HYDROCARBON-SOLUBLE, BIMETALLIC CATALYST PRECURSORS AND METHODS FOR MAKING SAME

Abstract

Bimetallic catalyst precursors are manufactured from a plurality of molybdenum atoms and a plurality of atoms of a secondary transition metal (e.g., one or more of cobalt, iron, or nickel). The molybdenum atoms and the secondary transition metal atoms are each bonded with a plurality of organic anions (e.g., 2-ethyl hexanoate) to form a mixture of an oil-soluble molybdenum salt and an oil-soluble secondary transition metal salt. The molybdenum and/or the secondary transition metals are preferably reacted with the organic agent in the presence of a strong reducing agent such as hydrogen. To obtain this mixture of metal salts, an organic agent is reacted with the molybdenum at a temperature between about 100° C. and about 350° C. The secondary transition metal is reacted with the organic agent at a different temperature, preferably between 50° C. and 200° C. The metal salts are capable of forming a hydroprocessing metal sulfide catalyst in heavy oil feedstocks.

Description

Claims

1. A bimetallic catalyst precursor suitable for forming a molybdenum sulfide catalyst in situ for use in hydrocracking heavy oil, comprising: a molybdenum salt comprising a plurality of molybdenum atoms, each bonded to a plurality of organic anions; anda secondary transition metal salt comprising a plurality of transition metal atoms other than molybdenum, each metal atom being bonded to a plurality of organic anions, wherein the weight ratio of the molybdenum to the secondary transition metal is between about 98:1 and about 1:10.

2. A bimetallic catalyst precursor as in claim 1, wherein the weight ratio of the molybdenum to the secondary transition metal is between about 95:1 and about 1:5.

3. A bimetallic catalyst precursor as in claim 1, wherein the weight ratio of the molybdenum to the secondary transition metal is between about 10:1 and about 1:1.

4. A bimetallic catalyst precursor as in claim 1, wherein the weight ratio of the molybdenum to the secondary transition metal is between about 8:1 and about 2:1.

5. A bimetallic catalyst precursor as in claim 1, wherein the secondary transition metal comprises at least one of cobalt, nickel, iron, or manganese.

6. A bimetallic catalyst precursor as in claim 1, wherein the organic anions comprise carboxylate anions having 2 to 14 carbon atoms.

7. A bimetallic catalyst precursor as in claim 6, wherein the carboxylate anions are selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, 2-ethyl butanoic acid, 2-methyl pentanoic acid, 2-ethyl hexanoic acid, and combinations thereof.

8. A diluted bimetallic catalyst precursor comprising the bimetallic catalyst precursor of claim 1 and a diluent mixed therewith.

9. A method for making a bimetallic catalyst precursor for hydroprocessing heavy oil, comprising: (i) providing a plurality of molybdenum atoms and a plurality of secondary transition metal atoms, wherein the secondary transition metal atoms comprise one or more transition metals other than molybdenum;(ii) providing an organic agent comprising a plurality of organic molecules, each organic molecule having at least one functional group that is reactive to the molybdenum atoms and the secondary transition metal atoms;(iii) reacting the molybdenum atoms with a portion of the organic agent at a temperature greater than about 100° C. to yield a hydrocarbon-soluble molybdenum salt; and(iv) mixing the secondary transition metal with the molybdenum salt and reacting the secondary transition metal with a second portion of the organic agent to yield a hydrocarbon-soluble secondary transition metal salt mixed with the molybdenum salt, wherein the reaction temperature during step (iv) is less than the reaction temperature during step (iii).

10. A method as in claim 9, wherein the secondary transition metal comprises at least one of cobalt, nickel, iron, or manganese.

11. A method as in claim 9, wherein the organic anions comprise carboxylate anions having 2 to 14 carbon atoms.

12. A method as in claim 9, wherein the carboxylate anions are selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, 2-ethyl butanoic acid, 2-methyl pentanoic acid, 2-ethyl hexanoic acid, and combinations thereof.

13. A method as in claim 9, wherein the molybdenum atoms are provided as molybdic acid.

14. A method as in claim 9, wherein the reaction temperature during step (iv) is at least 5° C. less than the reaction temperature during step (iii).

15. A method as in claim 9, wherein the reaction temperature during step (iv) is at least 10° C. less than the reaction temperature during step (iii).

16. A method as in claim 9, wherein the reaction temperature during step (iv) is at least 25° C. less than the reaction temperature during step (iii).

17. A method as in claim 9, wherein the reaction of the molybdenum atoms with the organic agent and/or the reaction of the secondary transition metal atoms with the organic agent is carried out in the presence of a reducing agent.

18. A method as in claim 17, wherein the reducing agent is hydrogen gas.

19. A hydroprocessing catalyst precursor manufactured according to the method of claim 9.

20. A heavy oil feedstock comprising the molybdenum catalyst precursor of claim 19 mixed therewith.

21. A method for making a bimetallic catalyst precursor for hydroprocessing heavy oil, comprising: providing a plurality of molybdenum atoms and a plurality of secondary transition metal atoms, wherein the secondary transition metal atoms comprise one or more transition metals other than molybdenum;providing an organic agent comprising a plurality of organic molecules having between 2 and 14 carbon atoms and at least one functional group that is reactive to the molybdenum atoms and the secondary transition metal atoms;reacting the molybdenum atoms with a portion of the organic agent at a temperature greater than about 100° C. to yield a hydrocarbon-soluble molybdenum salt;in a separate reaction, reacting the secondary transition metal atoms with a second portion of the organic agent at a temperature less than about 350° C. to yield a hydrocarbon-soluble cobalt salt; andmixing the hydrocarbon-soluble secondary transition metal salt with the hydrocarbon-soluble molybdenum salt to yield a bimetallic catalyst precursor.

22. A method as in claim 21, wherein the secondary transition metal comprises at least one of cobalt, nickel, iron, or manganese.

23. A method as in claim 21, wherein the molybdenum salt is mixed with the secondary transition metal salt at a temperature below about 100° C.

24. A method as in claim 21, wherein the organic molecules comprise a carboxylic acid functional group.

25. A method as in claim 21, wherein the organic molecules are selected from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, 2-ethyl butanoic acid, 2-methyl pentanoic acid, 2-ethyl hexanoic acid, and combinations thereof.

26. A method as in claim 21, wherein the molybdenum atoms are provided as molybdic acid.

27. A method as in claim 21, wherein the reaction of the molybdenum atoms with the organic agent and/or the reaction of the secondary transition metal atoms with the organic agent is carried out in the presence of a reducing agent.

28. A method as in claim 27, wherein the reducing agent is hydrogen gas.

29. A hydroprocessing catalyst manufactured according to the method of claim 28.

30. A heavy oil feedstock comprising the molybdenum catalyst precursor of claim 29 mixed therewith.