Preparation of aluminosilicate zeolites

• US 5,558,851 A
• Filed: 09/20/1994
• Issued: 09/24/1996
• Est. Priority Date: 12/16/1992
• Status: Expired due to Term

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Miller, Stephen J.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): NOT, DEFINED
• Application Number:
  US08/309,216
• Time in Patent Office: 735 Days
• Field of Search: 423/700, 423/702, 423/704, 423/705, 423/706, 423/707, 423/708, 423/716, 502/66, 502/70, 502/71, 502/74, 502/77
• US Class Current: 423/702
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/06 Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• CPC Class Codes: B01J 29/068 Noble metals
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/44 Noble metals
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: B01J 29/7007 Zeolite Beta
• CPC Class Codes: B01J 29/7034 MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
• CPC Class Codes: B01J 29/7415 Zeolite Beta
• CPC Class Codes: B01J 29/86 Borosilicates; Aluminoborosilicates B01J29/005 takes precedence
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/04 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• CPC Class Codes: C01B 39/40 using at least one organic template directing agent
• CPC Class Codes: C01B 39/42 Type ZSM-12
• CPC Class Codes: C01B 39/48 using at least one organic template directing agent
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 5/325 of the platinum group
• CPC Class Codes: C07C 5/3337 of the platinum group
• CPC Class Codes: C10G 35/095 containing crystalline alumino-silicates, e.g. molecular sieves C10G35/065 takes precedence
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: Y10S 423/22 : MFI, e.g. ZSM-5. silicalite, LZ-241
• CPC Class Codes: Y10S 423/27 : Beta, e.g. NU-2
• CPC Class Codes: Y10S 423/33 : MTW, e.g. ZSM-12, NU-13, CZH-5, TPZ-3
• CPC Class Codes: Y10S 423/36 : MTT, e.g. ZSM-23, ISI-1, KZ-1, EU-1, EU-4, EU-13

Abstract

A method is disclosed for preparing a crystalline aluminosilicate zeolite from a reaction mixture containing only sufficient water so that the reaction mixture may be shaped if desired. In the method, the reaction mixture is heated at crystallization conditions and in the absence of an external liquid phase, so that excess liquid need not be removed from the crystallized material prior to drying the crystals.

Claims

1. A method for preparing a crystalline zeolite, said method comprising:

a. preparing a reaction mixture comprising at least one active source of a first oxide selected from the group consisting of an oxide of silicon, germanium or both, optionally at least one active source of a second oxide selected from the group consisting of an oxide of aluminum, boron, gallium, iron or a mixture thereof, an organic templating agent capable of forming said crystalline zeolite, and sufficient water to shape said mixture; and

b. heating said reaction mixture at crystallization conditions and in the absence of an added external liquid phase for sufficient time to form a crystallized material containing crystals of said zeolite, wherein said zeolite crystals have a first oxide/second oxide molar ratio greater than 12.

2. The method according to claim 1 wherein said reaction mixture has a water/first oxide molar ratio during crystallization of no greater than about 5.

3. The method of claim 2 wherein said reaction mixture during crystallization has a water/first oxide molar ratio between about 1 and about 4.

4. The method according to claim 1 wherein said zeolite has a constraint index of greater than 1.

5. The method according to claim 1 wherein said zeolite crystals within said crystallized material have a crystallite size of less than 10 microns.

6. The method according to claim 5 wherein said zeolite crystals within said crystallized material have a crystallite size of less than 1.0 micron.

7. The method according to claim 1 wherein said crystallized material comprises greater than about 50 weight percent crystalline zeolite.

8. The method according to claim 7 wherein said crystallized material comprises greater than about 90 weight percent crystalline zeolite.

9. The method according to claim 1 wherein the reaction mixture contains no added seed crystals.

10. The method according to claim 1 wherein the crystalline zeolite is ZSM-5.

11. The method according to claim 1 wherein the crystalline zeolite is beta zeolite.

12. The method according to claim 1 wherein the

crystalline zeolite is ZSM-12.

13. The method according to claim 1 wherein the crystalline zeolite is silicalite.

14. The method according to claim 1 wherein the crystalline zeolite is SSZ-35.

15. The method according to claim 1 wherein the crystalline zeolite is ZSM-23.

16. The method according to claim 1 wherein the crystalline zeolite is SSZ-32.

17. The method according to claim 1 wherein the crystalline zeolite is boron beta.

18. The method according to claim 1 wherein said reaction mixture has the following molar composition ranges:

space="preserve" listing-type="equation">SiO.sub.2 /Al.sub.2 O.sub.3 =12-∞

space="preserve" listing-type="equation">M.sup.+ /SiO.sub.2 =0-1

space="preserve" listing-type="equation">R/SiO.sub.2 =0.01-0.5

space="preserve" listing-type="equation">OH.sup.- /SiO.sub.2 =0.05-0.4

space="preserve" listing-type="equation">H.sub.2 O/SiO.sub.2 =0.5-5

wherein M⁺ is a alkali cation and R is a templating agent.

19. The method according to claim 18 wherein said reaction mixture has the following molar composition ranges:

space="preserve" listing-type="equation">SiO.sub.2 /Al.sub.2 O.sub.3 =12-∞

space="preserve" listing-type="equation">M.sup.+ /SiO.sub.2 =0.03-0.5

space="preserve" listing-type="equation">R/SiO.sub.2 =0.01-0.3

space="preserve" listing-type="equation">OH.sup.- /SiO.sub.2 =0.05-0.3

space="preserve" listing-type="equation">H2O/SiO.sub.2 =1-4

wherein M⁺ is a alkali cation and R is a templating agent.

20. The method according to claim 1 wherein said reaction mixture comprises at least one active source of alumina.

21. The method according to claim 20 wherein said zeolite crystals formed in the step of heating said reaction mixture have a silica/alumina molar ratio in the range of 12 to about 5000.

22. The method according to claim 1 wherein said reaction mixture further comprises at least one active source of a Group VIII metal.

23. The method according to claim 22 wherein said Group VIII metal is selected from platinum, palladium and a combination thereof.

24. The crystalline zeolite prepared by the method according to claim 23.

51. The method to claim 1 wherein said reaction mixture has a composition, in terms of mole ratios, falling within the following ranges:

space="preserve" listing-type="equation">YO.sub.2 /W.sub.2 O.sub.3 12-∞

space="preserve" listing-type="equation">M.sup.+ /YO.sub.2 0-1

space="preserve" listing-type="equation">R/YO.sub.2 0-0.5

space="preserve" listing-type="equation">OH/YO.sub.2 0.01-0.5

space="preserve" listing-type="equation">H.sub.2 O/YO.sub.2 0.5-5

wherein Y is silicon, germanium or both, W is aluminum, boron, gallium, iron, or a mixture thereof, M⁺ is an alkali metal ion, an R is a templating agent.

52. The method according to claim 51 wherein said reaction mixture has a composition, in terms of mole ratios, falling within the following ranges:

space="preserve" listing-type="equation">YO.sub.2 W.sub.2 O.sub.3 12-∞

space="preserve" listing-type="equation">M.sup.+ /YO.sub.2 0.04-0.7

space="preserve" listing-type="equation">R/YO.sub.2 0.01-0.3

space="preserve" listing-type="equation">OH/YO.sub.2 0.05-0.3

space="preserve" listing-type="equation">H.sub.2 O/YO.sub.2 1-4

wherein Y is silicon, germanium or both, W is aluminum, boron, gallium, iron, or a mixture thereof, M⁺ is an alkali metal ion, and R is a templating agent.

25. A method for preparing a shaped crystalline zeolite, said method comprising:

a. preparing a reaction mixture comprising at least one active source of a first oxide selected from the group consisting of an oxide of silicon, germanium or both, optionally at least one active source of a second oxide selected from the group consisting of an oxide of aluminum, boron, gallium, iron or a mixture thereof, an organic templating agent capable of forming said crystalline zeolite, and sufficient water to shape said mixture;

b. forming said reaction mixture into shaped particles; and

c. heating said shaped particles at crystallization conditions and in the absence of an added external liquid phase for sufficient time to form crystals of said zeolite within said shaped particles, wherein said zeolite crystals have a first oxide/second oxide molar ratio greater than 12.

26. The method according to claim 25 where said shaped particles have a water/first oxide molar ratio during crystallization of no greater than about 5.

27. The method of claim 26 wherein said shaped particles during crystallization have a water/first oxide mole ratio between about 1 and about 4.

28. The method according to claim 25 wherein said zeolite has a constraint index of greater than 1.

29. The method according to claim 25 wherein said zeolite crystals have a crystallite size of less than 10 microns.

30. The method according to claim 29 wherein said zeolite crystals have a crystallite size of less than 1.0 micron.

31. The method according to claim 25 wherein said shaped particles containing said crystallized zeolite comprise greater than about 50 weight percent crystalline zeolite.

32. The method according to claim 31 wherein said shaped particles containing said crystallized zeolite comprise greater than about 90 weight percent crystalline zeolite.

33. The method according to claim 25 wherein the reaction mixture contains no added seed crystals.

34. The method according to claim 25 wherein said crystalline zeolite is ZSM-5.

35. The method according to claim 25 wherein said crystalline zeolite is beta zeolite.

36. The method according to claim 25 wherein said crystalline zeolite is ZSM-12.

37. The method according to claim 25 wherein said crystalline zeolite is silicalite.

38. The method according to claim 25 wherein said crystalline zeolite is SSZ-35.

39. The method according to claim 25 wherein said crystalline zeolite is ZSM-23.

40. The method according to claim 25 wherein said crystalline zeolite is SSZ-32.

41. The method according to claim 25 wherein said crystalline zeolite is boron beta.

42. The method according to claim 25 wherein said reaction mixture has the following molar composition ranges:

space="preserve" listing-type="equation">SiO.sub.2 /Al.sub.2 O.sub.3 =12-∞

space="preserve" listing-type="equation">M.sup.+ /SiO.sub.2 =0-1

space="preserve" listing-type="equation">R/SiO.sub.2 =0.01-0.5

space="preserve" listing-type="equation">OH.sup.- /SiO.sub.2 =0.05-0.4

space="preserve" listing-type="equation">H2O/SiO.sub.2 =0.5-5

wherein M⁺ is a alkali metal cation and R is a templating agent.

43. The method according to claim 42 wherein said reaction mixture has the following molar composition ranges:

space="preserve" listing-type="equation">SiO.sub.2 /Al.sub.2 O.sub.3 =12-∞

space="preserve" listing-type="equation">M.sup.+ /SiO.sub.2 =0.03-0.5

space="preserve" listing-type="equation">R/SiO.sub.2 =0.01-0.3

space="preserve" listing-type="equation">OH.sup.- /SiO.sub.2 =0.05-0.3

space="preserve" listing-type="equation">H.sub.2 O/SiO.sub.2 =1-4

wherein M⁺ is a alkali metal cation and R is a templating agent.

44. The method according to claim 25 wherein the shaped crystalline zeolite is a spherical or cylindrical particle having a cross sectional diameter between about 1/64 inch and about 1/2 inch.

45. The method according to claim 42 wherein the shaped crystalline zeolite is a spherical or cylindrical particle having a cross sectional diameter between about 1/32 inch and about 1/4 inch in diameter.

46. The method according to claim 25 wherein said reaction mixture comprises at least one active source of alumina wherein the silica/alumina molar ratio in the reaction mixture is in the range of 12 to about 5000.

47. The method according to claim 25 wherein said zeolite crystals formed in the step of heating said reaction mixture have a silica/alumina molar ratio in the range of 12 to about 5000.

48. The method according to claim 25 wherein said reaction mixture further comprises at least one active source of a Group VIII metal.

49. The method according to claim 48 wherein said Group VIII metal is selected from platinum, palladium and a combination thereof.

50. The crystalline zeolite prepared by the method according to claim 49.