EP0466266B1 - Elektrolyseur mit mindestens zwei, längs einer gemeinsamen Trennwand elektrisch seriengeschalteten Elementarzellen - Google Patents

Elektrolyseur mit mindestens zwei, längs einer gemeinsamen Trennwand elektrisch seriengeschalteten Elementarzellen Download PDF

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Publication number
EP0466266B1
EP0466266B1 EP91201753A EP91201753A EP0466266B1 EP 0466266 B1 EP0466266 B1 EP 0466266B1 EP 91201753 A EP91201753 A EP 91201753A EP 91201753 A EP91201753 A EP 91201753A EP 0466266 B1 EP0466266 B1 EP 0466266B1
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EP
European Patent Office
Prior art keywords
electrolyser
plates
chamber
weight
cells
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 - Lifetime
Application number
EP91201753A
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English (en)
French (fr)
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EP0466266A1 (de
Inventor
Frédéric Muret
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Solvay SA
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Solvay SA
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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • C25B9/66—Electric inter-cell connections including jumper switches
    • 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
    • C25B11/036—Bipolar electrodes
    • 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
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • the invention relates to electrolysers of the series type, comprising a succession of elementary electrolysis cells electrically coupled in series.
  • It relates more particularly to an electrolyser in which two successive elementary cells comprise a common metallic vertical wall which ensures the electrical connection between the cells.
  • the common vertical wall of the two cells generally carries, on one side, an anode of one of the cells and, on the other side, a cathode of the other cell.
  • the common wall usually consists of two plates of different metals, joined to one another, for example by welding.
  • the plate carrying the anode is generally made of titanium, the other plate being of iron, steel, nickel or an alloy of these metals. The presence of a titanium plate associated with a different metal plate can lead to difficulties in the operation of the electrolyser.
  • the invention overcomes the aforementioned drawbacks of known electrolysers, by providing the means of producing a metal wall common to two consecutive electrolysis cells, which reconciles low electrical resistance and an efficient escape of a gas migrating inside the wall.
  • the invention relates to an electrolyser comprising at least two elementary electrolysis cells coupled in electrical series along a common vertical wall which comprises two vertical metal plates, arranged opposite one another. by forming between them a vertical chamber, one of the plates carrying an anode of one of the cells and the other plate carrying a cathode of the other cell; according to the invention, the chamber contains a mass metal whose melting temperature is lower than the temperature prevailing in said chamber during the operation of the electrolyser.
  • the two cells are contiguous.
  • One of the plates constitutes a wall element of one of the two cells and carries an anode of this cell, and the other plate constitutes a wall element of the other cell of which it carries a cathode.
  • the plates can constitute these electrodes or serve as electrode supports, as is for example the case of the cells described in patent US-A-4088551.
  • the plates are made of an electrically conductive material, capable of withstanding the mechanical, thermal and chemical conditions normally prevailing in the cells during the operation of the electrolyser.
  • the plate carrying the anode can be made of a film-forming metal selected from titanium, tantalum, niobium, zirconium and the tungsten and the plate carrying the cathode can be made of a material selected from iron, nickel, cobalt and the alloys of these metals.
  • the film-forming metal plate constitutes at least part of the anode, this plate is covered, on at least part of its face situated in the cell, with an electrically conductive coating, having a low overvoltage in the oxidation of chloride ions.
  • This coating can for example be selected from the metals of the platinum group (platinum, ruthenium, rhodium, palladium, iridium, osmium), the alloys of these metals and their oxides; it can advantageously be formed from mixed crystals of platinum group metal oxide and film-forming metal oxide as described above. It is also recommended to coat the film-forming metal plate, which is located inside the vertical chamber, with a nickel film. This nickel film can be obtained by any suitable nickel plating technique. Its function is to improve the wetting of the plate by the molten metal mass.
  • the two plates of the wall common to the two cells are arranged opposite one another, on either side of a peripheral frame, so as to delimit a vertical chamber.
  • the assembly of the frame and the plates must be hermetic, so that the chamber can retain a liquid mass during the normal operation of the electrolyser.
  • a frame of elastic material which is compressed between the two plates, or a rigid frame, for example of metal or of polymeric material, which is inserted between the two plates, with interposition. of gaskets or that are welded or hermetically sealed to the two plates.
  • the chamber between the two plates contains a metallic mass, the melting point of which is lower than the temperature which normally prevails in said chamber during the normal operation of the electrolyser.
  • the choice of metal mass will depend on the normal operating temperature of the electrolyser and, consequently, on the electrolysis process used.
  • a metallic mass is chosen whose melting temperature is less than 100 ° C., for example mercury.
  • the metal mass ensures the transfer of electric current through the wall common to the two cells. Furthermore, being brought to a temperature above its melting temperature, it liquefies; the hydrogen which migrates through the wall and reaches the chamber can thus escape from it by passing through the liquid metallic mass.
  • the metallic mass has a melting temperature which is higher than ambient temperature, for example greater than 25 ° C.
  • This embodiment presents thus the particularity that the metallic mass is solid at ambient temperature and liquid at the normal operating temperature of the electrolyser.
  • This embodiment of the invention has the advantage of facilitating the assembly and disassembly of the electrolyser.
  • Examples of metallic masses which can be used in this embodiment of the invention are the eutectic binary alloy of rubidium (68.0% by weight) and potassium (32.0% by weight) (melting temperature: 33 ° C ); the eutectic quaternary alloy of bismuth (49.5% by weight), lead (17.6% by weight), tin (11.6% by weight) and indium (21.3% by weight) (melting temperature: 58.2 ° C); the eutectic ternary alloy of indium (51.0% by weight), bismuth (32.5% by weight), and tin (16.5% by weight) (melting temperature: 60.5 ° C ); Wood's alloy [quaternary alloy of bismuth (50.0% by weight), lead (25.0% by weight), tin (12.5% by weight) and cadmium (12.5% by weight) weight) (melting temperature: 70 ° C)]; the eutectic binary alloy of indium (67% by weight) and bismuth (33% by weight)
  • the electrolyser according to the invention is specially adapted to the methods of electrolysis of aqueous sodium chloride solutions using temperatures in the region of 100 ° C., for example between 80 and 120 ° C.
  • the invention therefore finds an advantageous application in the construction of electrolysers intended for the production of aqueous solutions of sodium chlorate by electrolysis of aqueous solutions of sodium chloride. It finds another interesting application in the construction of electrolysers with diaphragms or membranes selectively permeable to cations, used for the production of chlorine and aqueous solutions of hydroxide of sodium by electrolysis of aqueous solutions of sodium chloride.
  • the electrolyser shown in FIG. 1 is designed for the manufacture of aqueous solutions of sodium chlorate by electrolysis of aqueous solutions of sodium chloride. It comprises elementary cells 1 juxtaposed between two elementary end cells 2 and 3.
  • Cells 1 include an electrolysis chamber delimited by a horizontal side wall 5 of rectangular section and two end walls 6 which are common to two cells contiguous.
  • the two end cells 2 and 3 also include a horizontal side wall 5, an end wall 6 interposed between it and the adjoining cell 1 and an end wall 7 connected to a DC source, not shown.
  • Two pipes 8 and 9, in communication with the electrolysis chamber, are intended to be connected, one to a general intake manifold for an aqueous solution of sodium chloride, the other to a general intake manifold. evacuation of electrolysis products.
  • FIGS 2 and 3 show on a larger scale, the end wall 6 common to two adjoining cells.
  • the wall 6 comprises two vertical metal plates 10 and 11 arranged opposite one another, on either side of a peripheral frame 12.
  • the plate 10 is made of titanium and carries an anode consisting of a series of vertical sheets 13 welded transversely to the plate 10.
  • the sheets 13 are made of titanium and have a coating formed of mixed crystals of ruthenium oxide and titanium oxide.
  • the plate 11 is made of steel and carries a cathode made up of a series of vertical steel plates 14, welded to the plate 11.
  • the frame 12 is made of steel and it is pierced with a series of openings 15 in its upper part .
  • the plates 10 and 11 are fixed in sealed manner to the frame 12, so as to form a sealed chamber 16.
  • the plates 10 and 11 are moreover fixed in sealed manner to the side walls 5 of two contiguous cells.
  • the fixing of the plates 10 and 11 to the frame 12 and to the side walls 5 can be carried out by welding. It is preferable to use an assembly by bolts and nuts, which has the advantage of facilitating the assembly and disassembly of the electrolyser.
  • the end wall 7 of the cell 2 is a titanium plate, identical to the plate 10 of the common wall 6 and, like it, it carries an anode consisting of a series of vertical sheets 13 of titanium carrying a coating d titanium oxide and ruthenium oxide.
  • the end wall 7 of the cell 3 is a steel plate, identical to the plate 11 of the common wall 6 and, like it, it carries a cathode made up of vertical steel sheets 14.
  • the fixing of the plates 7 to the wall 5 of cells 2 and 3 is similar to that of plates 10 and 11.
  • the chamber 16 of the common wall 6 contains a metallic alloy of bismuth (50.0% by weight), lead (25.0% by weight), tin (12.5% by weight ) and cadmium (12.5% by weight) (Wood alloy), the melting temperature of which is approximately 70 ° C.
  • the alloy fills almost all of the chamber 16. A slight gap 17 must however be provided above the alloy, to allow its expansion during the operation of the electrolyser.
  • an aqueous solution of sodium chloride is introduced into the electrolysis cells, through the tubes 8 and the end walls 7 are connected to the terminals of a direct current source, not shown. .
  • the sodium chloride solution undergoes electrolysis in the electrolysis cells and an aqueous solution of sodium chlorate and hydrogen generated on the sheets 14 of the cathodes are collected by the tubes 9.
  • the metallic mass contained in the chambers 16 melts. If atomic hydrogen diffuses through the plate 11 into the chamber 16, it bubbles through the liquid metallic mass therein and escapes through the openings 15.
  • the liquid metallic mass of the chambers 16 also provides the flow of electric current between the adjoining cells.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Control Of Indicators Other Than Cathode Ray Tubes (AREA)
  • Two-Way Televisions, Distribution Of Moving Picture Or The Like (AREA)
  • Channel Selection Circuits, Automatic Tuning Circuits (AREA)
  • Hybrid Cells (AREA)
  • Secondary Cells (AREA)
  • Conductive Materials (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Claims (10)

  1. Elektrolysegerät, umfassend mindestens zwei Elementarelektrolysezellen (1), die entlang einer gemeinsamen vertikalen Wand (6) elektrisch in Reihe geschaltet sind, welche zwei vertikale Metallplatten (10, 11) umfaßt, die einander gegenüberliegend auf beiden Seiten eines Umfangsrahmens (12) derart angeordnet sind, daß sie eine vertikale Kammer (16) begrenzen, wobei eine der Platten (10) eine Anode (13) von einer der Zellen trägt, und die andere Platte (11) eine Kathode (14) der anderen Zelle trägt, dadurch gekennzeichnet, daß die Kammer (16) eine metallische Masse enthält, deren Schmelzpunkt niedriger liegt als die während des Betriebs des Elektrolysegerätes in der besagten Kammer (16) herrschende Temperatur.
  2. Elektrolysegerät nach Anspruch 1, dadurch gekennzeichnet, daß im oberen Teil des Rahmens (12) Öffnungen (15) angebracht sind.
  3. Elektrolysegerät nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Rahmen (12) starr ist und durch eine Schrauben- und Mutternverbindung an den Platten (10, 11) befestigt ist.
  4. Elektrolysegerät nach einem beliebigen der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Schmelzpunkt der metallischen Masse zwischen 25 und 100°C liegt.
  5. Elektrolysegerät nach Anspruch 4, dadurch gekennzeichnet, daß die metallische Masse eine Legierung aus Wismut (50,0 Gew.-%), Blei (25,0 Gew.-%), Zinn (12,5 Gew.-%) und Cadmium (12,5 Gew.-%) ist.
  6. Elektrolysegerät nach Anspruch 4, dadurch gekennzeichnet, daß die metallische Masse eine binäre eutektische Legierung aus Indium und Wismut ist.
  7. Elektrolysegerät nach einem beliebigen der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Platte (10), welche die Anode (13) trägt, aus Titan ist, und die Platte (11), welche die Kathode (14) trägt, aus einem unter Eisen, Nickel, Kobalt und den Legierungen dieser Metalle ausgewählten Material ist.
  8. Elektrolysegerät nach einem beliebigen der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Anode (13) und die Kathode (14) von vertikalen Blechen gebildet werden, die quer an den Platten (10, 11) befestigt sind.
  9. Verwendung eines Elektrolysegerätes nach einem beliebigen der Ansprüche 1 bis 8 für die Elektrolyse von wäßrigen Lösungen.
  10. Verwendung nach Anspruch 9 für die Erzeugung von wäßrigen Natriumchloratlösungen durch Elektrolyse von wäßrigen Natriumchloridlösungen.
EP91201753A 1990-07-12 1991-07-05 Elektrolyseur mit mindestens zwei, längs einer gemeinsamen Trennwand elektrisch seriengeschalteten Elementarzellen Expired - Lifetime EP0466266B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9000714 1990-07-12
BE9000714A BE1004490A3 (fr) 1990-07-12 1990-07-12 Electrolyseur comprenant au moins deux cellules d'electrolyse elementaires couplees en serie electrique le long d'une paroi verticale commune.

Publications (2)

Publication Number Publication Date
EP0466266A1 EP0466266A1 (de) 1992-01-15
EP0466266B1 true EP0466266B1 (de) 1995-10-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91201753A Expired - Lifetime EP0466266B1 (de) 1990-07-12 1991-07-05 Elektrolyseur mit mindestens zwei, längs einer gemeinsamen Trennwand elektrisch seriengeschalteten Elementarzellen

Country Status (15)

Country Link
US (1) US5141619A (de)
EP (1) EP0466266B1 (de)
AT (1) ATE129026T1 (de)
AU (1) AU634666B2 (de)
BE (1) BE1004490A3 (de)
BR (1) BR9102938A (de)
CA (1) CA2046758A1 (de)
CS (1) CS217391A3 (de)
DE (1) DE69113693D1 (de)
ES (1) ES2080238T3 (de)
FI (1) FI913392A (de)
NO (1) NO304032B1 (de)
NZ (1) NZ238898A (de)
PT (1) PT98243B (de)
ZA (1) ZA915244B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1004688A3 (fr) * 1991-03-20 1993-01-12 Solvay Electrode bipolaire pour electrolyseur du type serie et electrolyseur du type serie.
US5306410A (en) * 1992-12-04 1994-04-26 Farmer Thomas E Method and device for electrically coupling a conductor to the metal surface of an electrolytic cell wall
JP6333073B2 (ja) * 2014-06-02 2018-05-30 株式会社アルス 次亜塩素酸ナトリウム水溶液の製造装置
US10106901B2 (en) 2015-02-03 2018-10-23 Edward E. Johnson Scalable energy demand system for the production of hydrogen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1094981A (en) * 1972-09-15 1981-02-03 James D. Mcgilvery Bipolar electrodes
SE377140B (de) * 1973-08-20 1975-06-23 Kema Nord Ab
DE2616482A1 (de) * 1975-04-14 1976-11-04 Georgy Mikirtychevits Kamarian Elektrolyseur
US4088551A (en) * 1977-02-15 1978-05-09 Ppg Industries, Inc. Electrolytic cell and method of electrolysis
US4132622A (en) * 1977-11-30 1979-01-02 Hooker Chemicals & Plastics Corp. Bipolar electrode
FR2434215A1 (fr) * 1978-08-21 1980-03-21 Electricite De France Procede et dispositif de mise en court-circuit de cellules d'electrolyseur et installation d'electrolyse en comportant application
CA1231918A (en) * 1984-11-23 1988-01-26 C-I-L Inc. Bipolar electrode assembly

Also Published As

Publication number Publication date
AU8034891A (en) 1992-01-16
BR9102938A (pt) 1992-02-11
PT98243A (pt) 1993-09-30
ZA915244B (en) 1992-11-25
FI913392A0 (fi) 1991-07-12
PT98243B (pt) 1999-01-29
US5141619A (en) 1992-08-25
NO304032B1 (no) 1998-10-12
ES2080238T3 (es) 1996-02-01
BE1004490A3 (fr) 1992-12-01
NO912725L (no) 1992-01-13
CA2046758A1 (fr) 1992-01-13
CS217391A3 (en) 1992-02-19
EP0466266A1 (de) 1992-01-15
DE69113693D1 (de) 1995-11-16
NZ238898A (en) 1992-05-26
ATE129026T1 (de) 1995-10-15
AU634666B2 (en) 1993-02-25
FI913392A (fi) 1992-01-13
NO912725D0 (no) 1991-07-11

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