Modified Y-type molecular sieve and preparation method thereof, hydrocracking catalyst and preparation method thereof, and method for hydrocracking hydrocarbon oil

Patent metadata

Field	Value
Publication number	US-11179705-B2
Application number	US-201716768070-A
Country	US
Kind code	B2
Filing date	Nov 29, 2017
Priority date	Nov 29, 2017
Publication date	Nov 23, 2021
Grant date	Nov 23, 2021

Abstract

A modified Y-type molecular sieve contains 0.5-2 wt. % of Na 2 O based on the total amount of the modified Y-type molecular sieve. In the modified Y-type molecular sieve, the ratio between the total acid amount measured by pyridine and infrared spectrometry and total acid amount measured by n-butyl pyridine and infrared spectrometry is 1-1.2. The total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve is 0.1-1.2 mmol/g. The acid center sites of the molecular sieve of the modified Y-type molecular sieve are distributed in the large pore channels. The molecular sieve is used in the hydrocracking reaction process of a wax oil.

First claim

The invention claimed is:

1. A modified Y-type molecular sieve, comprising 0.5-2 wt. % of Na 2 O based on a total amount of the modified Y-type molecular sieve, wherein a ratio between a total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve and a total acid amount measured by n-butyl pyridine and infrared spectrometry of the modified Y-type molecular sieve is 1-1.2 and the total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve is 0.1-1.2 mmol/g.

2. The modified Y-type molecular sieve of claim 1 , wherein the modified Y-type molecular sieve contains 0.8-1.8 wt. % of Na 2 O based on the total amount of the modified Y-type molecular sieve, the ratio between the total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve and the total acid amount measured by n-butyl pyridine and infrared spectrometry of the modified Y-type molecular sieve is 1.02-1.1501, and the total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve is 0.2-1 mmol/g.

3. The modified Y-type molecular sieve of claim 2 , wherein the modified Y-type molecular sieve contains 1-1.5 wt. % of Na 2 O based on the total amount of the modified Y-type molecular sieve, the ratio between the total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve and the total acid amount measured by n-butyl pyridine and infrared spectrometry of the modified Y-type molecular sieve is 1.05-1.12, and the total acid amount measured by pyridine and infrared spectrometry of the modified Y-type molecular sieve is 0.3-0.8 mmol/g.

4. The modified Y-type molecular sieve of claim 1 , wherein the modified Y-type molecular sieve has a specific surface area of 500-900 m 2 /g, a pore volume of 0.28-0.7 mL/g, a relative crystallinity of 50%-130% a lattice parameter of 2.425-2.45 nm and a silica-alumina molar ratio within a range of (6-80):1.

5. The modified Y-type molecular sieve of claim 4 , wherein the modified Y-type molecular sieve has a specific surface area of 550-850 m 2 /g, a pore volume of 0.3-0.65 mL/g, a relative crystallinity of 60%-110%, a lattice parameter of 2.428-2.448 nm, and a silica-alumina molar ratio within a range of (8-60):1.

6. The modified Y-type molecular sieve of claim 5 , wherein the modified Y-type molecular sieve has a specific surface area of 600-750 m 2 /g, a pore volume of 0.35-0.6 mL/g, a relative crystallinity of 70%-100%, a lattice parameter of 2.43-2.445 nm, and a silica-alumina molar ratio within a range of (10-50):1.

7. A method for preparing the modified Y-type molecular sieve of claim 1 , comprising:
(1) pretreating a NaY molecular sieve to obtain a desodiumized and dealuminated Y-type molecular sieve;
(2) subjecting the desodiumized and dealuminated Y-type molecular sieve to sodium ion exchange to obtain a sodium-containing Y-type molecular sieve;
(3) immersing the sodium-containing Y-type molecular sieve in a macromolecular ammonium salt solution; and
(4) subjecting the sodium-containing Y-type molecular sieve obtained from step (3) to drying and calcination to obtain the modified Y-type molecular sieve.

8. The method of claim 7 , wherein step (2) comprises subjecting the desodiumized and dealuminated Y-type molecular sieve to reaction with an aqueous solution of NaNO 3 at a temperature of 40-80° C. for 1-4 h, and a mass fraction of NaNO 3 in the aqueous solution of NaNO 3 is 0.1-3 wt. %.

9. The method of claim 7 , wherein step (3) comprises immersing the sodium-containing Y-type molecular sieve in the macromolecular ammonium salt solution at a temperature of 40-80° C. for 2-6 h and the macromolecular ammonium salt is a benzyl quaternary ammonium salt.

10. The method of claim 7 , wherein the drying process in step (4) is carried out at a temperature of 100-150° C. for 1-4 h, and the calcination process is carried out at a temperature of 500-700° C. for 2-6 h.

11. The method of claim 7 , wherein the pretreatment process in step (1) comprises one process selected from ammonium ion exchange, hydrothermal dealumination, aluminum salt dealumination, fluorosilicate dealumination, acid dealumination, and a combination thereof.

12. The method of claim 11 , wherein the pretreatment process in step (1) comprises the following steps:
(a) subjecting the NaY molecular sieve and an ammonium salt aqueous solution to an ammonium ion exchange reaction to obtain a desodiumized Y-type molecular sieve;
(b) hydrothermally dealuminating the desodiumized Y-type molecular sieve to obtain a hydrothermally dealuminized product; and
(c) subjecting the hydrothermally dealuminized product to a chemical dealumination to prepare the desodiumized and dealuminated Y-type molecular sieve,
wherein the chemical dealumination is aluminum salt dealumination, fluorosilicate dealumination, or acid dealumination.

13. The method of claim 12 , wherein step (a) comprises carrying out exchanging process of the NaY molecular sieve with the ammonium salt aqueous solution at a temperature 60-120° C. for 1-3 h for 1-4 times to obtain the desodiumized Y-type molecular sieve, and the desodiumized Y-type molecular sieve contains less than 3 wt. % of Na 2 O,
wherein the NaY molecular sieve has a SiO 2 /Al 2 O 3 molar ratio within a range of (3-6):1 and a Na 2 O content of 6-12 wt. %, the ammonium salt is one or more selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, and ammonium oxalate, and a molar concentration of the aqueous solution of ammonium salt is 0.3-6 mol/L.

14. The method of claim 12 , wherein step (b) comprises contacting the desodiumized Y-type molecular sieve with water vapor at a temperature of 520-700° C. and at a pressure of 0.01-0.5 MPa for 1-6 h for 1-3 times.

15. The method of claim 12 , wherein step (c) comprises subjecting the hydrothermal dealuminization product to a constant temperature reaction with an aluminum salt solution, an ammonium fluorosilicate solution, or a nitric acid solution at a temperature of 50-120° C. for 0.5-3 h.

16. A hydrocracking catalyst comprising a silica-alumina carrier and a hydrogenation active metal, wherein, based on a total amount of the hydrocracking catalyst, a content of the silica-alumina carrier is 55-85 wt. %, and a content of the hydrogenation active metal is 15-45 wt. % on the basis of metal oxide, wherein the silica-alumina carrier contains the modified Y-type molecular sieve of claim 1 , and a content of the modified Y-type molecular sieve in the silica-alumina carrier is 5-90 wt. %.

17. The hydrocracking catalyst of claim 16 , wherein the hydrogenation active metal is selected from Group VIII and Group VI in the periodic table, and the hydrocracking catalyst contains, on the basis of metal oxide, 3-15 wt. % of the Group VIII metal and 10-40 wt. % of the Group VI metal, based on the total amount of the hydrocracking catalyst.

18. The hydrocracking catalyst of claim 17 , wherein the hydrogenation active metal is selected from Ni, Co, W, Mo, and mixtures thereof.

19. The method of claim 9 , wherein the benzyl quaternary ammonium salt is selected from benzyl tripropyl ammonium bromide, benzyl tributyl ammonium bromide, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, and mixtures thereof.

20. The method of claim 15 , wherein the aluminum salt solution, the ammonium fluorosilicate solution, or the nitric acid solution has a molar conce

Assignees

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

Inventors

• Liu Wei
• Guan Minghua
• Du Yanze
• Wang Fenglai
• Qin Bo
• Gao Hang

Classifications

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J2235/10

  Infrared [IR] · CPC title

• B01J29/00

  Catalysts comprising molecular sieves {(molecular sieves per se C01B)} · CPC title

• B01J29/08

  of the faujasite type, e.g. type X or Y · CPC title