Production of alkali metal carbonates in a cell having a carboxyl membrane

• US 4,147,599 A
• Filed: 07/19/1977
• Issued: 04/03/1979
• Est. Priority Date: 07/19/1977
• Status: Expired due to Term

• Current Assignee: Eltech Systems Corporation (Industrie De Nora S.p.A)
• Original Assignee: Diamond Shamrock Corp (Valero Energy Corporation)
• Inventors: O'Leary, Kevin J., DeRespiris, Donald L., Hora, Charles J.
• Primary Examiner(s): Tung, T.
• Application Number:
  US05/817,007
• Time in Patent Office: 623 Days
• Field of Search: 204/87, 204/98, 204/296
• US Class Current: 205/482
• CPC Class Codes: C08J 2327/12 containing fluorine atoms
• CPC Class Codes: C08J 5/2237 containing fluorine
• CPC Class Codes: C25B 1/14 Alkali metal compounds

Abstract

An alkali metal carbonate substantially free of alkali metal chloride is efficiently produced by electrolyzing an alkali metal chloride in an electrolytic cell having anolyte and catholyte compartments separated by a cation-exchange hydraulically impermeable membrane comprised of a thin film of a fluorinated polymer having pendant carboxylic acid or alkali metal carboxylate groups and a cathode spaced apart from the membrane, injecting into the catholyte compartment of the cell carbon dioxide in a quantity sufficient to convert substantially all the alkali metal hydroxide forming therein to the alkali metal carbonate salt, and utilizing a magnitude of electrolyzing current that reduces alkali metal chloride in the catholyte solids to less than 400 ppm.

Claims

1. In a method for producing an alkali metal carbonate wherein:

A. an alkali metal chloride is electrolyzed in an electrolytic cell having an anode and cathode in anolyte and catholyte compartments separated by a permselective cation-exchange membrane that is impervious to hydraulic flow and is spaced apart from the cathode;

B. carbon dioxide is injected into the catholyte compartment to give catholyte solids wherein substantially all of the alkali metal hydroxide formed therein is converted to alkali metal carbonate; and

C. catholyte containing the alkali metal carbonate is removed from the catholyte compartment;

the improvement which comprises;

D. utilizing a membrane which;

1. consists essentially of a film having a thickness not exceeding 8 mils of a copolymer having recurring structural units of the formula;

##STR6## and

space="preserve" listing-type="equation">(II) --CXX'"'"'--CF.sub.2 --

wherein R represents the group

space="preserve" listing-type="equation">--OCF.sub.2 --CFY--.sub.m O--CF.sub.2 --(G).sub.e --

in which Y is fluorine or trifluoromethyl, G is --CF₂ -- or ##STR7## m is 1, 2 or 3, e is 0 or 1, and a is an integer from 1 to 10;

n is 0 or 1;

A is H, Na, or K;

X is fluorine, chlorine, or trifluoromethyl;

X'"'"' is X or CF₃ --CF₂ --_z wherein z is 0 or an integer from 1 to 5;

the units of formula (I) being present in an amount to provide a copolymer having in the acid form an --CO₂ H equivalent weight of about 800 to 1400; and

2.

3. The method of claim 1 wherein the electrolyzing current density utilized is of sufficient magnitude to reduce the alkali metal chloride impurity in the catholyte solids to less than 200 parts per million.

4. The method of claim 1 wherein the membrane copolymer film has a thickness not exceeding about 5 mils.

5. The method of claim 3 wherein the electrolyzing current density utilized is of sufficient magnitude to reduce the alkali metal chloride impurity in the catholyte solids to less than 200 parts per million.

6. The method of claim 1 wherein the membrane film consists essentially of a copolymer having recurring structural units of the formula:

space="preserve" listing-type="equation">--CF.sub.2 --CF.sub.2 --

and ##STR8## and has an --CO₂ H equivalent weight of about 900 to 1200.

7. The method of claim 5 wherein the electrolyzing current density utilized is of sufficient magnitude to reduce the alkali metal chloride impurity in the catholyte solids to less than 200 parts per million.

8. The method of claim 5 wherein the membrane copolymer film has a thickness not exceeding about 5 mils.

9. The method of claim 7 wherein the electrolyzing current density utilized is of sufficient magnitude to reduce the alkali metal chloride impurity in the catholyte solids to less than 200 parts per million.

10. The method of claim 5 wherein the alkali metal chloride electrolyzed is potassium chloride and A is potassium.

11. The method of claim 5 wherein the alkali metal chloride electrolyzed is sodium chloride and A is sodium.

12. The method of claim 1 wherein the alkali metal chloride electrolyzed is potassium chloride and A is potassium.

13. The method of claim 1 wherein the alkali metal chloride electrolyzed is sodium chloride and A is sodium.

14. The method of claim 1 further characterized in that the membrane film comprises two layers having a total thickness not exceeding about 8 mils:

the first layer comprising a copolymer as defined in paragraph D.1. wherein e is 0;

the second layer comprising a copolymer having recurring structural units of the formula

space="preserve" listing-type="equation">(II) --CXX'"'"'--CF.sub.2 --

and ##STR9## wherein X, X'"'"', R, n, and A are the same as in the copolymer of the first layer with the exception that e is 1 and G is --CF₂ --, and having the capability of absorbing at least 15 percent by weight water when immersed in 100°

C. water.

15. The method of claim 13, wherein ##STR10##

16. The method of claim 14 wherein the alkali metal chloride electrolyzed is potassium chloride and A is potassium.

17. The method of claim 14 wherein the alkali metal chloride electrolyzed is sodium chloride and A is sodium.

18. The method of claim 13 wherein the alkali metal chloride electrolyzed is potassium chloride and A is potassium.

19. The method of claim 13 wherein the alkali metal chloride electrolyzed is sodium chloride and A is sodium.

2. is capable when immersed in 100°

C. water of absorbing at least 15% by weight water; and

E. utilizing an electrolyzing current density in excess of one ampere per square inch of membrane area of sufficient magnitude to reduce alkali metal chloride in the catholyte solids to less than 400 parts per million.