Catalyst and process for the manufacture of ultra-low sulfur distillate product
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-027/19
C10G-045/12
B01J-023/882
B01J-023/883
B01J-027/185
B01J-035/10
B01J-037/00
B01J-037/04
C01G-045/08
출원번호
US-0932471
(2013-07-01)
등록번호
US-8883673
(2014-11-11)
발명자
/ 주소
Bhan, Opinder Kishan
출원인 / 주소
Shell Oil Company
대리인 / 주소
Stewart, Charles W.
인용정보
피인용 횟수 :
1인용 특허 :
9
초록▼
Described is a catalyst and process useful in the hydrodesulfurization of a distillate feedstock to manufacture a low-sulfur distillate product. The catalyst comprises a calcined mixture of inorganic oxide material, a high concentration of a molybdenum component, and a high concentration of a Group
Described is a catalyst and process useful in the hydrodesulfurization of a distillate feedstock to manufacture a low-sulfur distillate product. The catalyst comprises a calcined mixture of inorganic oxide material, a high concentration of a molybdenum component, and a high concentration of a Group VIII metal component. The mixture that is calcined to form the calcined mixture comprises molybdenum trioxide in the form of finely divided particles, a Group VIII metal compound, and an inorganic oxide material. The catalyst is made by mixing the aforementioned starting materials and forming therefrom an agglomerate that is calcined to yield the calcined mixture that may be used as the catalyst or catalyst precursor.
대표청구항▼
1. A composition for use as a distillate hydrodesulfurization catalyst in the manufacture of an ultra-low sulfur distillate product, wherein said composition comprises: a calcined mixture made by calcining a co-mulled mixture comprising an inorganic oxide material, molybdenum trioxide in the form of
1. A composition for use as a distillate hydrodesulfurization catalyst in the manufacture of an ultra-low sulfur distillate product, wherein said composition comprises: a calcined mixture made by calcining a co-mulled mixture comprising an inorganic oxide material, molybdenum trioxide in the form of finely divided particles having a maximum dimension of less than 150 μm, and a Group VIII metal compound selected from the group consisting of a nickel compound, a cobalt compound and a combination thereof, wherein said calcined mixture has a molybdenum content in the range of from 10 weight percent to 22 weight percent with the weight percent being based upon the molybdenum as metal and the total weight of said calcined mixture, and a Group VIII metal content in the range of from 3 weight percent to 12 weight percent with the weight percent being based upon the Group VIII metal in its elemental form and the total weight of said calcined mixture, wherein said calcined mixture further comprises a promoter component selected from the group of phosphorous compounds, wherein said calcined mixture has a mean pore diameter in the range of from 50 angstroms to 100 angstroms, and wherein said calcined mixture has less than or equal to 66.14% of the total pore volume contained in pores of 150 angstroms or less in diameter. 2. A composition as recited in claim 1, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 60 Å to 95 Å. 3. A composition as recited in claim 2, wherein said calcined mixture has a surface area that exceeds 250 m2/g. 4. A composition as recited in claim 3, wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 50 to 90 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina. 5. A composition as recited in claim 4, wherein said molybdenum content is in the range of from 10 weight percent to 20 weight percent, wherein said Group VIII metal content is in the range of from 4 weight percent to 11 weight percent, and wherein said Group VIII metal component is selected from the group compounds consisting of nickel compounds and cobalt compounds. 6. A composition as recited in claim 5, wherein said molybdenum content is in the range of from 12 weight percent to 16 weight percent, as metal. 7. A composition as recited in claim 6, wherein said calcined mixture has a surface area that exceeds 300 m2/g. 8. A composition as recited in claim 7, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 70 Å to 90 Å. 9. A composition as recited in claim 8, wherein at least 50 percent of particulate molybdenum trioxide has a maximum dimension in the range from 2 to 15 μm. 10. A composition as recited in claim 9, wherein said co-mulled mixture contains a substantial absence of less than 0.5 weight percent, based on the total dry weight of said mixture, of a molybdenum compound in a form other than as molybdenum trioxide. 11. A composition as recited in claim 1, wherein said molybdenum trioxide of said mixture is in a finely divided state of particulate molybdenum trioxide either as a finely divided powdered solid or as a suspension wherein said particulate molybdenum trioxide has a maximum dimension of less than 100 μm. 12. A composition as recited in claim 11, wherein said co-mulled mixture contains a substantial absence of less than 2 weight percent, based on the total dry weight of said mixture, of a molybdenum compound in a form other than as molybdenum trioxide. 13. A composition as recited in claim 12, wherein said calcined mixture has a surface area that exceeds 275 m2/g; wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 55 to 88 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina; wherein said molybdenum content is in the range of from 12 weight percent to 18 weight percent, wherein said Group VIII metal content is in the range of from 4.5 weight percent to 10.5 weight percent; and wherein said co-mulled mixture contains a substantial absence of less than 1 weight percent, based on the total dry weight of said mixture, of a molybdenum compound in a form other than as molybdenum trioxide. 14. A composition as recited in claim 1, wherein said co-mulled mixture comprises a solid inorganic oxide starting material. 15. A composition for use as a distillate hydrodesulfurization catalyst in the manufacture of an ultra-low sulfur distillate product, wherein said composition comprises: a calcined mixture made by calcining a mixture comprising a substantial absence of a molybdenum compound that is in a form other than molybdenum trioxide and further comprising a co-mulled mixture of an inorganic oxide material, molybdenum trioxide in the form of finely defined particles having a maximum dimension of less than 150 μm, and a Group VIII metal compound selected from the group consisting of a nickel compound, a cobalt compound and a combination thereof, wherein said calcined mixture has a molybdenum content in the range of from 10 weight percent to 22 weight percent with the weight percent being based upon the molybdenum as metal and the total weight of said calcined mixture, and a Group VIII metal content in the range of from 3 weight percent to 12 weight percent with the weight percent being based upon the Group VIII metal in its elemental form and the total weight of said calcined mixture, wherein said calcined mixture further comprises a promoter component selected from the group of phosphorous compounds, and wherein said calcined mixture has a pore structure that includes a mean pore diameter in the range of from 50 angstroms to 100 angstroms, and wherein said calcined mixture has less than or equal to 66.14 percent of the total pore volume in pores having a diameter of 150 angstroms or less. 16. A composition as recited in claim 15, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 60 Å to 95 Å. 17. A composition as recited in claim 16, wherein said calcined mixture has a surface area that exceeds 250 m2/g. 18. A composition as recited in claim 17, wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 50 to 90 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina. 19. A composition as recited in claim 18, wherein said molybdenum content is in the range of from 10 weight percent to 20 weight percent, and wherein said Group VIII metal content is in the range of from 4 weight percent to 11 weight percent. 20. A composition as recited in claim 19, wherein said substantial absence of a molybdenum compound in a form other than as molybdenum trioxide is less than 2 weight percent, based on the total dry weight of said mixture. 21. A composition as recited in claim 20, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 70 Å to 90 Å, wherein said calcined mixture has a surface area that exceeds 275 m2/g; wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 55 to 88 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina; wherein said molybdenum content is in the range of from 12 weight percent to 18 weight percent, wherein said Group VIII metal content is in the range of from 4.5 weight percent to 10.5 weight percent, and wherein said Group VIII metal component is selected from the group compounds consisting of nickel compounds and cobalt compounds; and wherein in said mixture said substantial absence of a molybdenum compound in a form other than as molybdenum trioxide is less than 1 weight percent. 22. A composition for use as a distillate hydrodesulfurization catalyst in the manufacture of an ultra-low sulfur distillate product, wherein said composition comprises: a calcined mixture made by calcining a co-mulled mixture consisting essentially of an inorganic oxide material, molybdenum trioxide in the form of finely divided particles having a maximum dimension of less than 150 μm, and a Group VIII metal compound selected from the group consisting of a nickel compound and a cobalt compound, wherein said calcined mixture has a molybdenum content in the range of from 7 weight percent to 22 weight percent with the weight percent being based upon the molybdenum as metal and the total weight of said calcined mixture, and a Group VIII metal content in the range of from 3 weight percent to 12 weight percent with the weight percent being based upon the Group VIII metal in its elemental form and the total weight of said calcined mixture, wherein said calcined mixture has a mean pore diameter in the range of from 50 angstroms to 100 angstroms, and wherein said calcined mixture has less than or equal to 66.14 percent of the total pore volume in pores having a pore diameter of 150 angstroms or less. 23. A composition as recited in claim 22, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 65 Å to 95 Å. 24. A composition as recited in claim 23, wherein said calcined mixture has a surface area that exceeds 275 m2/g. 25. A composition as recited in claim 24, wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 50 to 90 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina. 26. A composition as recited in claim 25, wherein said molybdenum content is in the range of from 10 weight percent to 20 weight percent, wherein said Group VIII metal content is in the range of from 4 weight percent to 11 weight percent, and wherein said Group VIII metal component is selected from the group compounds consisting of nickel compounds and cobalt compounds and combinations thereof. 27. A composition as recited in claim 26, wherein said molybdenum trioxide of said mixture is in a finely divided state of particulate molybdenum trioxide either as a finely divided powdered solid or as a suspension wherein said particulate molybdenum trioxide has a maximum dimension of less than 100 μm. 28. A composition as recited in claim 27, wherein said mixture contains a substantial absence of less than 2 weight percent, based on the total dry weight of said mixture, of a molybdenum compound in a form other than as molybdenum trioxide. 29. A composition as recited in claim 28, wherein said mixture further consists essentially of a promoter component selected from the group of phosphorous compounds. 30. A composition as recited in claim 29, wherein said pore structure is such that the mean pore diameter of the pores of said calcined mixture is in the range of from 70 Å to 90 Å; wherein said calcined mixture has a surface area that exceeds 300 m2/g; wherein said inorganic oxide material in said calcined mixture is present in an amount in the range of from 55 to 88 weight percent of said calcined mixture and said inorganic oxide material is selected from the group consisting of alumina, silica and silica-alumina; wherein said molybdenum content is in the range of from 12 weight percent to 18 weight percent, wherein said Group VIII metal content is in the range of from 4.5 weight percent to 10.5 weight percent, and wherein said Group VIII metal component is selected from the group compounds consisting of nickel compounds and cobalt compounds; wherein said molybdenum trioxide of said mixture is in a finely divided state of particulate molybdenum trioxide either as a finely divided powdered solid or as a suspension wherein said particulate molybdenum trioxide has a maximum dimension of less than 150 μm; and wherein said mixture contains a substantial absence of less than 1 weight percent, based on the total dry weight of said mixture, of a molybdenum compound in a form other than as molybdenum trioxide.
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이 특허에 인용된 특허 (9)
Simpson Howard D. (Irvine CA) Skripek Milan (Fullerton CA), Demetallation catalyst.
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