IP Library Granted Patent US 9,695,056
Granted Patent B2
US 9,695,056 · App. 14/744,248 · Granted Jul 4, 2017

Separation and storage of fluids using ITQ-55

Inventors: Edward W. Corcoran, Jr. (Easton, PA); Pavel Kortunov (Flemington, NJ); Charanjit S. Paur (Phillipsburg, NJ); Peter I. Ravikovitch (Princeton, NJ); Yu Wang (Lebanon, NJ); Avelino Corma Canos (Valencia, ES); Fernando Rey Garcia (Valencia, ES); Susana Valencia Valencia (Valencia, ES); Angel Cantin Sanz (Valencia, ES); Miguel Palomino Roca (Valencia, ES)
Assignee: ExxonMobil Research and Engineering Company
C01B39/48B01D53/02B01D53/04B01D53/047B01D53/0407B01D53/0462B01D53/228B01D53/229B01D71/028B01J20/18B01J20/3078B01J29/70C01B3/508C01B17/167C01B21/0466C01B37/002C01B37/007C01B37/02C01B39/06C01B39/08C01B39/12C01C1/12C07C1/20C07C1/322C07C2/76C07C29/00C07C41/01B01D2253/108B01D2256/10B01D2256/12B01D2256/16B01D2256/18B01D2256/20B01D2256/22B01D2256/24B01D2256/245B01D2256/26B01D2257/302B01D2257/304B01D2257/40B01D2257/404B01D2257/406B01D2257/50B01D2257/504B01D2257/70B01D2257/702B01D2257/7022B01D2257/80C01B2203/0405C01B2210/0018C07C2529/70C07C2529/76C07C2529/78Y02C10/08
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Quick Facts
Patent No.
US 9,695,056
App. No.
14/744,248
Granted
Jul 4, 2017
Kind
B2
Abstract

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.

Claims (245)

1. A method for adsorbing and storing fluids, comprising:

exposing an input fluid stream comprising a first fluid component to an adsorbent comprising zeolite ITQ-55 at a first pressure and a first temperature;

maintaining the adsorbent at a second pressure and a second temperature for a storage period of time;

forming an adsorbed product fluid stream comprising the first fluid component; 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 essentially zero, c) g takes a value of essentially zero, or d) a combination thereof.

5. 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.

6. The method of claim 1 , wherein the first temperature and the second temperature are the same, wherein the first pressure and the second pressure are the same, or a combination thereof.

7. The method of claim 1 , wherein forming an adsorbed product fluid stream comprises modifying the second temperature of the adsorbent.

8. 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.

9. 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.

10. The method of claim 1 , wherein maintaining the adsorbent at a second pressure and a second temperature for a storage period of time comprises exposing the adsorbent to an environment having a partial pressure of the first fluid component of about 0.1 MPaa or less.

11. The method of claim 1 , wherein the input fluid stream further comprises a second component, a molar ratio of the first component to the second component in the adsorbed product stream is greater than a molar ratio of the first component to the second component in the input fluid stream.

12. The method of claim 11 , wherein the second fluid component is methane, ethane, methanol, dimethyl ether, an organic compound containing 3 or more heavy atoms, or a combination thereof.

13. The method of claim 12 , wherein the first fluid component is CO 2 .

14. The method of claim 11 , 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.

15. The method of claim 14 , wherein the input fluid stream comprises syngas.

16. 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.

17. The method of claim 1 , wherein the first fluid component is CO 2 , H 2 , or a combination thereof.

18. The method of claim 1 , wherein the first fluid component is ethylene, acetylene, formaldehyde, or a combination thereof.

19. The method of claim 1 , wherein the first fluid component is a noble gas, a molecular halogen, a halogen hydride, or a combination thereof.

20. The method of claim 1 , wherein the first fluid component is methane, ethylene, ethane, methanol, dimethyl ether, or a combination thereof.

21. A method for adsorbing and storing fluids, comprising:

exposing an input fluid stream comprising a first fluid component to an adsorbent comprising zeolite ITQ-55 at a first pressure and a first temperature;

maintaining the adsorbent at a second pressure and a second temperature for a storage period of time;

forming an adsorbed product fluid stream comprising the first fluid component; 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%.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 29, 2015
From: CORCORAN, EDWARD W., JR; KORTUNOV, PAVEL; PAUR, CHARANJIT S.; RAVIKOVITCH, PETER I.; WANG, YU; CANOS, AVELINO CORMA; GARCIA, FERNANDO REY; VALENCIA, SUSANA VALENCIA; SANZ, ANGEL CANTIN; ROCA, MIGUEL PALOMINO
To: EXXONMOBIL RESEARCH AND ENGINEERING COMPANY
Reel/Frame 036685/0435 →
Priority Claims (1)
ES 201430935 · Jun 20, 2014 · national
Continuity (1)
Related Publication 20160008754A1 · Jan 14, 2016