Hydrocracking catalyst, preparation method therefor and application thereof

Patent metadata

Field	Value
Publication number	US-11779909-B2
Application number	US-201917312923-A
Country	US
Kind code	B2
Filing date	Dec 12, 2019
Priority date	Dec 13, 2018
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

Abstract

Disclosed is a hydrocracking catalyst, a preparation method and an application thereof. The catalyst comprises a carrier, silicon dioxide and active ingredients loaded on the carrier, wherein the carrier comprises Y molecular sieves and SAPO-34 molecular sieves. The preparation method of the hydrocracking catalyst comprises the following steps: (1) mixing materials comprising Y molecular sieves and SAPO-34 molecular sieves, and then subjecting the mixture to molding, drying and calcinating to obtain a carrier; (2) introducing silane and the active ingredients into the carrier prepared in the step (1), subsequently performing the drying and calcinating to prepare the hydrocracking catalyst. The catalyst prepared with the method can be used for hydrocracking reaction, thereby significantly increase yield of jet fuel.

First claim

The invention claimed is:

1. A hydrocracking catalyst comprising a carrier, silica and an active ingredient,
wherein:
the silica and the active ingredient are loaded on the carrier,
the carrier comprises one or more Y molecular sieves and SAPO-34 molecular sieve, and, based on a weight of the carrier, a content of the one or more Y molecular sieves is within a range of 2-35 wt %, and a content of the SAPO-34 molecular sieve is within a range of 2-25 wt %;
the active ingredient comprises VIB group metal and/or VIII group metal;
based on a weight of the catalyst, a content of silica loaded on the carrier is within a range of 0.5-5 wt %;
a content of the VIB group metal in terms of oxide is within a range of 10-25 wt %; and
a content of the VIII group metal in terms of oxide is within a range of 4-10 wt %.

2. The catalyst of claim 1 , wherein the silica and the active ingredient are jointly distributed on an outer surface of the carrier and an inner surface of a pore channel of the carrier.

3. The catalyst of claim 1 , wherein the one or more Y molecular sieves has a molar ratio of SiO 2 /Al 2 O 3 within a range of 25-150, a specific surface area within a range of 550-1,000 m 2 /g, and a total pore volume within a range of 0.3-0.6 mL/g.

4. The catalyst of claim 1 , wherein the SAPO-34 molecular sieve has a molar ratio of SiO 2 /Al 2 O 3 within a range of 0.05-0.5, a specific surface area within a range of 200-800 m 2 /g, and a total pore volume within a range of 0.3-0.6 mL/g.

5. The catalyst of claim 1 , wherein the carrier further comprises a binder, and a content of the binder in the carrier is within a range of 15-85 wt %.

6. The catalyst of claim 1 , wherein the catalyst has a specific surface area within a range of 120-500 m 2 /g, a pore volume within a range of 0.30-0.65 mL/g, and a pore volume of pores having a diameter of 4-10 nm accounts for 65-95% of a total pore volume of the catalyst.

7. A preparation method of a hydrocracking catalyst, comprising:
(1) subjecting a material comprising one or more Y molecular sieves and SAPO-34 molecular sieve to molding, drying and calcinating to obtain a carrier;
(2) introducing silane and an active ingredient into the carrier prepared in the step (1) to form a mixture, wherein the active ingredient comprises VIB group metal and/or VIII group metal; and
(3) drying and calcinating the mixture obtained in the step (2).

8. The method of claim 7 , wherein the material in step (1) further comprises a binder or a precursor thereof, or the binder or the precursor thereof is mixed with the one or more Y molecular sieves and SAPO-34 molecular sieve during molding.

9. The method of claim 7 , wherein the material in the step (1) further comprises microcrystalline cellulose, and a content of the microcrystalline cellulose in the material is within a range of 0.2-6 wt %.

10. The method of claim 7 , wherein the drying conditions in the step (1) comprise a drying temperature within a range of 60-180° C., and a drying time within a range of 0.5-20 hours; and
the calcinating conditions in the step (1) comprise a calcinating temperature within a range of 350-750° C., and a calcinating time within a range of 0.5-20 hours.

11. The method of claim 7 , wherein the one or more Y molecular sieves has a molar ratio of SiO 2 /Al 2 O 3 within a range of 25-150, a specific surface area within a range of 550-1,000 m 2 /g, and a total pore volume within a range of 0.3-0.6 mL/g; and
the SAPO-34 molecular sieve has a molar ratio of SiO 2 /Al 2 O 3 within a range of 0.05-0.5, a specific surface area within a range of 200-800 m 2 /g, and a total pore volume within a range of 0.3-0.6 mL/g.

12. The method of claim 7 , wherein the silane in step (2) is one or more selected from the group consisting of aminosilane, alkylsilane, and sulfur-containing silane.

13. The method of claim 7 , wherein in the step (2), the active ingredient and the silane are introduced simultaneously or separately.

14. The method of claim 13 , wherein the active ingredient or the silane is introduced by impregnation in an aqueous solution.

15. The method of claim 7 , wherein in step (3), the drying temperature is within a range of 60-200° C., and the drying time is within a range of 0.5-20 hours; the calcinating temperature is within a range of 300-500° C., and the calcinating time is within a range of 0.5-20 hours.

16. A process for producing jet fuel, comprising contacting a heavy feedstock oil under hydrocracking conditions with the hydrocracking catalyst in claim 1 .

17. The process of claim 16 , wherein the hydrocracking conditions comprise a reaction temperature within a range of 340-430° C., a hydrogen partial pressure within a range of 5-20 Mpa, a hydrogen-oil volume ratio within a range of 500-2000:1, and a liquid hourly space velocity within a range of 0.5-1.8 h −1 .

18. The catalyst of claim 1 , wherein:
based on the weight of the carrier, the content of the one or more Y molecular sieves is within a range of 8-25 wt %, and the content of the SAPO-34 molecular sieve is within a range of 2-8 wt %;
the VIB group metal is molybdenum (Mo) and/or tungsten (W), the VIII group metal is cobalt (Co) and/or nickel (Ni); and,
based on the weight of the catalyst, the content of silica loaded on the carrier is within a range of 1-4 wt %, the content of the VIB group metal in terms of oxide is within a range of 15-20 wt %, and the content of the VIII group metal in terms of oxide is within a range of 5-8 wt %.

19. The catalyst of claim 18 , wherein based on the weight of the carrier, the content of the one or more Y molecular sieves is within a range of 10-20 wt %, and the content of the SAPO-34 molecular sieve is within a range of 2.5-6 wt %; and based on the weight of the catalyst, the content of silica loaded on the carrier is within a range of 1.5-3 wt %.

20. The catalyst of claim 6 , wherein the catalyst has a specific surface area within a range of 170-300 m 2 /g, a pore volume within a range of 0.35-0.60 mL/g and a pore volume of pores having a diameter of 4-10 nm accounts for 70-90% of a total pore volume of the catalyst.

Assignees

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

Inventors

• Tang Zhaoji
• Du Yanze
• Fan Hongfei
• Wang Jifeng
• Yu Zhengmin
• Sun Xiaoyan

Classifications

• B01J29/85 Primary

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01J6/001

  Calcining · CPC title

• B01J21/08

  Silica · CPC title

• B01J29/14

  Iron group metals or copper · CPC title

• B01J29/146

  Y-type faujasite · CPC title