Hydrocracking catalyst, process for preparing the same and use thereof

Patent metadata

Field	Value
Publication number	US-9937485-B2
Application number	US-201615335586-A
Country	US
Kind code	B2
Filing date	Oct 27, 2016
Priority date	Jul 7, 2010
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

The present invention relates to a hydrocracking catalyst, a process for preparing the same and use thereof. The present catalyst comprises a cracking component and a hydrogenation component, wherein the cracking component comprises from 0 to 20 wt. % of a molecular sieve and from 20 wt. % to 60 wt. % of an amorphous silica-alumina, the hydrogenation component comprises at least one hydrogenation metal in a total amount of from 34 wt. % to 75 wt. % calculated by the mass of oxides, each amount is based on the total weight of the catalyst. The present catalyst is prepared by directly mixing an acidic component powder material with an impregnating solution, impregnating, filtering, drying, molding, and drying and calcining.

First claim

The invention claimed is:

1. A process for preparing a hydrocracking catalyst, comprising:
(1) conducting a neutralization and gelatinization reaction of an acidic aluminum salt solution with a mixed solution of alkaline sodium silicate and sodium aluminate at a temperature ranging from 20° C. to 80° C. and a pH value ranging from 4.0 to 9.5;
(2) adding at least one organosilicon source after gelatinization, wherein the at least one organosilicon source is chosen from organic silicon oils or silicon esters, the at least one organosilicon is added in an amount ranging from 5% to 40% relative to the total silicon amount present in an amorphous gelatinous silica-alumina dry powder, ageing at a temperature ranging from 60° C. to 80° C., a pH value ranging from 6.0 to 10.0, for an ageing time ranging from 60 minutes to 300 minutes to obtain a sol;
(3) filtering and washing the sol obtained in step (2); and
(4) drying and pulverizing a filter cake obtained in step (3) to obtain the amorphous gelatinous silica-alumina powder;
(5) optionally mixing the amorphous gelatinous silica-alumina with a molecular sieve, or an alumina, or both the molecular sieve and the alumina to form a first mixture;
(6) formulating an impregnating solution comprising at least one hydrogenation metal;
(7) impregnating the first mixture from step (5) or the amorphous gelatinous silica-alumina powder from step (4) with the impregnating solution from step (6); and
(8) filtering, drying, pulverizing, adding an adhesive or a peptizing agent, molding, drying, and calcining to obtain the hydrocracking catalyst.

2. The process according to claim 1 , wherein the hydrocracking catalyst comprises 0% to 20% by weight of the molecular sieve, 20% to 60% by weight of the amorphous silica-alumina, 34% to 75% by weight of the at least one hydrogenation metal (calculated based on the weight of metal oxides), and all the weight percentages are relative to a total weight of the hydrocracking catalyst.

3. The process according to claim 2 , wherein the hydrocracking catalyst has a specific surface area ranging from 150 m 2 /g to 350 m 2 /g, a pore volume ranging from 0.20 cm 3 /g to 0.50 cm 3 /g, and a product (M×S) of the weight percentage of the at least one hydrogenation metal (M) and the specific surface area (S) is equal to or higher than 100 m 2 /g.

4. The process according to claim 1 , wherein the at least one hydrogenation metal is chosen from W, Mo, Ni or Co.

5. The process according to claim 3 , wherein the M×S ranges from 100 to 170 m 2 /g.

6. The process according to claim 3 , wherein the M×S ranges from 120 to 160 m 2 /g.

7. The process according to claim 3 , wherein the weight percentage of the at least one hydrogenation metal is ranges from 40% to 60%.

8. The process according to claim 3 , wherein the specific surface area of the hydrocracking catalyst ranges from 160 m 2 /g to 300 m 2 /g, and the pore volume of the hydrocracking catalyst ranges from 0.30 cm 3 /g to 0.45 cm 3 /g.

9. The process according to claim 3 , wherein the hydrocracking catalyst further comprises alumina, clay, and/or at least one auxiliary agent chosen from phosphorous, fluorine, boron, titanium, or zirconium.

10. The process according to claim 1 , wherein the optional molecular sieve is chosen from Y-type molecular sieves, β molecular sieves, ZSM-5 molecular sieves, SAPO molecular sieves, or MCM-41 mesoporous molecular sieves.

11. The process according to claim 3 , wherein the amorphous silica-alumina has a specific surface area ranging from 400 m 2 /g to 650 m 2 /g, a pore volume ranging from 1.0 cm 3 /g to 2.0 cm 3 /g, a silica amount ranging from 20% to 80% by weight relative to the total weight of the amorphous silica-alumina, an average pore diameter ranging from 10 nm to 20 nm, and an infrared acid amount ranging from 0.3 mmol/g to 0.8 mmol/g.

12. The process according to claim 3 , wherein the amorphous silica-alumina has a specific surface area ranging from 400 to 550 m 2 /g, a pore volume ranging from 1.2 cm 3 /g to 1.6 cm 3 /g, a silica amount ranging from 30% to 65% by weight relative to the total weight of the at least one amorphous silica-alumina, and an average pore diameter ranging from 10 to 15 nm.

13. The process according to claim 1 , wherein the at least one hydrogenation metal is W or Mo.

14. The process according to claim 1 , where in the at least one hydrogenation metal is W or Ni.

15. A single-stage hydrocracking process, comprising contacting a vacuum gas oil is with a catalyst contains the hydrocracking catalyst produced according to the process of claim 1 in the presence of hydrogen gas.

16. The single-stage hydrocracking process according to claim 15 , wherein the hydrocracking reaction is conducted at a temperature ranging from 350° C. to 480° C., a pressure ranging from 8 MPa to 20 MPa, a liquid hourly volume space velocity of the vacuum gas oil ranging from 0.4 h −1 to 5 h −1 , and a volume ratio of hydrogen gas to the vacuum gas oil under the standard condition ranging from 100:1 to 3,000:1.

17. The single-stage hydrocracking process according to claim 15 , wherein the catalyst further comprises a hydrorefining catalyst in an amount ranging from 5% to 90% by volume relative to the volume of the hydrocracking catalyst disposed upstream or downstream from the hydrocracking catalyst.

18. The single-stage hydrocracking process according to claim 17 , wherein the hydrorefining catalyst is in an amount ranging from 30% to 80% by volume relative to the volume of the hydrocracking catalyst.

19. The single-stage hydrocracking process according to claim 15 , wherein the vacuum gas oil has a final boiling point temperature ranging from 500° C. to 630° C.

Assignees

• China Petroleum & Chem Corp
• Fushun Res Institute Of Petroleum And Petrochemicals Sinopec

Inventors

• Du Yanze
• Guan Minghua
• Wang Fenglai
• Liu Chang

Classifications

• B01J23/30

  Tungsten · CPC title

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01J37/009

  Preparation by separation, e.g. by filtration, decantation, screening · CPC title

• B01J37/0236

  Drying, e.g. preparing a suspension, adding a soluble salt and drying · CPC title

• B01J29/166

  Y-type faujasite · CPC title