Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same

• US 6,755,900 B2
• Filed: 12/18/2002
• Issued: 06/29/2004
• Est. Priority Date: 12/20/2001
• Status: Expired due to Term

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.), University of Texas System
• Inventors: Wallace, David, Koros, William J., Vu, De Q., Wind, John D., Miller, Stephen J., Staudt-Bickel, Claudia
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US10/323,090
• Publication Number:
  US 20030140789A1
• Time in Patent Office: 559 Days
• Field of Search: 95/51, 96/4, 96/8, 96/10, 96/14, 55D/IG.5
• US Class Current: 96/10
• CPC Class Codes: B01D 2313/18 Specific valves
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 63/02 Hollow fibre modules
• CPC Class Codes: B01D 63/021 Manufacturing thereof
• CPC Class Codes: B01D 63/0233 forming the bundle
• CPC Class Codes: B01D 63/031 Two or more types of hollow fibres within one bundle or within one potting or tube-sheet
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 67/00931 by introduction of specific groups after membrane formation, e.g. by grafting
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 69/1411 containing dispersed material in a continuous matrix
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/643 Polyether-imides
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: Y02C 20/20 of methane
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 55/05 Methods of making filter

Abstract

A composition of and a method of making high performance mixed matrix hollow fiber membranes is described. The membranes have a high resistance to plasticization by use of a predetermined amount of crosslinking. The preferred polymer material for the membrane is a polyimide polymer continuous phase comprising ester crosslinks and a molecular sieve material dispersed within the polymer continuous phase. The resultant mixed matrix hollow fiber membrane exhibits a high permeance of CO₂ in combination with a high CO₂/CH₄ selectivity. Another embodiment provides a method of making the mixed matrix hollow fiber membrane from a monesterified polymer followed by final crosslinking after hollow fiber formation.

Claims

1. A hollow fiber polymer membrane, comprising:

a) a crosslinked polymer continuous phase; and

b) a molecular sieve material dispersed within said continuous phase;

wherein said membrane has a CO₂ permeance of at least 20 GPU and a CO₂/CH₄ selectivity of greater than 20, at 35 degrees C. and a pressure of 100 psia.

2. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 1 micron.

3. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 0.1 micron.

19. The hollow fiber polymer membrane of claims 1, 4 or 5 wherein the molecular sieve is a zeolite.

20. The hollow fiber polymer membrane of claims 1, 4 or 5 wherein the molecular sieve is carbon molecular sieve.

21. The hollow fiber polymer membrane of claims 1, 4 or 5 wherein the molecular sieve is an aluminophosphate zeolite.

22. The hollow fiber polymer membrane of claims 1, 4 or 5 wherein the molecular sieve is a borosilicate.

23. The hollow fiber polymer membrane of claims 1, 4 or 5 wherein the molecular sieve is a SAPO.

4. A hollow fiber mixed matrix polymer membrane, comprising:

a) a continuous phase polymer comprising a polyimide having crosslinkable sites; and

b) a molecular sieve material dispersed within said continuous phase polymer;

wherein the ratio of crosslinkable sites to imide groups is between 3;

8 and 1;

16.

5. A hollow fiber mixed matrix polymer membrane material, comprising:

a molecular sieve dispersed within a continuous polymer phase wherein said continuous polymer phase comprises a polyimide polymer made from the monomers A+B+C;

where A is a dianhydride of the formula;

where X₁ and X₂ are independently a halogenated alkyl group, phenyl or halogen;

where R₁, R₂, R₃, R₄, R₅, and R₆ are independently H, alkyl, or halogen;

where B is a diamino cyclic compound without a carboxylic acid functionality;

where C is a diamino cyclic compound with a carboxylic acid functionality; and

wherein the ratio of B to C is between 1;

4 and 8;

1.

6. The hollow fiber polymer membrane material of claim 5 where X₁ and X₂ are CF₃.

7. The hollow fiber polymer membrane material of claim 5 where R₁, R₂, R₃, R₄, R₅, and R₆ are H.

8. The hollow fiber polymer membrane material of claim 5 wherein the dianhydride is 6FDA.

9. The hollow fiber polymer membrane material of claim 5 wherein C is DABA.

10. The hollow fiber polymer membrane material of claim 5 wherein B is a diamino aromatic compound.

11. The hollow fiber polymer membrane material of claim 5 wherein B is a diamino benzene compound having one or more methyl groups attached to the benzene ring.

12. The hollow fiber polymer membrane material of claim 5 wherein the ratio of B to C is between 17:

3 and 3;

2.

13. The hollow fiber polymer membrane material of claim 5 wherein the ratio of B to C is between 17:

3 and 3;

1.

14. The hollow fiber polymer membrane material of claim 5 wherein said membrane is subjected to esterification conditions in the presence of a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, benzenedimethanol, and 1,3 butanediol to form a hollow fiber polymer membrane monoester.

15. The hollow fiber polymer membrane material of claim 14 wherein at least 60% of the carboxylic acid functionality is converted to a monoester.

16. The hollow fiber polymer membrane material of claim 14 wherein the hollow fiber membrane monoester is subjected to transesterification conditions to form a crosslinked hollow fiber polymer membrane.

17. The hollow fiber polymer membrane material of claim 5 wherein B is diamino durene.

18. The hollow fiber polymer membrane material of claim 14 wherein at least 80% of the carboxylic acid functionality is converted to a monoester.

24. A method of making a crosslinked hollow fiber membrane, comprising:

preparing a continuous phase polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer;

forming a hollow fiber from said continuous phase polyimide polymer;

treating the hollow fiber with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified hollow fiber; and

subjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane.

25. A method of making a crosslinked hollow fiber membrane, comprising:

preparing a polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer;

treating the polyimide polymer with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified membrane material;

forming a monoesterified hollow fiber from the monoesterified membrane material; and

subjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane.