Para-xylene selective adsorbent compositions and methods
Adsorbent compositions for vapor-phase adsorption processes, which are selective for para-xylene. Such compositions can be used in gas-phase adsorption processes for the separation of para-xylene or the separation of para-xylene and ethylbenzene from mixed xylenes or a C 8 aromatic mixture, respectively. The adsorbent compositions generally comprise materials of a molecular sieve material and a binder, wherein the adsorbent composition has a macropore volume of at least about 0.20 cc/g and a mesopore volume of less than about 0.20 cc/g.
1. An adsorbent composition comprising:
(a) a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aromiatics and having a pore size in the range of 5 Å to 6 Å; and,
(b) a binder,
wherein the adsorbent composition has a macropore volume of pores having a radius greater than about 600 angstroms of at least about 0.20 cc/g, and a mesopore volume of pores having a radius less than about 600 angstroms of less than about 0.20 cc/g.
2. The adsorbent composition of claim 1 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, aluminas, and aluminum phosphates.
3. The adsorbent composition of claim 1 , wherein the binder comprises up to about 50 wt. % of the composition.
4. The adsorbent composition of claim 1 , wherein the macropore volume is at least about 0.30 cc/g.
5. The adsorbent composition of claim 1 , wherein the mesopore volume is less than about 0.15 cc/g.
6. The adsorbent composition of claim 1 , wherein the weight ratio of molecular sieve material to binder is at least about 1.
7. The adsorbent composition of claim 1 , wherein the adsorbent composition has a volumetric ratio of macropores to mesopores of at least about 2.
8. The adsorbent composition of claim 7 , wherein the adsorbent composition has a volumetric ratio of macropores to mesopores of at least about 5.
9. The adsorbent composition of claim 1 , wherein the adsorbent composition has less than about 2 wt. % of materials consisting of gamma-alumina.
10. The adsorbent composition of claim 9 , wherein the adsorbent composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
11. The adsorbent composition of claim 1 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
12. The adsorbent composition of claim 11 , wherein the molecular sieve material is of the MFI structural type.
13. The adsorbent composition of claim 1 , wherein the molecular sieve material is substantially non-acidic.
14. An adsorbent composition comprising:
(a) a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aromatics and having a pore size in the range of 5 Å to 6 Å; and,
(b) a binder selected from the group consisting of clays, silicas, silicates, zirconias, titanias, aluminas, and aluminum phosphates,
wherein the adsorbent composition has a volumetric ratio of macropores having a radius less than about 600 angstroms to mesopores having a radius less than about 600 angstroms of at least about 2.
15. The adsorbent composition of claim 14 , wherein the molecular sieve material has a unit cell formula M x/n [(A) x (B) y O 2x+2y ],
wherein M is a compensating cation, n is the cation valence, A is a Group IIIA element, B is a Group IVA element, and y/x is at least about one.
16. The adsorbent composition of claim 15 , wherein y/x is at least about 500.
17. The adsorbent composition of claim 14 , wherein the volumetric ratio of macropores to mesopores is a least about 5.
18. The adsorbent composition of claim 14 , wherein the adsorbent composition has a macropore volume of at least about 0.20 cc/g.
19. The adsorbent composition of claim 14 , wherein the adsorbent composition has a mesopore volume of less than about 0.20 cc/g.
20. The adsorbent composition of claim 14 , wherein the binder comprises up to about 50 wt. % of the composition.
21. The adsorbent composition of claim 14 , wherein the weight ratio of molecular sieve material to binder is at least about 1.
22. The adsorbent composition of claim 14 , wherein the composition has less than about 2 wt. % of materials consisting of gamma-alumina.
23. The adsorbent composition of claim 22 , wherein the composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
24. The adsorbent composition of claim 14 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
25. The adsorbent composition of claim 24 , wherein the molecular sieve material is of the MFI structural type.
26. The adsorbent composition of claim 14 , wherein the molecular sieve material is substantially non-acidic.
27. An adsorbent composition comprising:
a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aroniatics and having a pore size in the range of 5 Å to 6 Å,
wherein the adsorbent composition has a macropore volume of pores having a radius greater than about 600 angstroms of at least about 0.20 cc/g, the adsorbent composition has a mesopore volume of pores having a radius greater than about 600 angstroms of less than about 0.20 cc/g, and the adsorbent composition has less than about 2 wt. % of materials consisting of gamma-alumina.
28. The adsorbent composition of claim 27 , wherein the macropore volume is at least about 0.30 cc/g.
29. The adsorbent composition of claim 27 , wherein the mesopore volume is less than about 0.15 cc/g.
30. The adsorbent composition of claim 27 , wherein the adsorbent composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
31. The adsorbent composition of claim 27 , wherein the adsorbent composition has a volumetric ratio of macropores to mesopores of at least about 2.
32. The adsorbent composition of claim 27 , further comprising a binder.
33. The adsorbent composition of claim 32 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, and aluminum phosphates.
34. The adsorbent composition of claim 32 , wherein the binder comprises up to about 50 wt. % of the composition.
35. The adsorbent composition of claim 32 , wherein the weight ratio of molecular sieve material to binder is at least about 1.
36. The adsorbent composition of claim 27 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
37. The adsorbent composition of claim 27 , wherein the molecular sieve material is substantially non-acidic.
38. An adsorbent composition comprising:
a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbezene from a mixture of C 8 aromatics and having a pore size in the range of 5 Å to 6 Å,
wherein the adsorbent composition has a volumetric ratio of macropores having a radius greater than about 600 angstroms to mesopores having a radius less than about 600 angstroms of at least about 2 and less than about 2 wt. % of materials consisting of gamma-alumina.
39. The adsorbent composition of claim 38 , wherein the volumetric ratio of macropores to mesopores is at least about 5.
40. The adsorbent composition of claim 38 , wherein the adsorbent composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
41. The adsorbent composition of claim 38 , further comprising a binder.
42. The adsorbent composition of claim 41 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, and aluminum phosphates.
43. The adsorbent composition of claim 41 , wherein the binder comprises up to about 50 wt. % of the composition.
44. The adsorbent composition of claim 41 , wherein the weight ratio of molecular sieve material to binder is at least about 1.
45. The adsorbent composition of claim 38 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
46. The adsorbent composition of claim 38 , wherein the molecular sieve material is substantially non-acidic.
47. A method comprising:
(a) forming a powder from a composition comprising a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aromatics and having a pore size in the range of 5 Å to 6 Å;
(b) forming an aqueous mixture from the powder;
(c) extruding the mixture to form an extrudate; and,
(d) drying the extrudate to form an adsorbent having a macropore volume of pores having a radius greater than about 600 angstroms of at least about 0.20 cc/g and a mesopore volume of pores having a radius less than about 600 angstroms of less than about 0.20 cc/g.
48. The method of claim 47 , wherein the composition further comprises a binder.
49. The method of claim 48 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, aluminas, and aluminum phosphates.
50. The method of claim 48 , wherein the binder comprises up to about 50 wt. % of the composition.
51. The method of claim 47 , wherein the macropore volume is at least about 0.30 cc/g.
52. The method of claim 47 , wherein the mesopore volume is less than about 0.15 cc/g.
53. The method of claim 47 , wherein the composition has less than about 2 wt. % of materials consisting of gamma-alumina.
54. The method of claim 53 , wherein the adsorbent composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
55. The method of claim 47 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
56. The method of claim 55 , wherein the molecular sieve material is of the MFI structural type.
57. The method of claim 47 , wherein the molecular sieve material is substantially non-acidic.
58. A method comprising:
(a) forming a powder from a composition comprising a substantially non-catalytically active molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aromatics and having a pore size in the range of 5 Å to 6 Å;
(b) forming an aqueous mixture from the powder;
(c) extruding the mixture to form an extrudate; and,
(d) drying the extrudate to form an adsorbent having a volumetric ratio of macropores having a radius less than about 600 angstroms to mesopores having a radius less than about 600 angstroms of at least about 2.
59. The method of claim 58 , wherein the molecular sieve material has a unit cell formula M x/n [(A) x (B) y O 2x+2y ],
wherein M is a compensating cation, n is the cation valence, A is a Group IIIA element, B is a Group IVA element, and y/x is at least about one.
60. The method of claim 59 , wherein y/x is at least about 500.
61. The method of claim 58 , wherein the volumetric ratio of macropores to mesopores is at least about 5.
62. The method of claim 58 , wherein the composition further comprises a binder.
63. The method of claim 62 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, aluminas, and aluminum phosphates.
64. The method of claim 62 , wherein the binder comprises up to about 50 wt. % of the composition.
65. The method of claim 58 , wherein the composition has less than about 2 wt. % of materials consisting gamma-alumina.
66. The method of claim 65 , wherein the composition has less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
67. The method of claim 58 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-live (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
68. The method of claim 67 , wherein the molecular sieve material is of the MFI structural type.
69. The method of claim 58 , wherein the molecular sieve material is substantially non-acidic.
70. An adsorbent composition comprising:
(a) a molecular sieve material capable of selectively adsorbing para-xylene and ethylbenzene from a mixture of C 8 aromatics and having a pore size in the rangeof5Å to 6 Å; and,
(b) a binder,
wherein the adsorbent composition has a macropore volume of pores having a radius greater than about 600 angstroms of at least about 0.20 cc/g, a mesopore volume of pores having a radius less than about 600 angstroms of less than about 0.20 cc/g, and less than about 2 wt. % of materials consisting of Al 2 O (3−x) (OH) 2x , wherein x ranges from 0 to about 0.8.
71. The adsorbent composition of claim 70 , wherein the binder is selected from the group consisting of clays, silicas, silicates, zirconias, titanias, aluminas, and aluminum phosphates.
72. The adsorbent composition of claim 70 , wherein the binder comprises up to about 50 wt. % of the composition.
73. The adsorbent composition of claim 70 , wherein the macropore volume is at least about 0.30 cc/g, and the mesopore volume is less than about 0.15 cc/g.
74. The adsorbent composition of claim 70 , wherein the weight ratio of molecular sieve material to binder is at least about 1.
75. The adsorbent composition of claim 70 , wherein the adsorbent composition has a volumetric ratio of macropores to mesopores of at least about 2.
76. The adsorbent composition of claim 74 , wherein the adsorbent composition has a volumetric ratio of macropores to mesopores of at least about 5.
77. The adsorbent composition of claim 70 , wherein the molecular sieve material has a structural type selected from the group consisting of Mobil-five (MFI), Mobil-eleven (MEL), Mobil-twenty three (MTT), ferrierite (FER), Edinburgh University-one (EUO), Mobil-fifty seven (MFS), theta-one (TON), aluminophosphate-eleven (AEL), new-eighty seven (NES), Mobil-twelve (MTW), and aluminophosphate-thirty one (ATO).
78. The adsorbent composition of claim 76 , wherein the molecular sieve material is of the MFI structural type.
79. The adsorbent composition of claim 76 , wherein the molecular sieve material is substantially non-acidic.