EP0033262B1 - Diaphragma für die Elektrolyse und Verfahren zu seiner Herstellung - Google Patents

Diaphragma für die Elektrolyse und Verfahren zu seiner Herstellung Download PDF

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Publication number
EP0033262B1
EP0033262B1 EP81400058A EP81400058A EP0033262B1 EP 0033262 B1 EP0033262 B1 EP 0033262B1 EP 81400058 A EP81400058 A EP 81400058A EP 81400058 A EP81400058 A EP 81400058A EP 0033262 B1 EP0033262 B1 EP 0033262B1
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EP
European Patent Office
Prior art keywords
microporous
diaphragm according
parts
carboxylic acid
preparation
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP81400058A
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English (en)
French (fr)
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EP0033262A1 (de
Inventor
Jean Bachot
Jean Grosbois
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pall Corp
Original Assignee
Atochem SA
Elf Atochem SA
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 Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT81400058T priority Critical patent/ATE24550T1/de
Publication of EP0033262A1 publication Critical patent/EP0033262A1/de
Application granted granted Critical
Publication of EP0033262B1 publication Critical patent/EP0033262B1/de
Expired legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • the present invention relates to a diaphragm for electrolysis, based on fluorinated resins, having a marked hydrophilic character, as well as the process for preparing this diaphragm.
  • hydrophilic diaphragms that is to say easily wetted with an electrolyte, can be obtained by a simple process which gives them properties favorable for electrolysis, particularly in contact with concentrated detergents.
  • One of the objects of the invention is a microporous diaphragm based on fluorinated resin, intended in particular for the electrolysis of alkali metal halide, coated on at least part of the internal surface of the pores with a carboxylic acid copolymer unsaturated and non-ionic unsaturated monomer.
  • Another object of the invention is the process for obtaining this diaphragm comprising the formation of a porous sheet based on fluorinated resin, the impregnation of this sheet with a mixture containing at least one unsaturated carboxylic acid, at least one nonionic monomer and at least one polymerization initiator, this mixture having a low viscosity, the copolymerization of this mixture, the draining of the sheet after impregnation and copolymerization of the comonomers in said sheet.
  • microporous sheet can be prepared by a wide variety of methods, many of these methods being well known today.
  • the fluorinated resins which can be used are in particular polytetrafluoroethylene, polytrifluoroethylene, polyhexafluoropropylene, polyvinyl fluoride, polyvinylidene fluoride, polyperfluoroalkoxyethylene, polyhaloethylenes comprising one or two chlorine atoms and three or two fluorine atoms on each ethylene unit and in particular polychlorotrifluoroethylene, the corresponding polyhalopropopropenes, copolymers of ethylene and / or of propylene and halogenated unsaturated hydrocarbons at least partially fluorinated having 2 or 3 carbon atoms.
  • these compounds mention may be made in particular of the products known under the brands "TEFLON by Du Pont de Nemours," SOREFLON by the company Produits Chimiques Ugine Kuhlmann, "HALAR by Allied Chemicals Co.
  • resins can be reinforced with different fibers, either inorganic such as asbestos, glass, zirconia or carbon fibers, or organic, such as polypropylene or optionally halogenated and especially fluorinated, polyhalogenovinylidene fibers. etc ...
  • the proportion of reinforcing fibers can be from 0 to 200% of the weight of the resin. As already mentioned above when a relatively high proportion of asbestos is present, greater than 30% of the weight of resin, the diaphragm generally has satisfactory wettability without additional treatment.
  • the overall porosity should preferably be 50 to 95% and the equivalent mean pore diameter is between 0.1 and 12 micrometers and preferably between 0.2 and 6 micrometers, this equivalent diameter being the diameter of a cylindrical pore theoretical which allows the same speed of passage of a slightly viscous liquid, under a determined pressure, as the real pore.
  • the carboxylic acid monomers used carry one or two carboxylic groups. It can be acrylic, methacrylic acids and their halogenated, phenylacrylic, ethylacrylic, maleic, itaconic, butyl-acrylic, vinylbenzoic acids, etc. Acrylic and methacrylic acids are preferred.
  • the nonionic monomers can carry a single ethylenic bond, such as styrene, methylstyrene, ethylvinylbenzene, chloro- or fluorostyrenes, or -methylstyrenes, as well as vinylpyridine or pyrrolidone. They can have several unsaturations and also promote crosslinking of the polymer layer formed.
  • divinylbenzenes and in particular the para isomer which is preferred, trivinylbenzene, divinylnaphthalenes, divinylethyl or methylbenzenes. trivinyl 1-3-4 cyclohexane etc ...
  • At least one non-ionic monounsaturated monomer and one pluri-unsaturated monomer is then between 0.1 and 10 and preferably between 0.4 and 2.5.
  • the divinylbenzene mixture commercially available ethylvinylbenzene is advantageously used.
  • the proportion by weight of unsaturated acid on all of the carboxylic and nonionic comonomers is between 40 and 98% by weight and preferably between 70 and 95% and it is important that this mixture of monomers optionally and preferably added with diluent, present a low viscosity preferably less than 2 cp so as to be able to penetrate under a slight depression (from 1 to 100 mmHG below atmospheric pressure) in the pores of the microporous substrate.
  • an inert diluent is added to the mixture of monomers, in particular methanol, ethanol, isopropanol, butanols, acetone, methyl isobutyl ketone, dioxane , chloro or dibromomethane, optionally halogenated aliphatic hydrocarbons having from 2 to 10 carbon atoms, dimethylformamide, dimethylacetamide, dimethyl sulfoxide etc ...
  • Ethanol is the preferred diluent; in general, the diluents must have a relatively low voltage at room temperature and be miscible with the comonomers and possibly with water.
  • comonomers preferably 1,600 to 30 parts of diluent are used.
  • the copolymer formed from the comonomers thus diluted will be present in an at least monomolecular layer on at least part of the internal surface of the pores.
  • a radical polymerization initiator is added to the mixture of comonomers; it must not cause significant polymerization at room temperature in the absence of activating radiation (ultraviolet), but cause polymerization of the comonomers in a time preferably less than 12 h, at a temperature below that of softening of the fluorinated polymer put in ceown, and preferably less than 100 ° C. Mention may be made, among the polymerization initiators, of benzoyl, lauroyl, t-butyl, cumyl peroxides, t-butyl peracetate or perbenzoate and also azobisisobutyronitrile.
  • the temperature conditions of the polymerization can be adapted to the choice of diluent so as to prevent it from leaving too quickly during the polymerization in situ.
  • Activators can be used for this, for example dimethylaniline which, combined with benzoyl peroxide, makes it possible to obtain a polymerization around 40 ° C.
  • the process for preparing these wettable microporous diaphragms therefore comprises in its first phase the preparation of a microporous sheet.
  • porophoric fillers as described in the French patents published under the numbers 2 229 739; 2,280,435; 2280609 and 2,280,435, the descriptions of which are incorporated herein by reference.
  • a porophore filler into a latex of fluorinated resin and in particular of polytetrafluoroethylene containing a plasticizing agent, 900 to 1,200 and preferably 400 to 900 parts by weight of porophores, 0.5 to 2 parts of agent plasticizer and 1 to 20 parts of water being added to 100 parts of a latex resin containing 40 to 60% by weight of dry matter, mix the whole in a moderately stirred mixer, that is to say the rotor rotates at less than 100 revolutions / min, to preform by rolling a sheet using the paste obtained, to dry it and then to sinter it at a temperature of the order of the melting point of the polymer used.
  • the porophore agent which is preferably calcium carbonate is then removed by immersion in acid which is preferably acetic acid in aqueous solution at 15-20% by weight.
  • porous sheets in particular in the case where the fluorinated polymer used is a copolymer of ethylene and chlorotrifluoroethylene, or a PTFE latex, associated with mineral or organic fibers (asbestos, zirconia, fibrillated polyolefins) by dispersing the copolymer in an amount of 5 to 50% of the weight of fibers in the electrolyte, that is to say containing about 15% of sodium hydroxide and 15% of sodium chloride to which a surfactant is added.
  • the fluorinated polymer used is a copolymer of ethylene and chlorotrifluoroethylene, or a PTFE latex, associated with mineral or organic fibers (asbestos, zirconia, fibrillated polyolefins)
  • This suspension is deposited on a surface allowing filtration; this surface can in particular be a perforated cathode. After spinning and drying, the sheet formed during filtration is heated to 260 ° C temperature which is maintained from 30 mm to 1 hour.
  • the porous sheet thus formed is then impregnated with a mixture of comonomers and of polymerization initiator and, in general of inert diluent.
  • the proportion of diluent mentioned above must be chosen according to various other parameters and in particular, the proportion of the crosslinking agent comonomer, in particular divinylbenzene, relative to the unsaturated carboxylic acids and the proportion of polymerization initiator in particular. benzoyl peroxide.
  • the overall condition which must be met, and which leads to a choice in the combination of the various other parameters, is that 0.1 to 6% of the total pore volume, before the in situ copolymerization, of the microporous-support sheet, are occupied by carboxylic copolymer.
  • the proportion by weight of divinylbenzene can be between 2.5 and 25 parts per 100 parts of unsaturated carboxylic acid. It is also good to use only small amounts of polymerization initiator, for example, less than 5 parts by weight of benzoyl peroxide per 100 parts of comonomers and little or no copolymerization accelerator such as dimethylaniline (less than 2 parts).
  • This impregnation can be done for example by immersion in a tank containing this liquid mixture and filtration under vacuum from 10 to 100 mmHg.
  • the sheet optionally on its support, and in particular on a cathode, is then introduced into an enclosure where the temperature, or actinic rays, in particular ultraviolet rays, allow the action of the polymerization initiators. It can be immersed in a liquid, water for example. He imports that the temperature is not too high, generally less than 150 ° C. and does not substantially modify the structure of the microporous sheet by too rapid departure of the diluent or destruction of the deposited copolymer.
  • the polymerization time (which corresponds approximately to the half-life of the initiator used) is preferably less than 12 hours.
  • a preferred means of polymerization is immersion in water between 40 ° C and 100 ° C.
  • Table I given with the examples below clearly illustrates the influence of various factors such as the porosity of the diaphragm or, which is directly the cause, the proportion of porophore agent, the weight ratio between the carboxylic acids and the nonionic monomers and the amount of diluent added on the pressure drop of the electrolyte through the diaphragm or in other words on the hydrostatic pressure, due to the anolyte, necessary to ensure satisfactory percolation and on the electrical voltage in the cell.
  • the factors mentioned can be chosen to achieve a specific goal.
  • the mixture is homogenized for 5 minutes in a WERNER type mixer whose Z-shaped rotors rotate at a speed of 45 revolutions / min.
  • the dough obtained is put into sheets using a LESCUYER type roller mixer.
  • the thickness is reduced to 1.2 mm.
  • the initial cylinder rotation speed of 15 rpm is gradually reduced to 5 rpm in 2 to 4 minutes.
  • the sheet thus formed is dried for 15 hours at 90 ° C then 2 hours at 120 ° C and then sintered in a hot air circulation oven whose temperature has risen, at a rate of 100 ° C / h, to 360 ° C where it is kept for 15 minutes.
  • the calcium carbonate is removed by immersion for 72 hours in an aqueous solution of acetic acid at 25% by weight supplemented with 2 g / I of fluorinated surfactant brand "ZONYL F.S.N. from E-I Du Pont De Nemours Co. •.
  • the diaphragm is then rinsed with water and then immersed for 12 hours in ethanol.
  • divinylbenzene contains 45% by weight of ethylvinylbenzene and 55% of divinylbenzene.
  • the copolymerization is brought about by immersion for 2 hours in water at 80 ° C.
  • This diaphragm which has been given remarkable wettability, is kept in water until it is used. It is then placed, in contact with a cathode, in braided laminated iron from the company GANTOIS •, an electrolysis cell.
  • the anode is made of expanded titanium coated with Pt-Ir alloy.
  • the distance between the electrodes is 5.5 mm: it is maintained by a rubber seal.
  • the electrolyte introduced into the anode compartment is a brine containing 300 g / l of sodium chloride.
  • the temperature is 85 ° C.
  • the current density is 25 A / dm 2
  • the electric voltage is 3.35 V
  • the electrolyte charge is 40 cm.
  • the sodium hydroxide of the catholyte has a concentration of 123 g / I
  • the faradic yield (OH ion) is 94 % .
  • Example 1 The test of Example 1 is repeated by varying the quantity of calcium carbonate and the proportion of the diluent and peroxide comonomers of the impregnation mixture.
  • test 235 The first two control tests (1 and 2) had to be stopped after 25 hours, which is the time when the load h and voltage U measurements were made. The same is true of test 235.
  • the electrolyte charge R is the hydrostatic pressure on the diaphragm expressed in cm or the electrolyte height of density 1.2 approximately, multiplied by this last figure.
  • the amount of NaOH is expressed in grams / liter.
  • the yield R (OH)% is a faradic yield calculated from the sodium hydroxide formed.
  • T% is the percentage of the pore volume occupied by the dry polymer. (See Table on page 6)

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)

Claims (8)

1. Poröses Diaphragma für die Elektrolyse auf der Basis von fluorierten Polymeren, dadurch gekennzeichnet, daß es mikroporös und auf mindestens einem Teil der Innenfläche seiner Poren mit einem Copolymeren aus einer ungesättigten Carbonsäure und einem nicht ionischen ungesättigten Monomeren überzogen ist.
2. Poröses Diaphragma nach Anspruch 1, dadurch gekennzeichnet, daß seine Porosität 50 bis 95 % beträgt und der mittlere äquivalente Durchmesser der Poren zwischen 0,1 und 12 µm, vorzugsweise zwischen 0,2 und 6 f.l.m liegt, wobei 0,1 bis 6 % des Porenvolumens von trockenem Polymerem eingenommen sind.
3. Poröses Diaphragma nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das in den Poren vorhandene Copolymer ein Copolymer einer Säure aus der Gruppe der Acryl- und Methacrylsäuren und mindestens zweier nichtionischer Monomeren ist, von denen das eine aus der Gruppe Styrol und Ethylbenzol genommen wird und das andere Divinylbenzol ist.
4. Verfahren 'zur Herstellung des porösen Diaphragmas nach Anspruch 1, dadurch gekennzeichnet. daß man eine mikroporöse Folie auf der Basis fluorierter Polymerer formt, diese Folie mit Hilfe eines flüssiges Gemisches umfassend mindestens eine ungesättigte Carbonsäure, ein nichtionisches Monomer und einen Polymerisationsinitiator imprägniert und die Copolymerisation bewirkt.
5. Verfahren zur Herstellung des porösen Diaphragmas nach Anspruch 1, dadurch gekennzeichnet, daß man ein Gemisch umfassend mindestens eine Säure aus der Gruppe der Acryl- und Methacrylsäuren und mindestens ein nichtionisches Comonomer aus der Gruppe Styrol und Divinylbenzol sowie ein Verdünnungsmittel einsetzt.
6. Verfahren zur Herstellung des mikroporösen Diaphragmas nach Anspruch 5, dadurch gekennzeichnet, daß man als Verdünnungsmittel Ethanol einsetzt.
7. Verfahren zur Herstellung des mikroporösen Diaphragmas nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß der Gewichtsanteil der ungesättigten Carbonsäure in dem Comonomerengemisch 40 bis 98 %, vorzugsweise 70 bis 95 % ausmacht und daß 1 600 bis 30 Teile Verdünnungsmittel auf 100 Gew.-Teile Comonomere eingesetzt werden, wobei das Gewichtsverhältnis zwischen Divinylbenzol und Carbonsäure so beschaffen ist, daß auf 100 Teile ungesättigte Carbonsäure 2,5 bis 25 Teile Divinylbenzol eingesetzt werden.
8. Verfahren zur Herstellung des mikroporösen Diaphragmas nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, daß die mikroporöse Folie dadurch imprägniert wird, daß das flüssige, die Comonomeren enthaltende Gemisch unter leichtem Unterdruck durch die Folie filtriert wird.
EP81400058A 1980-01-29 1981-01-19 Diaphragma für die Elektrolyse und Verfahren zu seiner Herstellung Expired EP0033262B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81400058T ATE24550T1 (de) 1980-01-29 1981-01-19 Diaphragma fuer die elektrolyse und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8001843 1980-01-29
FR8001843 1980-01-29

Publications (2)

Publication Number Publication Date
EP0033262A1 EP0033262A1 (de) 1981-08-05
EP0033262B1 true EP0033262B1 (de) 1986-12-30

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EP81400058A Expired EP0033262B1 (de) 1980-01-29 1981-01-19 Diaphragma für die Elektrolyse und Verfahren zu seiner Herstellung

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US (2) US4341615A (de)
EP (1) EP0033262B1 (de)
JP (1) JPS5932550B2 (de)
AT (1) ATE24550T1 (de)
CA (1) CA1165276A (de)
DE (1) DE3175761D1 (de)

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US4505797A (en) * 1983-03-24 1985-03-19 Ionics, Incorporated Ion-exchange membranes reinforced with non-woven carbon fibers
JPS61130347A (ja) * 1984-11-30 1986-06-18 Asahi Glass Co Ltd 新規な電解用複層隔膜
US4689134A (en) * 1985-04-18 1987-08-25 Dorr-Oliver Inc. Non ion selective membrane in an EAVF system
US4647360A (en) * 1985-10-04 1987-03-03 The Dow Chemical Company Inert carbon fiber diaphragm
GB2181158B (en) * 1985-10-08 1989-11-15 Electricity Council Electrolytic process for the manufacture of salts
US4879316A (en) * 1987-02-26 1989-11-07 The University Of Tennessee Research Corporation Interpenetrating polymer network ion exchange membranes and method for preparing same
US5152898A (en) * 1989-10-23 1992-10-06 Texaco Inc. Separation of organic oxygenates
US5198505A (en) * 1991-04-11 1993-03-30 Pall Corporation Uniform polyvinylidene difluoride membranes
US5196508A (en) * 1991-04-11 1993-03-23 Pall Corporation Method for making uniform polyvinylidene difluoride membranes
US5458719A (en) * 1993-03-24 1995-10-17 Pall Corporation Method for bonding a porous medium to a substrate
JP2999365B2 (ja) * 1994-05-10 2000-01-17 倉敷紡績株式会社 フッ素樹脂製多孔質体の親水化法
US5599614A (en) * 1995-03-15 1997-02-04 W. L. Gore & Associates, Inc. Integral composite membrane
US5547551A (en) * 1995-03-15 1996-08-20 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
USRE37307E1 (en) 1994-11-14 2001-08-07 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
USRE37701E1 (en) * 1994-11-14 2002-05-14 W. L. Gore & Associates, Inc. Integral composite membrane
US6254978B1 (en) * 1994-11-14 2001-07-03 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
US6054230A (en) * 1994-12-07 2000-04-25 Japan Gore-Tex, Inc. Ion exchange and electrode assembly for an electrochemical cell
US6635384B2 (en) * 1998-03-06 2003-10-21 Gore Enterprise Holdings, Inc. Solid electrolyte composite for electrochemical reaction apparatus
US6689501B2 (en) 2001-05-25 2004-02-10 Ballard Power Systems Inc. Composite ion exchange membrane for use in a fuel cell
US6613203B1 (en) 2001-09-10 2003-09-02 Gore Enterprise Holdings Ion conducting membrane having high hardness and dimensional stability
US20100252445A1 (en) * 2007-07-07 2010-10-07 Donald James Highgate Electrolysis of Salt Water
CN102576891A (zh) 2009-09-03 2012-07-11 纳幕尔杜邦公司 用于直接甲醇燃料电池的具有复合材料、薄膜和薄阴极的改善的催化剂涂覆膜
ES2838924T3 (es) * 2016-06-27 2021-07-02 Siemens Energy Global Gmbh & Co Kg Un separador de gas reforzado con fibras inorgánicas para procesos de conversión electroquímica

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US3291632A (en) * 1963-09-16 1966-12-13 Pittsburgh Plate Glass Co Method of preparing a membrane of divinyl benzene, styrene and maleic anhydride
FR2024291A1 (de) * 1968-11-26 1970-08-28 Du Pont
GB1213472A (en) * 1966-12-03 1970-11-25 Siemens Ag Improvements in or relating to membranes
FR2250793A1 (de) * 1973-11-09 1975-06-06 Commissariat Energie Atomique
US4056447A (en) * 1975-03-06 1977-11-01 Oronzio De Nora Impianti Elettrochimici S.P.A. Electrolyzing alkali metal chlorides using resin bonded asbestos diaphragm
FR2361439A1 (fr) * 1976-08-10 1978-03-10 Sumitomo Electric Industries Structures poreuses hydrophiles de resine fluorocarbonee et leur procede de preparation
FR2364690A1 (fr) * 1976-09-17 1978-04-14 Fujikura Ltd Procede pour la fabrication de separateurs pour cellules electrochimiques
EP0004029A1 (de) * 1978-03-01 1979-09-19 De Nora Permelec S.P.A. Aniondurchdringliche, flüssigkeitundurchdringliche Membran, ein Verfahren zur Herstellung derselben, eine elektrolytische Zelle die die Membran enthält und ein elektrolytisches Verfahren wobei die Membran angewendet wird
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US4178218A (en) * 1974-03-07 1979-12-11 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane and use thereof in the electrolysis of sodium chloride

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Publication number Priority date Publication date Assignee Title
US3291632A (en) * 1963-09-16 1966-12-13 Pittsburgh Plate Glass Co Method of preparing a membrane of divinyl benzene, styrene and maleic anhydride
GB1213472A (en) * 1966-12-03 1970-11-25 Siemens Ag Improvements in or relating to membranes
FR2024291A1 (de) * 1968-11-26 1970-08-28 Du Pont
FR2250793A1 (de) * 1973-11-09 1975-06-06 Commissariat Energie Atomique
US4178218A (en) * 1974-03-07 1979-12-11 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane and use thereof in the electrolysis of sodium chloride
US4056447A (en) * 1975-03-06 1977-11-01 Oronzio De Nora Impianti Elettrochimici S.P.A. Electrolyzing alkali metal chlorides using resin bonded asbestos diaphragm
FR2361439A1 (fr) * 1976-08-10 1978-03-10 Sumitomo Electric Industries Structures poreuses hydrophiles de resine fluorocarbonee et leur procede de preparation
FR2364690A1 (fr) * 1976-09-17 1978-04-14 Fujikura Ltd Procede pour la fabrication de separateurs pour cellules electrochimiques
EP0004029A1 (de) * 1978-03-01 1979-09-19 De Nora Permelec S.P.A. Aniondurchdringliche, flüssigkeitundurchdringliche Membran, ein Verfahren zur Herstellung derselben, eine elektrolytische Zelle die die Membran enthält und ein elektrolytisches Verfahren wobei die Membran angewendet wird
EP0004237A1 (de) * 1978-03-14 1979-09-19 Elf Atochem S.A. Ionenaustauschermembranen; deren Herstellung; deren Verwendung bei der Chloralkalielektrolyse

Also Published As

Publication number Publication date
JPS56152985A (en) 1981-11-26
EP0033262A1 (de) 1981-08-05
ATE24550T1 (de) 1987-01-15
US4410638A (en) 1983-10-18
CA1165276A (fr) 1984-04-10
JPS5932550B2 (ja) 1984-08-09
US4341615A (en) 1982-07-27
DE3175761D1 (en) 1987-02-05

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