Process for demetallizing and desulfurizing heavy crude oil

• US 4,885,080 A
• Filed: 05/25/1988
• Issued: 12/05/1989
• Est. Priority Date: 05/25/1988
• Status: Expired due to Fees

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Hogan, Robert J., Coombs, Daniel M., Brown, Ronald E., Kukes, Simon G.
• Primary Examiner(s): Myers, Helane
• Application Number:
  US07/198,767
• Time in Patent Office: 559 Days
• Field of Search: 208/218, 208/211, 208/251 H, 208/303, 208/254 H, 208/80, 208/93
• US Class Current: 208/218
• CPC Class Codes: C10G 65/16 including only refining steps

Abstract

A heavy crude oil is fractionated into at least three liquid fractions which include a distillate fraction boiling in the 400° F.-650° F. range and a 650° F.+ boiling range residuum. The distillate cut is hydrodesulfurized and the residuum is hydrodemetallized. The cuts thus hydrotreated, and at least a part of the third liquid fraction, are then combined to form an upgraded synthetic crude oil of relatively low sulfur content and relatively low vanadium and nickel content.

Claims

1. A process for producing a synthetic crude oil of improved properties by desulfurizing, denitrogenating and demetallizing a heavy crude oil feed stock, said feed stock being a crude oil having an average boiling point at least as high as 500°

F., an °

API gravity at 60°

F. of less than 20, and containing at least about 1 weight percent sulfur, which process comprises;

separating said heavy crude oil feed stock into four fractions including an atmospheric residuum fraction having an initial boiling point at least as high as 650°

F., a distillate fraction having a boiling range of from about 400°

F. to about 650°

F., a naphtha fraction having a boiling range of from about that of C₅ hydrocarbons to about 400°

F., and a light hydrocarbon gas overhead containing predominantly hydrocarbon gases;

contacting the distillate fraction with a desulfurization catalyst, and with hydrogen gas, in a first hydrodesulfurization zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate, catalytic activity and space velocity such as to remove a substantial portion of the sulfur and nitrogen from the distillate fraction;

concurrently with such contacting of the distillate fraction, contacting at least a substantial portion of said residuum fraction with hydrogen gas in the presence of a hydrodemetallation catalyst also having hydrodesulfurizing activity, in a hydrodemetallation zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate, and space velocity such that a major portion of the nickel and vanadium metal content of the residuum is removed therefrom, and a substantial potion of the sulfur content of the residuum is concurrently removed therefrom;

then

recombining the naphtha fraction, the hydrotreated distillate, and the hydrotreated residuum fractions to yield an improved, synthetic crude oil.

2. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein the hydrogen gas used in the first hydrodesulfurization zone is derived from the reformation of natural gas.

3. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein light hydrocarbon fuel gases produced in said hydrodesulfurization zone and in said hydrodemetallation zone are combined with said light hydrocarbon gas overhead.

4. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein said conditions in said hydrodesulfurization zone include a temperature in the range of from about 550°

F. to about 850°

F., a hydrogen partial pressure of from about 250 p.s.i.g. to about 900 p.s.i.g., a hydrogen flow rate of from about 100 s.c.f./bbl. to about 600 s.c.f./bbl., and a space velocity of from about 2 LHSV to about 3 LHSV.

5. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein said conditions in said hydrodemetallation zone include a temperature in the range of from about 600°

F. to about 900°

F., a hydrogen partial pressure of from about 500 p.s.i.g. to about 3,000 p.s.i.g., a hydrogen flow rate of from about 2,000 s.c.f./bbl. to about 9000 s.c.f./bbl., and a space velocity of from about 0.1 to about 5.0 LHSV.

6. A process for producing a synthetic crude oil of improved properties as defined in claim 1 and further characterized as including the step of contacting said naphtha fraction, prior to recombining it with the hydrotreated distillate and residuum fractions, with a desulfurization catalyst, and with hydrogen gas, in a second hydrodesulfurization zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate, catalytic activity and space velocity such as to remove a substantial portion of the sulfur and nitrogen from the naphtha fraction.

7. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein said hydrodesulfurization catalyst comprises a refractory inorganic oxide substrate having supported thereon, a first component selected from the group consisting of Group VIII metals and Group VIII metal compounds, and a second component selected from the group consisting of Group VI-B metals and compounds of Group VI-B metals.

8. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein said hydrodemetallation catalyst comprises a refractory inorganic oxide substrate having supported thereon, a first compound selected from the group consisting of the Group VI-B metals and the compounds of Group VI-B metals, and a second component selected from the group consisting of Group VIII metals.

9. A process for producing a synthetic crude oil of improved properties as defined in claim 1 wherein sulfur and ammonia are recovered as by-products derived from the desulfurization reactions occurring in the hydrodesulfurization zone and the hydrodemetallation zone.

10. A process for producing a synthetic crude oil of improved properties as defined in claim 4 wherein said temperature is in the range of from about 700°

F. to about 800°

F. and the hydrogen partial pressure is in the range of from about 400 p.s.i.g. to about 700 p.s.i.g.

11. A process for producing a synthetic crude oil of improved properties as defined in claim 5 wherein the temperature is in the range of from about 100°

F. to about 800°

F. and the hydrogen partial pressure is in the range of from about 600 p.s.i.g. to about 2,500 p.s.i.g., and the hydrogen flow rate is from about 4,000 s.c.f./bbl. to about 8,000 s.c.f./bbl.

12. A process for producing a synthetic crude oil of improved properties as defined in claim 7 wherein said desulfurization catalyst is further characterized in that the refractory inorganic oxide substrate comprises alumina having an average pore diameter in the range of from about 65°

A. to about 130°

A., and a pore volume in the range of from about 0.3 cc/gram to about 1.00 cc/gram.

13. A process for producing a synthetic crude oil of improved properties as defined in claim 5 wherein said conditions in said hydrodesulfurization zone include a temperature in the range of from about 550°

F. to about 850°

F., a hydrogen partial pressure of from about 250 p.s.i.g. to about 900 p.s.i.g., a hydrogen flow rate of from about 100 s.c.f./bbl. to about 600 s.c.f./bbl., and a space velocity of from about 2 LHSV to about 3 LHSV.

14. A process for producing a synthetic crude oil of improved properties as defined in claim 13 and further characterized as including the step of contacting said naphtha fraction, prior to recombining it with the hydrotreated distillate and residuum fractions, with a desulfurization catalyst, and with hydrogen gas, in a second hydrodesulfurization zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate, catalytic activity and space velocity such as to remove a substantial portion of the sulfur and nitrogen from the naphtha fraction.

15. A process for producing a synthetic crude oil of improved properties as defined in claim 13 wherein said hydrodesulfurization catalyst comprises a refractory inorganic oxide substrate having supported thereon, a first component selected from the group consisting of Group VIII metals and Group VIII metal compounds, and a second component selected from the group consisting of Group VI-B metals and compounds of Group VI-B metals.

16. A process for producing a synthetic crude oil of improved properties as defined in claim 15 wherein said hydrodemetallation catalyst comprises a refractory inorganic oxide substrate having supported thereon, a first compound selected from the group consisting of the Group VI-B metals and the compounds of Group VI-B metals, and a second component selected from the group consisting of Group VIII metals.

17. A process for upgrading a heavy crude oil having an average boiling point at least as high as 500? F., an °

API gravity at 60? F. of less than 20, containing at least about 1.0 weight percent sulfur, and having a combined nickel and vanadium ion content of at least about 1,000 ppm, which process comprises;

fractionating the heavy crude oil at atmospheric pressure to yield at least three fractions which include;

an atmospheric residuum fraction having an initial boiling point at least as high as 650°

F.;

a distillate fraction having a boiling range of from about 400°

F. to about 650°

F.;

a third fraction having a boiling range having its highest temperature at least as low as 400°

F.;

contacting the residuum fraction with a hydroemetallation catalyst in the presence of hydrogen under conditions of temperature, hydrogen partial pressure, hydrogen flow rate and space velocity such that major portions of the nickel, vanadium and sulfur present in the heavy crude oil are removed from the residuum fraction;

substantially concurrently with such contacting of at least a major portion of residuum fraction, contacting the distillate fraction with a hydrodesulfurization catalyst in the presence of hydrogen gas under conditions of temperature, hydrogen partial pressure, hydrogen flow rate and space velocity such as to remove a substantial portion of the sulfur and nitrogen from the distillate fraction;

then

recombining the hydrotreated distillate fraction and the hydrotreated residuum and a selected portion derived from the remainder of the fractionated heavy crude oil to yield a synthetic crude oil of selected characteristics.

18. A process for upgrading a heavy crude oil as defined in claim 17 wherein said hydrodemetallation catalyst comprises:

a porous refractory inorganic substrate material having supported thereon a first metal selected from the group consisting of molybdenum, tungsten and chromium and a second metal selected from the group consisting of iron, cobalt and nickel; and

wherein said hydrodesulfurization catalyst comprises a porous refractory inorganic substrate material having supported thereon a first component selected from the group consisting of molybdenum, tungsten and chromium and compounds thereof, and a second component selected from the group consisting of iron, cobalt and nickel and compounds thereof.

19. A process for upgrading a heavy crude oil as defined in claim 17 wherein said three fractions further include, as said third fraction, a naphtha having an initial boiling range of from about 400°

F. down to about the boiling point of normal pentane, and further characterized as including the step of desulfurizing said naphtha fraction to yield said selected portion derived from the remainder of the fractionated crude oil.

20. A process for upgrading a heavy crude oil as defined in claim 17 wherein said selected portion comprises a naphtha fraction having a boiling range of from about 400°

F. down to about the boiling point of normal pentane.

21. A process for upgrading a heavy crude oil as defined in claim 17 wherein sulfur and ammonia are recovered as by-products derived from desulfurization reactions occurring in the hydrodesulfurizing zone and the hydrodemetallation zone.

22. A process for upgrading a heavy crude oil as defined in claim 19 wherein said hydrodemetallation catalyst comprises:

a porous, refractory, inorganic substrate material comprising alumina and having supported thereon a first component selected from the group consisting of molybdenum, tungsten and chromium and compounds thereof, and a second component selected from the group consisting of iron, cobalt and nickel and compounds thereof; and

wherein said naphtha fraction is desulfurized by the use of a desulfurization catalyst in the presence of hydrogen gas, and said desulfurization catalyst corresponds to the desulfurization catalyst utilized in contacting the distillate fraction in the presence of hydrogen gas.

23. A process for producing a synthetic crude oil of improved properties by desulfurizing, denitrogenating and demetallizing a heavy crude oil feedstock, said feedstock being a crude oil having an average boiling point at atmospheric pressure which is at least as high as 500°

F., and API gravity at 60°

F. of less than 20, and containing at least about 1.0 weight percent sulfur, which process comprises;

separating the heavy crude oil feed stock into four fractions which include;

a relatively heavy residuum fraction having an initial boiling point at atmospheric pressure of at least -650°

F;

a distillate fraction having a boiling range of from about 400°

F. to about 650°

F. at atmospheric pressure; and

a relatively light naptha fraction having a higher boiling range than said distillate fraction and having a maximum boiling point of about 400°

F. at atmospheric pressure; and

a light hydrocarbon gas overhead containing predominantly hydrocarbon gas;

contacting the distillate fraction with a desulfurizing catalyst and with hydrogen gas in a first hydrodesulfurization zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate, catalyst activity and space velocity such as to remove a substantial portion of the sulfur and nitrogen from the distillate fraction;

contacting at least a substantial portion of said residuum fraction with hydrogen gas in the presence of a hydrodesulfurization catalyst also having hydrodesulfurizing activity, in a hydrodemetallation zone under conditions of temperature, hydrogen partial pressure, hydrogen flow rate and space velocity such that a major portion of the nickel and vanadium metal contact of the residuum is removed therefrom, and a substantial portion of the sulfur content of the residuum is concurrently removed therefrom;

then

recombining the naptha fraction, the hydrotreated distillate, and the hydrotreated residuum fractions to yield an improved synthetic crude oil.