Separation and storage of fluids using ITQ-55
This invention refers to a microporous crystalline material of zeolitic nature that has, in its calcined state and in the absence of defects in its crystalline matrix manifested by the presence of silanols, the empirical formula x (M 1/n XO 2 ): y YO 2 :g GeO 2 :(1 −g )SiO2 in which M is selected between H + , at least one inorganic cation of charge +n, and a mixture of both, X is at least one chemical element of oxidation state +3, Y is at least one chemical element with oxidation state +4 different from Si, x takes a value between 0 and 0.2, both included, y takes a value between 0 and 0.1, both included, g takes a value between 0 and 0.5, both included that has been denoted ITQ-55, as well as a method for its preparation. This invention also relates to uses of the crystalline material of zeolitic nature for adsorption of fluid components, membrane separation of fluid components, storage of fluid components, and catalysis of various conversion reactions.
1. A method for separating fluids, comprising:
exposing an input fluid stream comprising a first fluid component and a second fluid component to an adsorbent comprising zeolite ITQ-55 to form a rejection product fluid stream, a molar ratio of the first fluid component to the second fluid component in the rejection product fluid stream being less than a molar ratio of the first fluid component to the second fluid component in the input fluid stream;
collecting the rejection product fluid stream;
forming an adsorbed product fluid stream, a molar ratio of the first fluid component to the second fluid component in the adsorbed product stream being greater than the molar ratio of the first fluid component to the second fluid component in the input fluid stream; and
collecting the adsorbed product stream,
wherein the zeolite ITQ-55 has a framework of tetrahedral (T) atoms connected by bridging atoms, wherein the tetrahedral atom is defined by connecting the nearest T atoms in the manner described in the following Table:
ITQ-55 tetrahedral atom interconnections
T atom
Connected to:
T1
T6, T7, T55, T73
T2
T3, T5, T9, T56
T3
T2, T7, T21, T27
T4
T8, T9, T58, T73
T5
T2, T8, T52, T59
T6
T1, T8, T53, T60
T7
T1, T3, T50, T61
T8
T4, T5, T6, T51
T9
T2, T4, T21, T63
T10
T15, T16, T64, T74
T11
T12, T14, T18, T65
T12
T11, T16, T30, T36
T13
T17, T18, T67, T74
T14
T11, T17, T43, T68
T15
T10, T17, T44, T69
T16
T10, T12, T41, T70
T17
T13, T14, T15, T42
T18
T11, T13, T30, T72
T19
T24, T25, T37, T73
T20
T21, T23, T27, T38
T21
T3, T9, T20, T25
T22
T26, T27, T40, T73
T23
T20, T26, T41, T70
T24
T19, T26, T42, T71
T25
T19, T21, T43, T68
T26
T22, T23, T24, T69
T27
T3, T20, T22, T45
T28
T33, T34, T46, T74
T29
T30, T32, T36, T47
T30
T12, T18, T29, T34
T31
T35, T36, T49, T74
T32
T29, T35, T50, T61
T33
T28, T35, T51, T62
T34
T28, T30, T52, T59
T35
T31, T32, T33, T60
T36
T12, T29, T31, T54
T37
T19, T42, T43, T75
T38
T20, T39, T41, T45
T39
T38, T43, T57, T63
T40
T22, T44, T45, T75
T41
T16, T23, T38, T44
T42
T17, T24, T37, T44
T43
T14, T25, T37, T39
T44
T15, T40, T41, T42
T45
T27, T38, T40, T57
T46
T28, T51, T52, T76
T47
T29, T48, T50, T54
T48
T47, T52, T66, T72
T49
T31, T53, T54, T76
T50
T7, T32, T47, T53
T51
T8, T33, T46, T53
T52
T5, T34, T46, T48
T53
T6, T49, T50, T51
T54
T36, T47, T49, T66
T55
T1, T60, T61, T75
T56
T2, T57, T59, T63
T57
T39, T45, T56, T61
T58
T4, T62, T63, T75
T59
T5, T34, T56, T62
T60
T6, T35, T55, T62
T61
T7, T32, T55, T57
T62
T33, T58, T59, T60
T63
T9, T39, T56, T58
T64
T10, T69, T70, T76
T65
T11, T66, T68, T72
T66
T48, T54, T65, T70
T67
T13, T71, T72, T76
T68
T14, T25, T65, T71
T69
T15, T26, T64, T71
T70
T16, T23, T64, T66
T71
T24, T67, T68, T69
T72
T18, T48, T65, T67
T73
T1, T4, T19, T22
T74
T10, T13, T28, T31
T75
T37, T40, T55, T58
T76
T46, T49, T64, T67.
2. The method of claim 1 , wherein the zeolite ITQ-55 has, in calcined state and in absence of defects in its crystalline matrix manifested by the presence of silanols, an empiric formula
x (M 1/n XO 2 ): y YO 2 :g GeO 2 :(1 −g )SiO 2
in which
M is selected between H + , at least one inorganic cation of charge +n, and a mixture of both,
X is at least one chemical element of oxidation state +3,
Y is at least one chemical element with oxidation state +4 different from Si,
x takes a value between 0 and 0.2, both included,
y takes a value between 0 and 0.1, both included,
g takes a value between 0 and 0.5, both included.
3. The method of claim 2 , wherein x takes a value of essentially zero, y takes a value of essentially zero, and g takes a value of essentially zero.
4. The method of claim 2 , wherein a) x takes a value of greater than zero, b) y takes a value of greater than zero, c) g takes a value of greater than zero, or d) a combination thereof.
5. The method of claim 1 , wherein forming an adsorbed product fluid stream comprises modifying at least one of a temperature or a pressure of the adsorbent.
6. The method of claim 1 , wherein forming an adsorbed product fluid stream comprises exposing a fluid stream comprising a third component to the adsorbent comprising zeolite ITQ-55, at least a portion of the third component being adsorbed by the adsorbent comprising zeolite ITQ-55.
7. The method of claim 1 , wherein exposing the input fluid stream to an adsorbent comprises exposing the input fluid stream to an adsorbent in a swing adsorption vessel.
8. The method of claim 7 , wherein exposing the input fluid stream to an adsorbent comprises exposing the input fluid stream to the adsorbent under pressure swing adsorption conditions, temperature swing adsorption conditions, rapid cycle pressure swing adsorption conditions, or a combination thereof.
9. The method of claim 7 , wherein the input fluid stream comprises natural gas.
10. The method of claim 9 , wherein the input fluid stream is exposed to the adsorbent comprising zeolite ITQ-55 at a pressure of about 5 psia (about 0.03 MPa) to about 5000 psia (about 35 MPa), optionally at least about 250 psia (about 1.7 MPa), or at least about 500 psia (about 3.4 MPa), or at least about 1000 psia (about 6.9 MPa).
11. The method of claim 9 , wherein the input fluid stream is exposed to the adsorbent at a temperature of about −18° C. to about 399° C., or about 316° C. or less, or about 260° C. or less.
12. The method of claim 9 , wherein the first fluid component is N 2 , H 2 O, CO 2 , or a combination thereof.
13. The method of claim 9 , wherein the first fluid component is at least one of N 2 and H 2 O.
14. The method of claim 9 , wherein the first fluid component is N 2 .
15. The method of claim 9 , wherein the second fluid component is CH 4 , a hydrocarbon having a higher molecular weight than CH 4 , or a combination thereof.
16. The method of claim 1 , wherein the input fluid stream is exposed to the adsorbent at effective conditions for performing a kinetic separation of the first component from the second component.
17. The method of claim 1 , wherein the input fluid stream is exposed to the adsorbent at effective conditions for performing an equilibrium separation of the first component from the second component.
18. The method of claim 1 , wherein the adsorbent has less than about 20% of open pore volume in pores having diameters greater than about 20 Angstroms and less than about 1 micron.
19. The method of claim 1 , wherein the second fluid component is methane, ethane, methanol, dimethyl ether, an organic compound containing 3 or more heavy atoms, or a combination thereof.
20. The method of claim 19 , wherein the first fluid component is CO, CO 2 , H 2 , H 2 O, or a combination thereof.
21. The method of claim 20 , wherein the first fluid component is CO 2 and the second fluid component is CH 4 .
22. The method of claim 21 , wherein the input fluid stream comprises natural gas.
23. The method of claim 19 , wherein the first fluid component is ethylene, acetylene, formaldehyde, or a combination thereof.
24. The method of claim 19 , wherein the first fluid component is H 2 S, NH 3 , or a combination thereof.
25. The method of claim 19 , wherein the first fluid component is SO 2 , N 2 O, NO, NO 2 , a sulfur oxide, or a combination thereof.
26. The method of claim 19 , wherein the first fluid component is N 2 .
27. The method of claim 26 , wherein the input fluid stream is exposed to the adsorbent at a temperature of about 223 K to about 523 K.
28. The method of claim 19 , wherein the first fluid component is a noble gas, a molecular halogen, a halogen hydride, or a combination thereof.
29. The method of claim 1 , wherein the first fluid component is methane, ethylene, ethane, methanol, dimethyl ether, or a combination thereof.
30. The method of claim 1 , wherein the second fluid component is nitrogen, the first fluid component being hydrogen, a noble gas, oxygen, a nitrogen oxide, CO 2 , CO, a molecular halogen, a halogen hydride, or a combination thereof.
31. The method of claim 30 , wherein the first fluid component is CO 2 .
32. The method of claim 31 , wherein the input fluid stream comprises a flue gas.
33. The method of claim 30 , wherein the first fluid component is O 2 .
34. The method of claim 33 , wherein the input fluid stream comprises air.
35. The method of claim 30 , wherein the molecular halogen or the halogen halide comprise F, Cl, Br, or a combination thereof as the halogen.
36. The method of claim 1 , wherein the first fluid component is CO 2 and the second fluid component comprises one or more hydrocarbons.
37. The method of claim 36 , wherein the one or more hydrocarbons are methane, ethane, ethylene, or a combination thereof.
38. The method of claim 1 , wherein the first fluid component is ethylene and the second fluid component is ethane, methane, or a combination thereof.
39. The method of claim 1 , wherein the first fluid component is a nitrogen oxide and the second fluid component is a sulfur oxide.
40. The method of claim 1 , wherein the first fluid component is H 2 and the second fluid component is a nitrogen oxide, a sulfur oxide, a hydrocarbon, a carbon oxide, or a combination thereof.
41. The method of claim 1 , wherein the first fluid component is H 2 and the second fluid component is H 2 S, NH 3 , or a combination thereof.
42. The method of claim 1 , wherein the first fluid component is H 2 O and the second fluid component is H 2 .
43. The method of claim 1 , wherein the first fluid component is He, Ne, Ar, Kr, or a combination thereof and the second fluid component is N 2 , H 2 O, CO, CO 2 , a hydrocarbon, or a combination thereof.
44. The method of claim 1 , wherein the first fluid component is methanol, dimethyl ether, or a combination thereof.
45. The method of claim 1 , wherein the second fluid component is methanol, dimethyl ether, or a combination thereof.
46. The method of claim 1 , wherein the first fluid component is acetylene and the second fluid component is ethylene, methane, ethane, or a combination thereof.
47. A method for separating fluids, comprising:
exposing an input fluid stream comprising a first fluid component and a second fluid component to an adsorbent comprising zeolite ITQ-55 to form a rejection product fluid stream, a molar ratio of the first fluid component to the second fluid component in the rejection product fluid stream being less than a molar ratio of the first fluid component to the second fluid component in the input fluid stream;
collecting the rejection product fluid stream;
forming an adsorbed product fluid stream, a molar ratio of the first fluid component to the second fluid component in the adsorbed product stream being greater than the molar ratio of the first fluid component to the second fluid component in the input fluid stream; and
collecting the adsorbed product stream, wherein the zeolite ITQ-55, as synthesized, has an X-ray diffraction pattern with, at least, the angle values 2θ (degrees) and relative intensities (I/I 0 ):
2θ (degrees) ± 0.5
Intensity (I/I 0 )
5.8
w
7.7
w
8.9
w
9.3
mf
9.9
w
10.1
w
13.2
m
13.4
w
14.7
w
15.1
m
15.4
w
15.5
w
17.4
m
17.7
m
19.9
m
20.6
m
21.2
f
21.6
f
22.0
f
23.1
mf
24.4
m
27.0
m
where I 0 is the intensity from the most intense pick to which is assigned a value of 100
w is a weak relative intensity between 0 and 20%,
m is an average relative intensity between 20 and 40%,
f is a strong relative intensity between 40 and 60%,
and mf is a very strong relative intensity between 60 and 100%.