Process and catalyst for the hydroconversion of a heavy hydrocarbon feedstock
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C01F-007/34
C01F-007/02
B01J-021/04
B01J-023/85
B01J-023/883
B01J-027/185
B01J-027/19
B01J-035/10
B01J-037/02
B01J-037/03
C01F-007/14
C10G-047/12
C10G-047/14
B01J-037/00
출원번호
US-0836451
(2010-07-14)
등록번호
US-8969239
(2015-03-03)
발명자
/ 주소
Ginestra, Josiane Marie-Rose
Ackerman, Russell Craig
Michel, Christian Gabriel
출원인 / 주소
Shell Oil Company
대리인 / 주소
Stewart, Charles W.
인용정보
피인용 횟수 :
3인용 특허 :
6
초록▼
A method of hydroprocessing a heavy hydrocarbon feedstock using a hydroprocessing catalyst having specific properties making it effective in the hydroconversion of at least a portion of the heavy hydrocarbon feedstock to lighter hydrocarbons. The hydroprocessing catalyst comprises a Group VIB metal
A method of hydroprocessing a heavy hydrocarbon feedstock using a hydroprocessing catalyst having specific properties making it effective in the hydroconversion of at least a portion of the heavy hydrocarbon feedstock to lighter hydrocarbons. The hydroprocessing catalyst comprises a Group VIB metal component (e.g., Cr, Mo, and W), a Group VIII metal component (e.g., Ni and Co) and, optionally, a potassium metal component that are supported on a support material comprising alumina. The alumina has novel physical properties that, in combination with the catalytic components, provide for the hydroprocessing catalyst. The hydroprocessing catalyst is particularly effective in the conversion of the heavy hydrocarbon feedstock. The alumina is characterized as having a high pore volume and a high surface area with a large proportion of the pore volume being present in the pores within a narrow pore diameter distribution about a narrowly defined range of median pore diameters. The support material preferably does not contain more than a small concentration of silica. The alumina component is preferably made by a specific method that provides for an alumina having the specific physical properties required for the hydroprocessing catalyst.
대표청구항▼
1. A support material suitable for use as a component of a catalyst composition for use in the hydroconversion of a heavy hydrocarbon feedstock, said support material consists essentially of: alumina; wherein said support material has a single-modal pore volume characteristic and comprises pores hav
1. A support material suitable for use as a component of a catalyst composition for use in the hydroconversion of a heavy hydrocarbon feedstock, said support material consists essentially of: alumina; wherein said support material has a single-modal pore volume characteristic and comprises pores having a median pore diameter in the range of from 110 Angstroms to 126 Angstroms, a pore size distribution width of less than 33 Angstroms, a pore volume that is related to said pore size distribution width such that said pore volume (PV) is greater than or equal to a value as determined by 0.7 +0.004 x (w) wherein (w) is said pore size distribution width in Angstroms of said support material, and wherein less than 5 percent of said pore volume is present in said pores having a pore diameter of greater than about 210 Angstroms and wherein said support material includes no more than a small concentration of silica. 2. A support material as recited in claim 1, wherein said small concentration of silica is less than 3 weight percent of said support material. 3. A support material as recited in claim 2, wherein said alumina is made by the method comprising the steps of: forming a first aqueous slurry of alumina by mixing, in a controlled fashion, a first aqueous sodium aluminate solution and a first aqueous solution of aluminum sulfate so as to thereby provide said first aqueous slurry having a first pH in the range of from about 9 to about 10 while maintaining a first aqueous slurry temperature in the range of from about 25 to 30° C.;thereafter, increasing said first aqueous slurry temperature to the range of from about 45 ° C. to 70° C. to provide a temperature adjusted first aqueous slurry;forming a second aqueous slurry, comprising alumina, by adding in a controlled fashion to said temperature adjusted first aqueous slurry a second aqueous solution of a second aluminum compound and a second aqueous alkaline solution so as to thereby provide said second aqueous slurry having a second pH in the range of from about 8.5 to 9 while maintaining a second aqueous slurry temperature in the range of from about 45° C. to 70° C.; andrecovering at least a portion of said alumina of said second aqueous slurry and utilizing the thus-recovered alumina as said alumina of said support material. 4. A support material as recited in claim 2, wherein the median pore diameter of the pores of the alumina support material is in the range of from 112 Angstroms to 122 Angstroms. 5. A support material as recited in claim 4, wherein the pore size distribution is less than 25 Angstroms. 6. A support material as recited in claim 2, wherein the median pore diameter of the pores of the alumina support material is in the range of from 114 Angstroms to 120 Angstroms. 7. A support material as recited in claim 6, wherein the pore size distribution is less than 20 Angstroms. 8. A method of making an alumina suitable for an alumina support material, said method comprising a two-step precipitation process which comprises the steps of: forming a first aqueous slurry of alumina by mixing, in a controlled fashion, a first aqueous sodium aluminate solution and a first aqueous solution of aluminum sulfate in such proportions so as to thereby provide said first aqueous slurry that contains a desired amount of from 25 weight percent to 35 weight percent of the total amount of the total alumina made by the two-step precipitation process, and having a first pH in the range of from about 9 to about 10while maintaining a first aqueous slurry temperature in the range of from about 25 to 30 ° C.;thereafter, when the first desired amount of alumina has been formed, increasing said first aqueous slurry temperature to the range of from about 45° C. to 75° C. to provide a temperature adjusted first aqueous slurry;forming a second aqueous slurry, comprising alumina, by adding in a controlled fashion to said temperature adjusted first aqueous slurry a second aqueous solution of a aluminum sulfate and a second aqueous sodium aluminate solution so as to thereby provide said second aqueous slurry that contains an alumina concentration of from 4 weight percent to 8 weight percent of the total weight of the alumina, based on the alumina precipitate being calcined, and having a second pH in the range of from about 8.5 to 9 while maintaining a second aqueous slurry temperature in the range of from about 50° C. to 65° C.;recovering at least a portion of said alumina of said second aqueous slurry to thereby provide an alumina precursor, comprising at least 90 weight percent pseudo-boehmite, and having a high mesopore volume and a surface area exceeding 200 m2/g; andmixing said alumina precursor with water and a dilute acid to form a paste having a pH in the range of from about 5 to about 9 and forming said paste into a particle and calcining said particle to thereby provide an alumina support material, which comprises at least 90 weight percent gamma alumina and less than 3 weight percent silica, and wherein said alumina support material has a single-modal pore volume distribution characteristic, pores having a median pore diameter in the range of from 110 Angstroms to 126 Angstroms, a pore size distribution width of less than 33 Angstroms, a pore volume that is related to said pore size distribution width such that said pore volume (PV) is greater than or equal to a value as determined by 0.7 +0.004 x (w) wherein (w) is said pore size distribution width in Angstroms of said alumina support material, wherein less than 5 percent of said pore volume is present in said pores having a pore diameter of greater than about 210 Angstroms. 9. A method as recited in claim 8, further comprising: incorporating a hydrogenation component into said heat treated shaped particle to provide a hydroconversion catalyst, wherein said hydrogenation component is selected from the group of compounds consisting of Group VIII metal components, Group VIB metal components, phosphorous components and any combination thereof. 10. A method as recited in claim 8, wherein the pH of the paste is in the range of from 6 to 8. 11. A method of making a composition, said method comprising a two-step precipitation process which comprises the steps of: forming a first aqueous slurry of alumina by mixing, in a controlled fashion, a first aqueous sodium aluminate solution and a first aqueous solution of aluminum sulfate so as to thereby provide said first aqueous slurry that contains a desired amount of from 25 weight percent to 35 weight percent of the total amount of the total alumina made by the two-step precipitation process, and having a first pH in the range of from about 9 to about 10 while maintaining a first aqueous slurry temperature in the range of from about 20 to 40 ° C.;thereafter, increasing said first aqueous slurry temperature to the range of from about 45° C. to 70° C. to provide a temperature adjusted first aqueous slurry;forming a second aqueous slurry, comprising alumina, by adding in a controlled fashion to said temperature adjusted first aqueous slurry a second aqueous solution of aluminum sulfate and a second aqueous sodium aluminate solution so as to thereby provide said second aqueous slurry that contains an alumina concentration of from 4 weight percent to 8 weight percent of the total weight of the alumina, based on the alumina precipitate being calcined, and having a second pH in the range of from about 8.5 to 9 while maintaining a second aqueous slurry temperature in the range of from about 45° C. to 70° C.;recovering at least a portion of said alumina of said second aqueous slurry to thereby provide a recovered alumina; and forming an alumina support material comprising said recovered alumina by mixing said recovered alumina with water and a dilute acid to thereby form a paste having a pH in the range of from about 5 to about 9;forming a shaped particle of said paste;drying and heat treating said shaped particle to thereby provide a heat treated shaped particle, which comprises at least 90 weight percent gamma alumina and less than 3 weight percent silica, and wherein said heat treated shaped particle has a single-modal pore volume distribution characteristic, pores having a median pore diameter in the range of from 110Angstroms to 126 Angstroms, a pore size distribution width of less than 33 Angstroms, a pore volume that is related to said pore size distribution width such that said pore volume (PV) is greater than or equal to a value as determined by 0.7 +0.004 x (w) wherein (w) is said pore size distribution width in Angstroms of said heat treated shaped particle, wherein less than 5percent of said pore volume is present in said pores having a pore diameter of greater than about 210 Angstroms. 12. A composition suitable for use as a component of an alumina support material, said composition consists essentially of: alumina capable of providing for said alumina support material having a single-modal pore volume distribution characteristic and comprising pores having a median pore diameter in the range of from 112 Angstroms to 122 Angstroms, a pore size distribution width of less than 33 Angstroms, a pore volume that is related to said pore size distribution width such that said pore volume (PV) is greater than or equal to the value as determined by 0.7 +0.004 x (w) wherein (w) is said pore size distribution width in Angstroms, wherein less than 5percent of said pore volume is present in said pores having a pore diameter of greater than about 210 Angstroms and wherein said alumina includes no more than a small concentration of silica. 13. A composition as recited in claim 12, wherein said small concentration of silica is less than 3 weight percent of said support material. 14. A composition as recited in claim 13, wherein said alumina is substantially entirely pseudo-boehmite. 15. A composition as recited in claim 14, wherein said alumina comprises at least 90 weight percent pseudo-boehmite. 16. A composition as recited in claim 15, wherein said alumina is made by the method comprising the steps of: forming a first aqueous slurry of alumina by mixing, in a controlled fashion, a first aqueous alkaline solution and a first aqueous solution of a first aluminum compound so as to thereby provide said first aqueous slurry having a first pH in the range of from about 9 to about 10 while maintaining a first aqueous slurry temperature in the range of from about 25 to 30 ° C.;thereafter, increasing said first aqueous slurry temperature to the range of from about 50 ° C. to 65° C. to provide a temperature adjusted first aqueous slurry;forming a second aqueous slurry, comprising said alumina, by adding in a controlled fashion to said temperature adjusted first aqueous slurry a second aqueous solution of a second aluminum compound and a second aqueous alkaline solution so as to thereby provide said second aqueous slurry having a second pH in the range of from about 8.5 to 9 while maintaining a second aqueous slurry temperature in the range of from about 50° C. to 65° C.;recovering at least a portion of said alumina of said second aqueous slurry.
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이 특허에 인용된 특허 (6)
Simpson Howard D. (Irvine CA) Abdo Suheil F. (Placentia CA), Hydrocarbon conversion process.
Ginestra, Josiane M.; Ackerman, Russell C.; Michel, Christian G., Method of making alumina having bimodal pore structure, and catalysts made therefrom.
Wakabayashi Motoyoshi (Omi JPX) Ono Takeo (Kawasaki JPX) Togari Osamu (Sagamihara JPX) Nakamura Munekazu (Kamakura JPX), Process for the production of alumina suitable for use as a catalyst carrier.
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