Upgrading heavy oils by selective oxidation

Patent metadata

Field	Value
Publication number	US-9816039-B2
Application number	US-201514810130-A
Country	US
Kind code	B2
Filing date	Jul 27, 2015
Priority date	Aug 26, 2014
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

A heavy petroleum oil feed is upgraded by having its amenability to cracking improved by subjecting the oil to selective partial oxidation with a catalytic oxidation system to partially oxidize aromatic ring systems in the heavy oil. The partially oxidized oil can then be cracked in the conventional manner but at lower severities to lower molecular weight cracking products. The cracking following the partial oxidation step may be thermal in nature as by thermal cracking, delayed, contact or fluid coking or fluid catalytic cracking or hydrogenative as in hydrocracking.

First claim

The invention claimed is:

1. A process of upgrading a heavy petroleum oil stream which comprises subjecting the heavy oil stream to selective partial oxidation with a catalytic oxidation system to partially oxidize aromatic ring systems in the heavy oil to improve its crackability and then cracking the partially oxidized oil to lower molecular weight cracking products by fluid catalytic cracking, hyrdrocracking, coking, or a combination thereof.

2. A process according to claim 1 in which the cracking of the partially oxidized oil is by fluid catalytic cracking.

3. A process according to claim 1 in which the cracking of the partially oxidized oil is by hydrocracking.

4. A process according to claim 1 in which the cracking of the partially oxidized oil is by coking.

5. A process according to claim 1 in which the catalytic oxidation system comprises a metal salt or a metal oxide as catalyst and a peroxy oxidant.

6. A process according to claim 1 in which the catalytic oxidation system comprises a ruthenium tetroxide and sodium periodate.

7. A process according to claim 1 in which the catalytic oxidation system comprises an aqueous solution of a metal salt as catalyst and an oxidant.

8. A process according to claim 1 in which the heavy oil stream comrpises a vacuum resid containing aromatic compounds of 3, 4 and 5-membered fused aromatic rings.

9. A process according to claim 8 in which 4 and 5-membered fused aromatic rings of the vacuum resid are oxidized to form 3 or fewer membered fused aromatic rings.

10. A process for reducing the boiling point range of a petroleum vacuum resid feed which comprises subjecting the resid feed to selective partial oxidation with a catalytic oxidation system to partially oxidize aromatic ring systems in the resid to improve its crackability and then cracking the partially oxidized oil in a fluid catalytic cracking process to lower molecular weight cracking products.

11. A process according to claim 10 in which the catalytic oxidation system comprises a ruthenium salt and a peroxy oxidant.

12. A process according to claim 10 in which the catalytic oxidation system comprises a ruthenium tetroxide and sodium periodate.

13. A process according to claim 10 in which the catalytic oxidation system comprises an aqueous solution of a metal catalyst and oxidant.

14. A process according to claim 10 in which the heavy oil stream comrpises a vacuum resid containing aromatic compounds of 3, 4 and 5-membered fused aromatic rings.

15. A process according to claim 14 in which 4 and 5-membered fused aromatic rings of the vacuum resid are oxidized to form 3 or fewer membered fused aromatic rings.

16. A process for reducing the boiling point range of a petroleum vacuum resid feed which comprises subjecting the resid feed to selective partial oxidation with a catalytic oxidation system to partially oxidize aromatic ring systems in the resid to improve its crackability and then cracking the partially oxidized oil in a hydrocracking process to lower molecular weight cracking products.

17. A process according to claim 16 in which the catalytic oxidation system comprises a ruthenium salt and a peroxy oxidant.

18. A process according to claim 17 in which the catalytic oxidation system comprises a ruthenium tetroxide and sodium periodate.

Assignees

• Francisco Manuel A
• Degnan Jr Thomas Francis
• Beswick Colin L
• Sundararaman Ramanathan
• Exxonmobil Res & Eng Co

Inventors

• Francisco Manuel A
• Degnan Jr Thomas Francis
• Beswick Colin L
• Sundararaman Ramanathan

Classifications

• C10G67/12 Primary

  including oxidation as the refining step in the absence of hydrogen · CPC title

• C10G55/04

  including at least one thermal cracking step · CPC title

• C10G55/06

  including at least one catalytic cracking step · CPC title

• C10G27/04

  with oxygen or compounds generating oxygen · CPC title

• C10G2300/1077

  Vacuum residues · CPC title