Combined desulfurization and hydroconversion with alkali metal hydroxides

• US 4,003,823 A
• Filed: 04/28/1975
• Issued: 01/18/1977
• Est. Priority Date: 04/28/1975
• Status: Expired due to Term

• Current Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Original Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Inventors: Bearden, Roby Jr., Baird, William C. Jr.
• Primary Examiner(s): Levine, Herbert
• Assistant Examiner(s): Schmitkons, G. E.
• Application Number:
  US05/571,912
• Time in Patent Office: 631 Days
• Field of Search: 208/108-112, 208/208 R, 208/208 M, 264/209, 264/226, 283/230, 283/235
• US Class Current: 208/108
• CPC Class Codes: C10G 19/00 Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
• CPC Class Codes: C10G 19/08 Recovery of used refining agents
• CPC Class Codes: C10G 47/22 Non-catalytic cracking in the presence of hydrogen

Abstract

Processes for the simultaneous desulfurization and hydroconversion of heavy carbonaceous feeds, including various sulfur-containing heavy petroleum oils, are disclosed. These feeds are contacted with alkali metal hydroxides in a conversion zone, in the presence of added hydrogen, and at elevated temperatures, whereby the feeds are substantially desulfurized, while at the same time significant upgrading of these feedstocks is obtained as demonstrated by decreased Conradson carbon, increased API gravity, and the conversion of a substantial portion of the 1,050° F+ portion of the feedstream. In addition, methods for the regeneration of alkali metal hydroxides from the alkali metal salts produced in the conversion zone are disclosed.

Claims

1. A process for the simultaneous desulfurization and hydroconversion of a sulfur-containing hydrocarbon feedstock containing at least 10 wt.% of materials boiling above about 1,050°

F, which comprises contacting said hydrocarbon feedstock, substantially in a liquid state, with an alkali metal hydroxide in a conversion zone, in the presence of added hydrogen, said conversion zone being maintained at elevated temperatures ranging between 500°

-1,500°

F, whereby the sulfur and metals content of said hydrocarbon feedstock is reduced and wherein at least a portion of the 1,050°

F+ fraction of said feedstock is converted to lower boiling products.

2. The process of claim 1 wherein between about 50 and 80% of said 1,050°

F+ fraction of said feedstock is converted to lower boiling products.

3. The process of claim 1 wherein said elevated temperatures range from between about 750°

and 1000°

F.

4. The process of claim 1 wherein said alkali metal hydroxide comprises a hydroxide of a metal selected from the group consisting of sodium, lithium, potassium, rubidium, cesium, and mixtures thereof.

5. The process of claim 1 wherein said alkali metal hydroxide comprises potassium hydroxide.

6. The process of claim 1 wherein said alkali metal hydroxide is present in said conversion zone in a molten state.

7. The process of claim 1 wherein said alkali metal hydroxide is present in said conversion zone in an amount ranging from about 5 to 15 weight percent of said feedstock.

8. The process of claim 1 wherein said hydrocarbon feedstock is maintained in a substantially liquid phase within said conversion zone.

9. The process of claim 1 wherein said hydrogen is maintained in said conversion zone at a pressure of between about 500 and 5000 psig.

10. The process of claim 1 wherein said hydrogen is maintained in said conversion zone at a pressure of between about 1500 and 3000 psig.

11. The process of claim 1 wherein said sulfur content of said feedstock is reduced by at least about 50%.

21. The process of claim 4 wherein the feedstock containing at least about 25 wt.% of materials boiling above 1,050°

F.

12. A process for the simultaneous desulfurization and hydroconversion of a sulfur-containing feedstock, said feedstock containing at least 10 wt.% of materials boiling above about 1,050°

F, which comprises contacting said hydrocarbon feedstock, substantially in a liquid state, with an alkali metal hydroxide in a conversion zone being maintained at a temperature of between about 700° and

1,500°

F, so that at least a portion of said alkali metal hydroxides are converted to alkali metal sulfides in said conversion zone, and whereby the sulfur and metals content of said feedstock is reduced, and furthermore wherein at least a portion of the 1,050°

F+ portion of said feedstock is converted to lower boiling materials, withdrawing said desulfurized and hydroconverted feedstock and said alkali metal sulfides from said conversion zone, separating said alkali metal hydroxides and alkali metal sulfides from the products withdrawn from said conversion zone, regenerating said alkali metal hydroxides from said alkali metal sulfides, and recycling said alkali metal hydroxides to said conversion zone.

13. The process of claim 12 wherein said hydrogen maintained in said conversion zone is maintained at a pressure of between about 500 and 5000 psig.

14. The process of claim 12 wherein said alkali metal hydroxides are regenerated by contacting with steam at a temperature between about 600°

and 1500°

F, and at atmospheric pressure.

15. The process of claim 12 wherein said alkali metal hydroxide comprises potassium hydroxide.

16. The process of claim 12 wherein said selected temperature ranges from between about 750°

and 1000°

F.

17. The process of claim 15 wherein said alkali metal hydroxide is present in said conversion zone in an amount ranging from between about 5 and 15 weight percent of said feedstock.

18. The process of claim 13 wherein said hydrogen is maintained in said conversion zone at a pressure of between about 1500 and 3000 psig.

19. The process of claim 12 wherein between about 50 and 80% of said 1,050°

F+ fraction of said feedstock is converted to lower boiling products.

20. The process of claim 13 wherein the feedstock contains at least about 25 wt.% of materials above 1,050°

F.