Claims
- 1. A process for the demetallization and conversion of the 1050.degree.F.+ materials of a heavy metals containing heavy crude or residua feed to 1050.degree.F.- material comprising
- contacting said feed, in the presence of added hydrogen with catalyst comprising a composite of a porous inorganic oxide support and an admixture of from about 0.1 to about 10 percent of a Group IVA metal, from about 5 to about 30 percent of a Group VIB metal, and from about 1 to about 12 percent of a Group VIII metal, said catalyst including a combination of properties comprising, when the catalyst is of size ranging from about 1/500 to 1/50 inch average particle size diameter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100A to about 200A; when the catalyst is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150A to about 250A; when the catalyst is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175A to about 275A; a surface area ranging at least abot 200 m.sup.2 /g to about 600 m.sup.2 /g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g,
- at severity sufficient to convert at least about 30 percent of the 1050.degree.F.+ material to 1050.degree.F.- material, while removing at least about 80 percent of the heavy metals from the feed.
- 2. The process of claim 1 wherein from about 40 percent to about 60 percent of the 1050.degree.F.+ material is converted to 1050.degree.F.-, and from about 85 percent to about 90 percent of the metals are removed from the feed.
- 3. The process of claim 1 wherein the feed is characterized as follows:
- ______________________________________Gravity, .degree.API -5 to 20Heavy Metals, ppm 5-10001050.degree.F. +, Wt.% 10-100Asphaltenes (C.sub.5 insoluble), Wt.% 5-50Con Carbon, Wt.% 5-50______________________________________
- 4. The process of claim 1 wherein the product of the reaction is characterized as follows:
- ______________________________________Gravity, .degree.API 0 to 14Heavy Metals, ppm 200-6001050.degree.F.+, Wt.% 40-100Asphaltenes (C.sub.5 insoluble), Wt.% 15-30Con Carbon, Wt.% 10-30______________________________________
- 5. The process of claim 1 wherein the conditions of the reaction are characterized as follows:
- ______________________________________Temperature, .degree.F. (E.I.T.) Start-of-Run 700 End-of-Run 850Pressure, Psi 2000-10,000Hydrogen Rate, SCF/B 3000-20,000Space Velocity, LHSV 0.25-5.0______________________________________
- 6. The process of claim 1 wherein the catalyst when of particle size diameter ranging from about 1/500 to 1/50 inch is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <20% 100-200A >20% 300A+ <30% Pore Volume, cc/g 0.8-1.4 Surface Area, m.sup.2 /g 300-450______________________________________
- 7. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/500 to 1/50 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <10% 100-200A >25% 300A+ <25% Pore Volume, cc/g 0.9-1.5 Surface Area, m.sup.2 /g 310-500______________________________________
- 8. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/500 to 1/50 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <2% 100-200A >70% 300A+ <1% Pore Volume, cc/g 1.1-1.7 Surface Area, m.sup.2 /g 325-550______________________________________
- 9. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/50 to 1/25 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <10% 150-250A >15% 350A+ <35% Pore Volume, cc/g 1.1-1.7 Surface Area, m.sup.2 /g 320-475______________________________________
- 10. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/50 to 1/25 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <5% 150-250A >20% 350A+ <30% Pore Volume, cc/g 1.3-1.9 Surface Area, m.sup.2 /g 340-575______________________________________
- 11. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/50 to 1/25 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <1% 150-250A >45% 350A+ <7% Pore Volume, cc/g 1.5-2.1 Surface Area, m.sup.2 /g 360-600______________________________________
- 12. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/25 to 1/8 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <5% 175-275A >15% 350A+ <40% Pore Volume, cc/g 1.3-1.9 Surface Area, m.sup.2 /g 340-500______________________________________
- 13. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/25 to 1/8 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <4% 175-275A >20% 350A+ <35% Pore Volume, cc/g 1.5-2.1 Surface Area, m.sup.2 /g 350-600______________________________________
- 14. The process of claim 1 wherein the catalyst, when of particle size diameter ranging from about 1/25 to 1/8 inch, is characterized as follows:
- ______________________________________ Distribution of Pore Diameters 0-50A <3% 175-275A >30% 350A+ <25% Pore Volume, cc/g 1.8-2.3 Surface Area, m.sup.2 /g 370-650______________________________________
- 15. The process of claim 1 wherein said catalyst comprises an admixture of from about 2 to about 5 percent of a Group IVA metal, from about 10 to about 20 percent of a Group VIB metal, and from about 4 to about 8 percent of a Group VIII metal.
- 16. The process of claim 15 wherein the product of the reaction is characterized as follows:
- ______________________________________Gravity, .degree.API 14 to 30Heavy Metals, ppm 10-1001050.degree.F.+, Wt.% 10-50Asphaltenes, (C.sub.5 insoluble), Wt.% 3-20Con Carbon, Wt. % 3-20______________________________________
- 17. The process of claim 15 wherein the product of the reaction is characterized as follows:
- ______________________________________Gravity, .degree.API 15 to 25Heavy Metals, ppm 40-801050.degree.F.+, Wt. % 25-40Asphaltenes (C.sub.5 insoluble), Wt. % 5-15Con Carbon, Wt. % 5-10______________________________________
- 18. A process for the demetallization, conversion and reduction of the Con carbon content of the 1050.degree.F. materials of a heavy metals containing heavy crude or residua feed to 1050.degree.F.- material comprising
- contacting said feed, in the presence of added hydrogen, with a catalyst comprising a composite of a porous inorganic oxide support and an admixture of from about 0.1 to about 10 percent of a Group IVA metal, from about 5 to about 30 percent of a Group VIB metal, and from about 1 to about 12 percent of a Group VIII metal, said catalyst including a combination of properties comprising at least about 55 percent of its total pore volume of absolute pore diameters ranging from about 100A to about 200A, less than 10 percent of its total pore volume are of absolute pore diameters ranging from 0 to about 50A, less than about 25 percent of its total pore volume of absolute pore diameters ranging 300A+, surface area ranges at least about 200 m.sup.2 to about 600 m.sup.2 and pore volume ranges from about 0.6 cc/g to about 1.5 cc/g,
- at severity sufficient to convert at least about 50 percent of the 1050.degree.F+ material to 1050.degree.F.- material, remove at least about 90 percent of the heavy metals from the feed, and reduce Con carbon from about 50 percent to about 100 percent.
- 19. The process of claim 18 wherein from about 60 percent to about 75 percent of the 1050.degree.F.+ material is converted to 1050.degree.F.-, and from about 97 percent to about 100 percent of the metals are removed from the feed.
- 20. The process of claim 18 wherein Con carbon is reduced from about 75 percent to about 90 percent.
- 21. The process of claim 18 wherein the feed is characterized as follows:
- ______________________________________Gravity, .degree.API 14-30Heavy Metals (Ni & V), ppm 10-1001050.degree.F.+, Wt.% 10-50Asphaltenes (C.sub.5 insoluble), Wt.% 3-20Con Carbon, Wt. % 3-20______________________________________
- 22. The process of claim 18 wherein the feed is characterized as follows:
- ______________________________________Gravity, .degree.API 15-25Heavy Metals (Ni & V), ppm 40-801050.degree.F.+, Wt. % 25-40Asphaltenes (C.sub.5 insoluble), Wt. % 5-15Con Carbon, Wt. % 5-10______________________________________
- 23. The process of claim 18 wherein the product of the reaction is characterized as follows:
- ______________________________________Gravity, .degree.API 18-30Heavy Metals (Ni & V), ppm <501050.degree.F.+, Wt. % 5-30Asphaltenes (C.sub.5 insoluble), Wt. % <3Con Carbon, Wt. % <5______________________________________
- 24. The process of claim 18 wherein the product of the reaction is characterized as follows:
- ______________________________________Gravity, .degree.API 20-28Heavy Metals (Ni & V), ppm <51050.degree.F.+, Wt. % 10-25Asphaltenes (C.sub.5 insoluble), Wt. % <1Con Carbon, Wt. % <3______________________________________
- 25. The process of claim 18 wherein the conditions of the reaction are characterized as follows:
- ______________________________________Temperature, .degree.F. (E.I.T.) Start-of-Run 600 End-of-Run 850Pressure, Psi 2000-10,000Hydrogen Rate, SCF/B 3000-20,000Space Velocity, LHSV 0.25-5.0______________________________________
- 26. The process of claim 18 wherein the conditions of the reaction are characterized as follows:
- ______________________________________Temperature, .degree.F. (E.I.T.) Start-of-Run 650 End-of-Run 775Pressure, Psi 2000-5000Hydrogen Rate, SCF/B 3000-10,000Space Velocity, LHSV 0.25-2.0______________________________________
- 27. The process of claim 18 wherein the catalyst is of particle size diameter ranging from about 1/500 to 1/8 inch and characterized as follows:
- ______________________________________ Distribution of Pore Diameters______________________________________ 0-50A <1% 100-200A >70% -300A <1%______________________________________
- 28. The process of claim 1 wherein the Group IVA metal of the catalyst is germanium.
- 29. The process of claim 18 wherein the Group IVA metal of the catalyst is germanium.
RELATED APPLICATION
This is a continuation-in-part of application Ser. No. 440,285, filed Feb. 7, 1974, (now abandoned) which application is herewith incorporated by reference.
US Referenced Citations (17)
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
440285 |
Feb 1974 |
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