Removal of sulfur from a hydrocarbon stream by low severity adsorption

• US 5,919,354 A
• Filed: 05/13/1997
• Issued: 07/06/1999
• Est. Priority Date: 05/13/1997
• Status: Expired due to Term

• Current Assignee: Marathon Oil Company (Marathon Oil Corporation)
• Original Assignee: Marathon Oil Company (Marathon Oil Corporation)
• Inventors: Bartek, Robert
• Primary Examiner(s): MYERS, HELANE ELEANORA
• Application Number:
  US08/855,503
• Time in Patent Office: 784 Days
• Field of Search: 208/299, 208/300, 208/208, 208/310 Z, 585/820
• US Class Current: 208/299
• CPC Class Codes: C10G 25/05 Removal of non-hydrocarbon compounds, e.g. sulfur compounds

Abstract

A process is provided for reducing the sulfur content of a hydrocarbon stream, wherein a hydrocarbon stream containing sulfur constituents is contacted with a sorbent under temperature and pressure conditions of low severity. The sorbent includes a metal-exchanged zeolite selected from a group consisting of Y zeolites, ultra-stable Y zeolites, and mixtures thereof. A preferred sorbent is a fluid catalytic cracking (FCC) catalyst having a rare earth metal exchanged Y zeolite or ultra-stable Y zeolite. The sorbent adsorbs sulfur constituents contained in the hydrocarbon stream upon contact therewith to reduce the sulfur content of the hydrocarbon stream.

Claims

1. A process for reducing the sulfur content of a hydrocarbon stream under temperature and pressure conditions of low severity comprising:

providing a hydrocarbon stream containing a sulfur constituent;

heating said hydrocarbon stream to a contacting temperature greater than ambient, but not greater than the reflux temperature of said hydrocarbon stream;

contacting said heated hydrocarbon stream at said contacting temperature and at a contacting pressure not greater than about 698 kPa with a sorbent including a metal-exchanged zeolite having a silica to alumina ratio of at least about 1.5;

1; and

adsorbing said sulfur constituent contained in said hydrocarbon stream onto said sorbent to reduce the sulfur content of said hydrocarbon stream.

2. The process of claim 1 wherein said metal-exchanged zeolite is selected from a group consisting of Y zeolites, ultra-stable Y zeolites, and mixtures thereof.

3. The process of claim 1 wherein said hydrocarbon stream is a liquid hydrocarbon selected from the group consisting of refinery feedstocks, refinery intermediates, refinery products, and mixtures thereof.

4. The process of claim 1 wherein said hydrocarbon stream is a liquid hydrocarbon fuel having a carbon number within a range between about 5 and about 20.

5. The process of claim 1 wherein said sulfur constituent is naturally-occurring in said hydrocarbon stream.

6. The process of claim 1 wherein said metal-exchanged zeolite is a rare earth metal-exchanged zeolite.

7. The process of claim 1 wherein said sorbent is a fresh or used fluid catalytic cracking catalyst.

8. The process of claim 7 wherein said used fluid catalytic cracking catalyst is an equilibrium fluid catalytic cracking catalyst.

9. The process of claim 1 wherein said sorbent includes a matrix of relatively inert material.

10. The process of claim 9 wherein said relatively inert material is selected from a group consisting of clay, alumina and silica/alumina.

11. The process of claim 9 wherein said matrix is intimately mixed with said zeolite.

12. The process of claim 1 wherein said sorbent includes a substrate supporting said zeolite.

13. The process of claim 1 further comprising regenerating said sorbent having said sulfur constituent adsorbed thereon to produce a regenerated sorbent having substantially less of said sulfur constituent adsorbed thereon.

14. The process of claim 1 wherein said zeolite has a loading of a metal contaminant selected from a group consisting of iron, vanadium, nickel, copper and mixtures thereof.

15. The process of claim 1 wherein said hydrocarbon stream is contacted with said sorbent in the absence of oxygen.

16. The process of claim 1 wherein said sulfur constituent is selected from a group consisting of mercaptans, disulfides, sulfides, thiophene and mixtures thereof.

17. A process for reducing the sulfur content of a hydrocarbon stream under temperature and pressure conditions of low severity comprising:

providing a hydrocarbon stream containing a sulfur constituent;

heating said hydrocarbon stream to a contacting temperature greater than ambient, but not greater than the reflux temperature of said hydrocarbon stream;

contacting said heated hydrocarbon stream at said contacting temperature and at a contacting pressure not greater than about 698 kPa with a fluid catalytic cracking catalyst including a rare earth metal-exchanged zeolite having a silica to alumina ratio of at least about 1.5;

1; and

adsorbing said sulfur constituent contained in said hydrocarbon stream onto said fluid catalytic cracking catalyst acting as a sorbent to reduce the sulfur content of said hydrocarbon stream.

18. The process of claim 17 wherein said rare earth metal-exchanged zeolite is selected from a group consisting of Y zeolites, ultra-stable Y zeolites, and mixtures thereof.

19. The process of claim 17 wherein said hydrocarbon stream is a liquid hydrocarbon selected from the group consisting of refinery feedstocks, refinery intermediates, refinery products, and mixtures thereof.

20. The process of claim 17 wherein said hydrocarbon stream is a liquid hydrocarbon fuel having a carbon number within a range between about 5 and about 20.

21. The process of claim 17 further comprising regenerating said sorbent having said sulfur constituent adsorbed thereon to produce a regenerated sorbent having substantially less of said sulfur constituent adsorbed thereon.

22. The process of claim 17 wherein said hydrocarbon stream is contacted with said sorbent in the absence of oxygen.

23. The process of claim 17 wherein said sulfur constituent is naturally-occurring in said hydrocarbon stream.

24. The process of claim 17 wherein said fluid catalytic cracking catalyst is an equilibrium fluid catalytic cracking catalyst.

25. The process of claim 17 wherein said sulfur constituent is selected from a group consisting of mercaptans, disulfides, sulfides, thiophene and mixtures thereof.

26. A process for reducing the sulfur content of a hydrocarbon stream under temperature and pressure conditions of low severity comprising:

providing a hydrocarbon stream containing a sulfur constituent selected from a group consisting of mercaptans, disulfides, sulfides, thiophene and mixtures thereof;

heating said hydrocarbon stream to a contacting temperature greater than ambient, but not greater than the reflux temperature of said hydrocarbon stream;

contacting said heated hydrocarbon stream with a metal-exchanged zeolite selected from a group consisting of Y zeolites, ultra-stable Y zeolites, and mixtures thereof at said contacting temperature and at a contacting pressure not greater than about 698 kPa, wherein said metal-exchanged zeolite has an exchanged metal cation selected from a group consisting of rare earth metal cations, palladium cations, platinum cations and mixtures thereof; and

adsorbing said sulfur constituent contained in said hydrocarbon stream onto said metal-exchanged zeolite to reduce the sulfur content of said hydrocarbon stream.