High performance bipolar membranes

• US 5,227,040 A
• Filed: 10/25/1991
• Issued: 07/13/1993
• Est. Priority Date: 07/30/1987
• Status: Expired due to Term

• Current Assignee: Unisearch Limited (University Of New South Wales)
• Original Assignee: Unisearch Limited (University Of New South Wales)
• Inventors: Simons, Raymond G.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Phasge, Arun S.
• Application Number:
  US07/781,660
• Time in Patent Office: 627 Days
• Field of Search: 204/295, 204/301, 204/296, 521/27, 521/30
• US Class Current: 204/631
• CPC Class Codes: C08J 2381/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
• CPC Class Codes: C08J 5/2275 Heterogeneous membranes

Abstract

A low electrical resistance bipolar membrane formed by the conjoining of treated anion and cation exchange membranes is disclosed. The treatment comprises contacting the membranes with an aqueous solution of at least one cation prior to conjoining and contacting at least one face of the membranes with an aqueous alkaline solution.

A process for the preparation of acid and alkali using these bipolar membranes is also disclosed.

Claims

1. A bipolar membrane comprising conjoined, modified anion and cation exchange membranes, said modified membranes comprising anion and cation exchange membranes modified by

(a) treatment with an aqueous solution of at least one monovalent or higher oxidation state cation, excluding sodium and potassium, prior to being conjoined, and

(b) treatment of at least one face of one of the anion and cation exchange membranes with an aqueous alkaline solution, at least one of said aqueous solution and of said aqueous alkaline solution being hot,

said bipolar membrane when tested in an electrodialysis cell containing 2N sodium hydroxide and 2N hydrochloric acid exhibiting a potential difference across said membrane substantially lower than that exhibited by a bipolar membrane formed from unmodified anion and cation exchange membranes for a period of at least 100 hours.

2. A bipolar membrane as in claim 1, wherein the membranes are treated, prior to conjoining, by immersion in an aqueous solution of at least one monovalent or higher oxidation state cation, excluding potassium and sodium.

3. A bipolar membrane as in claim 2, wherein the membranes are conjoined prior to treatment with the aqueous alkaline solution.

4. A bipolar membrane as in claim 2, wherein the membranes are treated with the aqueous alkaline solution prior to conjoining.

5. A bipolar membrane as in claim 4, wherein the aqueous alkaline solution includes the at least one monovalent or higher oxidation state cation, excluding sodium and potassium.

6. A bipolar membrane as in claim 5, wherein both membranes are treated by immersion in the aqueous alkaline solution.

7. A bipolar membrane as in claim 6, wherein the aqueous alkaline solution is at a temperature between about 70°

C. and about 100°

C.

8. A bipolar membrane as in claim 4, wherein prior to conjoining, both membranes are treated by immersion in the hot aqueous state cation, excluding sodium and potassium, and then treated by immersion in the hot aqueous alkaline solution.

9. A bipolar membrane as in claim 8, wherein treatment with the aqueous alkaline solution consists of contacting a membrane face with said solution.

10. A bipolar membrane as in claim 9, wherein both of the membrane faces are contacted with the aqueous alkaline solution.

11. A bipolar membrane as in claim 10, wherein the aqueous alkaline solution is at a temperature of about 75°

C.

12. A bipolar membrane as in claim 2, wherein the at least one cation is included as a salt in a concentration of from 5 to 15% w/v.

13. A bipolar membrane as in claim 12, wherein the at least one cation is selected from the group consisting of Cr³⁺, Ru³⁺, Ce³⁺, Ni²⁺, Zr⁴⁺, In³⁺, Sn²⁺ and Fe²⁺.

14. A bipolar membrane as in claim 13, wherein the salt is selected from the group consisting of chromic nitrate, chromic chloride, ruthenium trichloride, indium sulphate, cerrous sulphate, thorium nitrate and zirconium chloride.

15. A bipolar membrane as in claim 2, wherein the aqueous alkaline solution concentration is from 0.2 to 2.0 molar.

16. A bipolar membrane as in claim 2, wherein the anion and cation exchange membranes include quaternary ammonium and sulphonic acid groups.

17. A method for the preparation of a bipolar membrane from modified anion and cation exchange membranes which bipolar membrane when tested in an electrodialysis cell containing 2N hydrochloric acid and 2N hydroxide exhibits a potential difference across said membrane substantially lower than that exhibited by a bipolar membrane formed from unmodified anion and cation exchange membranes for a period of at least 100 hours, said method comprising modifying anion and cation exchange membranes by

(a) treating an anion exchange membrane and a cation exchange membrane with an aqueous solution of a salt, said salt yielding in the solution at least one monovalent or higher oxidation state cation, excluding sodium and potassium;

(b) conjoining the treated anion and cation exchange membranes; and

(c) treating at least one face of the conjoined membranes with an aqueous alkaline solution, to give said bipolar membrane, at least one of said aqueous salt solution and said aqueous alkaline solution being hot, to thereby obtain said membrane.

18. A method as in claim 17, wherein the treatment comprises immersion of the anion exchange membrane in the aqueous salt solution.

19. A method as in claim 17, wherein the treatment with the aqueous alkaline solution consists of contacting a membrane face with said solution.

20. A method as in claim 19, wherein both faces of the bipolar membrane are contacted with the aqueous alkaline solution.

21. A method as in claim 17, wherein the aqueous alkaline solution is in a concentration of 0.2 to 2.0 molar.

22. A method as in claim 21, wherein the alkaline solution contacts the membrane for from 15 to 30 minutes.

23. A method as in claim 22, wherein the alkaline solution is at a temperature of about 75°

C.

24. A method as in claim 17, wherein the anion and cation exchange membranes are treated by immersion in the aqueous salt solution.

25. A method as in claim 17, wherein the salt is in a concentration of from 5 to 15% w/v.

26. A method as in claim 25, wherein the salt is selected from the group consisting of chromic nitrate, chromic chloride, ruthenium trichloride, ferrous chloride, indium sulphate, cerrous sulphate, thorium nitrate and zirconium chloride.

27. A method as in claim 17, wherein the membrane are conjoined by pressing together at a temperature below the onset of deformation or degradation of the membranes.

28. A method for the preparation of a bipolar membrane from modified anion and cation exchange membranes which bipolar membrane when tested in an electrodialysis cell containing 2N hydrochloric acid and 2N sodium hydroxide exhibits a potential difference across said membrane substantially lower than that exhibited by a bipolar membrane formed from unmodified anion and cation exchange membranes for a period of at least 100 hours, said method comprising modifying anion and cation exchange membranes by

treating an anion exchange and a cation exchange membrane with a hot aqueous alkaline solution of a salt, said salt yielding in the solution at least one monovalent or higher oxidation state cation, excluding sodium and potassium;

and then conjoining the modified membranes to give said bipolar membrane.

29. A method as in claim 28, wherein the alkali is in a concentration of from 0.2 to 2.0 molar.

30. A method as in claim 28, wherein the salt is in a concentration of from 5 to 15% w/v.

31. A method as in claim 30, wherein the salt is selected from the group consisting of chromic nitrate, chromic chloride, ruthenium trichloride, ferrous chloride, indium sulphate, cerrous sulphate, thorium nitrate and zirconium chloride.

32. A method as in claim 28, wherein the membranes are treated by immersion in the aqueous alkaline salt solution.

33. A method a in claim 32, wherein the solution containing the membranes is at a temperature of between about 70°

C. and about 100°

C.

34. A method as in claim 28, wherein the membranes are washed prior to conjoining.

35. A method as in claim 28, wherein the membranes are conjoined by pressing together at a temperature below the onset of deformation or degradation of the membranes.