Composite carbon fluid separation membranes

• US 5,288,304 A
• Filed: 03/30/1993
• Issued: 02/22/1994
• Est. Priority Date: 03/30/1993
• Status: Expired due to Term

• Current Assignee: University of Texas System
• Original Assignee: University of Texas System
• Inventors: Jones, Cheryl W., Koros, William J.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US08/052,423
• Time in Patent Office: 329 Days
• Field of Search: 55/16, 55/158, 55/524
• US Class Current: 95/45
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 2325/32 Melting point or glass-transition temperatures
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0067 by carbonisation or pyrolysis
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01D 71/44 Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42

Abstract

The invention provides carbon membranes for use in fluid separation processes, particularly gas separations, which are treated with a coating that provides a protective barrier which significantly limits permeation of water vapor or other impurities such as hydrocarbons without significantly inhibiting permeation of the faster fluid component or lowering selectivity. The composite membranes retain good fluid separation properties and are resistant to the adverse effects on membrane performance commonly observed in environments having high humidity. The coating is preferably an amorphous polymer of perfluoro-2,2-dimethyl-1,3-dioxole. The membranes can be of a varied configuration: sheet form, hollow fiber, asymmetrical membranes and the like.

Claims

1. A membrane for the separation of fluids comprising a carbon membrane coated with a coating that reduces the partial pressure of water or other condensible agents or impurities relative to the other permeable components and having resistance to the permeation of water or other impurities without causing significant losses to the selectivity or productivity of the membrane.

2. A membrane of claim 1 wherein the coating is selected from the group of poly( 4-methyl-1-pentene), polyethylene and silicon-containing polymers.

3. A membrane of claim 2 wherein the coating is polysiloxane or poly(1-trimethyl silyl) propyne.

4. A membrane of claim 1, wherein the carbon membrane is in sheet form having a thickness from about 1 μ

m to about 300 μ

m.

5. A membrane of claim 1, wherein the carbon membrane is in the form of hollow fibers, having a diameter from about 50 μ

m to about 1000 μ

m diameter and with a wall thickness of about 10 μ

m to about 300 μ

m.

6. A membrane of claim 1, wherein the carbon membrane is of asymmetrical construction.

7. A membrane of claim 1, wherein the carbon membrane is the product of pyrolysis of a carbon-containing precursor at at temperature of about 250°

C. to about 2500°

C.

21. A process for separating fluids comprising contacting a mixture of fluids with the first side of the membrane described in any one of claims 1-19 in a manner to cause a portion of the mixture to pass through the membrane to a permeate side, the resulting mixture on the permeate side being enriched in one or more component over that of the mixture on the first side.

8. A membrane for the separation of fluids comprising a carbon membrane coated with a coating of a polymer having an aliphatic ring structure containing fluorine.

9. A membrane of claim 8 wherein the polymer comprises the group of repeating units represented by the following general formula:

##STR2## where n is an integer of 1 or 2, or copolymers thereof.

10. A membrane of claim 8 wherein the polymer is an amorphous polymer of perfluoro-2,2,-dimethyl-1,3-dioxole.

11. The membrane of claim 10 in which the polymer is a copolymer of perfluoro-2,2-dimethyl-1,3-dioxole.

12. The membrane of claim 11 in which the polymer is a copolymer of perfluoro-2,2-dimethyl-1,3-dioxole and a complementary amount of at least one monomer selected from the group consisting of tetrafluoroethylene, perfluoromethyl vinyl ether, vinylidene fluoride and chlorotrifluoroethylene.

13. The membrane of claim 10 in which the polymer is a homopolymer of perfluoro-2,2-dimethyl-1,3-dioxole.

14. The membrane of claim 10 in which the polymer is a dipolymer of perfluoro-2,2-dimethyl-1,3-dioxole and a complementary amount of tetrafluoroethylene.

15. The membrane of claim 14 in which the polymer is a dipolymer containing 65-99 mole % of perfluoro-2,2-dimethyl-1,3-dioxole and having a glass transition temperature of at least 140°

C.

16. A membrane of claim 8, wherein the carbon membrane is in sheet form having a thickness from about 1 μ

m to about 300 μ

m.

17. A membrane of claim 8, wherein the carbon membrane is in the form of hollow fibers, having a diameter from about 50 μ

m to about 1000 μ

m diameter and with a wall thickness of about 10 μ

m to about 300 μ

m.

18. A membrane of claim 8, wherein the carbon membrane is of asymmetrical construction.

19. A membrane of claim 8, wherein the carbon membrane is the product of pyrolysis of a carbon-containing precursor at temperature of about 250°

C. to about 2500°

C.

20. A separation module of the shell and tube type comprising a plurality of hollow membranes as described in claim 5 or 17.