Structurally enhanced cracking catalysts

• US 20040220046A1
• Filed: 02/03/2004
• Published: 11/04/2004
• Est. Priority Date: 09/22/2000
• Status: Active Grant

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Ryu, J.Y., Brown, Stephen H., Stockwell, David M.
• Granted Patent: US 6,942,784 B2
• Time in Patent Office: Days
• US Class Current: 502/64
• CPC Class Codes: B01J 21/16 Clays or other mineral silicates
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 2229/64 in or on refractory materials
• CPC Class Codes: B01J 29/084 Y-type faujasite
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/0246 Coatings comprising a zeolite
• CPC Class Codes: C10G 11/05 Crystalline alumino-silicates, e.g. molecular sieves

Abstract

Zeolite microsphere FCC catalysts having a novel morphology comprising a porous matrix and crystallized zeolite freely coating the walls of the pores of the matrix. The catalysts are formed from microspheres containing a metakaolin and an alumina source other than kaolin having a high pore volume.

Claims

1. A zeolite FCC catalyst comprising zeolite crystals contained as a layer on the surface of a porous alumina-containing matrix, said zeolite-layered matrix arranged in a configuration to provide pores in which the zeolite layer is provided on the walls of the pores, said catalyst having a mercury porosity of greater than 0.27 cc/gm for pores of 40-20,000 Å

diameter and a crystallized zeolite content of at least 40 wt %.

17. The catalyst of claim 1, wherein said zeolite is zeolite Y.

18. The catalyst of claim 17 wherein said zeolite is crystallized in-situ on the surface of said matrix.

19. The catalyst of claim 1 which is substantially free of an added binder.

45. A method of cracking a hydrocarbon feed under FCC conditions, comprising contacting said hydrocarbon feed with the catalyst of claims 1, 2 or 28.

46. The method of claim 45, wherein said hydrocarbon feed and catalyst are contacted for a time of no more than 3 seconds.

47. The method of claim 45, wherein said catalyst and said hydrocarbon feed are contacted for a time of no more than 1 second.

48. The method of claim 45, wherein said catalyst has a mercury porosity of at least 0.27 cc/g for pores of 40-20,000 Å

diameter.

49. The method of claim 45, wherein said catalyst has a mercury porosity of at least 0.07 cc/gm for pores having a size of 600-20,000 Å

in diameter.

50. The method of claim 45, wherein said catalyst has a mercury porosity of at least 0.10 cc/gm for pores having a size of 600-20,000 Å

in diameter.

51. The method of claim 45, wherein said catalyst has a BET surface area of less than 500 m²/g.

52. The method of claim 45, wherein said catalyst has a BET surface area of less than 475 m²/g.

53. The method of claim 45, wherein said catalyst has a BET surface area of between 300-475 m²/g.

54. The method of claim 46, wherein said catalyst comprises 0.5 to 8 wt. % REO.

2. A zeolite FCC catalyst comprising zeolite crystals contained as a layer on the surface of a porous alumina-containing matrix derived essentially from an alumina source other than kaolin, said zeolite-layered matrix arranged in a configuration to provide pores in which the zeolite layer is provided on the walls of the pores, said catalyst having a mercury porosity of greater than 0.20 cc/gm for pores of 40-20,000 Å

diameter.

3. The catalyst of claim 2, wherein said zeolite is zeolite Y.

4. The catalyst of claim 2 having a mercury porosity of greater than 0.27 cc/gm for pores of 40-20,000 Å

diameter.

5. The catalyst of claim 2 having a mercury porosity of at least 0.30 cc/gm for pores of 40-20,000 Å

diameter.

6. The catalyst of claim 2 wherein said zeolite is crystallized in-situ on the surface of said matrix.

7. The catalyst of claim 2, wherein said porous matrix contains a modal distribution of pores characterized as a peak at a diameter of at least 600 Å

.

8. The catalyst of claim 2 which is substantially free of an added binder.

9. The catalyst of claim 7 having a mercury porosity of at least 0.07 cc/gm for pores of 600-20,000 Å

diameter.

10. The catalyst of claim 4 having a mercury porosity of at least 0.07 cc/gm for pores of 600-20,000 Å

diameter.

11. The catalyst of claim 2 having a mercury porosity of at least 0.10 cc/gm for pores of 600-20,000 Å

diameter.

12. The catalyst of claim 2 having a BET surface area of less than 500 m²/g.

13. The catalyst of claim 2 having a BET surface area of less than 475 m²/g.

14. The catalyst of claim 2 having a BET surface area of between about 300-450 m²/g.

15. The catalyst of claim 9 having a BET surface area of less than 500 m²/g.

16. The catalyst of claim 10 having a BET surface area of less than 500 m²/g.

20. The catalyst of claim 2 wherein said alumina source is derived from aluminum trihydrates.

21. The catalyst of claim 20 wherein said aluminum trihydrates include bayerite or gibbsite.

22. The catalyst of claim 2 wherein said alumina source comprises transitional aluminas.

23. The catalyst of claim 2 wherein said alumina source comprises aluminum monohydrates.

24. The catalyst of claim 23 wherein said aluminum monohydrates include boehmite or pseudoboehmite.

25. The catalyst of claim 2 wherein said alumina source comprises foamed alumina.

26. The catalyst of claim 22 wherein said alumina source comprises bauxite.

27. The catalyst of claim 2 wherein said alumina source comprises silica-alumina cogels.

28. A fluid catalytic cracking catalyst comprising microspheres containing in-situ crystallized Y-faujasite, and having a mercury porosity of greater than about 0.20 cc/g for pores having diameters in the range of 40-20,000 Å

, said microspheres comprising an alumina-matrix derived essentially from an alumina source other than kaolin.

29. The fluid catalytic cracking catalyst of claim 28, having a mercury porosity of at least about 0.27 cc/g for pores having diameters in the range of 40-20,000 Å

.

30. The fluid catalytic cracking catalyst of claim 28 containing 0-12% by weight rare earth oxides.

31. The fluid catalytic cracking catalyst of claim 28 having a mercury porosity of at lest 0.07 cc/gm for pores of 600-20,000 Å

diameter.

32. The fluid catalytic cracking catalyst of claim 28 having a mercury porosity of at lest 0.10 cc/gm for pores of 600-20,000 Å

diameter.

33. The fluid catalytic cracking catalyst of claim 28 having a BET surface area of less than 500 m²/g.

34. The fluid catalytic cracking catalyst of claim 28 having a BET surface area less than 475 m²/g.

35. The fluid catalytic cracking catalyst of claim 28 having a BET surface area in the range of about 300-450 m²/g.

36. The fluid catalytic cracking catalyst of claim 28 containing rare earth oxides in an amount of from about 0.5 to 12 wt. %.

37. The catalyst of claim 28 wherein said alumina source is derived from aluminum trihydrates.

38. The catalyst of claim 37 wherein said aluminum trihydrates include bayerite or gibbsite.

39. The catalyst of claim 28 wherein said alumina source comprises transitional aluminas.

40. The catalyst of claim 28 wherein said alumina source comprises aluminum monohydrates.

41. The catalyst of claim 40 wherein said aluminum monohydrates include boehmite or pseudoboehmite.

42. The catalyst of claim 28 wherein said alumina source comprises foamed alumina.

43. The catalyst of claim 28 wherein said alumina source comprises bauxite.

44. The catalyst of claim 28 wherein said alumina source comprises silica-alumina cogels.