Hydrocarbon-soluble molybdenum catalyst precursors and methods for making same
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-031/00
B01J-021/02
B01J-023/00
B01J-021/04
B01J-023/02
출원번호
UP-0327085
(2006-01-06)
등록번호
US-7670984
(2010-04-21)
발명자
/ 주소
Wu, Zhihua
Zhou, Zhenhua
Zhou, Bing
출원인 / 주소
Headwaters Technology Innovation, LLC
대리인 / 주소
Workman Nydegger
인용정보
피인용 횟수 :
5인용 특허 :
78
초록▼
Hydrocarbon-soluble molybdenum catalyst precursors include a plurality of molybdenum cations that are each bonded with a plurality of organic anions to form an oil soluble molybdenum salt. A portion of the molybdenum atoms are in the 3+ oxidation state such that the plurality of molybdenum atoms has
Hydrocarbon-soluble molybdenum catalyst precursors include a plurality of molybdenum cations that are each bonded with a plurality of organic anions to form an oil soluble molybdenum salt. A portion of the molybdenum atoms are in the 3+ oxidation state such that the plurality of molybdenum atoms has an average oxidation state of less than 4+, e.g., less than about 3.8+, especially less than about 3.5+. The catalyst precursors can form a hydroprocessing molybdenum sulfide catalyst in heavy oil feedstocks. The oil soluble molybdenum salts are manufactured in the presence of a reducing agent, such as hydrogen gas, to obtain the molybdenum in the desired oxidation state. Preferably the reaction is performed with hydrogen or an organic reducing agent and at a temperature such that the molybdenum atoms are reduced to eliminate substantially all molybdenum oxide species.
대표청구항▼
What is claimed is: 1. A method of making a molybdenum catalyst precursor for hydrocracking heavy oil, comprising: providing a plurality of molybdenum atoms; providing an organic agent comprising a plurality of organic molecules having at least one functional group that is reactive with the molybde
What is claimed is: 1. A method of making a molybdenum catalyst precursor for hydrocracking heavy oil, comprising: providing a plurality of molybdenum atoms; providing an organic agent comprising a plurality of organic molecules having at least one functional group that is reactive with the molybdenum atoms; and reacting the plurality of molybdenum atoms with the organic agent in the presence of a reducing agent and in a molar ratio of molybdenum atoms to organic molecules of less than 1:4 to yield the molybdenum catalyst precursor comprised of a molybdenum salt having a plurality of molybdenum atoms with an average oxidation state of less than 4+. 2. A method as in claim 1, wherein the reducing agent comprises hydrogen or an organic reducing agent or both. 3. A method as in claim 1, wherein the plurality of organic anions comprises anions having between 2 and 14 carbon atoms. 4. A method as in claim 1, wherein the organic anion is a carboxylate anion. 5. A molybdenum catalyst precursor as in claim 4, 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. 6. A method as in claim 1, wherein the weight percent molybdenum in the molybdenum catalyst precursor is greater than about 15.5%. 7. A method as in claim 1, wherein the percent of molybdenum in the molybdenum catalyst precursor is greater than about 17%. 8. A method as in claim 1, further comprising reacting one or more additional metal salts comprising a transition metal other than molybdenum with the organic agent. 9. A method as in claim 1, further comprising forming a diluted molybdenum catalyst precursor by mixing the molybdenum catalyst precursor with a diluent. 10. A method as in claim 9, further comprising forming a blended heavy oil feedstock by mixing the diluted molybdenum catalyst precursor with a heavy oil feedstock. 11. A method as in claim 1, further comprising forming a blended heavy oil feedstock by mixing the molybdenum catalyst precursor with a heavy oil feedstock. 12. A method as in claim 1, wherein the reducing agent comprises hydrogen and optionally an organic reducing agent selected from the group consisting of methane, ethane, olefins, ethylene, propylene, aldehydes and formaldehyde. 13. A method as in claim 1, wherein the reaction between the plurality of molybdenum atoms and organic agent in the presence of the reducing agent is carried out at a temperature above about 100° C. such that water in the reaction product is removed as the reaction product is formed. 14. A method as in claim 1, wherein the reaction between the plurality of molybdenum atoms and organic agent in the presence of the reducing agent is performed at a temperature greater than 155° C. 15. A method as in claim 1, wherein the reaction mixture is purged with an inert gas prior to reducing with the reducing agent. 16. A method as in claim 1, wherein the average oxidation state of the molybdenum atoms of the molybdenum catalyst precursor is less than about 3.8+. 17. A method as in claim 1, wherein the average oxidation state of the molybdenum atoms of the molybdenum catalyst precursor is less than about 3.5+. 18. A method as in claim 1, wherein the molybdenum catalyst precursor forms a molybdenum salt having fewer complexed molecules that inhibit the molybdenum salt from forming a molybdenum sulfide compound than catalyst precursors manufactured without the use of the reducing agent. 19. A method of making a molybdenum catalyst precursor suitable for hydrocracking heavy oil, comprising: providing a plurality of molybdenum atoms; providing an organic agent comprising a plurality of organic molecules having at least one functional group that is reactive with the molybdenum atoms; reacting the plurality of molybdenum atoms with the organic agent in the presence of hydrogen and/or an organic reducing agent selected from the group consisting of methane, ethane, olefins, ethylene, propylene, aldehydes and formaldehyde at a temperature greater than about 90° C. to form a reaction product comprising a hydrocarbon-soluble molybdenum salt including a plurality of molybdenum atoms with an average oxidation state of less than 3.8+. 20. A method as in claim 19, wherein the organic agent 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. 21. A method as in claim 19, wherein the molybdenum atoms are reacted with the organic agent in the presence of the hydrogen and/or the organic reducing agent at a temperature greater than about 100° C. 22. A method as in claim 19, wherein the molybdenum atoms are reacted with the organic agent in the presence of the hydrogen and/or the organic reducing agent at a temperature greater than 155° C. 23. A method as in claim 19, wherein the molybdenum catalyst precursor forms a molybdenum salt having higher solubility than a catalyst precursor prepared without the presence of hydrogen. 24. A method of making a molybdenum catalyst precursor for hydrocracking heavy oil, comprising: providing a plurality of molybdenum atoms; providing an organic agent comprising a plurality of organic molecules having at least one functional group that is reactive with the molybdenum atoms; and reacting the plurality of molybdenum atoms with the organic agent in the presence of hydrogen at a temperature greater than about 100° C. and in a molar ratio of molybdenum atoms to organic molecules of less than about 1:3.5 to yield the molybdenum catalyst precursor comprised of a molybdenum salt having a plurality of molybdenum atoms with an average oxidation state of less than about 3.5. 25. A method as in claim 1, wherein the molar ratio of molybdenum atoms to organic molecules is less than about 1:3.5.
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이 특허에 인용된 특허 (78)
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