Thin-film composite membrane and processes for the separation of alkenes from a gaseous feed mixture

• US 10,639,591 B1
• Filed: 04/11/2019
• Issued: 05/05/2020
• Est. Priority Date: 01/07/2019
• Status: Active Grant

• Current Assignee: Compact Membrane Systems Inc.
• Original Assignee: Compact Membrane Systems Inc.
• Inventors: Lousenberg, Robert Daniel, Loprete, Kenneth Evan
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US16/381,333
• Time in Patent Office: 390 Days
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0083 Thermal after-treatment
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/107 Organic support material
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: B01D 71/36 Polytetrafluoroethene
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment

Abstract

This invention discloses an improved thin-film composite membrane and processes that use the membrane for the separation of gaseous mixtures that include an alkene. The membrane is particularly useful for separation of alkenes from alkanes or the separation of alkenes from other non-hydrocarbon gases. The membrane has a more mechanically durable and defect-free gas-separation layer that is fabricated from an ionomer solution that is substantially free of dissolved ionic species not associated with the ionomer and the mean helium permeability of the thin-film composite membrane is less than two times greater than the intrinsic helium permeability of the gas-separation layer.

Claims

1. A thin-film composite membrane comprising:

a) a porous-layer support; and

b) a gas-separation layer comprising an ionomer comprising silver-sulfonate groups;

said gas-separation layer is coplanar in direct contact to said porous-layer support, and predominantly laminar; and

wherein the gas-separation layer is formed from an ionomer solution that is substantially free of dissolved ionic species not associated with the ionomer and a mean helium permeability of the thin-film composite membrane is less than two times greater than an intrinsic helium permeability of the gas-separation layer.

2. The thin-film composite membrane of claim 1 wherein the ionomer is comprised of repeat units A and B in which A is a polymerized derivative of a fluorinated monomer and B comprises silver sulfonate groups.

3. The thin-film composite membrane of claim 2 wherein repeat unit A is selected from a group consisting of:

tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinyl fluoride, or vinylidene fluoride.

4. The thin-film composite membrane of claim 2 wherein a precursor to the repeat unit B is a monomer of structure CF₂═

CFOR^fSO₂F wherein R^f is a perfluoroalkylene group of 1 to 10 carbon atoms.

5. The thin-film composite membrane of claim 4, wherein the perfluoroalkylene group comprises ether oxygens.

6. The thin-film composite membrane of claim 1 wherein a precursor to the ionomer in the gas-separation layer is a copolymer comprising tetrafluoroethylene and CF₂═

CFOCF₂CF₂SO₂F.

7. The thin-film composite membrane of claim 1 wherein a precursor to the ionomer in the gas-separation layer is a copolymer comprising tetrafluoroethylene and CF₂═

CFOCF₂CF(CF₃)OCF₂CF₂SO₂F.

8. The thin-film composite membrane of claim 1 wherein the ionomer has an equivalent weight that is less than 800-grams/mole.

9. The thin-film composite membrane of claim 1 wherein the gas-separation layer has a thickness that is less than 2-μ

m wherein at least 50% of the gas-separation layer extends on top of the porous-layer support and is not interpenetrating into the porous-layer support.

10. A spiral wound gas-separation module comprising the thin-film composite membrane of claim 1.

11. A method of constructing a thin-film composite membrane comprising:

providing a porous-layer support and an ionomer solution comprising a solvent and sulfonate groups, selected from;

silver sulfonate, sulfonic acid, or non-silver sulfonate;

contacting the porous-layer support with said ionomer solution comprising sulfonate groups; and

removal of the solvent contained in the ionomer solution to form a gas-separation layer that is coplanar and in direct contact to said porous-layer support; and

treatment of the gas-separation layer comprising sulfonic acid or non-silver sulfonate groups with a solution comprising water and at least one dissolved silver compound to convert at least some of the sulfonic acid or non-silver sulfonate groups to silver sulfonate groups; and

wherein the gas-separation layer is formed from said ionomer solution that is substantially free of dissolved ionic species not associated with an ionomer in the ionomer solution and a mean helium permeability of the thin-film composite membrane is less than two times greater than an intrinsic helium permeability of the gas-separation layer.

12. The method of claim 11 wherein the thin-film composite membrane is subjected to a thermal treatment step.

13. The method of claim 11 in wherein the ionomer is comprised of repeat units A and B in which A is a polymerized derivative of a fluorinated monomer and B comprises sulfonate groups.

14. The method of claim 13 wherein repeat unit A is selected from a group consisting of:

tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinyl fluoride, or vinylidene fluoride.

15. The method of claim 13 wherein a precursor to repeat unit B is a monomer of structure CF₂═

CFOR^fSO₂F wherein R^f is a perfluoroalkylene group of 1 to 10 carbon atoms.

16. The method of claim 15 wherein the perfluoroalkylene group comprises ether oxygens.

17. The method of claim 11 wherein a precursor to the ionomer is a copolymer comprising tetrafluoroethylene and CF₂═

CFOCF₂CF₂SO₂F.

18. A method for separating a gaseous composition comprising an alkene using a thin-film composite membrane, and comprising:

a) constructing a thin-film composite membrane according to claim 15;

the membrane having a feed side and a permeate side; and

b) exposing the feed-side to a flowing gaseous feed-side composition comprising an alkene; and

c) providing a driving force and producing a gaseous permeate-side composition at the permeate-side of the thin-film composite membrane having a higher concentration of alkene than the feed-side.

19. The method of claim 18 wherein the alkene is selected from a group consisting of:

ethylene, propylene, butene, or butene isomers.

20. The method of claim 18 wherein the gaseous feed mixture comprises an alkane selected from a group consisting of:

methane, ethane, propane, butane, or butane isomers.

21. The method of claim 18 wherein the gaseous feed mixture comprises a non-hydrocarbon gas selected from a group consisting of:

helium, hydrogen, nitrogen, oxygen, or argon.