from the neutralized and washed hydrocarbon are recycled after being partially purged.

23. A process according to claim 1, wherein the aqueous slurry phase, comprising the spent oxidant solution and iron oxide catalyst, is decanted to separate the solid catalyst phase.

24. A process according to claim 23, wherein the solid catalyst phase is disposed off.

25. A process according to claim 23, wherein the solid catalyst phase is reused after being washed and dried.

26. A process according to claim 25, wherein a portion of the solid reused catalyst is purged and made up with fresh limonite in order to replace spent catalyst.