EP0037140B1 - Verfahren zur Elektrolyse wässriger Alkalihalogenidlösungen mittels eines durchlässigen Diaphragmas aus einem organischen hydrophobischen polymeren Material für eine für die Elektrolyse wässriger Alkalichloridlösungen geeignete Zelle - Google Patents

Verfahren zur Elektrolyse wässriger Alkalihalogenidlösungen mittels eines durchlässigen Diaphragmas aus einem organischen hydrophobischen polymeren Material für eine für die Elektrolyse wässriger Alkalichloridlösungen geeignete Zelle Download PDF

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Publication number
EP0037140B1
EP0037140B1 EP81200298A EP81200298A EP0037140B1 EP 0037140 B1 EP0037140 B1 EP 0037140B1 EP 81200298 A EP81200298 A EP 81200298A EP 81200298 A EP81200298 A EP 81200298A EP 0037140 B1 EP0037140 B1 EP 0037140B1
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EP
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Prior art keywords
diaphragm
polymeric material
metal oxide
process according
electrolysis
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Expired
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EP81200298A
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English (en)
French (fr)
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EP0037140A1 (de
Inventor
Jean Indeherbergh
Edgard Nicolas
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Solvay SA
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Solvay SA
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Priority to AT81200298T priority Critical patent/ATE8154T1/de
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    • 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 subject of the present invention is a process for the electrolysis of an aqueous solution of an alkali metal halide, in particular of sodium chloride brines, in which a permeable diphragm of organic polymer material is opened.
  • hydrophilic additives into these diaphragms; these are usually mineral compounds in the particulate state, such as asbestos fibers, mica, talc, or even particles of titanate dioxide, alumina, silica or potassium titanate.
  • a permeable diaphragm for an electrolysis cell obtained by coagulation of a dispersion of polytetrafluoroethylene and an additive.
  • hydrophilic inorganic in the particulate state alumina, silica, titanium oxide
  • a diaphragm of controlled permeability for an electrolysis cell which is obtained by coagulation of a colloidal suspension of a mineral compound hydrophilic (potassium titanate, titanium dioxide, thorium dioxide, zirconium oxide) on cellulosic fibers, coagulation of a colloidal suspension of a fluoropolymer on cellulosic fibers coated with the hydrophilic mineral compound, formation of a sheet with the resulting coagulum, drying the sheet and heating it to melt the polymer and burn the cellulosic fibers. In this way a coherent porous sheet is obtained, the pores of which are lined with the hydrophilic mineral compound.
  • hydrophilic potassium titanate, titanium dioxide, thorium dioxide, zirconium oxide
  • Patent US 4036729 to Patil et al published on July 19, 1977, relates to a permeable diaphragm which consists of a felt formed on the perforated cathode of an electrolysis cell, starting from a dispersion of a polymeric material fibrous and a hydrophilic mineral compound (Asbestos, mica, talc, barium or potassium titanate, titanium dioxide, boron nitride) in an aqueous medium containing acetone and a surfactant.
  • a hydrophilic mineral compound Asbestos, mica, talc, barium or potassium titanate, titanium dioxide, boron nitride
  • these known diaphragms generally have the advantage of being inert with respect to the aggressive chemical media present in electrochemical cells, such as acid brines of sodium chloride or aqueous solutions of sodium hydroxide.
  • a diaphragm for an electrolysis cell by impregnating a support fabric of polymeric material, with a substance containing a compound siliceous.
  • the impregnating substance may optionally also contain an additive intended to improve the ionic conductivity of the diaphragm, such as magnesium oxide or alumina.
  • the siliceous compound of the impregnating substance must moreover be in the form of particles whose diameter must be greater than 1 ⁇ m and is preferably fixed between 1 and 75 ⁇ m.
  • This known diaphragm has the disadvantage of being of delicate and expensive construction; its intrinsic properties, in particular its permeability to aqueous electrolytes, are difficult to reproduce, because they are highly dependent on the nature and the origin of the siliceous compound.
  • the carboxylic functional groups of the fluoropolymer have the function of conferring the desired hydrophilicity on the diaphragms, while the magnesium compound, chemically bonded to the polymer, has the function of improving the stability and the consistency of the properties of the diaphragms.
  • porous sheet-shaped products are described, formed from an aggregate of fibers of organic polymer, inert, hydrophobic and suitable for various applications, such as diaphragms for electrolytic cells, separators for accumulators, fuel cell elements, dialysis membranes and filters.
  • These porous products may optionally contain a wettable additive, examples of which are inorganic oxides and hydroxides such as, in particular, zirconium oxide, titanium oxide, chromium oxide and the oxides and magnesium and calcium hydroxides.
  • a wettable additive examples of which are inorganic oxides and hydroxides such as, in particular, zirconium oxide, titanium oxide, chromium oxide and the oxides and magnesium and calcium hydroxides.
  • zirconium oxide titanium oxide, chromium oxide and the oxides and magnesium and calcium hydroxides.
  • the object of the invention is to provide a process for the electrolysis of an aqueous solution of alkali metal halide in a cell with a permeable diaphragm made of hydrophobic organic polymeric material, which has good mechanical cohesion, which is either a moderate cost which, all other things being equal, ensures improved performance for the electrolysis cells of aqueous solutions of alkali metal halide.
  • the invention therefore relates to a process for the electrolysis of an aqueous alkali metal halide solution in a cell with a permeable diaphragm in which or implements a permeable diaphragm made of hydrophobic organic polymeric material for a cell for the electrolysis of aqueous solutions.
  • the choice of the polymer of the organic polymeric material is dictated by the need to obtain a diaphragm which resists the chemical and thermal conditions normally prevailing in the electrolysis cells. It is possible, for example, to use thermoplastic polymers chosen from polyolefins, polycarbonates, polyesters, polyamides, polyimides, polyphenylenes, polyphenylene oxides, polyphenylene sulfides, polysulfones and mixtures of these polymers. In general, fluorinated polymers are preferably used, according to the invention.
  • Polymers containing fluorinated monomer units derived from ethylene or propylene are advantageously chosen, preferably polymers containing at least 50%, and more particularly at least 75%, of such monomer units.
  • Particularly suitable polymers are those containing only monomeric units derived from ethylene or propylene in which all the hydrogen atoms have been substituted by chlorine or fluorine atoms.
  • polymers which are suitable in the case where the diaphragm according to the invention is intended for the electrolysis of sodium chloride brines are those chosen from polytetrafluoroethylene, polychlortrifluoroethylene, polyvinylidene fluoride, copolymers of ethylene and chlorotrifluoroethylene, copolymers of ethylene and tetrafluoroethylene, copolymers of chlorotrifluoroethylene and vinylidene fluoride, copolymers of hydropentafluorpropylene and vinylidene fluoride, copolymers of hexafluoroisobutylene and vinylidene fluoride, copolymers of tetrafluoroethylene and perfluorvinyl ether sulphonyls, copolymers of tetrafluoroethylene and perfluoralkylvinyl ether.
  • Particularly preferred copolymers are those of tetrafluoroethylene and perfluoroprolylene.
  • a first characteristic of the invention consists in the fact that the hydrophilic additive of the diaphragm is an oxide of a metal chosen from those of group lla of the Periodic Table of the Elements.
  • Magnesium oxide has been found to be especially advantageous. All other things being equal, the performance of the electrolysis cells of aqueous sodium chloride solutions equipped with a diaphragm according to the invention are in fact optimum when the hydrophilic metal oxide is magnesium oxide.
  • the hydrophilic metal oxide is distributed in the form of particles among the organic polymer material. These particles can be in the amorphous state, in the state of single crystals or in the state of polycrystals, and they can have the form of grains or fibers.
  • the hydrophilic metal oxide particles have an average diameter which does not exceed 0.5 ⁇ m, the average diameter of a particle being by definition, the diameter of a sphere having a volume equal to that of the particle.
  • hydrophilic metal oxide particles whose mean diameter is between 0.002 ⁇ m and 0.2 ⁇ m, the values less than 0.1 ⁇ m being preferred.
  • metal oxide particles having an average diameter of between 0.005 and 0.05 ⁇ m have been found to be especially advantageous.
  • the quantity of hydrophilic metal oxide in the diaphragm according to the invention is generally chosen to be sufficient to give the diaphragm a wettability acceptable by aqueous electrolytes but without exceeding a limit value beyond which the cohesion or the mechanical resistance of the diaphragm becomes insufficient for the function for which it is intended.
  • hydrophilic metal oxide The choice of the optimum quantity of hydrophilic metal oxide to be used depends on a large number of parameters, among which appear in particular the nature of the organic polymeric material, the choice of the metal or metals of group lla entering into the composition. oxide metal, the shape and the average diameter of the metal oxide particles, as well as the destination of the diaphragm and the desired performance for the electrolysis cell for which the diaphragm is intended. In general, the optimum amount of hydrophilic metal oxide to be used must be determined in each particular case, by routine work in the laboratory.
  • diaphragms in accordance with the invention which have proved adequate in the majority of cases are those having a weight content of hydrophilic metal oxide at least equal to 5% of the total weight of the diaphragm, and generally between 10 and 80% of this weight. Weight contents of between 20 and 60% are however preferred.
  • the particles of the hydrophilic metal oxide can be distributed in the individual state among the mass of organic polymeric material or, alternatively, they can be contained in situ in the polymeric material, of which they constitute a filler.
  • a part of the particles of the hydrophilic metal oxide of the diaphragm can be distributed individually among the polymeric material, the remaining part of the particles being included in situ in the polymeric material of which it constitutes a filler.
  • the diaphragm according to the invention can be obtained by any technique commonly used for the manufacture of diaphragms made of organic polymeric material.
  • the organic polymeric material is in the fibrous state.
  • the organic polymeric material can be either in the form of fibers or fibrils; alternatively, it can also comprise a mixture of fibers and fibrils.
  • fibrils is intended to denote a specific structure of the polymeric material.
  • the fibrils consist of an aggregate of a multitude of very fine filaments, with a film-like appearance, connected together so as to form a three-dimensional network.
  • the fibrillated aggregates In appearance flaky, the fibrillated aggregates have an oblong shape; their length varies from 0.5 to 50 mm approximately and their diameter from a few microns to approximately 5 mm. They are characterized by a high specific surface, greater than 1 m 2 / g and even, in many cases, 10 m 2 / g.
  • the fibrils used in the context of the invention can, for example, be produced by subjecting a mixture of a polymer in the molten state and of a solvent, to a sudden expansion through an appropriate orifice, as described in particular in French patents 1,596,107 of December 13, 1968, 2,148,449 and 2,148,450 of August 1, 1972 and in Belgian patents 811,778 of March 1, 1974 and 824,844 of January 17, 1975, all in the name of the Applicant.
  • the fibrils used in the context of the invention can also be manufactured by other methods, for example by one or other of the methods described in French patents 1,214,157 or June 10, 1958 and 1,472,989 of September 24, 1965, on behalf of E.1. du Pont de Nemours and Co. In these manufacturing processes, however, continuous fibrillated locks are obtained, which must then be shredded, for example by grinding.
  • the organic polymeric material is in the form of fibers
  • fibers whose diameter is substantially between 0.1 and 25 microns fibers which are very suitable are those having a diameter of between 1 and 15 microns.
  • the hydrophilic metal oxide is contained in situ in the fibrous polymeric material, of which it constitutes a charge. It has in fact been observed that the diaphragms according to this variant of the invention have optimum cohesion and lead to particularly advantageous electrolysis results.
  • the diaphragms which lead to the most advantageous electrolysis results are those in which the polymeric material organic is perfluorinated and in a fibrous state, and in which, according to the invention, the hydrophilic metal oxide is magnesium oxide in particles which have an average diameter of between 0.005 and 0.05 I lm and which are contained in situ in the polymeric material, of which they constitute a filler.
  • the diaphragm can advantageously be in the form of a felt. This is generally obtained by decantation or filtration of a suspension of the fibrous polymeric material and the metal oxide particles in a suitable liquid which does not dissolve the polymeric material or the metal oxide.
  • a felt is formed from a suspension of the polymeric material in the fibrous state and hydrophilic metal oxide particles in water or an aqueous solution.
  • Suitable aqueous solutions include aqueous solutions of sodium chloride and aqueous solutions of sodium hydroxide.
  • Caustic brines containing 150 to 200 g of sodium chloride and 100 to 150 g of sodium hydroxide have been found to be particularly advantageous per liter; they are generally obtained by electrolysis of sodium chloride brines in diaphragm electrolysis cells.
  • a surfactant In order to facilitate the dispersion of the polymeric material and the hydrophilic metal oxide in water or the aqueous solution, it may be desirable to add a surfactant thereto. Fluorinated surfactants have been found to be especially advantageous, such as fluorinated or perfluorinated fatty acids, fluorinated or perfluorinated sulfonic acids and the salts of these acids.
  • the surfactant can be introduced individually in the aqueous solution.
  • the optimum amount of surfactant to be used depends on various factors, among which are in particular the nature of the polymer, the dimensions of the fibers or fibrils of the polymer, the nature of the aqueous solution and the nature of the surfactant. It can be determined in each particular case by routine laboratory work.
  • the surfactant is used in an amount of between 0.5 and 10% of the weight of the polymeric material, the values of between 2 and 7% being however preferred.
  • the felt is sufficient to decant or filter it.
  • the felt by filtering the above suspension directly through an openwork support of the diaphragm by applying a technique analogous to that commonly used for the manufacture of asbestos diaphragms and described in particular in the United States patents. 1 865152 in the name of KE STUART, of June 28, 1932, and 3 344 053 in the name of NEIPERT et al., Of May 4, 1964.
  • the perforated support of the diaphragm can advantageously be the perforated cathode of a diaphragm electrolysis cell .
  • This embodiment has the advantage of making it possible to manufacture the diaphragm in situ on cathodes of complicated shape, with non-developable surface, for example of the type equipping the electrolysis cells described in French patents 2,223,083 of 28 3. 1973 and 2,428,335 of October 14, 1974 in the name of the Claimant.
  • the dispersion of the polymeric material and the metal oxide in water or the aqueous solution and the filtration of the resulting aqueous suspension through the perforated support are executed in a single device, known per se for the manufacture of asbestos diaphragms, and described in French patent 2,308,702 of 25. 4.1975, in the name of the Applicant.
  • the diaphragm according to the invention has the advantage of having good mechanical cohesion and of being of stable dimensions during its use in an electrolysis cell. It has the advantageous property of an excellent wettability by aqueous electrolytes, in particular by sodium chloride brines.
  • the diaphragm according to the invention has the particularly advantageous characteristic of generally having a permeability to aqueous electrolytes of the same order of magnitude as that of asbestos diaphragms normally fitted to the electrolysis cells with sodium chloride brines. , so that it is well suited to be substituted for the asbestos diaphragms of existing electrolysis cells, for example of the type described in French patents 2 164 623 of 12.12.1972, 2 223 083 of 28. 3. 1973 , 2 230 411 dated 27. 3. 1974 and 2 248 335 dated 14.10.1974, all in the name of the Claimant.
  • the diaphragm according to the invention also has the interesting and surprising characteristic of having, from the start of its use, the optimum characteristics required for wettability and permeability.
  • This feature of the diaphragm according to the invention provides the appreciable advantage that the electrolysis cells are henceforth capable of operating under normal conditions, with optimum energy efficiency, from the start of their commissioning with a new diaphragm.
  • the diaphragm according to the invention may optionally contain, in addition to the polymeric material and the hydrophilic metal oxide, other usual constituents of the permeable diaphragms of the aimed at giving it additional properties.
  • some electrolysis tests were carried out in a laboratory cell comprising a vertical anode and a cathode separated by a diaphragm.
  • the anode consisted of a circular titanium plate of 113 cm 2 , carrying an active coating consisting of an equimolar mixture of ruthenium dioxide and titanium dioxide.
  • the cathode was formed from a 113 cm 2 mild steel circular lattice, and bore the diaphragm on its face opposite the anode. The distance between the anode and the cathode was 5 mm.
  • Examples 1 to 3 relate to electrolysis tests with diaphragms in accordance with the invention.
  • the fibrils have an average specific surface of approximately 23 m 2 / g. They were obtained, by subjecting a biphasic mixture of the polymer in the molten state and of an appropriate solvent, to a sudden expansion through an orifice of small section, as described in French patents 1,596,107 of December 13, 1968, 2 148,449 of 2,148,450 of August 1, 1972 and in the Belgian patents 811,778 of March 1, 1974 and 824,844 of January 17, 1975, all in the name of the Applicant.
  • the magnesium oxide particles have an average diameter of between 0.02 and 0.04 ⁇ m.
  • the fibrils and magnesium oxide particles were dispersed in caustic brine containing approximately 8% by weight of sodium hydroxide and 16% by weight of sodium chloride.
  • the caustic brine also contained, per liter, 400 mg of the product known as "Polymin P" (BASF) which is a polyethyleneimine retaining agent.
  • BASF Polymin P
  • the cathode of the cell was immersed therein and the suspension was sucked through it so as to deposit on its surface a felt formed from a mixture of fibrils and particles of magnesium oxide .
  • the felt had a weight corresponding to approximately 1.3 kg / m 3 of cathode surface area, and it contained approximately 68% by weight of fibrils and 32% by weight of magnesium oxide.
  • the felt on the cathode After forming the felt on the cathode, it was immediately mounted in the laboratory cell and there was electrolysis of a brine containing 255 g of sodium chloride per kg, at a constant current density, equal to 2 kA / m 2 of anode. The temperature in the cell was maintained at about 85 ° C for the duration of the test.
  • the magnesium oxide powder and a surfactant were combined with the polymer (copolymer of tetrafluoroethylene and perfluoropropylene) in situ in the fibrils, at the time of their manufacture.
  • the particles of magnesium oxide and the surfactant were incorporated into this mixture.
  • the respective amounts of magnesium oxide and of surfactant used have been adjusted so that the fibrils obtained contain approximately 58% by weight of polymer, 39% by weight of magnesium oxide and 3% by weight of agent. fluorinated surfactant.
  • the magnesium oxide particles used had an average diameter of between 0.02 and 0.04 ⁇ m.
  • the fibrils thus obtained had a specific surface area of approximately 25 m 2 / g.
  • a diaphragm consisting exclusively of such fibrils was deposited on the cathode of the laboratory cell, applying the method described in Example 1, but omitting however to incorporate the retaining agent »Polymin P « in the caustic brine bath. .
  • the weight of the diaphragm obtained corresponded to approximately 1.3 kg / m 2 of the cathode.
  • the diaphragm used in this test consisted of a felt formed from a mixture of individual particles of magnesium oxide identical to those used in Example 1 and of fibrils charged with magnesium oxide and a fluorinated surfactant, identical to the fibrils used in the test of Example 2.
  • the quantities used were adjusted so that the diaphragm formed on the cathode had a weight equivalent to 1.4 kg / m 2 of cathode surface and contained approximately 93% of fibrils loaded with magnesium oxide and surfactant and 7% of individual particles of magnesium oxide.
  • Example 4 relates to an electrolysis test with a diaphragm prior to the invention.
  • fibrils made of a copolymer of tetrafluoroethylene and perfluoropropylene, loaded with a powder of titanium dioxide and a fluorinated surfactant were manufactured.
  • the fibrils were manufactured by a technique comparable to that used to obtain the fibrils of Example 2.
  • the particles of titanium dioxide used in the manufacture of the fibrils had an average diameter equal to approximately 0.02 J lm.
  • the respective amounts of polymer, titanium dioxide and surfactant used were adjusted so that the fibrils obtained contain approximately 48.75% by weight of polymer, 48.75% by weight of titanium dioxide and 2 , 50% by weight of fluorosurfactant.
  • a diaphragm consisting exclusively of such fibrils was deposited on the cathode of the laboratory cell, by applying the method described in Example 2.
  • the weight of the diaphragm obtained corresponded to approximately 1.3 kg / m 2 of the cathode.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)

Claims (10)

1. Verfahren zur Elektrolyse einer wäßrigen Alkalimetallhalogenidlösung in einer Zelle mit durchlässigem Diaphragma, wobei für das Diaphragma eine poröse Folie aus einem organischen hydrophobischen polymeren Material verwendet wird, das ein hydrophiles Metalloxid im Partikelzustand enthält, dadurch gekennzeichnet, daß eine poröse Folie verwendet wird, für die das Metalloxid ausgewählt ist unter den Oxiden der Metalle der Gruppe Ila des periodischen Systems, und zwar im Partikelzustand bei einem mittleren Durchmesser der Partikel von höchstens 0,5 Mikrometer.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Metalloxid Magnesiumoxid ist.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Partikel des Metalloxids einen mittleren Durchmesser zwischen 0,002 und 0,2 Mikrometer besitzen.
4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Metalloxid in einer Menge zwischen 20 und 60% des Gesamtgewichts des Diaphragmas verwendet wird.
5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das organische polymere Material im Faserzustand verwendet wird.
6. Verfahren nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß eine Folie verwendet wird, in der das Metalloxid in situ in dem organischen polymeren Material eingebracht ist, für das es einen Füllstoff bildet.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß eine Folie mit einem oberflächenaktiven Mittel verwendet wird, das in situ in dem organischen polymeren Material eingebracht ist, für das es einen Füllstoff bildet.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das oberflächenaktive Mittel in einer Menge zwischen 2 und 7% des Gewichts des organischen polymeren Materials verwendet wird.
9. Verfahren nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß eine Folie verwendet wird, in der das organische polymere Material ein Copolymer von Tetrafluoräthylen und Perfluorpropylen ist.
10. Verfahren nach irgendeinem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß die Folie im Zustand eines Filzes verwendet wird, der erhalten ist in situ auf einem durchbrochenen Träger ausgehend von einer wäßrigen Suspension des polymeren Materials im fasrigen Zustand und des hydrophilen Metalloxids.
EP81200298A 1980-03-27 1981-03-17 Verfahren zur Elektrolyse wässriger Alkalihalogenidlösungen mittels eines durchlässigen Diaphragmas aus einem organischen hydrophobischen polymeren Material für eine für die Elektrolyse wässriger Alkalichloridlösungen geeignete Zelle Expired EP0037140B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81200298T ATE8154T1 (de) 1980-03-27 1981-03-17 Verfahren zur elektrolyse waessriger alkalihalogenidloesungen mittels eines durchlaessigen diaphragmas aus einem organischen hydrophobischen polymeren material fuer eine fuer die elektrolyse waessriger alkalichloridloesungen geeignete zelle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8006919 1980-03-27
FR8006919A FR2485041A1 (fr) 1980-03-27 1980-03-27 Diaphragme permeable en matiere polymerique organique pour cellule d'electrolyse de solutions aqueuses d'halogenure de metal alcalin

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EP0037140A1 EP0037140A1 (de) 1981-10-07
EP0037140B1 true EP0037140B1 (de) 1984-06-27

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US (1) US4482441A (de)
EP (1) EP0037140B1 (de)
JP (1) JPS56150193A (de)
AT (1) ATE8154T1 (de)
AU (1) AU6865481A (de)
BR (1) BR8101810A (de)
DE (1) DE3164380D1 (de)
ES (1) ES500728A0 (de)
FI (1) FI68671C (de)
FR (1) FR2485041A1 (de)
NO (1) NO811030L (de)
PT (1) PT72734B (de)
ZA (1) ZA811739B (de)

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US4853101A (en) * 1984-09-17 1989-08-01 Eltech Systems Corporation Porous separator comprising inorganic/polymer composite fiber and method of making same
MX169225B (es) * 1984-09-17 1993-06-24 Eltech Systems Corp Compuesto de fibras no organicas/polimero metodo para elaborarlo y uso del mismo, incluyendo un separador dimensionalmente estable
US4707228A (en) * 1986-06-06 1987-11-17 Treadwell Corporation Diaphragm for electrolytic and electrochemical cells
AU3603393A (en) * 1992-02-13 1993-09-03 Dow Chemical Company, The Separators for electrolytic cells and processes for making
EP1528126A1 (de) * 2003-10-30 2005-05-04 Vandenborre Hydrogen Systems N.V. Integriertes Elektrolysiermodul mit internem Gas/Flüssigkeit-Abscheider

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Publication number Publication date
PT72734A (fr) 1981-04-01
US4482441A (en) 1984-11-13
FI68671B (fi) 1985-06-28
ATE8154T1 (de) 1984-07-15
BR8101810A (pt) 1981-09-29
JPS56150193A (en) 1981-11-20
DE3164380D1 (en) 1984-08-02
NO811030L (no) 1981-09-28
ZA811739B (en) 1982-04-28
FI68671C (fi) 1985-10-10
FR2485041B1 (de) 1983-11-04
FI810932L (fi) 1981-09-28
FR2485041A1 (fr) 1981-12-24
ES8207592A1 (es) 1982-09-16
ES500728A0 (es) 1982-09-16
EP0037140A1 (de) 1981-10-07
PT72734B (fr) 1982-03-22
AU6865481A (en) 1981-10-01

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