Dithiolene functionalized polymer membrane for olefin/paraffin separation

• US 7,160,356 B2
• Filed: 04/15/2004
• Issued: 01/09/2007
• Est. Priority Date: 04/15/2003
• Status: Expired due to Fees

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Koros, William J., Burns, Ryan L.
• Primary Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US10/824,772
• Publication Number:
  US 20050000899A1
• Time in Patent Office: 999 Days
• Field of Search: 95/43, 95/45, 95/50, 96/4, 96/14, 210/650, 210/500.27, 210/500.28, 210/500.38, 210/500.39
• US Class Current: 95/50
• CPC Class Codes: B01D 2257/7022 Aliphatic hydrocarbons
• CPC Class Codes: B01D 2325/022 Asymmetric membranes
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0011 Casting solutions therefor
• CPC Class Codes: B01D 69/142 with "carriers"
• CPC Class Codes: B01D 71/56 Polyamides, e.g. polyester-amides
• CPC Class Codes: B01D 71/62 Polycondensates having nitrogen-containing heterocyclic rings in the main chain
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 7/144 using membranes, e.g. selective permeation

Abstract

A polymeric composite may be used for forming fluid separation membranes. The membranes may be formed from polyimide, polyamide or poly (pyrrolone-imide) materials. Polyamides may be formed by the condensation of a tetraamine, a tetraacid, and a diamine. Polyimides and poly (pyrrolone-imides) may be formed by the cyclization of a polymer precursor. A polymeric composite may include a dithiolene or a mixture of dithiolenes. A polymer matrix incorporating dithiolenes may exhibit an olefin/paraffin solubility selectivity. A solubility selectivity may be between about 1.1 and about 2.0.

Claims

1. A fluid separation membrane for separating one or more components from a fluid, the fluid comprising two or more components, wherein the fluid separation membrane comprises at least one polymer and at least one dithiolene having the structure:

2. The fluid separation membrane of claim 1, wherein the membrane exhibits an olefin/paraffin solubility selectivity.

3. The fluid separation membrane of claim 1, wherein the membrane exhibits an olefin/paraffin solubility selectivity of 1.1 to 2.0.

4. The fluid separation membrane of claim 1, wherein at least one dithiolene is resistant to poisoning by impurities.

5. The fluid separation membrane of claim 1, wherein the metal is Ni, Pd, or Pt.

6. The fluid separation membrane of claim 1, wherein at least one dithiolene further comprises a valence charge, and wherein the valence charge is 0, −

1, or −

2.

7. The fluid separation membrane of claim 1, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises a counter ion.

8. The fluid separation membrane of claim 1, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises at least one counter ion having the structure;

9. The fluid separation membrane of claim 1, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises at least one counter ion having the structure;

10. The fluid separation membrane of claim 1, wherein at least one dithiolene is capable of complexing with an olefin.

11. The fluid separation membrane of claim 1, wherein the fluid comprises a liquid.

12. The fluid separation membrane of claim 1, wherein the fluid comprises a gas stream.

13. The fluid separation membrane of claim 1, wherein the fluid comprises a gas stream, and wherein the gas stream comprises a hydrocarbon.

14. The fluid separation membrane of claim 1, wherein R₁, R₂, R₃, and R₄ are CH₃, at least one dithiolene having the structure:

15. The fluid separation membrane of claim 1, wherein R₁, R₂, R₃, and R₄ are CF₃, at least one dithiolene having the structure:

16. The fluid separation membrane of claim 1, wherein R₁, R₂, R₃, and R₄ are C₆H₄OCH₃, at least one dithiolene having the structure:

17. The fluid separation membrane of claim 1, wherein R₁ and R₂ combine to form C₆H₃CH₃, and wherein R₃ and R₄ combine to form C₆H₃CH₃, at least one dithiolene having the structure:

18. The fluid separation membrane of claim 1, wherein R₁ and R₂ combine to form C₆H₄S₄, and wherein R₃ and R₄ are CF₃, at least one dithiolene having the structure:

19. The fluid separation membrane of claim 1, wherein at least one polymer comprises the reaction product of a tetraacid compound and a diamine.

20. The fluid separation membrane of claim 1, wherein at least one polymer comprises the reaction product of a tetraacid compound and a diamine, wherein the tetraacid compound comprises an aromatic dianhydride having the structure:

21. The fluid separation membrane of claim 1, wherein at least one polymer comprises a polyimide polymer, a polyamide polymer, a polypyrrolone polymer, or a poly (pyrrolone-imide) polymer.

22. The fluid separation membrane of claim 1, wherein at least one polymer comprises a polyimide polymer, wherein the polyimide polymer comprises recurring units, a portion of the recurring units having the structure:

23. A fluid separation membrane for separating one or more components from a fluid, the fluid comprising two or more components, wherein the fluid separation membrane comprises at least one polymer and at least one dithiolene having the structure:

24. The fluid separation membrane of claim 23, wherein the membrane exhibits an olefin/paraffin solubility selectivity.

25. The fluid separation membrane of claim 23, wherein the membrane exhibits an olefin/paraffin solubility selectivity of 1.1 to 2.0.

26. The fluid separation membrane of claim 23, wherein the metal is Ni, Pd, or Pt.

27. The fluid separation membrane of claim 23, wherein at least one dithiolene further comprises a valence charge, and wherein the valence charge is 0, −

1, or −

2.

28. The fluid separation membrane of claim 23, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises a counter ion.

29. The fluid separation membrane of claim 23, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises at least one counter ion having the structure;

30. The fluid separation membrane of claim 23, wherein at least one dithiolene further comprises a valence charge, wherein the valence charge is −

1 or −

2, and wherein the dithiolene comprises at least one counter ion having the structure;

31. The fluid separation membrane of claim 23, wherein at least one dithiolene is capable of complexing with an olefin.

32. The fluid separation membrane of claim 23, wherein the fluid comprises a liquid.

33. The fluid separation membrane of claim 23, wherein the fluid comprises a gas stream.

34. The fluid separation membrane of claim 23, wherein the fluid comprises a gas stream, and wherein the gas stream comprises a hydrocarbon.

35. The fluid separation membrane of claim 23, wherein at least one polymer comprises the reaction product of a tetraacid compound and a diamine.

36. The fluid separation membrane of claim 23, wherein at least one polymer comprises the reaction product of a tetraacid compound and a diamine, wherein the tetraacid compound comprises an aromatic dianhydride having the structure:

37. The fluid separation membrane of claim 23, wherein at least one polymer comprises a polyimide polymer, a polyamide polymer, a polypyrrolone polymer, or a poly (pyrrolone-imide) polymer.

38. The fluid separation membrane of claim 23, wherein at least one polymer comprises a polyimide polymer, wherein the polyimide polymer comprises recurring units, a portion of the recurring units having the structure:

39. A method of preparing a fluid separation membrane for separating one or more components from a fluid, the fluid comprising two or more components, comprising adding at least one dithiolene to at least one polymer, the dithiolene having the structure:

40. A method of separating one or more components from a fluid, the fluid comprising two or more components, comprising bringing the fluid stream into contact with a face of a fluid separation membrane, the fluid separation membrane comprising at least one polymer and at least one dithiolene having the structure:

41. An apparatus for separating one or more components from a fluid, the fluid comprising two or more components, comprising:

a body;

a fluid separation membrane disposed within the body, the fluid separation membrane comprising at least one polymer and at least one dithiolene having the structure;