WO2002103083A1 - Fluorine-containing cation-exchange membrane and electroytic soda process - Google Patents
Fluorine-containing cation-exchange membrane and electroytic soda process Download PDFInfo
- Publication number
- WO2002103083A1 WO2002103083A1 PCT/JP2002/005973 JP0205973W WO02103083A1 WO 2002103083 A1 WO2002103083 A1 WO 2002103083A1 JP 0205973 W JP0205973 W JP 0205973W WO 02103083 A1 WO02103083 A1 WO 02103083A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exchange membrane
- cation exchange
- fluorine
- cathode
- layer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
- C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
Definitions
- the present invention relates to a fluorinated cation exchange membrane and a salt electrolysis method.
- a common method of adjusting the concentration is to supply water to the cathode chamber.
- this method has the following problems. First, if the liquid circulation in the cathode chamber is insufficient, the concentration of the catholyte near the water supply decreases, and on the contrary, the concentration of the catholyte in the hardly diluted portion increases. As a result, the current efficiency decreases. Also, if the supply of water to the cathode chamber stops due to some trouble, the catholyte concentration will rise sharply and the current efficiency will drop significantly. In such a case, it is difficult to return the current efficiency once reduced to its original value, and the membrane needs to be replaced.
- a conductive spacer is placed between the electrode plate and the electrode sheet to provide a downward flow path for the electrolyte (Japanese Patent Application Laid-Open No. 61-197889).
- a current distribution member in the form of a tube (Japanese Patent Application Laid-Open No. 63-116686), and with a cylindrical internal circulation duct that serves as a circulation flow path for the electrolyte (Japanese Patent Application Laid-Open No. 4-28991 84).
- the present invention relates to a cation exchange membrane comprising at least two layers, a first layer made of a fluoropolymer having a sulfonic acid group and a second layer made of a fluoropolymer having a carboxylic acid group on the cathode side.
- the salt concentration in the anode compartment is 200 g / L
- the sodium hydroxide concentration in the cathode compartment is 32 mass%.
- Figure 1 Example of X-ray diffraction pattern of the film.
- the vertical axis is intensity (arbitrary unit).
- the present invention has found that the object can be achieved by using a membrane having a high water permeability as a membrane capable of minimizing the amount of water supplied to the cathode chamber. It has been known that lowering the salt concentration increases the amount of water permeation. However, too low a salt water concentration is not preferable because the current efficiency decreases or the membrane deteriorates in long-term operation. It is also known that increasing the current density increases the amount of water permeation. However, if the current density is too high, the current efficiency decreases or the membrane deteriorates during long-term operation, which is not preferable.
- the fluorine-containing cation exchange membrane used in the present invention is a salt electrolysis using a cation exchange membrane as a diaphragm between an anode compartment and a cathode compartment, and has a water permeability of 4.8 mo. Must be at least 1 / F. Below, water permeability Means the value under the above conditions. A water permeability of 4.9mo 1 ZF or more is more preferable. If the water permeation amount is too large, the concentration of the catholyte may decrease from a range suitable for electrolysis, so that it is preferably 6.4 mol 1 ZF or less.
- a typical optimum catholyte concentration in salt electrolysis using an ion-exchange membrane method is 28 to 35% by mass, depending on the membrane configuration. This catholyte concentration is considered to be determined by the following factors.
- sodium ions enter the membrane from the anode side as hydrated ions and are transported to the cathode side. That is, it passes through the membrane with the accompanying water.
- the amount of sodium ion permeated per unit time depends on the current and the current efficiency.
- the water in the cathode chamber evaporates because it is usually at a high temperature of 60 to 90 ° C. Normally, the amount of entrained water (hereinafter referred to as the amount of permeate) is about 3 to 4.5mo1 / F. However, since the amount of water evaporation exceeds this, it is necessary to supply water separately to the cathode compartment in order to maintain the optimum catholyte concentration.
- the concentration of caustic soda in the catholyte is determined by a function of current, current efficiency, water permeation, evaporating water, and water supply to the cathode compartment, and is expressed by the following equation.
- Tw Permeability (mo1 / ⁇ ).
- the water permeability of 4.9 mol / F depends on the amount of water evaporated from the catholyte, but the concentration of sodium hydroxide in the cathode chamber is maintained at about 35% by mass without supplying water to the cathode chamber.
- 6.4 mol / F means that the concentration of sodium hydroxide in the cathode chamber is maintained at about 28% by mass without supplying water to the cathode chamber.
- the first layer forming the fluorinated cation exchange membrane is made of a fluorinated polymer having a sulfonic acid group.
- the first layer itself may be a laminate of two or more fluoropolymer layers having a sulfonic acid group.
- the second layer forming the fluorine-containing cation exchange membrane preferably has a crystallinity obtained from an X-ray diffraction spectrum of 18 to 22%. If the crystallinity of the second layer exceeds 22%, the water permeability may decrease, which is not preferable. If the crystallinity of the second layer is less than 18%, it is not preferable because the current efficiency during electrolysis may decrease.
- the crystallinity is determined by the area of the crystalline peak (I c) and the area of the amorphous halo (I c) obtained from the X-ray diffraction pattern of the dried membrane in which the counter ion of the ion exchange group is Na ion. It is defined by the following formula based on I a)
- Figure 1 shows three examples of X-ray diffraction patterns of the film. As shown in the figure, a peak around 18 ° (crystalline peak) due to the crystalline portion and a broad peak (amorphous halo) having a peak around 16 ° due to the amorphous portion are shown. Is recognized. Therefore, when 2 ⁇ of the diffraction pattern is in the range of 11 to 24 °, peak separation is performed assuming that only these two types of peaks exist, and I c and la are determined. FIG. 1 shows that the degree of crystallinity decreases from top to bottom. Also, 0.661 in the equation is an empirically known constant.
- the thickness of the second layer is preferably 2 to 15 m. If the thickness exceeds 15 m, it is not preferable because the water permeability may decrease. When the thickness is less than, it is not preferable because current efficiency may be reduced in long-term operation.
- the more preferred thickness of the second layer is 4 to 12 m.
- a cation exchange comprising at least two layers of a first layer made of a fluorinated polymer having a sulfonic acid group and a second layer made of a fluorinated polymer having a carboxylic acid group on the cathode side.
- the first layer forming the fluorinated cation exchange membrane preferably has a water content of 24% by mass or more. If the water content is less than 24% by mass, the water permeability may decrease, which is not preferable. It is more preferable that the water content is 26% by mass or more because the water permeability is in a more preferable range. However, if the water content (W) is too high, the film strength is reduced. Therefore, the water content is preferably 44% by mass or less.
- the moisture content was determined by immersing a film made of the ion-exchange resin constituting the first layer in a 12% by mass aqueous sodium hydroxide solution at 90 ° C for 16 hours, taking it out, and measuring the mass at room temperature. After the film was vacuum dried at a temperature of 150 ° C. for 16 hours, the film was taken out, and the mass measured at room temperature was determined as W 2 by the following equation.
- the thickness of the first layer is preferably from 20 to 300 / xm. If the thickness is less than 20 m, it is not preferable because the strength of the film is reduced. If the thickness exceeds 300 im, the resistance of the film increases, which is not preferable.
- a more preferred thickness of the second layer is from 30 to L00 m.
- the fluorinated cation exchange membrane of the present invention can be used as it is, it is preferably used on at least one surface of the cation exchange membrane, particularly preferably at least on the anode side surface of the cation exchange membrane for releasing chlorine gas. By performing the treatment, the long-term stability of the current efficiency can be further improved.
- a method of performing a gas release treatment on the surface of the cation exchange membrane A method of providing fine irregularities (Japanese Patent Publication No. 60-26495), a method of supplying a liquid containing an iron compound, zirconium oxide, or the like to an electrolytic cell and attaching a gas-opening coating layer containing hydrophilic inorganic particles to the film surface ( JP-A-56-152980) and a method of providing a porous layer containing gas and liquid-permeable particles having no electrode activity (JP-A-56-75583 and JP-A-57-39185).
- the gas release coating on the surface of the cation exchange membrane not only has the effect of improving the long-term stability of current efficiency, but can further reduce the voltage during electrolysis.
- the fluorinated cation exchange membrane of the present invention can be reinforced, if necessary, with a woven fabric, a nonwoven fabric fibril, a porous body, or the like, preferably made of a fluorinated polymer such as polytetrafluoroethylene.
- the electrolytic cell at this time may be a monopolar type or a bipolar type.
- the material of the electrolytic cell is made of a material having a resistance to saline solution and chlorine in the case of the anode chamber, for example, titanium, and stainless steel or nickel having a resistance to sodium hydroxide and hydrogen in the case of the cathode chamber. Etc. are used.
- the cathode may be disposed in contact with the ion exchange membrane, or may be disposed at an appropriate interval.
- a monofilament PTFE yarn obtained by rapidly stretching a polytetrafluoroethylene (PTFE) film and slitting it to a thickness of 100 denier, Six-denier polyethylene terephthalate (PET) fibers are arranged and twisted together to form a multifilament PET yarn.
- PTFE polytetrafluoroethylene
- PET Six-denier polyethylene terephthalate
- One PTFE yarn and two PET yarns are alternately woven, and the yarn density is 30 Z cm of reinforced woven fabric was obtained.
- This woven fabric was flattened using a roll press machine so that the woven fabric thickness was about 80 m.
- the obtained woven fabric and film are laminated in the following order: film B, woven fabric, film A (so that the resin A layer is on the PET film side for release), and PET film for release (100 ⁇ m thick).
- the layers were laminated using a heating roll. Then, the PET film for release was peeled off to obtain a reinforced laminated film.
- zirconium oxide having an average particle diameter of 1 / xm is composed of 29.0, methylcellulose 1.3% by mass, cyclohexanol 4.6% by mass, cyclohexane 1.5% by mass, and water 63.6% by mass.
- the paste was transferred to the film B side of the laminated film by a roll press to attach a gas-releasing coating layer. At this time, the attached amount of zirconium oxide was 20 g / m 2 .
- dimethyl sulfoxide 30 wt% was immersed in an aqueous solution of potassium hydroxide 15% by weight, was hydrolyzed C_ ⁇ 2 CH 3 groups and S_ ⁇ 3 F group. Then, the counter ion of the ion exchange group was converted to Na ion by immersion in a 4% by mass aqueous solution of sodium hydrogen carbonate.
- the acid type polymer resin B 2. ethanol solution containing 5 wt%, to prepare a dispersion liquid prepared by 13 wt% dispersion of zirconium oxide of average one particle size 5 m, the lamination dispersions of this The film was sprayed onto the film A side to apply a gas-releasing coating layer. At this time, the attached amount of zirconium oxide was 10 gZm 2 .
- the resin A was formed into a film, subjected to the hydrolysis treatment, and the crystallinity was measured to be 19.3%.
- resin B was formed into a film, subjected to the hydrolysis treatment, and the water content was measured to be 31% by mass.
- the fluorinated cation-exchange membrane thus obtained was disposed in an electrolytic cell so that the film A faced the cathode, and the aqueous sodium chloride solution was electrolyzed. Electrolysis is such that where the catholyte is hardly circulated occurring cathode compartment frame, cathode feed water inlet of the cathode chamber using the electrolytic cell of the effective conduction area 1. 5 dm 2 (height 5 cm, width 30 cm) The lower part of the room, The outlet of the generated aqueous sodium hydroxide solution was disposed above the cathode chamber.
- anode a punched metal of titanium (short diameter 4 mm, long diameter 8 mm) coated with a solid solution of ruthenium oxide, iridium oxide, and titanium oxide is used.
- cathode a punched metal made of S US 304 (short diameter) is used. A 5mm, 10mm long diameter electrodeposited with Raney nickel containing ruthenium was used.
- the cathode side was pressurized so that the anode and the membrane were in contact with each other, and 290 g / L sodium chloride aqueous solution and water were supplied to the anode chamber and the cathode chamber, respectively, while being discharged from the anode chamber.
- the electrolysis was carried out for 1 week at a temperature of 90 and a current density of 5 kAZm 2 while maintaining the sodium concentration of 200 gZL and the sodium hydroxide concentration discharged from the cathode chamber at 32% by mass.
- the electrolysis was carried out for 1 week at a temperature of 90 and a current density of 5 kAZm 2 while maintaining the sodium concentration of 200 gZL and the sodium hydroxide concentration discharged from the cathode chamber at 32% by mass.
- the permeability was 5.
- the sodium chloride concentration discharged from the anode chamber was adjusted to 180 gZL.
- Electrolysis at a temperature of 90 ° C and a current density of 6 kAZm 2 the concentration of sodium hydroxide discharged from the cathode chamber was 32.8% by mass, the current efficiency was 96.5%, The quantity was 5. SmolZF.
- Electrolysis was carried out by changing the ion exchange capacity and the thickness of the resin A layer of the film A and the ion exchange capacity of the Z or the resin B layer of the film A according to the film forming method and the electrolysis conditions described in Example 1.
- a resin B having a thickness of 22 m was used.
- Examples 6 to 9 are comparative examples.
- Examples 6 and 10 are examples in which a cation exchange membrane having low crystallinity and a water permeability of less than 4.8 mol / F was used as the film A.
- Example 7 is an example in which the crystallinity of the film A is high, and as a result, the cation exchange membrane having a water permeability of the cation exchange membrane of less than 4.8 mo 1ZF is employed.
- Example 8 is an example in which the thickness of the film A is large and the cation exchange membrane having a water permeability of the cation exchange membrane of less than 4.8 mol / l ZF is employed.
- Example 9 is an example in which the water content of the film B is low and a cation exchange membrane having a water permeability of less than 4.8 mol / l ZF is used.
- the catholyte concentration in the portion hardly diluted by the supplied water was locally increased, and the current efficiency was reduced.
- the fluorinated cation exchange membrane for electrolysis of the present invention can be used for electrolysis without special liquid circulation means. It has an excellent effect of maintaining a uniform catholyte concentration even when mounted in a bath. In particular, it is possible to operate with the supply of water stopped, so additional equipment such as a water purification device, piping to the electrolytic cell, a valve for adjustment, a flow meter, and a structure for uniformly dispersing in the cathode chamber are provided. It can be eliminated. In addition, since the decomposition rate of salt can be increased, there is an effect of reducing the amount of raw material salt used.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003505392A JP4168932B2 (ja) | 2001-06-15 | 2002-06-14 | 含フッ素陽イオン交換膜および食塩電解方法 |
EP02736112.0A EP1398397B1 (en) | 2001-06-15 | 2002-06-14 | Fluorine containing cation exchange membrane and electroytic soda process |
US10/703,443 US6984669B2 (en) | 2001-06-15 | 2003-11-10 | Fluorinated cation exchange membrane and electrolytic soda process |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001181863 | 2001-06-15 | ||
JP2001-181863 | 2001-06-15 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/703,443 Continuation US6984669B2 (en) | 2001-06-15 | 2003-11-10 | Fluorinated cation exchange membrane and electrolytic soda process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002103083A1 true WO2002103083A1 (en) | 2002-12-27 |
Family
ID=19022065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/005973 WO2002103083A1 (en) | 2001-06-15 | 2002-06-14 | Fluorine-containing cation-exchange membrane and electroytic soda process |
Country Status (4)
Country | Link |
---|---|
US (1) | US6984669B2 (ja) |
EP (1) | EP1398397B1 (ja) |
JP (1) | JP4168932B2 (ja) |
WO (1) | WO2002103083A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015163238A1 (ja) * | 2014-04-21 | 2015-10-29 | 旭硝子株式会社 | 陽イオン交換膜および水酸化カリウム水溶液の製造方法 |
JP2017043700A (ja) * | 2015-08-27 | 2017-03-02 | 株式会社Ihi | 親水性フィルム、電解質膜、及びその親水性フィルムの製造方法 |
WO2020100684A1 (ja) * | 2018-11-12 | 2020-05-22 | 旭化成株式会社 | 陽イオン交換膜、電解槽及び陽イオン交換膜の製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008012037A1 (de) | 2008-03-01 | 2009-09-03 | Bayer Materialscience Ag | Verfahren zur Herstellung von Methylen-diphenyl-diisocyanaten |
CA2751045A1 (en) * | 2009-02-23 | 2010-08-26 | Asahi Glass Company, Limited | Cation exchange membrane, production process thereof and electrolytic cell using the same |
CA2783850C (en) * | 2009-12-11 | 2016-07-12 | Shandong Huaxia Shenzhou New Material Co., Ltd | Perfluorinated ion exchange resin, preparation method and use thereof |
US9090723B2 (en) | 2009-12-15 | 2015-07-28 | Shandong Huaxia Shenzou New Material Co., Ltd. | High exchange capacity perfluorinated ion exchange resin, preparation method and use thereof |
EP2594665B1 (en) * | 2010-07-13 | 2020-05-13 | Kaneka Corporation | Electrolytic cell for manufacturing chlorine and sodium hydroxide and method for manufacturing chlorine and sodium hydroxide |
US9761085B2 (en) | 2014-01-30 | 2017-09-12 | Gamblit Gaming, Llc | Record display of an interleaved wagering system |
CN105066934B (zh) * | 2015-09-15 | 2017-10-24 | 武汉理工大学 | 一种片状矿物水化膜厚度的测量方法 |
JP6996495B2 (ja) | 2016-04-13 | 2022-01-17 | Agc株式会社 | 塩化アルカリ電解用イオン交換膜、その製造方法、及び塩化アルカリ電解装置 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0045603A1 (en) * | 1980-07-31 | 1982-02-10 | Asahi Glass Company Ltd. | Ion exchange membrane cell and electrolytic process using the same |
JPH05125579A (ja) * | 1991-11-01 | 1993-05-21 | Asahi Glass Co Ltd | 電解槽の再起用方法 |
JPH06330369A (ja) * | 1993-05-19 | 1994-11-29 | Asahi Glass Co Ltd | アルカリ金属塩化物水溶液用電解槽 |
JP2000001794A (ja) * | 1998-06-15 | 2000-01-07 | Asahi Glass Co Ltd | 食塩水の電解方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5792028A (en) * | 1980-11-29 | 1982-06-08 | Asahi Chem Ind Co Ltd | Fluorocarbon cation exchange membrane |
JPS5834805A (ja) * | 1981-08-24 | 1983-03-01 | Tokuyama Soda Co Ltd | カルボキシル基を有する含弗素化合物の製造方法 |
US4544471A (en) * | 1981-11-02 | 1985-10-01 | E. I. Du Pont De Nemours And Company | Electrolytic cell with cation exchange membrane having high equivalent weight component |
US4604323A (en) * | 1985-02-22 | 1986-08-05 | E. I. Du Pont De Nemours And Company | Multilayer cation exchange membrane |
US5716504A (en) * | 1995-07-10 | 1998-02-10 | Asahi Glass Company Ltd. | Cation exchange membrane for electrolysis and process for producing potassium hydroxide of high purity |
-
2002
- 2002-06-14 WO PCT/JP2002/005973 patent/WO2002103083A1/ja active Application Filing
- 2002-06-14 JP JP2003505392A patent/JP4168932B2/ja not_active Expired - Fee Related
- 2002-06-14 EP EP02736112.0A patent/EP1398397B1/en not_active Expired - Lifetime
-
2003
- 2003-11-10 US US10/703,443 patent/US6984669B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0045603A1 (en) * | 1980-07-31 | 1982-02-10 | Asahi Glass Company Ltd. | Ion exchange membrane cell and electrolytic process using the same |
JPH05125579A (ja) * | 1991-11-01 | 1993-05-21 | Asahi Glass Co Ltd | 電解槽の再起用方法 |
JPH06330369A (ja) * | 1993-05-19 | 1994-11-29 | Asahi Glass Co Ltd | アルカリ金属塩化物水溶液用電解槽 |
JP2000001794A (ja) * | 1998-06-15 | 2000-01-07 | Asahi Glass Co Ltd | 食塩水の電解方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015163238A1 (ja) * | 2014-04-21 | 2015-10-29 | 旭硝子株式会社 | 陽イオン交換膜および水酸化カリウム水溶液の製造方法 |
JPWO2015163238A1 (ja) * | 2014-04-21 | 2017-04-13 | 旭硝子株式会社 | 陽イオン交換膜および水酸化カリウム水溶液の製造方法 |
US10370511B2 (en) | 2014-04-21 | 2019-08-06 | AGC Inc. | Cation exchange membrane and method for producing potassium hydroxide aqueous solution |
JP2017043700A (ja) * | 2015-08-27 | 2017-03-02 | 株式会社Ihi | 親水性フィルム、電解質膜、及びその親水性フィルムの製造方法 |
WO2020100684A1 (ja) * | 2018-11-12 | 2020-05-22 | 旭化成株式会社 | 陽イオン交換膜、電解槽及び陽イオン交換膜の製造方法 |
JP6777833B1 (ja) * | 2018-11-12 | 2020-10-28 | 旭化成株式会社 | 陽イオン交換膜、電解槽及び陽イオン交換膜の製造方法 |
EP3882025A4 (en) * | 2018-11-12 | 2021-12-29 | Asahi Kasei Kabushiki Kaisha | Positive ion exchange membrane, electrolytic bath, and positive ion exchange membrane production method |
Also Published As
Publication number | Publication date |
---|---|
EP1398397A4 (en) | 2004-09-08 |
EP1398397A1 (en) | 2004-03-17 |
US20040092611A1 (en) | 2004-05-13 |
US6984669B2 (en) | 2006-01-10 |
JP4168932B2 (ja) | 2008-10-22 |
JPWO2002103083A1 (ja) | 2004-09-30 |
EP1398397B1 (en) | 2018-08-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4872958A (en) | Ion exchange membrane for electrolysis | |
US4142950A (en) | Apparatus and process for electrolysis using a cation-permselective membrane and turbulence inducing means | |
EP3348673B1 (en) | Production method for ion exchange membrane for alkali chloride electrolysis, and production method for alkali chloride electrolysis apparatus | |
JP2003041388A (ja) | イオン交換膜電解槽および電解方法 | |
CA1113421A (en) | Electrolysis in a cell employing uniform membrane spacing actuated by pressure | |
WO2002103083A1 (en) | Fluorine-containing cation-exchange membrane and electroytic soda process | |
US4983264A (en) | Four layer cation exchange fluoropolymer membrane | |
CA1225615A (en) | Process for electrolyzing aqueous solution of alkali metal chloride | |
US4969981A (en) | Cell and method of operating a liquid-gas electrochemical cell | |
US4144146A (en) | Continuous manufacture of sodium dithionite solutions by cathodic reduction | |
US5716504A (en) | Cation exchange membrane for electrolysis and process for producing potassium hydroxide of high purity | |
US4253923A (en) | Electrolytic process for producing potassium hydroxide | |
EP0094587B1 (en) | Improved electrolytic cation exchange membrane | |
JP4329339B2 (ja) | 食塩電解方法 | |
EP0327313B1 (en) | Membrane electrolytic process for producing concentrated caustic | |
EP0139133B1 (en) | Electrolytic cell for the electrolysis of an alkali metal chloride | |
JPH0660250B2 (ja) | 強化されたカチオン交換膜及び方法 | |
JPH0288645A (ja) | 電解用陽イオン交換膜 | |
EP0360536A2 (en) | Cell and method of operating a liquid-gas electrochemical cell | |
JPH0633281A (ja) | 塩化アルカリ水溶液の電解方法 | |
JPH01263288A (ja) | 塩化アルカリの電解方法 | |
JPS62199629A (ja) | 新規な電解用複層隔膜 | |
JPS61235587A (ja) | 電解方法 | |
JPH08158085A (ja) | アルカリイオン水製造用電解槽 | |
JPS61166991A (ja) | 食塩電解方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2003505392 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002736112 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10703443 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2002736112 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |