Gas separation membrane, gas separation module, gas separation apparatus, gas separation method, and method for producing asymmetric gas separation membrane

Patent metadata

Field	Value
Publication number	US-10543455-B2
Application number	US-201715669968-A
Country	US
Kind code	B2
Filing date	Aug 7, 2017
Priority date	Feb 27, 2015
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

A gas separation membrane has a gas separation layer containing a crosslinked cellulose resin. The crosslinked cellulose resin has a particular linking structure in a crosslinked structure. The gas separation layer contains an organic solvent in a particular amount.

First claim

What is claimed is:

1. A gas separation membrane comprising:
a gas separation layer containing a crosslinked cellulose resin,
wherein the crosslinked cellulose resin has, in a crosslinked structure, at least one linking structure selected from the group consisting of *—O-M-O—* and *—S-M-S—*, and
the gas separation layer contains 10 to 5,000 ppm of an organic solvent,
where M represents a divalent to tetravalent metal atom which is selected from the group consisting of iron (Fe), beryllium (Be), gallium (Ga), vanadium (V), indium (In), copper (Cu), cobalt (Co), nickel (Ni), zinc (Zn), calcium (Ca), yttrium (Y), scandium (Sc), chromium (Cr), manganese (Mn), molybdenum (Mo), and boron (B); and the symbol * represents a linking site.

2. The gas separation membrane according to claim 1 , wherein the crosslinked cellulose resin is a resin obtained by crosslinking a cellulose resin having a repeating unit represented by General formula (A):

where R 1 , R 2 , and R 3 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, and an acyl group.

3. The gas separation membrane according to claim 1 , wherein the linking structure represented by *—O-M-O—S* and the linking structure represented by *—S-M-S—* are linking structures formed by coordination of a cellulose resin to a metal atom selected from the group consisting of Zn, B, and Ga through an oxygen atom and a sulfur atom, respectively.

4. The gas separation membrane according to claim 1 , wherein the crosslinked cellulose resin contains 40.0% to 99.8% by mass of an insoluble component, and
the insoluble component is insoluble in chloroform.

5. The gas separation membrane according to claim 1 , wherein the gas separation layer contains cellulose nanofibers.

6. The gas separation membrane according to claim 5 , wherein the cellulose nanofibers have a maximum fiber diameter of 30 to 90 nm and a ratio of an average fiber length to an average fiber diameter of 2,000 to 10,000.

7. The gas separation membrane according to claim 1 , wherein the gas separation membrane is an asymmetric membrane.

8. The gas separation membrane according to claim 7 , wherein the gas separation membrane has a thickness of 10 to 200 μm.

9. The gas separation membrane according to claim 7 , wherein the gas separation membrane is the asymmetric membrane supported by a nonwoven fabric.

10. The gas separation membrane according to claim 1 , further comprising:
a functional polymer layer disposed in contact with the gas separation layer,
wherein the functional polymer layer has a group selected from the group consisting of an amino group, a thiol group, a hydrosilyl group, a vinyl group, an acryloyl group, a methacryloyl group, an acid anhydride group, a hydroxy group, and an alkoxy group.

11. The gas separation membrane according to claim 10 , wherein the functional polymer layer has a polydimethylsiloxane structure.

12. The gas separation membrane according to claim 1 , the gas separation membrane being used to be selectively permeated by carbon dioxide from gas containing carbon dioxide and methane.

13. A gas separation module comprising the gas separation membrane according to claim 1 .

14. A gas separation apparatus comprising the gas separation module according to claim 13 .

15. A gas separation method comprising supplying gas to the gas separation membrane according to claim 1 .

16. The gas separation method according to claim 15 , wherein carbon dioxide is selectively permeated through the gas separation membrane to be separated from methane contained in the gas.

17. A method for producing an asymmetric gas separation membrane, the method comprising:
applying, onto a support, a coating solution containing a metal complex and a cellulose resin having an active hydrogen-containing group;
drying a surface of the coating solution on the support; and
bringing the coating solution on the support into contact with a coagulating liquid to form an asymmetric structure by phase inversion,
wherein the metal complex is represented by Formula (B):
M L) q   (B)

where M represents a divalent to tetravalent metal atom which is selected from the group consisting of iron (Fe), beryllium (Be), gallium (Ga), vanadium (V), indium (In), copper (Cu), cobalt (Co), nickel (Ni), zinc (Zn), calcium (Ca), yttrium (Y), scandium (Sc), chromium (Cr), manganese (Mn), molybdenum (Mo), and boron (B); L represents an alkoxy group, an aryloxy group, an acetylacetonato group, an acyloxy group, a hydroxy group, or a halogen atom; and q represents an integer of 2 to 4.

Assignees

• Fujifilm Corp

Inventors

• Sano Satoshi
• Hironaka Koji
• Kodama Keisuke

Classifications

• C10L2290/548

  Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel · CPC title

• B01D71/10

  Cellulose; Modified cellulose · CPC title

• B01D2257/504

  Carbon dioxide · CPC title

• B01D71/16

  Cellulose acetate · CPC title

• B01D69/02

  characterised by their properties · CPC title