Process for the production of alkaline earth hydroxide

• US 6,375,825 B1
• Filed: 10/28/1999
• Issued: 04/23/2002
• Est. Priority Date: 10/28/1999
• Status: Expired due to Term

• Current Assignee: Chemical Products Corporation
• Original Assignee: Chemical Products Corporation
• Inventors: Mauldin, Lloyd Ballard, Chai, Dennis M., Adams, Charles Jr., Randolph, Donald R., Genders, J. David, Mazur, Duane J.
• Primary Examiner(s): Phasge, Arun S.
• Application Number:
  US09/428,738
• Time in Patent Office: 908 Days
• Field of Search: 295/508
• US Class Current: 205/508
• CPC Class Codes: C25B 1/20 Hydroxides

Abstract

A process for the continuous production of alkaline earth metal hydroxide by continuously providing an aqueous alkaline earth metal halide solution to the anode compartment and an aqueous alkaline earth metal hydroxide solution or water to the cathode compartment of an electrolytic cell in which an anode and a cathode are maintained in separate anode and cathode compartments, respectively, by a stable, hydrated, cation selective, hydraulically impermeable, electrically conductive membrane interposed between said anode and said cathode; electrolyzing the alkaline earth metal halide solution; and continuously removing alkaline earth metal hydroxide solution and hydrogen from the cathode compartment and halogen from the anode compartment. The membrane is a film of a fluorinated polymer with pendant side chains containing sulfonyl groups present as ion exchange sites and attached to carbon atoms which have at least one fluorine atom attached thereto. In another embodiment the membrane is a laminate of two such polymers differing in equivalent weight.

Claims

1. A process for the continuous production of alkaline earth metal hydroxide comprising:

a. continuously providing an aqueous alkaline earth metal halide solution to the anode compartment of an electrolytic cell in which an anode and a cathode are maintained in separate anode and cathode compartments, respectively, by a hydrated, cation selective, hydraulically impermeable, ionically conductive membrane interposed between said anode and said cathode;

b. electrolyzing the alkaline earth metal halide solution;

c. continuously removing alkaline earth metal hydroxide solution and hydrogen from the cathode compartment and halogen from the anode compartment;

said membrane comprising a cation exchange membrane wherein sulfonyl groups serve as the predominant ion exchange site.

2. A process as claimed in claim 1, wherein said membrane comprises a film of a fluorinated polymer with pendant side chains containing sulfonyl groups, said sulfonyl groups present as ion exchange sites and attached to carbon atoms which have at least one fluorine atom attached thereto.

3. A process as claimed in claim 2, wherein said membrane comprises a film of perfluorinated sulfonate polymer.

4. A process as claimed in claim 3, further comprising the step of maintaining said alkaline earth metal halide solution at a pH of about 2.0 to about 4.0.

5. A process as claimed in claim 4, further comprising the step of maintaining said alkaline earth metal halide solution at a temperature of from about 70°

C. to about 90°

C.

6. A process as claimed in claim 3, wherein the source of water to the cathode compartment after startup being that transported through said membrane or added at a steady rate from an external source.

7. A process as claimed in claim 4, wherein said aqueous alkaline earth metal halide solution is barium chloride solution.

8. A process as claimed in claim 7, wherein barium hydroxide solution or water are initially added to the cathode compartment of the electrolytic cell.

9. A process as claimed in claim 4, wherein said aqueous alkaline earth metal halide solution is strontium chloride solution.

10. A process as claimed in claim 9, wherein strontium hydroxide solution or water is initially added to the cathode compartment of the electrolytic cell.

11. A process as claimed in claim 4, wherein said membrane further comprises a polytetrafluoroethylene cloth mesh reinforcement.

12. A process for the continuous production of alkaline earth metal hydroxide comprising:

a. continuously providing an aqueous alkaline earth metal halide solution to the anode compartment of an electrolytic cell in which an anode and a cathode are maintained in separate anode and cathode compartments, respectively, by a hydrated, cation selective, hydraulically impermeable, ionically conductive membrane interposed between said anode and said cathode;

b. electrolyzing the alkaline earth metal halide solution;

c. continuously removing alkaline earth metal hydroxide solution and hydrogen from the cathode compartment and halogen from the anode compartment;

said membrane comprising first and second layers of a fluorinated polymer with pendant side chains containing sulfonyl groups present as predominant ion exchange sites and attached to carbon atoms which have at least one fluorine atom attached thereto;

said first layer of the polymer having an equivalent weight greater than said second layer; and

said membrane being positioned so that said first layer of the polymer faces said cathode compartment.

13. A process as claimed in claim 12, wherein said polymer is a perfluorinated sulfonate polymer.

14. A process as claimed in claim 13, further comprising the step of maintaining said alkaline earth metal halide solution at a pH of about 2.0 to about 4.0.

15. A process as claimed in claim 14, further comprising the step of maintaining said alkaline earth metal halide solution at a temperature of from about 70°

C. to about 90°

C.

16. A process as claimed in claim 13, wherein the source of water to the cathode compartment after startup being that transported through said membrane or added at a steady rate from an external source.

17. A process as claimed in claim 14, wherein said aqueous alkaline earth metal halide solution is barium chloride solution.

18. A process as claimed in claim 17, wherein barium hydroxide solution or water are initially added to the cathode compartment of the electrolytic cell.

19. A process as claimed in claim 14, wherein said aqueous alkaline earth metal halide solution is strontium chloride solution.

20. A process as claimed in claim 19, wherein strontium hydroxide solution or water are initially added to the cathode compartment of the electrolytic cell.

21. A process as claimed in claim 14, wherein said membrane further comprises a polytetrafluoroethylene cloth mesh reinforcement within said second layer of polymer.

22. A process as claimed in claim 21, wherein said first layer has an equivalent weight of about 1500.

23. A process as claimed in claim 13, wherein said first layer of the polymer has an equivalent weight about 400 greater than said second layer.

24. A process for the continuous production of barium hydroxide comprising:

a. continuously providing an aqueous barium halide solution to the anode compartment of an electrolytic cell in which an anode and a cathode are maintained in separate anode and cathode compartments, respectively, by a hydrated, cation selective, hydraulically impermeable, ionically conductive membrane interposed between said anode and said cathode;

b. electrolyzing the barium halide solution;

c. continuously removing barium hydroxide solution and hydrogen from the cathode compartment and halogen from the anode compartment;

said membrane comprising a cation exchange membrane wherein sulfonyl groups serve as the predominant ion exchange site.

25. The process of claim 24, wherein said membrane comprises a film of a fluorinated polymer with pendant side chains containing sulfonyl groups, said sulfonyl groups present as ion exchange sites and attached to carbon atoms which have at least one fluorine atom attached thereto.

26. The process of claim 24, wherein said membrane comprises a film of perfluorinated sulfonate polymer.

27. The process of claim 24, further comprising the step of maintaining said barium halide solution at a pH of about 2.0 to about 4.0.

28. The process of claim 24, further comprising the step of maintaining said barium halide solution at a temperature of about 70°

C. to about 90°

C.

29. The process of claim 24, wherein said membrane comprises first and second layers of a fluorinated polymer with pendant side chains containing sulfonyl groups present as predominant ion exchange sites and attached to carbon atoms which have at least one fluorine atom attached thereto;

said first layer of the polymer having an equivalent weight greater than said second layer; and

said membrane being positioned so that said first layer of the polymer faces said cathode compartment.

30. The process of claim 29, wherein said membrane further comprises a polytetrafluoroethylene cloth mesh reinforcement within said second layer of polymer.

31. The process of claim 30, wherein said first layer of polymer has an equivalent weight about 400 greater than said second layer of the polymer.

32. The process of claim 30, wherein said first layer of polymer has an equivalent weight of about 1500.

33. A process for the continuous production of an alkaline earth metal hydroxide comprising:

providing an electrolytic cell having an anode compartment and a cathode compartment separated by a cation exchange membrane interposed therebetween, said cation exchange membrane having pendent sulfonyl side chains and being substantially free of side chains that are reactive with the alkaline earth metal to form water insoluble complexes;

providing a stream of alkaline earth metal halide solution to the anode compartment of the electrolytic cell;

electrolyzing the alkaline earth metal halide solution under conditions wherein said membrane is not adversely affected by deposition of water insoluble complexes;

continuously removing a stream of alkaline earth metal hydroxide solution and hydrogen from the cathode compartment and halogen from the anode compartment.

34. The process of claim 33, wherein said cation exchange membrane includes a first layer and a second layer, said first layer having an equivalent weight greater than said second layer;

and wherein said membrane is positioned so that said first layer faces said cathode compartment.

35. The process of claim 34, wherein said first layer has an equivalent weight about 400 greater than said second layer.

36. The process of claim 33, wherein said first layer has an equivalent weight of about 1500.