NaY molecular sieve with an aluminum-rich surface and a process of preparing same

Patent metadata

Field	Value
Publication number	US-11518684-B2
Application number	US-201915733843-A
Country	US
Kind code	B2
Filing date	May 27, 2019
Priority date	May 28, 2018
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

A NaY molecular sieve with an aluminum-rich surface is prepared using a process that includes the steps of: a. mixing a directing agent and a first silicon source to obtain a first mixture, wherein the directing agent has a molar composition of Na2O:Al2O3:SiO2:H2O=(6-25):1:(6-25):(200-400); b. mixing the first mixture obtained in the step a with a second silicon source, an aluminum source and water to obtain a second mixture; c. carrying out hydrothermal crystallization on the second mixture obtained in the step b, and collecting a solid product. Calculated as SiO2, the weight ratio of the first silicon source to the second silicon source is 1:(0.01-12). The NaY molecular sieve has larger aluminum distribution gradient from the surface to the center of the particle than the conventional molecular sieve.

First claim

The invention claimed is:

1. A NaY molecular sieve having a surface that is aluminum-enriched, wherein an Al distribution index, D, of the molecular sieve satisfies: 1.01≤D≤10,
wherein:
D=Al (S)/Al (C),

Al (S) denotes an aluminum content on the surface and in a region 2 to 6 nm below the surface of the molecular sieve, as measured by an XPS method, and
Al (C) denotes an aluminum content of the molecular sieve as a whole, as measured by an XRF method.

2. The NaY molecular sieve according to claim 1 , having a molar ratio of SiO 2 /Al 2 O 3 on the surface of 1 to 10 and a molar ratio of SiO 2 /Al 2 O 3 in a bulk phase of 2 to 20, wherein the bulk phase refers to a portion of the NaY molecular sieve in a region from a center to a location 6 mm beneath the surface of the NaY molecular sieve.

3. The NaY molecular sieve according to claim 1 , having an Al content, calculated as Al 2 O 3 , of 18-26 wt %.

4. The NaY molecular sieve according to claim 1 , having an average particle size of 200-600 nm.

5. A process of preparing the NaY molecular sieve according to claim 1 , comprising the steps of:
preparing a directing agent having a molar composition Na 2 O:Al 2 O 3 :SiO 2 :H 2 O=(3-50):1: (3-50):(100-600);
a. mixing Gall the directing agent with a first silicon source to obtain a first mixture;
b. mixing the first mixture with a second silicon source, an aluminum source, and water to obtain a second mixture; and
c. carrying out hydrothermal crystallization on the second mixture and collecting a solid product,
wherein, calculated as SiO 2 , a weight ratio of the first silicon source to the second silicon source is 1:(0.001-20).

6. The process according to claim 5 , wherein the directing agent is prepared by a method comprising:
mixing an aluminum source with water glass to obtain a preliminary mixture;
carrying out dynamic aging and standing aging on the preliminary mixture; and
mixing the preliminary mixture with water to obtain the directing agent.

7. The process according to claim 5 , wherein, in step a, the first silicon source is at least one selected from the group consisting of water glass, colloidal silica, and silica sol.

8. The process according to claim 5 , wherein in step a, the first silicon source is a solid silicon source, and is mixed with the directing agent under stirring for 30-180 min.

9. The process according to claim 5 , wherein in step b, the second mixture has a molar composition of Na 2 O:Al 2 O 3 :SiO 2 :H 2 O=(2-6):1:(8-20):(200-400).

10. The process according to claim 5 , wherein in step b, the second silicon source is at least one selected from the group consisting of water glass, silica-alumina gel, and silica-alumina sol.

11. The process according to claim 5 , wherein in step b, the aluminum source is at least one selected from the group consisting of sodium metaaluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, and pseudoboehmite.

12. The process according to claim 5 , wherein element aluminum in the directing agent accounts for 3 to 30% of the element aluminum in the second mixture, calculated as element in mol.

13. The process according to claim 5 , wherein in step c, the hydrothermal crystallization is carried out at a temperature of 40-100° C. for a duration of 10-60 hours.

14. A process of preparing a modified Y molecular sieve, comprising steps of:
preparing the NaY molecular sieve according to the process of claim 5 ;
d. reacting the NaY molecular sieve with ammonium to reduce a sodium content, carrying out hydrothermal treatment, and dealuminization and silica supplementation to obtain the modified Y molecular sieve.

15. The process according to claim 14 , wherein reducing the sodium content in step d comprises:
treating the NaY molecular sieve with an ammonium salt solution having an ammonium ion concentration of 0.1-1.0 mol/L at a temperature from normal temperature to 100° C. and a liquid-solid weight ratio of (8 to 15):1 for a duration of 0.2 to 3 hours.

16. The process according to claim 15 , wherein the ammonium salt is at least one selected from the group consisting of ammonium nitrate, ammonium sulfate, ammonium chloride, and ammonium acetate.

17. The process according to claim 14 , wherein the hydrothermal treatment comprises: treating the NaY molecular sieve having a reduced sodium content for 1-3 hours in 100% of steam at a gauge pressure of 0.1-0.3 MPa and a temperature of 400-700° C.

18. The process according to claim 14 , wherein, in step d, the dealuminization and silica supplementation comprise: pulping the NaY molecular sieve obtained from the hydrothermal treatment to obtain a slurry with a liquid-solid weight ratio of (3-10):1, adding (NH 4 ) 2 SiF 6 to the slurry at a dosage of 10-60 g (NH 4 ) 2 SiF 6 per 100 g of the NaY molecular sieve, stirring the slurry at 80-120° C. for 0.5-5 hours, and recovering the product.

19. A modified Y molecular sieve obtained by the process according to claim 14 .

20. The modified Y molecular sieve according to claim 19 , having a molar ratio of SiO 2 /Al 2 O 3 in the bulk phase of 6 to 20.

21. The modified Y molecular sieve according to claim 19 , wherein, measured by a BET method, the modified Y molecular sieve has a total pore volume of not less than 0.38 cm 3 /g, and a secondary pore volume of not less than 0.06 cm 3 /g, and cell parameters are a=b=c=2.44-2.46 nm.

22. The modified Y molecular sieve according to claim 19 , wherein the modified Y molecular sieve has a sodium oxide content of not more than 0.1 wt % based on a total weight of the modified Y molecular sieve.

23. The NaY molecular sieve according to claim 1 , wherein 1.1≤D≤6.

24. The NaY molecular sieve according to claim 2 , wherein the molar ratio of SiO 2 /Al 2 O 3 on the surface is 1 to 10, and the molar ratio of SiO 2 /Al 2 O 3 in the bulk phase is 4 to 15.

25. The NaY molecular sieve according to claim 3 , wherein the Al content, calculated as Al 2 O 3 , is 21-25 wt %.

26. The process of preparing the NaY molecular sieve according to claim 5 , wherein the molar composition of the directing agent is Na 2 O:Al 2 O 3 :SiO 2 :H 2 O=(6-25):1:(6-25):(200-400), and
wherein, calculated as SiO 2 , the weight ratio of the first silicon source to the second silicon source is 1:(0.01-12).

27. The process according to claim 6 , wherein the dynamic aging comprises aging under stirring at a temperature of 15-60° C. for 1-100 hours, and the standing aging comprises aging by standing at a temperature of 15-60° C. for 0.5-100 hours.

28. The process according to claim 10 , wherein, in step b, the molar ratio of SiO 2 /Al 2 O 3 of the silica-alumina gel is 6-16 and the molar ratio of SiO 2 /Al 2 O 3 of the silica-alumina sol is 6-16.

29. The modified Y molecular sieve according to claim 20 , wherein the molar ratio of SiO 2 /Al 2 O 3 in the bulk phase is 10.0 to 13.0.

30. The modified Y molecular sieve according to claim 21 , wherein the modified Y molecular sieve has a total pore volume of not less than 0.40 cm 3 /g and a secondary pore volume of not less than 0.09 cm 3 /g.

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Fu Qiang
• Li Yongxiang
• Zhang Chengxi
• Hu Hexin
• Mu Xuhong
• Shu Xingtian

Classifications

• C01B39/24 Primary

  Type Y {(C01B39/205 takes precedence)} · CPC title

• B01J2229/36

  Steaming · CPC title

• B01J2229/16

  to increase the Si/Al ratio; Dealumination · CPC title

• C01P2006/12

  Surface area · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title