Method of making molecular sieve catalyst

• US 6,710,008 B2
• Filed: 01/17/2002
• Issued: 03/23/2004
• Est. Priority Date: 01/17/2002
• Status: Expired due to Term

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Chang, Yun-Feng, Clem, Kenneth R., Shipley, Fran A., Sprinkle, Jeffery W., Vaughn, Stephen N.
• Primary Examiner(s): Wood, Elizabeth D.
• Application Number:
  US10/052,058
• Publication Number:
  US 20030135079A1
• Time in Patent Office: 796 Days
• Field of Search: 502/60, 502/63, 502/64, 502/68, 502/214
• US Class Current: 502/214
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/83 Aluminophosphates [APO compounds]
• CPC Class Codes: B01J 29/85 Silicoaluminophosphates [SAPO compounds]
• CPC Class Codes: B01J 29/90 Regeneration or reactivation
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• 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: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/10 in the presence of water, e.g. steam
• CPC Class Codes: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 2529/85 Silicoaluminophosphates (SAPO compounds)
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: Y02P 20/584 Recycling of catalysts
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

Disclosed is a method for making molecular sieve catalyst particles. Dried molecular sieve catalyst particles are used to make the catalyst. The dried molecular sieve catalyst particles are put into an aqueous solution and stirred to make a slurry. The slurry is dried to make the molecular sieve catalyst particles. Optionally, the dried molecular sieve catalyst particles made from the slurry are calcined.

Claims

1. A method of making molecular sieve catalyst particles, comprising

a) providing a first dried molecular sieve catalyst made of catalyst particles that contain molecular sieve particles bound together to form catalyst particles larger than the individual molecular sieve particles;

b) combining the first dried molecular sieve catalyst with water to form a water-catalyst composition;

c) mixing the water-catalyst composition to form a slurry; and

d) drying the slurry to form particles of a second dried molecular sieve catalyst.

2. The method of claim 1, wherein the water used in b) comprises at least 95 wt % water.

3. The method of claim 1, wherein the water used in b) is substantially free of any molecular sieve particle.

4. The method of claim 1, wherein the first dried molecular sieve catalyst contains template material.

5. The method of claim 4, wherein the template is selected from the group consisting of triethylanilne, cyclohexylanilne, piperidine, dipropylamine, pyridine, isopropylainine, tetraethyl ammonium salts, and mixtures thereof.

6. The method of claim 1, wherein the water-catalyst composition is mixed so that the slurry obtained in c) contains particles smaller than the particles contained in the first dried molecular sieve catalyst.

7. The method of claim 1, further comprising e) calcining the particles of said second dried molecular sieve catalyst.

8. The method of claim 1, wherein the particle size of the first dried molecular sieve catalyst is such that, after calcination, 10 wt % of the particles have an average particle diameter less than or equal to 20 μ

m.

9. The method of claim 1, wherein the water is at a substantially neutral pH prior to combining with the first dried molecular sieve catalyst.

10. The method of claim 1, wherein the slurry has a viscosity of from 100 cP to 9,000 cP measured using a Brookfield LV-DVE viscometer with a No. 3 spindle at 10 rpm.

11. The method of claim 1, wherein the slurry prepared in c) has a solids content of from 10 wt % to 75 wt %.

12. The method of claim 7, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 1 wt %/hr.

13. The method of claim 7, wherein the molecular sieve catalyst particles obtained in e) have a particle size such that 50% of the particles have a diameter larger than 30 μ

m and smaller than 150 μ

m.

14. The method of claim 1, wherein drying the slurry in d) is by spray drying.

15. The method of claim 1, wherein the first dried molecular sieve catalyst comprises a silicoaluminophosphate molecular sieve.

16. The method of claim 15, wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, metal containing molecular sieves thereof, and mixtures thereof.

17. The method of claim 16, wherein silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, ALPO-34 and ALPO-18, metal containing molecular sieves thereof, and mixtures thereof.

18. The method of claim 17, wherein the silicoaluminophosphate molecular sieve has a framework-type selected from the group consisting of CHA, AEI and a combination thereof.

19. The method of claim 1, wherein the first dried molecular sieve catalyst comprises an inorgarnic oxide sol binder.

20. The method of claim 19, wherein the binder is aluminium chlorohydrate.

21. The method of claim 1, wherein the first dried molecular sieve catalyst comprises a clay filler.

53. The method of claim 1, wherein the step of providing a first dried molecular sieve catalyst comprises:

(i) mixing a composition comprising molecular sieve, binder and water; and

(ii) drying the composition to form the first dried molecular sieve catalyst.

54. The method of claim 2, wherein the water used in b) comprises at least 97 wt % water.

55. The method of claim 54, wherein the water used in b) comprises at least 98 wt % water.

56. The method of claim 12, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.7 wt %/hr.

57. The method of claim 56, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.3 wt %/hr.

22. A method of recycling molecular sieve catalyst particles having undesired properties, comprising

(a) mixing a composition comprising molecular sieve, binder and water;

(b) drying the composition to form a first dried molecular sieve catalyst made of molecular sieve particles bound together to form particles larger than the individual molecular sieve particles;

(c) combining at least a portion of the first dried molecular sieve catalyst with water to form a water-catalyst composition;

(d) mixing the water-catalyst composition to form a slurry;

(e) drying the slurry to form particles of a second dried molecular sieve catalyst.

23. The method of claim 22, further comprising (f) calcining the particles of said second dried molecular sieve catalyst.

24. The method of claim 23, wherein the calcined catalyst particles have an EMARI of not greater than 1 wt %/hr.

25. The method of claim 23, wherein the calcined catalyst particles have a particle size such that 50% of the particles have a diameter larger than 30 μ

m and smaller than 150 μ

m.

26. The method of claim 22, wherein drying the slurry in b is by spray drying.

27. The method of claim 22, wherein the first dried molecular sieve catalyst comprises a silicoaluminophosphate molecular sieve.

28. The method of claim 27, wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, metal containing molecular sieves thereof, and mixtures thereof.

29. The method of claim 27, wherein silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, ALPO-34 and ALPO-18, metal containing molecular sieves thereof, and mixtures thereof.

30. The method of claim 27, wherein the silicoaluminophosphate molecular sieve has a framework-type selected from the group consisting of CHA, AEI and a combination thereof.

31. The method of claim 22, wherein the first dried molecular sieve catalyst comprises an inorganic oxide sol binder.

32. The method of claim 31, wherein the binder is aluminum chlorohydrate.

33. The method of claim 22, wherein the first dried molecular sieve catalyst comprises a clay filler.

58. The method of claim 24, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.7 wt %/hr.

59. The method of claim 58, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.3 wt %/hr.

34. A method of making a molecular sieve catalyst composition comprising;

providing first dried molecular sieve catalyst particles made of molecular sieve particles bound together to form particles larger than the individual molecular sieve particles, wherein the first dried molecular sieve catalyst particles yield, upon calcining, a calcined molecular sieve composition having greater than 5 wt % catalyst particles having an average particle diameter greater than or equal to 250 microns;

combining the dried molecular sieve catalyst particles with water to form a slurry; and

drying the slurry to form the molecular sieve catalyst composition.

35. The method of claim 34, wherein the provided first dried molecular sieve catalyst particles contain template material.

36. The method of claim 34, wherein the provided first dried molecular sieve catalyst particles are mixed with the water so that at least a portion of the first dried molecular sieve catalyst particles break apart.

37. The method of claim 34, wherein the provided first dried molecular sieve catalyst particles yield, upon calcining, a calcined molecular sieve composition having greater than 10 wt % catalyst particles having an average particle diameter less than or equal to 10 microns.

38. The method of claim 34, further comprising combining the provided first dried molecular sieve catalyst particles with water prior to mixing, wherein the water is at a substantially neutral pH prior to adding the particles.

39. The method of claim 34, wherein the slurry has a viscosity of from 100 cP to 9,000 cP measured using a Brookfield LV-DVE viscometer with a No. 3 spindle at 10 rpm.

40. The method of claim 34, wherein the slurry has a solids content of from 10 wt % to 75 wt %.

41. The method of claim 34, further comprising calcining the molecular sieve catalyst composition formed from drying the slurry.

42. The method of claim 41, wherein the calcined molecular sieve catalyst particles have an EMARI of not greater than 1 wt %/hr.

43. The method of claim 41, wherein the calcined molecular sieve catalyst particles have a particle size such that 50% of the particles have a diameter larger than 30 μ

m and smaller than 50 μ

m.

44. The method of claim 34, wherein drying the slurry is by spray drying.

45. The method of claim 34, wherein the provided first dried molecular sieve catalyst particles comprise silicoaluminophosphate molecular sieve.

46. The method of claim 45, wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, metal containing molecular sieves thereof, and mixtures thereof.

47. The method of claim 45, wherein silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-18, SAPO-34, ALPO-34 and ALPO-18, metal containing molecular sieves thereof, and mixtures thereof.

48. The method of claim 45, wherein the silicoaluminphosphate molecular sieve has a framework-type selected from the group consisting of CHA, AEI and a combination thereof.

49. The method of claim 34, wherein the provided first dried molecular sieve catalyst particles comprises an inorganic oxide sol binder.

50. The method of claim 49, wherein the binder is aluminium chlorohydrate.

51. The method of claim 50, wherein the provided first dried molecular sieve catalyst comprises a clay filler.

60. The method of claim 42, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.7 wt %/hr.

61. The method of claim 60, wherein the molecular sieve catalyst particles obtained in e) have an EMARI of not greater than 0.3 wt %/hr.

52. A calcined molecular sieve catalyst composition comprising catalyst particles that contain molecular sieve particles bound together to form catalyst particles larger than the individual molecular sieve particles, wherein the catalyst particles, after being submitted to calcination, have an EMARI of equal or less than 0.7 wt %/hr.

62. The calcined molecular sieve catalyst composition of claim 52, wherein the catalyst particles, after being submitted to calcination, have an EMARI of equal or less than 0.3 wt %/hr.