Process for hydrotreating heavy raw oils

Patent metadata

Field	Value
Publication number	US-9657236-B2
Application number	US-201313853195-A
Country	US
Kind code	B2
Filing date	Mar 29, 2013
Priority date	Mar 31, 2012
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

The present invention relates to a catalyst combination for hydrotreating raw oils and a process for hydrotreating raw oils with the catalyst combination. The catalyst combination comprises
one or both of at least one hydrogenation protection catalyst I and at least one hydrogenation demetalling catalyst I; at least one hydrogenation demetalling catalyst II; and at least one hydrogenation treatment catalyst III.

First claim

The invention claimed is:

1. A catalyst combination for hydrotreating raw oils, comprising:
one or both of at least one hydrogenation protection catalyst I and at least one hydrogenation demetalling catalyst I;
at least one hydrogenation demetalling catalyst II; and
at least one hydrogenation treatment catalyst III;
wherein a volume percentage of said hydrogenation demetalling catalyst II in said catalyst combination, based on a total volume of the catalyst combination, is 5-50%;
wherein said hydrogenation demetalling catalyst II comprises a shaped alumina support, the support has a pore volume measured by the mercury porosimetry of 0.9-1.2 mL/g, a specific surface area of 50-300 m 2 /g, a ratio of the volume of the pores having a diameter of 10 nm-30 nm to the total pore volume of 55-80%, and a ratio of the volume of the pores having a diameter of 300 nm-500 nm to the total pore volume of 18-35%.

2. The catalyst combination of claim 1 , wherein the catalyst combination comprises the hydrogenation protection catalyst I, the hydrogenation demetalling catalyst II and the hydrogenation treatment catalyst III, wherein, based on the total volume of the catalyst combination, a volume percentage of the hydrogenation protection catalyst I is 5-60%, the volume percentage of the hydrogenation demetalling catalyst II is 5-50%, and a volume percentage of the hydrogenation treatment catalyst III is 10-60%; the hydrogenation protection catalyst I has a bed voidage of 25-60%;
or
the catalyst combination comprises the hydrogenation demetalling catalyst I, the hydrogenation demetalling catalyst II and the hydrogenation treatment catalyst III, wherein, based on the total volume of the catalyst combination, a volume percentage of the hydrogenation demetalling catalyst I is 5-60%, a volume percentage of the hydrogenation demetalling catalyst II is 5-50%, and a volume percentage of the hydrogenation treatment catalyst III is 10-60%.

3. The catalyst combination of claim 1 , wherein the hydrogenation protection catalyst I comprises at least one hydrogenation active metal element and a support,
wherein the hydrogenation active metal element of the hydrogenation protection catalyst I comprises at least one metal element selected from the group consisting of the metal elements in the group VIII of the Periodic Table and at least one metal element selected from the group consisting of the metal elements in the group VIB of the Periodic Table,
wherein, calculated as oxide and based on a weight of the hydrogenation protection catalyst I, the weight percentage of the metal element in the group VIII of the Periodic Table is from more than zero to no more than 5 wt %,
wherein, calculated as oxide and based on a weight of the hydrogenation protection catalyst I, the weight percentage of the metal element in the group VIB of the Periodic Table is from more than zero to no more than 10 wt %, and
wherein the support has a crushing strength of 20-300 N/particle, a pore volume of 0.3-0.9 mL/g, and a specific surface area of from more than 30 m 2 /g to no more than 150 m 2 /g.

4. The catalyst combination of claim 1 , wherein the hydrogenation protection catalyst I has a support that is a titanium oxide-alumina shaped body, and the support of the hydrogenation protection catalyst I has an alumina weight percentage of 70-99 wt %, and a titanium oxide weight percentage of 1-30 wt %, based on a weight of the support.

5. The catalyst combination of claim 1 , wherein the hydrogenation demetalling catalyst I comprises a support that is a shaped alumina support and at least one hydrogenation active metal element,
wherein the shaped alumina support has a total pore volume of 0.8 mL/g-1.2 mL/g, a specific surface area of 90 m 2 /g-230 m 2 /g, an average pore diameter of 25 nm-35 nm, and a ratio of the volume of the pores having a diameter of 10 nm-60 nm to the total pore volume of 95%-99.8%,
wherein the at least one hydrogenation active metal element of the hydrogenation demetalling catalyst I comprises at least one metal element selected from the group consisting of the metal elements in the group VIII of the Periodic Table and at least one metal element selected from the group consisting of the metal elements in the group VIB of the Periodic Table,
wherein, calculated as oxide and based on a weight of the hydrogenation demetalling catalyst I, the weight percentage of the metal element in the group VIII of the Periodic Table is from more than zero to no more than 5 wt %; and
wherein, calculated as oxide and based on a weight of the hydrogenation demetalling catalyst I, the weight percentage of the metal element in the group VIB of the Periodic Table is from more than zero to no more than 15 wt %.

6. The catalyst combination of claim 1 , wherein the hydrogenation demetalling catalyst II comprises at least one hydrogenation active metal element, wherein the at least one hydrogenation active metal element of the hydrogenation demetalling catalyst II is a combination of at least one metal element selected from the group consisting of the metal elements in the group VIII of the Periodic Table and at least one metal element selected from the group consisting of the metal elements in the group VIB of the Periodic Table, and
wherein, calculated as oxide and based on a weight of the hydrogenation demetalling catalyst II, the weight percentage of the metal element in the group VIII of the Periodic Table is from more than zero to more than 3 wt %; and, calculated as oxide and based on the weight of the hydrogenation demetalling catalyst II, the weight percentage of the metal element in the group VIB of the Periodic Table is from more than zero to no more than 15 wt %.

7. The catalyst combination of claim 1 , wherein the hydrogenation treatment catalyst III comprises
at least one support selected from the group consisting of alumina, silica-alumina, and a combination thereof;
at least one hydrogenation active metal element selected from the group consisting of nickel, cobalt, molybdenum, tungsten and a combination thereof; and
optionally at least one auxiliary agent selected from the group consisting of fluorine, boron, phosphorus, and a combination thereof.

8. The catalyst combination of claim 1 , wherein said hydrogenation demetalling catalyst II comprises a shaped boron-containing alumina support, wherein the support has a boron weight percentage of 0.1-6 wt %, calculated based on B 2 O 3 .

9. The catalyst combination of claim 1 , wherein the support of hydrogenation demetalling catalyst II has a ratio of the volume of the pores having a diameter of 10 nm-30 nm to the total pore volume of 55-72%.

10. The catalyst combination of claim 9 , wherein the support of hydrogenation demetalling catalyst II has a ratio of the volume of the pores having a diameter of 10 nm-30 nm to the total pore volume of 59-66%.

11. The catalyst combination of claim 1 , wherein the support of hydrogenation demetalling catalyst II has a ratio of the volume of the pores having a diameter of 300 nm-500 nm to the total pore volume of 26-32%.

12. The catalyst combination of claim 6 , wherein the weight percentage of the metal element in the group VIII of the Periodic Table is from more than zero to no more than 0.8 wt %, and the weight percentage of the metal element in the group VIB of the Periodic Table is from more than zero to no more than 4 wt %.

13. The catalyst combination of claim 12 , wherein the weight percentage of the metal element in the group VIII of the Periodic Table is from more than 0.1 to no more than 0.6 wt %, and the weight percentage of the metal element in the group VIB of the Periodic Table is from more th

Assignees

• China Petroleum & Chem Corp
• Res Inst Petroleum Processing Sinopec
• Res Inst Of Pertroleum Proc Sinopec

Inventors

• Yang Qinghe
• Hu Dawei
• Sun Shuling
• Liu Jia
• Nie Hong
• Zhao Xinqiang
• Liu Xuefen
• Li Dadong
• Dai Lishun
• Shao Zhicai
• Liu Tao

Classifications

• B01J21/063

  Titanium; Oxides or hydroxides thereof · CPC title

• C10G2300/708

  Coking aspect, coke content and composition of deposits · CPC title

• B01J21/04

  Alumina · CPC title

• B01J23/888 Primary

  Tungsten · CPC title

• B01J23/883

  and nickel · CPC title