Ion exchange membrane for alkali chloride electrolysis, and alkali chloride electrolysis apparatus

Patent metadata

Field	Value
Publication number	US-10865489-B2
Application number	US-201715416618-A
Country	US
Kind code	B2
Filing date	Jan 26, 2017
Priority date	Aug 20, 2014
Publication date	Dec 15, 2020
Grant date	Dec 15, 2020

Abstract

To provide an ion exchange membrane for alkali chloride electrolysis, which has low membrane resistance and which reduces the electrolysis voltage during alkali chloride electrolysis, even if the spacing between reinforcing yarns is made narrow to increase the membrane strength. This ion exchange membrane 1 for alkali chloride electrolysis comprises a fluoropolymer containing ion exchange groups; a reinforcing material embedded in the fluoropolymer and formed of reinforcing yarns and optionally contained sacrificial yarns; and elution holes of the sacrificial yarns present between the reinforcing yarns, wherein in a cross section perpendicular to the length direction of the reinforcing yarns forming the reinforcing material, the average distance (d1) from the center of a reinforcing yarn 22 to the center of the adjacent reinforcing yarn 22 is from 750 to 1,000 μm, the total area (S) obtained by adding the cross-sectional area of an elution hole 28 and the cross-sectional area of a sacrificial yarn 24 remaining in the elution hole 28 is from 500 to 5,000 μm2 per elution hole, and the number n of elution holes 28 between adjacent reinforcing yarns 22 is from 4 to 6.

First claim

What is claimed is:

1. An ion exchange membrane for alkali chloride electrolysis comprising a fluoropolymer having at least one ion exchange group, a reinforcing material embedded in the fluoropolymer and formed of reinforcing yarns and sacrificial yarns, and elution holes, through which at least a portion of the sacrificial yarns has been eluted, present between the reinforcing yarns,
wherein in a cross section perpendicular to a length direction of the reinforcing yarns of the reinforcing material, an average distance (d1) from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn is from 800 μm to 1,000 μm, and a total area (S) obtained by adding a cross-sectional area of an elution hole and a cross-sectional area of a sacrificial yarn, when a portion of the sacrificial yarn remains in the elution hole, is from 500 μm 2 to 5000 μm 2 per elution hole, and
wherein the number n of elution holes between adjacent reinforcing yarns is from 4 to 6.

2. The ion exchange membrane according to claim 1 , wherein a relationship is established to satisfy the following formula (1) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.5<{ d 2/ d 1×( n+ 1)}<1.5  (1),

wherein
d1 is the average distance from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn,
d2 is an average distance from the center of an elution hole to the center of an adjacent elution hole, and
n is the number of elution holes between adjacent reinforcing yarns.

3. The ion exchange membrane according to claim 2 , wherein a relationship is established to satisfy the following formula (1′) at all measurement points measured to determine the average distance (d1) and the average distance (d2) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.4<{ d 2 ′/d 1×( n+ 1)}<1.6  (1′),

wherein
d2′ is a distance from the center of an elution hole to the center of an adjacent elution hole.

4. The ion exchange membrane according to claim 1 , wherein a relationship is established to satisfy the following formula (2) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.5<{ d 3/ d 1×( n+ 1)}<1.5  (2),

wherein d3 is an average distance from the center of a reinforcing yarn to the center of the adjacent elution hole,
d1 is the average distance from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn, and
n is the number of elution holes between adjacent reinforcing yarns.

5. The ion exchange membrane according to claim 4 , wherein a relationship is established to satisfy the following formula (2′) at all measurement points measured to determine the average distance (d1) and the average distance (d3) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.4<{ d 3′/ d 1×( n+ 1)}<1.6  (2′),

wherein
d3′ is a distance from the center of a reinforcing yarn to the center of the adjacent elution hole.

6. The ion exchange membrane according to claim 1 , wherein a width of the reinforcing yarns from the direction perpendicular to a surface of the membrane is from 70 μm to 160 μm.

7. The ion exchange membrane according to claim 1 , wherein the fluoropolymer comprises a fluoropolymer having at least one group carboxylic acid functional group and a fluoropolymer having at least one group sulfonic acid functional group, and wherein the reinforcing material is embedded in the fluoropolymer having at least one group sulfonic acid functional group.

8. An alkali chloride electrolysis apparatus comprising an electrolytic cell comprising a cathode, an anode, and the ion exchange membrane of claim 1 partitioning a cathode chamber on a cathode side and an anode chamber on an anode side in the electrolytic cell.

9. A method for producing an ion exchange membrane for alkali chloride electrolysis, the method comprising:
obtaining a reinforcing precursor membrane comprising a reinforcing fabric composed of reinforcing yarns and sacrificial yarns, embedded in a precursor membrane comprising a fluoropolymer having at least one group convertible to an ion exchange group, and
then contacting the reinforcing precursor membrane with an alkaline aqueous solution to convert the at least one group convertible to an ion exchange group, to the ion exchange group, and at the same time to elute at least a portion of the sacrificial yarn in the reinforcing fabric, thereby obtaining an ion exchange membrane comprising a fluoropolymer having at least one ion exchange group,
wherein a reinforcing material has at least a portion of the sacrificial yarns in an eluted reinforcing fabric and elution holes,
wherein in a cross section perpendicular to a length direction of the reinforcing yarns in the ion exchange membrane, a total area (S) obtained by adding a cross-sectional area of an elution hole and a cross-sectional area of a sacrificial yarn remaining in the elution hole, is from 500 μm 2 to 5000 μm 2 per elution hole, and the number n of elution holes between adjacent reinforcing yarns is from 4 to 6, and
wherein in a cross section perpendicular to a length direction of the reinforcing yarns of the reinforcing material, an average distance (d1) from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn is from 800 μm to 1,000 μm.

10. The method according to claim 9 , wherein a relationship is established to satisfy the following formula (1) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.5<{ d 2/ d 1×( n+ 1)}<1.5  (1),

wherein
d1 is the average distance from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn,
d2 is an average distance from the center of an elution hole to the center of an adjacent elution hole, and
n is the number of elution holes between adjacent reinforcing yarns.

11. The method according to claim 10 , wherein a relationship is established to satisfy the following formula (1′) at all measurement points measured to determine the average distance (d2) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.4<{ d 2′/ d 1×( n+ 1)}<1.6  (1′),

wherein d2′ is a distance from the center of an elution hole to the center of an adjacent elution hole.

12. The method according to claim 9 , wherein a relationship is established to satisfy the following formula (2) in the cross section perpendicular to the length direction of the reinforcing yarn:
0.5<{ d 3/ d 1×( n+ 1)}<1.5  (2),

wherein
d3 is an average distance from the center of a reinforcing yarn to the center of an adjacent elution hole or sacrificial yarn,
d1 is the average distance from the center of a reinforcing yarn to the center of an adjacent reinforcing yarn, and
n is the number of elution holes between adjacent reinforcing yarns.

13. The method according to claim 12 , wherein a relationship is established to satisfy the following formula (2′) at all measurement points measured to determine the average distance (d3) in the cross section perpendicular to the length direction of the reinforcing yarns:
0.4<{ d 3′/ d 1×( n+ 1)}<1.6  (2′),

wherein d3′ is a distance from the center of a reinforcing yarn to the center of an adjacent elution hole.

14. The method according to claim 9 , wherein a width of the reinforcing yarns in the direction perpendicular to a surface of the membrane is from 70 μm to 160 μm.

15. A method for producing an alkaline chloride electrolysis apparatus, the method comprising:
obtaining an ion exchange membrane for alkali chlorid

Assignees

• Agc Inc

Inventors

• Kaneko Takayuki
• Kusano Hiromitsu
• Yamaki Yasushi
• Nishio Takuo

Classifications

• B01J47/12

  characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes (electrodialysis or electro-osmosis B01D61/42) · CPC title

• C08J2427/18

  Homopolymers or copolymers of tetrafluoroethylene · CPC title

• C25B13/08 Primary

  based on organic materials · CPC title

• B32B27/00

  Layered products comprising {a layer of} synthetic resin {(fibrous or filamentary layer made of a synthetic resin B32B5/02; particulate layer made of a synthetic resin B32B5/16; foamed layer made of a synthetic resin B32B5/18)} · CPC title

• C08J5/2237

  containing fluorine · CPC title