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WO1985002419A1 - Cellule a ecartement zero - Google Patents

Cellule a ecartement zero

Info

Publication number
WO1985002419A1
WO1985002419A1 PCT/US1983/001871 US8301871W WO8502419A1 WO 1985002419 A1 WO1985002419 A1 WO 1985002419A1 US 8301871 W US8301871 W US 8301871W WO 8502419 A1 WO8502419 A1 WO 8502419A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
cell
electrode
openings
anode
Prior art date
Application number
PCT/US1983/001871
Other languages
English (en)
Inventor
Bruce Bjorge Johnson
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to JP59500347A priority Critical patent/JPS61500669A/ja
Priority to PCT/US1983/001871 priority patent/WO1985002419A1/fr
Publication of WO1985002419A1 publication Critical patent/WO1985002419A1/fr

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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • Membrane cells using fluorinated cation exchange membranes have been used for electrolysis, particularly for the electrolysis of aqueous alkali metal chloride solutions to make chlorine and alkaline metal hydroxides. If a suitable membrane with bubble release surfaces is used, the cell voltage can be reduced by using* a zero gap cell, in which both electrodes are urged against but not bonded to the membrane.
  • both electrodes may be of expensive fine metal mesh, backed with a current distributor (Japanese laid-open patent application J57/41387 to Asahi Glass) or the cathode may be backed with a resilient compressible material (U.S. 4,340,542 to Oronzio de Nora) or may use grooved anodes (U.S. 4,057,479 to Billings) or corrugated anodes (U.S. 4,056,452 to Billings) or tangled fibrous electrodes (Japanese laid-open patent- application J57/134579 to Showa Denko) .
  • One electrode preferably the anode, comprises a coarse porous conductor having less than 20
  • the other electrode comprises a fine mesh, e.g. a fine expanded metal mesh or a fine wire screen, having more than 20 openings/cm and at least 50% open area, supported by a coarser and more rigi .current distributor having less than 20 2 openings/cm .
  • the electrodes are urged-against the membrane by any suitable method, but are not bonded to it and may be disassembled when one component needs to be replaced.
  • the anode for a chlor-alkali cell should be electrically conductive material resistant to corrosion by brine and chlorine, resistant to erosion, and preferably may contain an electrocatalyst to minimize chlorine overvoltage.
  • the well-known dimensionally stable anode is among those that are suitable.
  • a suitable base metal is titanium, and the electrocatalysts include reduced platinum group metal oxides (such as Ru, etc.) singly or in mixtures, optionally admixed with a reduced oxide of Ti # Ta, Cb, Zr, Hf, V, Pt, or Ir.
  • An anodic electrocatalyst preferably comprises reduced oxides of ruthenium or such oxides in combination with at least one reduced oxide from the group consisting of the reduced oxides of iridium, tantalum, titanium, niobium, and hafnium, preferably iridium. More preferably a combination of 75 to 95% by wt., most preferably 75% by wt., of reduced oxides of ruthenium, and 25 to 5% by wt. , most preferably 25% by wt., of reduced oxides of iridium is used. It is best to thermally stabilize the reduced oxides of ruthenium by heating, to produce a composition which is stable against chlorine and oxygen evolution. Such electrocatalyst and its stabilization by heating are described i
  • Both the anode and the cathode must be porous so they are permeable to liquid electrolytes and gaseous products.
  • the open area must be at least
  • the cathode for a chloralkali cell should be electrically conductive material resistant to corrosion by the catholyte, resistant to erosion, and preferably may contain an electrocatalyst to minimize hydrogen overvoltage.
  • the cathode may be mild steel, nickel, or stainless steel, for example, and the electrocatalyst may be platinum black, palladium, gold, spinels, manganese, cobalt, nickel, Raney nickel, reduced platinum group metal oxides, or alpha-iron.
  • the electrode have open vertical channels or grooves to facilitate the evolution of the cathode gas, which is hydrogen in many cell processes. It may be desirable to have the cathode openings slanted so the gas is carried away from the membrane and catholyte flow past the membrane is maximized. This effect may be augmented by using downcomers' for catholyte which has been lifted by rising gas bubbles.
  • One electrode comprises a coarse conductor preferably coated with electrocatalyst, as described
  • the other electrode comprises a fine mesh, preferably coated with electrocatalyst, the mesh having more than 20
  • OMPI contacts the cathode may be made of any-metal wh-ich is a good conductor and is resistant to corrosion by the electrolyte, preferably nickel.
  • the current collector which contacts the anode may be made of any metal which is a good conductor and is resistant to corrosion by the electrolyte, preferably titanium coated to enhance its surface conductivity.
  • the carboxylic polymers with which the present invention is concerned have a fluorinated hydrocarbon backbone chain to which are attached the functional groups or pendant side chains which in turn carry the functional groups.
  • the pendant side chains can contain, for example,
  • the functional group in the side chains of the polymer will be present in terminal —O -CF- groups wherein t is 1 to 3.
  • fluorinated is meant a membrane in which, after loss of any R group by hydrolysis to ion exchange form, the number of F atoms is at least 90% of the total number of F, H and Cl atoms in the polymer.
  • perfluorinated membranes are preferred, though the R in any COOR group need not be fluorinated -because it is lost during hydrolysis.
  • CF 3 CF 3 chains in which m is 0, 1, 2, 3 or 4, are disclosed in U.S. 3,852,326.
  • the sulfonyl polymers with which the present invention is concerned are fluorinated polymers with side chains containing the group -CF-CFSO_X,_ wherein
  • R f is F, Cl, CF 2 C1 or a C, to C, 0 perfluoro- alkyl radical
  • X is F or Cl, preferably F.
  • the side chains will contain
  • fluorinated carries the same meaning as employed above in reference to carboxylate membranes. For use in chloralkali .synthesis, perfluorinated membranes are preferred.
  • ⁇ 3 where k is O or 1 and j is 3, 4, or 5, may be used. These are described in British 2,053,902A.
  • Preferred polymers contain the side chain -(OCF-CF) -OCF CFSO-X, where R-, Y, and X are as
  • Polymerization can be carried out by the methods described in the above references.
  • Polymerization can also be carried out by aqueous granular polymerization as in U.S. 2,393,967, or aqueous dispersion polymerization as in
  • copolymers used in the layers described herein should be of high enough molecular weight to produce films which are self-supporting in both the melt-fabricable precursor form and in the hydrolyzed ion exchange form.
  • OM groups in melt-fabricable for , - such as-made by - coextrusion, can be used as one of the component films in making the membrane of the invention.
  • Such a laminated structure may be referred to in this application as a bimembrane. Preparation of bimembranes is described in Japanese laid-open patent application J52/36589.
  • the customary way to specify the structural composition of films or membranes in this field of art is to specify the polymer composition, ion-exchange capacity or its reciprocal, equivalent weight, and thickness of the polymer films in melt-fabricable form, from which the membrane is fabricated. This is done because the measured thickness varies depending on whether the membrane is dry or swollen with water or an electrolyte, and even on the ionic species and ionic strength of the electrolyte, even though the amount of polymer remains constant.
  • the membrane should have all of the functional groups converted to ionizable functional groups.
  • sulfonic acid and carboxylic acid groups or preferably alkali metal salts thereof.
  • sulfonic ion exchange groups includes not only the sulfonic acid group but particularly the alkali metal salts thereof.
  • carboxylic ion exchange groups means the carboxylic acid group and particularly the alkali metal salts thereof.
  • the alkali metals preferred for use in this invention are potassium and sodium, particularly sodium, which leads to the production of sodium hydroxide.
  • Conversion to ionizabl functional groups is ordinarily and conveniently accomplished by hydrolysis with acid or base, such that the various functional groups described above in relation to the melt-fabricable polymers are converted respectively to the free acids or the alkali metal salts thereof.
  • hydrolysis can be carried out with an aqueous solution of a mineral acid or an alkali metal hydroxide.
  • Base hydrolysis is preferred as it is faster and more complete.
  • Use of hot solutions, such as near the boiling point of the solution is preferred for rapid hydrolysis.
  • the time required for hydrolysis increases with the thickness of the structure. It is also of advantage to include a water-miscible organic compound such as dimethyl sulfoxide in the hydrolysis bath, to swell the membrane to increase the rate of hydrolysis.
  • Membranes usually have an overall thickness of 50-250 micrometers, especially 125-200 micrometers.
  • the ion-exchange capacity of the carboxylate polymer is in the range of 0.7-1.4 meq/g, preferably 0.8-1.2 meq/g dry resin, with higher ion-exchange capacities providing more concentrated caustic during operation of a chlor-alkali cell at maximum current efficiency.
  • the ion-exchange capacity of the sulfonate polymer is in the range of 0.5-1.5 meq/g, preferably 0.7-1.2 meq/g dry resin.
  • the membrane may be unreinforced, but for dimensional stability and greater notched tear resistance, it is common to use a reinforcing material.
  • OM fluorocarbon resin may.be ,woven_into fabric using various weaves, such as the plain weave, basket weave, leno weave, or others. Relatively open weaves are favorable in that electrical resistance is lower. Porous sheet such as disclosed in US 3,962,153 may be used as a support. Other perhalogenated polymers such as polychlorotri- fluoroethylene may also be used, but perfluorinated supports have the best resistance to heat and chemicals.
  • the fibers used in the support fabrics may be onofilaments or multifilament yarns. They may be of ordinary round cross-section or may have specialized cross-sections.
  • the fabric employed may be calendered before lamination to reduce its thickness.
  • the fabric may be in the sulfonate or carboxylate layer or both, but is more often in the sulfonate layer, which is usually thicker.
  • non-woven fibrils can be used.
  • the membrane or bimembrane may be used flat in various known filter press cells, or may be shaped
  • New or used membranes may be swelled with polar solvents (such as lower alcohols or esters, tetrahydrofuran, or chloroform) and then dried, preferably between flat plates, to improve their electrolytic performance.
  • polar solvents such as lower alcohols or esters, tetrahydrofuran, or chloroform
  • the membrane Before mounting in commercial cell support frames, which may be 1-3 meters on a side, the membrane may be swelled so that it will not wrinkle after it is clamped in the frame and exposed to electrolytic fluids.
  • the swelling agents that can be used are water, brine, caustic, lower alcohols, glycols, and mixtures thereof.
  • Bipolar or monopolar cells can be used.
  • the carboxylate side of the membrane will face the cathode.
  • Cell (n) and catholyte flowing from cell (n) to cell (1) . All these cells may use identical membranes, or different membranes may be used in different cells. Membranes using only polymers having pendant side chains with terminal -CF 2 -S0 3 groups may be used in cell (n) and possibly others near it. Cell (n) may be two or more cells in parallel.
  • the membrane may be disposed horizontally or vertically in the cell, or at any angle from the vertical.
  • Brine fed to the cell is usually close to the saturation concentration, but lower brine concentration is acceptable.
  • Brine leaving the anolyte chamber may be as low as about 2% by weight NaCl, but is more often 10-15 wt % NaCl, or even higher. Because a bimembrane has lower electrical resistance than an all-carboxylate membrane, it can be operated at lower voltage or higher current density. Good results can be obtained at 10-70
  • A/dm 2 preferably 30-50 A/dm2.
  • Anolyte acidity is normally adjusted to a value in the range of pH 1-5 by addition of hydrochloric acid or hydrogen chloride to the recycle brine.
  • Recycle brine may be concentrated by addition of solid salt and/or by evaporating or distilling water from the stream.
  • OMPI While membrane cells are frequently operated at approximately atmospheric pressure, there can be advantages to operating them at elevated pressure. While direct current is ordinarily used in membrane cells, one can also use pulsed direct current or half-wave AC or rectified AC or DC with a square wave.
  • Chlor-alkali synthesis is normally carried out at about 70-100°C.
  • the catholyte can be kept 5-20° cooler than the anolyte temperature.
  • the membranes described herein should be modified on either surface or both surfaces so as to have enhanced gas release properties, for example by providing optimum surface roughness or smoothness by hot roll embossing or by embossing with a porous paper.
  • embossing with a porous paper a release paper can be applied to an outer surface of the membrane while passing it through a laminator used, for example, to apply a reinforcement for the membrane.
  • a laminator used, for example, to apply a reinforcement for the membrane.
  • the resulting surface roughness is about 2-5 microns- as measured, for example, on a Bendix Model 1020 profilometer.
  • the gas release properties of the membranes are enhanced by providing on at least one surface a gas- and liquid-permeable porous non-electrode layer, and if only one surface is coated, by roughening the other surface as described above.
  • a gas- and liquid-permeable porous non-electrode layer can be in the form of a thin hydrophilic coating and is ordinarily of an inert electroinactive or non-electrocatalytic substance.
  • Such non-electrode layer should have a porosity of 10 to 99%, preferably 30 to 70%, and an average pore diameter of 0.01 to 2000 microns, preferably 0.1 to 1000 microns, and a thickness generally in the range of 0.1 to 500 microns, preferably 1 to 300 microns.
  • a non-electrode layer ordinarily comprises an inorganic component and a binder;
  • the inorganic component can be an inorganic compound which is chemically stable in hot concentrated caustic and chlorine, and can be of a type as set forth in published UK Patent Application GB 2,064, 586A, preferably tin oxide, titanium oxide, zirconium oxide, or an iron oxide such as F e 2 ° 3 or Fe 3 0 4 .
  • Other information regarding non- electrode layers on ion-exchange membranes is found in published European Patent Application 0,031,660, and in Japanese Laid-open Patent Applications 56-108888 and 56-112487.
  • the particle size of the inorganic material can be about 1-100 microns, and preferably 1-10 microns.
  • the weight loading for each coated side is 0.1-5%, preferably 0.5-1.0%, of the weight of the coated membrane.
  • the binder component in a non-electrode layer can be, for example, (a) polytetrafluoro- ethylene, (b) a fluorocarbon polymer at least the surface of which is hydrophilic by virtue of treatment with ionizing radiation in air or a modifying agent to introduce functional groups such as -COOH or -S0 3 H (as described in published UK
  • Patent Application GB 2,060, 703A or treatment with an agent such as sodium in liquid ammonia, (c) a functionally substituted fluorocarbon polymer or copolymer which has carboxylate or sulfonate functional groups, or (d) polytetrafluoroethylene particles modified on their surfaces with fluorinated copolymer having acid type functional groups (GB 2,064, 586A).
  • Such binder can be used in an amount of about from 10 to 50% by wt. of the non-electrode layer.
  • the dispersion used to apply the inorganic component can include a thickener such as methyl cellulose or polyvinyl alcohol and a small amount of nonionic surfactant.
  • Composite structures having non-electrode layers thereon can be made by various techniques known in the art, which include preparation of a decal which is then pressed onto the membrane surface, spray application of a slurry in a liquid composition (e.g., dispersion or solution) of the binder followed by drying, screen or gravure printing of compositions in paste form, hot pressing of powders distributed on the membrane surface, and other methods as set forth in British Patent 2,064,586A or Japanese Laid-open patent application J57/89490.
  • Such structures can be made by applying the indicated layers onto membranes in melt- fabricable form, and by some of the methods onto membranes in ion-exchange form; the polymeric component of the resulting structures when in melt-fabricable form can be hydrolyzed in known manner to the ion-exchange form.
  • the cell of the invention operates at lower voltage and lower power consumption when compared to a similar cell having two coarse electrodes or to a similar cell having a narrow gap between the membrane and an electrode.
  • TFE/EVE refers to a copolymer of tetrafluoroethylene and methyl perfluoro(4, 7- dioxa-5-methyl-8-nonenoate) .
  • TFE/PSEPVE refers to a copolymer of tetrafluoroethylene and perfluoro(3,6- dioxa-4-methyl-7-octenesulfonyl fluoride) .
  • a first layer consisting of a 102 micron (4 mil) layer of TFE/PSEPVE copolymer having an equivalent weight of 1100.
  • a second layer consisting of a 38 micron (1.5 mil) layer of TFE/EVE copolymer having an equivalent weight of 1050.
  • the anode surface of the membrane was roughened by embossing with a release paper.
  • the membrane was then hydrolyzed in an aqueous bath containing 30% dimethyl sulfoxide and 11% KOH for 20 minutes at 90°C.
  • the cathode surface of this membrane was then coated with a dispersion of Zr0 2 and acid form TFE/PSEPVE having an equivalent weight of 950 in ethyl alcohol.
  • a membrane cell was assembled from the following components.
  • the cell was assembled with the membrane and cathode screen sandwiched between the anode and the cathodic current collector such that the anode and the membrane were in contact and both the membrane and the cathodic current collector were in contact with the cathode screen.
  • the cell was operated at
  • a membrane cell was assembled using the membrane and the anode of Example 1.
  • the cell was assembled with the membrane sandwiched between the anode and the cathode such that both the anode and the cathode were in contact with the membrane.
  • the cell was operated with an anolyte concentration of about 220 gpl at a current density of 3.1 kA/m to make chlorine and caustic soda. Current efficiency was 97%, cell voltage was 3.14 volts, and power consumption was 2162 kwh/metric ton of caustic.
  • the cell of Comparative Example A was then taken apart and reassembled with a gap of 3mm between the membrane and the platinized cathode.
  • the membrane was held against the anode by a hydraulic head.
  • the cell was operated at 90°C at a current

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Une cellule électrolytique à membrane à écartement zéro, utilisant une membrane pourvue d'une couche à libération de bulles de chaque côté, est utilisée avec une électrode poreuse à maille grossière d'un côté et une électrode poreuse à maille fine avec un distributeur de courant de l'autre côté.
PCT/US1983/001871 1983-11-30 1983-11-30 Cellule a ecartement zero WO1985002419A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP59500347A JPS61500669A (ja) 1983-11-30 1983-11-30 ゼロギヤツプ電解槽
PCT/US1983/001871 WO1985002419A1 (fr) 1983-11-30 1983-11-30 Cellule a ecartement zero

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1983/001871 WO1985002419A1 (fr) 1983-11-30 1983-11-30 Cellule a ecartement zero

Publications (1)

Publication Number Publication Date
WO1985002419A1 true WO1985002419A1 (fr) 1985-06-06

Family

ID=22175607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1983/001871 WO1985002419A1 (fr) 1983-11-30 1983-11-30 Cellule a ecartement zero

Country Status (2)

Country Link
JP (1) JPS61500669A (fr)
WO (1) WO1985002419A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170419A2 (fr) * 1984-07-02 1986-02-05 Olin Corporation Cellule à densité de courant élevée
WO2003093535A2 (fr) * 2002-05-01 2003-11-13 Newcastle University Ventures Limited Cellule d'electrolyse et procede
US7323090B2 (en) 2002-11-27 2008-01-29 Asahi Kasei Chemicals Corporation Bipolar zero-gap type electrolytic cell
WO2010055108A1 (fr) 2008-11-13 2010-05-20 Gima S.P.A. Réacteur électrochimique

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272353A (en) * 1980-02-29 1981-06-09 General Electric Company Method of making solid polymer electrolyte catalytic electrodes and electrodes made thereby
US4323434A (en) * 1979-02-16 1982-04-06 Asahi Kasei Kogyo Kabushiki Kaisha Process for electrolysis of alkali chloride
US4331521A (en) * 1981-01-19 1982-05-25 Oronzio Denora Impianti Elettrochimici S.P.A. Novel electrolytic cell and method
US4360416A (en) * 1980-05-02 1982-11-23 General Electric Company Anode catalysts for electrolysis of brine
US4364815A (en) * 1979-11-08 1982-12-21 Ppg Industries, Inc. Solid polymer electrolyte chlor-alkali process and electrolytic cell
US4389297A (en) * 1980-10-09 1983-06-21 Ppg Industries, Inc. Permionic membrane electrolytic cell
US4394229A (en) * 1980-06-02 1983-07-19 Ppg Industries, Inc. Cathode element for solid polymer electrolyte
US4411749A (en) * 1980-08-29 1983-10-25 Asahi Glass Company Ltd. Process for electrolyzing aqueous solution of alkali metal chloride
US4417959A (en) * 1980-10-29 1983-11-29 Olin Corporation Electrolytic cell having a composite electrode-membrane structure

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4323434A (en) * 1979-02-16 1982-04-06 Asahi Kasei Kogyo Kabushiki Kaisha Process for electrolysis of alkali chloride
US4364815A (en) * 1979-11-08 1982-12-21 Ppg Industries, Inc. Solid polymer electrolyte chlor-alkali process and electrolytic cell
US4272353A (en) * 1980-02-29 1981-06-09 General Electric Company Method of making solid polymer electrolyte catalytic electrodes and electrodes made thereby
US4360416A (en) * 1980-05-02 1982-11-23 General Electric Company Anode catalysts for electrolysis of brine
US4394229A (en) * 1980-06-02 1983-07-19 Ppg Industries, Inc. Cathode element for solid polymer electrolyte
US4411749A (en) * 1980-08-29 1983-10-25 Asahi Glass Company Ltd. Process for electrolyzing aqueous solution of alkali metal chloride
US4389297A (en) * 1980-10-09 1983-06-21 Ppg Industries, Inc. Permionic membrane electrolytic cell
US4417959A (en) * 1980-10-29 1983-11-29 Olin Corporation Electrolytic cell having a composite electrode-membrane structure
US4331521A (en) * 1981-01-19 1982-05-25 Oronzio Denora Impianti Elettrochimici S.P.A. Novel electrolytic cell and method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170419A2 (fr) * 1984-07-02 1986-02-05 Olin Corporation Cellule à densité de courant élevée
EP0170419A3 (fr) * 1984-07-02 1987-10-14 Olin Corporation Cellule à densité de courant élevée
WO2003093535A2 (fr) * 2002-05-01 2003-11-13 Newcastle University Ventures Limited Cellule d'electrolyse et procede
WO2003093535A3 (fr) * 2002-05-01 2004-07-29 Univ Newcastle Ventures Ltd Cellule d'electrolyse et procede
US7323090B2 (en) 2002-11-27 2008-01-29 Asahi Kasei Chemicals Corporation Bipolar zero-gap type electrolytic cell
EP2039806A1 (fr) 2002-11-27 2009-03-25 Asahi Kasei Chemicals Corporation Cellule electrolytique bipolaire sans interstice
WO2010055108A1 (fr) 2008-11-13 2010-05-20 Gima S.P.A. Réacteur électrochimique

Also Published As

Publication number Publication date
JPS61500669A (ja) 1986-04-10

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