Immobilization of vanadia deposited on sorbent materials during treatment of carbo-metallic oils

• US 4,513,093 A
• Filed: 03/30/1981
• Issued: 04/23/1985
• Est. Priority Date: 03/30/1981
• Status: Expired due to Fees

• Current Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Original Assignee: Ashland Oil, Inc. (Ashland Global Holdings, Inc.)
• Inventors: Hettinger, William P. Jr., Zandona, Oliver J., Beck, H. Wayne, Kovach, Stephen M., Carruthers, James D., Palmer, James L., Cornelius, Edward B.
• Primary Examiner(s): Dees, Carl F.
• Application Number:
  US06/277,752
• Time in Patent Office: 1,485 Days
• Field of Search: 252/455 R, 252/448, 252/454, 562/84, 562/521
• US Class Current: 502/84
• CPC Class Codes: C10G 25/00 Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 25/09 according to the "fluidised bed" technique
• CPC Class Codes: Y10S 502/521 Metal contaminant passivation

Abstract

A process is disclosed for the treatment of a hydrocarbon oil feed having a significant content of vanadium to provide a higher grade of oil products by contacting the feed under treatment conditions in a treatment zone with sorbent material containing a metal additive to immobilize vanadium compounds. Treatment conditions are such that coke and vanadium are deposited on the sorbent in the treatment zone. Coked sorbent is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the coke, and regenerated sorbent is recycled to the treatment zone for contact with fresh feed. The metal additive is present on the sorbent in an amount sufficient to immobilize the vanadium compounds in the presence of oxygen containing gas at the sorbent regeneration temperature. A sorbent composition disclosed comprises a kaolin clay containing the metal additive, which may be introduced into the clay during the treatment process or during sorbent manufacture. Metal additives include water soluble inorganic metal salts and hydrocarbon soluble organo-metallic compounds of select metals.

Claims

1. A sorbent material wherein the composition of said sorbent comprises kaolin clay, a titania gel in an amount in the range of about 1 to about 8 weight percent of sorbent, and a metal additive sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.

7. A composition of claim 1 wherein said sorbent comprises a clay and has a surface area below 50 m² /g and a pore volume of about 0.2 cc/g or greater.

11. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is in spherical form and ranges in size from 10-200 microns for use in a riser fluidized transfer zone.

12. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is in spherical form and ranges in size from greater than 200 microns to 1/4 inch for use in a moving bed treatment zone.

13. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is prepared from materials selected from the group consisting of bentonite, kaolin, montmorillonites, smectites, 2-layered lamellar silicates, mullite, pumice, silica, laterite or pillared inter-layered clays.

14. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a water soluble inorganic metal salt or a hydrocarbon soluble organo-metallic compound.

15. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive to immobilize vanadium compounds comprises Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Mi, In, Tl, Bi, Te, or an element in the lanthanide or actinide series, or an combination of two or more of said elements.

16. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive can react with vanadium compounds to form binary metal vanadates or mixtures of said vanadates or to form ternary or quaternary compounds, complexes, or alloys.

17. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is present in said sorbent in an amount in the range of about 1 to about 20 weight percent.

18. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is present in said sorbent in an amount in the range of about 1 to about 8 percent of said sorbent.

19. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said vanadium compounds deposited on said sodium include vanadium oxides, sulfides, sulfites, sulfates, or oxysulfates.

20. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is added to an aqueous slurry of the ingredients comprising said sorbent and said aqueous slurry containing said metal additive is spray dried.

21. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is added to a spray dried sorbent by impregnation techniques.

22. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is introduced into said sorbent by adding an aqueous solution of a metal salt or a hydrocarbon solution of an organo-metallic composition at any point in the processing cycle wherein said sorbent is used.

23. A composition of claims 1, 2, 3, 4, 5 or 6 wherein the concentration of vanadium deposited on said sorbent ranges from about 0.05 to about 5 weight percent of said sorbent based on the weight of said sorbent.

24. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a water soluble inorganic metal salt comprising a halide, nitrate, sulfite, sulfate, or carbonate or a combination of two or more of said salts.

25. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a hydrocarbon soluble metal compound comprised of an alcoholate, ester, phenolate, naphthenate, carboxylate, or dienyl sandwich compound or a combination of two or more of said compounds.

26. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is tetraisopropyl titanate.

27. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is titanium tetrachloride.

28. A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is methylcyclopentadienyl manganese tricarbonyl.

29. A composition of claim 1, 2, 3, 4, 5 or 6 wherein said metal additive is zirconia acetate.

2. A sorbent wherein the composition of said sorbent comprises a kaolin clay, an alumina gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.

8. A composition of claim 2 wherein said sorbent comprieses a clay and has a surface area below 50 m² /g and a pore volume of about 0.2 cc/g or greater.

3. A composition of matter for use as a sorbent comprising kaolin clay, a zirconia gel in an amount of the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.

9. A composition of claim 3 wherein said sorbent comprises a clay and has a surface area below 50 m² /g and a pore volume of about 0.2 cc/g or greater.

4. A composition of matter for use as a sorbent comprised of microspherical particles each containing clay, a titania gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.

10. A composition of claim 4, 5 and 6 wherein said sorbent comprises a clay and has a surface area below 50 m² /g and a pore volume of about 0.2 cc/g or greater.

5. A sorbent comprised of microspherical particles each containing a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, microspherical clay, and an alumina gel in an amount in the range of about 1 to about 8 weight percent.

6. A sorbent comprised of microspherical particles each containing a metal additive, in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, kaolin clay, a titania gel or a zirconia gel or a combination of titania gel and zirconia gel with an alumina gel, said gel material comprising about 1 to about 8 weight percent of said sorbent.