Hydrocarbon-soluble, bimetallic catalyst precursors and methods for making same
View Patent ↗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.
1. 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, wherein at least a portion of the secondary transition metal atoms form precipitated metal if heated together with an organic agent at or above a precipitation temperature for the secondary transition metal atoms;
(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 range from about 100° C. to about 300° C. to yield a hydrocarbon-soluble molybdenum salt; and
(iv) mixing the secondary transition metal atoms with the molybdenum salt and reacting the secondary transition metal atoms with a second portion of the organic agent to yield a hydrocarbon-soluble secondary transition metal salt mixed with the molybdenum salt and thereby form the bimetallic catalyst precursor, wherein the reaction temperature during step (iv) is less than the reaction temperature during step (iii) and also less than the precipitation temperature for the secondary transition metal atoms so that the secondary transition metal atoms preferentially react with the organic agent to form the hydrocarbon-soluble secondary transition metal salt rather than precipitated metal.
2. A method as in claim 1 , the bimetallic catalyst precursor comprising:
a molybdenum salt comprising a plurality of molybdenum atoms, each bonded to a plurality of organic anions; and
a 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 atoms to the secondary transition metal atoms is between about 98:1 and about 1:10.
3. A method as in claim 1 , wherein the weight ratio of the molybdenum atoms to the secondary transition metal atoms is between about 95:1 and about 1:5.
4. A method as in claim 2 , wherein the weight ratio of the molybdenum atoms to the secondary transition metal atoms is between about 10:1 and about 1:1.
5. A method as in claim 2 , wherein the weight ratio of the molybdenum atoms to the secondary transition metal atoms is between about 8:1 and about 2:1.
6. A method as in claim 2 , wherein the secondary transition metal atoms comprise at least one of cobalt, nickel, iron, or manganese.
7. A method as in claim 2 , wherein the organic anions comprise carboxylate anions having 2 to 14 carbon atoms.
8. A method as in claim 7 , 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.
9. A method as in claim 2 , further comprising forming a diluted bimetallic catalyst precursor by mixing the bimetallic catalyst precursor with a diluent.
10. A method as in claim 1 , wherein the secondary transition metal atoms comprise at least one of cobalt, nickel, iron, or manganese.
11. A method as in claim 1 , wherein the organic anions comprise carboxylate anions having 2 to 14 carbon atoms.
12. A method as in claim 1 , 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 1 , wherein the molybdenum atoms are provided as molybdic acid.
14. A method as in claim 1 , 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 1 , 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 1 , 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 1 , 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 method as in claim 1 , further comprising dispersing the bimetallic catalyst precursor throughout a heavy oil feedstock to yield a conditioned feedstock composition.
20. 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, wherein at least a portion of the secondary transition metal atoms form precipitated metal if heated together with an organic agent at or above a precipitation temperature for the secondary transition metal atoms;
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 range from about 100° C. to about 300° 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 that is less that the molybdenum reaction temperature and that is less than the precipitation temperature for the secondary transition metal atoms so that the secondary transition metal atoms react with the organic agent to preferentially yield a hydrocarbon-soluble secondary transition metal salt rather than precipitated metal; and
mixing the hydrocarbon-soluble secondary transition metal salt with the hydrocarbon-soluble molybdenum salt to yield the bimetallic catalyst precursor.
21. A method as in claim 20 , wherein the secondary transition metal atoms comprise at least one of cobalt, nickel, iron, or manganese.
22. A method as in claim 20 , wherein the molybdenum salt is mixed with the secondary transition metal salt at a temperature below about 100° C.
23. A method as in claim 20 , wherein the organic molecules comprise a carboxylic acid functional group.
24. A method as in claim 20 , 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.
25. A method as in claim 20 , wherein the molybdenum atoms are provided as molybdic acid.
26. A method as in claim 20 , 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.
27. A method as in claim 26 , wherein the reducing agent is hydrogen gas.
28. A method as in claim 20 , further comprising dispersing the bimetallic catalyst precursor throughout a heavy oil feedstock to yield a conditioned feedstock composition.