Separation membrane and method of preparing and using same

• US 4,527,999 A
• Filed: 03/23/1984
• Issued: 07/09/1985
• Est. Priority Date: 03/23/1984
• Status: Expired due to Fees

• Current Assignee: Koch Membrane Systems, Inc. (KOCH Industries Incorporated)
• Original Assignee: Abcor Incorporated
• Inventors: Lee, Cheng H.
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US06/592,519
• Time in Patent Office: 473 Days
• Field of Search: 55/16, 55/68, 55/158, 210/500.2, 210/654, 264/342 R, 264/344, 427/245, 427/246, 528/353
• US Class Current: 210/654
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 67/0095 Drying

Abstract

A differential pore-collapsed separation membrane particularly useful as a gas-separation membrane and a method of preparing such differential pore-collapsed membrane, which method comprises treating an asymmetric membrane, while under one-sided constraint, with a treating solution comprising a volatile nonsolvent and a swelling agent and/or a solvent, and drying the treated membrane, to provide for the controlled, differential pore collapse of the small pores of the top skin of the membrane to a smaller pore-size distribution in the membrane generally less than about 10 Angstroms.

Claims

1. A process of preparing an asymmetric separation membrane suitable for use as a gas-permeation or reverse-osmosis separation membrane, which process comprises:

(a) treating a preformed dried leached high-flux, asymmetric, polymeric membrane, having a top skin surface with large pores of about 50 angstroms or more and an underlying bulk porous layer, with a posttreatment solution which comprises a volatile nonsolvent for the polymer of the membrane in the presence of a swelling agent for the polymer or a solvent for the polymer; and

(b) drying the solution-treated, asymmetric membrane, while the membrane is under one-sided constraint, to provide for the evaoporating of the nonsolvent substantially through the top skin layer and for the differential collapsing of the pores of the top skin surface of the asymmetric membrane to a selected, smaller pore size of about 10 angstroms or less.

2. The process of claim 1 wherein the asymmetric separation membrane comprises a cellulose-acetate membrane.

3. The process of claim 1 which comprises differentially collapsing the small pores of the top skin of the asymmetric membrane, having a pore size of about 100 Angstroms or more, to a desired, smaller, open-pore size of about 0.1 to 10 Angstroms.

4. The process of claim 1 which includes treating the asymmetric membrane with a posttreatment solution comprising a volatile hydrocarbon non-solvent and less than about 5% by volume of a solvent for the polymer.

5. The process of claim 4 wherein the hydrocarbon non-solvent comprises heptane and the solvent is selected from the group consisting of dioxane, N-methyl pyrrolidone, dimethyl formamide and dimethyl acetamide.

6. The process of claim 5 wherein the solvent is present in an amount of from about 0.05% to 2% of the posttreatment solution.

7. The process of claim 1 which includes treating the asymmetric membrane with a posttreatment solution of a volatile hydrocarbon non-solvent and water as a swelling agent in an amount of less than about 5% of the solution.

8. The process of claim 1 wherein the high-flux, asymmetric, polymeric membrane is prepared by drying the membrane in a solvent exchange employing an aliphatic alcohol and a volatile hydrocarbon non-solvent.

9. The process of claim 1 wherein the dried high-flux, asymmetric, polymeric membrane is prepared by drying the membrane in a two-step, solvent-exchange process employing substantially water-free isopropanol as a first drying step and employing a volatile hydrocarbon miscible with the isopropanol as the second drying step.

10. The process of claim 1 which includes immersing the asymmetric membrane in the posttreatment solution and drying the posttreated membrane by evaporation of the posttreatment solution from the membrane, while evaporation through the opposite side of the treated asymmetric membrane is constrained by a nonporous substrate.

11. The process of claim 1 wherein the posttreatment solution contains a small amount of a polymeric agent.

12. The process of claim 11 wherein the polymeric agent comprises a silicone polymer or a urethane prepolymer or polybutadiene.

13. The process of claim 11 wherein the posttreatment solution comprises from about 0.1% to 5% by weight of a cross-linkable polymeric agent, having a molecular weight less than about 100,000, and a small cross-linking amount of a cross-linking agent for the polymer and a catalytic amount of a catalyst for the cross-linking reaction.

14. The process of claim 13 wherein the cross-linkable polymeric agent comprises a polydimethyl siloxane silanol prepolymer.

15. The process of claim 11 wherein the high-flux, asymmetric, polymeric membrane is prepared from a casting solution and contains a small, effective amount of a residual solvent from the casting solution as the solvent, and the high-flux membrane is treated with a volatile hydrocarbon nonsolvent.

16. The process of claim 15 wherein the polymeric membrane comprises a cellulose-acetate membrane which contains a small, effective amount of dioxane as a residual solvent in the membrane, and wherein the volatile hydrocarbon nonsolvent comprises heptane.

17. The process of claim 16 wherein the volatile hydrocarbon nonsolvent includes a small amount of a silicone silanol polymer having a terminal hydroxy group or alkylamino group or a polyurethane having free NCO groups.

18. The process of claim 11 wherein the posttreatment solution includes a small pore-coating amount of a silicone prepolymer, having a molecular weight of less than 100,000, and an OH or --N(CH₃)₂ terminal functional group.

19. The process of claim 11 wherein the posttreatment solution includes a small amount of a silicone silanol prepolymer and a cross-linking agent.

20. The process of claim 19 wherein the cross-linking agent comprises a vinyl-silicone oxime compound or a polyurethane prepolymer having free NCO groups.

21. The process of claim 19 which includes recovering a dry separator membrane having a gas-permeation rate of about 1 to 3 and a gas-separation factor, based on CO₂ /CH₄, of about 10 to 20.

22. The differentially pore-collapsed, asymmetric separation membrane prepared by the process of claim 19.

23. The differentially pore-collapsed, asymmetric separation membrane prepared by the process of claim 11.

24. The process of claim 1 wherein the dried high-flux, asymmetric membrane comprises a heat unannealed dry membrane.

25. The process of claim 1 which includes drying the solution-treated membrane under controlled humidity conditions of greater than about 50% relative humidity.

26. The differentially pore-collapsed, asymmetric separation membrane prepared by the process of claim 1.

27. A reverse-osmosis separation process for the separation of a feed fluid stream by a reverse osmosis separation membrane into a permeate fraction and a nonpermeate fraction, which process employs as the separation membrane the differential pore-collapsed separation membrane of claim 1.

28. A gas permeation separation process for the separation of a feed gas stream by a gas separation membrane into a gas permeate fraction and a gas nonpermeate fraction, which process employes as the gas separation membrane the differential pore-collapsed separation membrane of claim 1.

29. In a process for preparing a cellulose-ester separation membrane, which process comprises:

(a) preparing a casting solution which comprises a solvent and a cellulose-ester polymer;

(b) coating the casting solution to form a wet film of the casting solution;

(c) removing at least part of the solvent of the casting solution, to form a gelled membrane film;

(d) washing the gelled membrane film with water;

(e) removing the water by solvent exchange; and

(f) recovering a dry, high-flux, asymmetric, cellulose-ester, separation membrane having a top-skin surface membrane layer, having pores therein of about 50 Angstroms or more, and an integral, underlying, porous bulk layer, the improvement which comprises

(i) immersing the dry-film, washed high-flux, asymmetric membrane in a treating solution comprising a volatile hydrocarbon nonsolvent for the cellulose ester of the membrane and less than about 1% by volume of a solvent for the cellulose ester in the nonsolvent or present as residual solvent in the high-flux membrane, and

(ii) drying by evaporation the solution-treated, asymmetric membrane, while constraining evaporation of the treating solution from the porous bulk layer, to remove preferentially initially the volatile nonsolvent and to concentrate temporarily the solvent in the top skin surface, so as to cause differential pore collapse of the small pores of the top skin surface of the membrane to a controlled and selected smaller pore size of less than about 10 Angstroms.

30. The process of claim 29 wherein the cellulose ester comprises cellulose acetate.

31. The process of claim 29 wherein the small pore size of the top skin layer of the asymmetric membrane, prior to differential pore collapse, averages about 50 to 250 Angstroms.

32. The process of claim 29 wherein the differential pore-collapsed asymmetric membrane has a pore size ranging from less than about 0.1 to 10 Angstroms.

33. The process of claim 29 wherein the nonsolvent comprises heptane and the solvent comprises from about 0.05% to 2% by volume N-methyl pyrrolidone.

34. The process of claim 33 wherein the volatile hydrocarbon comprises heptane and the residual solvent comprises dioxane.

35. The process of claim 29 wherein the treating solution includes a small pore-coating amount of a silicone silanol prepolymer agent and a functional cross-linking agent in the treating solution.

36. The process of claim 35 wherein the small amount of the agent comprises an amount generally less than about 2% by weight of the treating solution, and the agent comprises a polydimethyl siloxane silanol prepolymer having a molecular weight less than about 100,000, and the cross-linking agent comprises an isocyanate-containing agent.

37. The differential, pore-collapsed asymmetric membrane prepared by the process of claim 29.

38. A process of separating a gas feed stream employing a gas separation membrane into a gas permeate fraction and a gas nonpermeate fraction, which process comprises employing the differential pore-collapsed, dry asymmetric separation membrane of claim 29 as the gas-separation membrane.

39. A process of separating a liquid feed stream into a permeate fraction and a nonpermeate fraction in a reverse osmosis process employing a reverse osmosis membrane, which process comprises employing as the reverse osmosis membrane the differential pore-collapsed dry asymmetric membrane of claim 29.

40. The process of separating a gas feed stream comprising carbon dioxide and methane employing a gas separation membrane into a carbon dioxide-enriched permeate fraction and into a methane-enriched nonpermeate fraction, which process comprises employing as the gas separation membrane the differential, pore-collapsed separation membrane of claim 29.