EP0412600A1 - Frame for electrolyzer of the filterpress type and monopolar electrolyzer of the filterpress type - Google Patents

Frame for electrolyzer of the filterpress type and monopolar electrolyzer of the filterpress type Download PDF

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Publication number
EP0412600A1
EP0412600A1 EP90202084A EP90202084A EP0412600A1 EP 0412600 A1 EP0412600 A1 EP 0412600A1 EP 90202084 A EP90202084 A EP 90202084A EP 90202084 A EP90202084 A EP 90202084A EP 0412600 A1 EP0412600 A1 EP 0412600A1
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EP
European Patent Office
Prior art keywords
vertical
electrolysis
bars
sheets
chassis
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Granted
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EP90202084A
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German (de)
French (fr)
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EP0412600B1 (en
Inventor
Emile Cabaraux
Eric Paulus
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Solvay SA
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Solvay SA
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Priority to AT90202084T priority Critical patent/ATE102661T1/en
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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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type

Definitions

  • the invention relates to electrolysers of the filter press type for the electrolytic production of a gas and chassis used in the construction of these electrolysers.
  • Electrolysers of the filter press type are generally formed by a stack of vertical frames which delimit alternately anodic and cathodic electrolysis chambers, in which electrodes are arranged vertically. Selectively permeable membranes or electrolyte permeable diaphragms can be inserted between the frames to separate the electrolysis chambers.
  • the invention relates mainly to chassis used in the construction of electrolysers of this type, these chassis each comprising a vertical frame delimiting an electrolysis chamber; this contains an electrode formed by a pair of metal sheets, vertical, perforated, facing each other; horizontal metal bars are inserted between the sheets and fixed to them by suitable joining elements.
  • the metal bars and the junction elements serve to support the sheets of the electrode in the electrolysis chamber and participate in their connection to a current source. They must be designed to allow vertical circulation of the electrolyte and the products of electrolysis between the plates of the electrode. To this end, it has been proposed to give the bars a cross section less than the spacing between the sheets and to use, for the junction elements of the vertical bars, inserted between the horizontal bars and the sheets of the electrode.
  • the vertical bars can have very diverse profiles (DE-A-2821984; JP-A-58-123885).
  • JP-A-58-123885 it is proposed to use, for the vertical bars, curved strips in the shape of a gutter.
  • the horizontal bars and the vertical bars form a lattice assembly in the electrolysis chamber, which harms the standardization of the conditions of electrolysis. This disadvantage is especially noticeable in the case where a gas is generated on the electrode during electrolysis, the trellis assembly constituting an obstacle to a circulation of the gas and the electrolyte in the electrolysis chamber.
  • the invention overcomes this disadvantage of the known chassis described above, by providing a chassis of new design which facilitates the natural circulation of the gas and the electrolyte during electrolysis and standardizes the conditions of electrolysis within the chamber. electrolysis.
  • the invention relates to a chassis for an electrolyser of the filter press type, said chassis comprising: - a vertical frame delimiting an electrolysis chamber, - an electrode in the electrolysis chamber, comprising a pair of metal, vertical, perforated sheets, arranged opposite one another, and a current supply to the electrode, said current supply comprising horizontal or oblique metal bars, disposed between the sheets and elements for joining the bars to the sheets, the joining elements comprising, in accordance with the invention, pairs vertical profiles in U or V, arranged symmetrically on either side of the bars and connected to each other by vertical plates joining the bars so as to form vertical chimneys in the electrolysis chamber.
  • the frame can have any profile compatible with the construction of an electrolyser of the filter press type. It can either have a circular or polygonal profile, for example square, trapezoidal or rectangular. It must be made of a material which chemically withstands the conditions of electrolysis. It can for example be made of titanium or nickel, depending on whether it is intended to form an anode chamber or a cathode chamber in an electrolyser for the electrolysis of aqueous solutions of sodium chloride.
  • the metal sheets forming the electrode can be, for example, metal sheets pierced with openings, expanded metal sheets or lattices.
  • the choice of sheet material depends on the destination of the electrode.
  • the sheets may be of iron, steel, nickel or in any other conductive material, active for the electrolytic production of hydrogen, such as, for example, those described in patents EP-A-8476, FR-A-2460343, EP-A-113931, EP-A-131978 ( SOLVAY & Cie).
  • the sheets can advantageously be made of a film-forming conductive material selected from titanium, the tantalum, niobium, zirconium, tungsten and the alloys of these metals, carrying an active conductive coating of a material selected from platinum, ruthenium, rhodium, palladium, osmium, iridium and alloys and compounds of these metals, especially their oxides.
  • Electrodes specially adapted for the production of chlorine by electrolysis of aqueous sodium chloride solutions are those in which the material of the active coating comprises a mixture of ruthenium oxide and titanium dioxide or one of the compounds described in the patents BE-A-769677, BE-A-769678, BE-A-769679, BE-A-776709, BE-A-785605 (SOLVAY & Cie).
  • the metal bars have a thickness less than the spacing between the two sheets forming the electrode. They are arranged horizontally or obliquely between the sheets to which they are connected by vertical metal U-shaped profiles.
  • U or V sections is intended to denote profiles of convex cross section, having the configuration of a gutter. According to the invention, the profiles can therefore have a semi-circular, semi-oval, or semi-polygonal cross section.
  • the bars and the profiles cooperate to convey the electric current between a current source and the sheets of the electrode during an electrolysis operation. Alternatively, they can also cooperate to support the sheets of the electrode in the frame. Their convex cross section also gives the profiles good resistance to bending, so that they also serve as stiffeners for the electrode sheets. Bars and profiles must be made of an electrically conductive material capable of withstanding the chemical environment during electrolysis.
  • composite bars are used, comprising a core made of a metal or alloy that is a good conductor of electricity (for example copper or aluminum) in a titanium or nickel sheath. Such composite bars can for example be obtained by a metallurgical operation of cofiling.
  • the vertical profiles can consist of metal strips, for example made of titanium or nickel, folded to give them the required U or V profile defined above.
  • the vertical plates can be made of any material capable of withstanding the stresses of a mechanical, thermal and chemical nature normally prevailing in electrolysers. They can be made of metal or of a polymeric material.
  • the U or V profiles are arranged symmetrically, in pairs, on either side of the bars.
  • the two profiles of each pair are connected to each other by the vertical plates joining the bars, so as to form a vertical chimney.
  • the space delimited between the two sheets of the electrode is thus partitioned by chimneys, so that, during the electrolysis, the electrolyte is subjected to an upward movement between the chimneys, under the action of the gas generated at the electrode and a downward movement in these chimneys.
  • the internal space of the chimneys is not the seat of a gas release.
  • the internal space of the chimneys must be isolated from the electrodes; in addition, the faces of the profiles and plates, which are oriented towards the inside of the chimneys must be made of a material which does not participate in the electrolysis reaction during the operation of the electrolyser.
  • the frame comprises two vertical uprights connected by two horizontal beams, and the two beams are designed to form two internal channels which are pierced with openings on their respective walls which face each other in the electrolysis chamber; one of the channels is connected to an electrolyte intake duct and the other channel is connected to a duct for discharging the electrolysis products.
  • the channels of the side members serve to distribute the electrolyte in the electrolysis chamber and to evacuate the products resulting from the electrolysis. It is preferably the channel of the lower beam which is connected to the electrolyte intake duct, the channel of the upper beam being connected to the duct for discharging the electrolysis products.
  • the chassis according to the invention is intended to be integrated into an electrolyser of the monopolar type.
  • the invention therefore also relates to an electrolyser of the monopolar type, filter press, comprising a stack of frames in accordance with the invention, delimiting electrolysis chambers alternately anodic and cathodic.
  • the invention applies especially to electrolysers of this type, in which the electrolysis chambers are separated by separators permeable to ions.
  • the separators are sheets interposed between the successive frames of the stack and made of a material capable of being traversed by an ion current during the operation of the electrolyser. They can be either diaphragms permeable to aqueous electrolytes or membranes with selective permeability.
  • diaphragms which can be used in the electrolysers according to the invention are asbestos diaphragms, such as those described in patent US-A-1855497 (STUART) and in patents FR-A-2400569, EP-A-1644 and EP -A-18034 (SOLVAY & Cie) and diaphragms made of organic polymers, such as those described in patents FR-A-2170247 (IMPERIAL CHEMICAL INDUSTRIES PLC) and in patents EP-A-7674 and EP-A-37140 ( SOLVAY & Cie).
  • asbestos diaphragms such as those described in patent US-A-1855497 (STUART) and in patents FR-A-2400569, EP-A-1644 and EP -A-18034 (SOLVAY & Cie)
  • diaphragms made of organic polymers such as those described in patents FR-A-2170247 (IMPERIAL CHEMICAL INDUSTRIES P
  • membranes with selective permeability is understood to mean thin, non-porous membranes comprising an ion-exchange material.
  • the choice of the material constituting the membranes and of the ion exchange material will depend on the nature of the electrolytes subjected to the electrolysis and on the products which it is sought to obtain.
  • the material of the membranes is chosen from those which are capable of withstanding the thermal and chemical conditions normally prevailing in the electrolyser during electrolysis, the ion-exchange material being chosen from anion-exchange materials or cation exchange materials, depending on the electrolysis operations for which the electrolyser is intended.
  • membranes which are well suited are cationic membranes in fluorinated polymer, preferably perfluorinated, containing cationic functional groups derived from sulfonic acids, carboxylic acids or phosphonic acids or mixtures of such functional groups.
  • membranes of this type are those described in patents GB-A-1497748 and GB-A-1497749 (ASAHI KASEI KOGYO KK), GB-A-1518387, GB-A-1522877 and US-A-4126588 (ASAHI GLASS COMPANY LTD) and GB-A-1402920 (DIAMOND SHAMROCK CORP.).
  • Membranes particularly suitable for this application of the cell according to the invention are those known under the names "NAFION” (DU PONT DE NEMOURS & Co) and "FLEMION” (ASAHI GLASS COMPANY LTD).
  • the electrolysers according to the invention find a especially advantageous application for the production of chlorine and aqueous solutions of sodium hydroxide by electrolysis of aqueous solutions of sodium chloride.
  • the invention is specifically applied to monopolar electrolysers of the filter press type with cationic membranes, for the production of chlorine, hydrogen and aqueous solutions of sodium hydroxide by electrolysis of aqueous solutions of chloride of sodium.
  • the chassis according to the invention is intended to form an anode chamber of the electrolyser. It comprises a vertical frame generally designated by the reference notation 1, having an approximately square cross section.
  • the frame 1 comprises two vertical uprights 2 and 3 made of titanium, welded to two longitudinal members 4 and 5 also made of titanium.
  • the space 13 circumscribed by the frame 1 constitutes a room anodic electrolysis.
  • This contains an anode formed by a pair of vertical sheets 6 of expanded metal, arranged on either side of several horizontal metal bars 7.
  • the sheets 6 are welded to vertical profiles 8 which are also welded to the bars horizontal 7.
  • the bars 7 are welded to the uprights 2 and 3 of the frame, which they pass through. They are fixed together to a junction bar 24, intended to be coupled to a current source.
  • the bars 6 and the profiles 8 thus cooperate in the coupling of the sheets 6 to the current source and to the support of these sheets inside the frame 1.
  • the sheets 6 are titanium sheets, carrying an electrically conductive coating, with low overvoltage for the electrochemical oxidation of chloride ions. Such coatings are well known in the art of electrolysis.
  • the bars 7 include a copper core lined in a titanium casing.
  • the vertical sections 8, better visible in Figures 2, 3 and 4 are each formed of a vertical strip of titanium, folded in the form of U or ⁇ , so as to have the shape of a gutter. They are fixed to the sheets 6 along the axial middle part 9 of the U and to the bars 7 along their marginal strips 10 ( Figure 4).
  • the vertical profiles 8 are arranged symmetrically, in pairs, on either side of the bars 7.
  • the two profiles 8 of each pair are joined by vertical plates 11, extending between the successive bars 7, so as to form a vertical chimney 12 between the two sheets 6.
  • the vertical plates 11 are titanium sheets, welded to the marginal strips 10 of the bars 8 ( Figure 4).
  • Each chimney 12 is thus isolated from the sheets 6 forming the anode, so that it is not the site of chlorine formation during the electrolysis of an aqueous solution of sodium chloride in contact with the sheets 6.
  • the upper and lower ends of the profiles 8 are kept apart from the side members 4 and 5 of the frame 1, so that the chimneys 12 open into the electrolysis chamber at their two ends.
  • the longitudinal members 5 and 4 and the upright 3 of the frame 1 are designed to form internal channels of square or rectangular section which will respectively serve to introduce an aqueous solution of sodium chloride into the electrolysis chamber 13 and to evacuate the products thereof resulting from the electrolysis (chlorine and a dilute aqueous solution of sodium chloride).
  • the side members 4 and 5 are pierced with openings 14 regularly distributed on their walls which face each other in the chamber 13.
  • the lower side member 5 is provided with a tube 15 for admission into its channel 16, of the aqueous sodium chloride solution to be electrolyzed.
  • the channel 17 delimited in the upper beam 4 serves as a degassing chamber, for separating the chlorine from the dilute aqueous solution of sodium chloride leaving the electrolysis chamber 13. It opens into the channel 18 formed in the upright 3, provided a tube 19 for the extraction of chlorine and a tube 20 for the extraction of the dilute sodium chloride solution.
  • a threshold 21 separating the channels 17 and 18 is used to maintain a constant level of solution in the channel
  • the electrolysis chamber 13 When the chassis shown in FIGS. 1 to 5 is in operation in an electrolyser, the electrolysis chamber 13 is filled with an aqueous solution of sodium chloride up to the upper threshold level 21.
  • An aqueous solution of sodium chloride is introduced continuously into the channel 16, via the tubing 15, enters the electrolysis chamber 13 through the openings 14 and is driven from bottom to top therein by the chlorine which is generated on the sheets 6 of l 'anode.
  • the vertical chimneys 12 are not the seat of a release of chlorine, so that the density of the solution which is there is greater than that of the emulsion in the remaining part of the chamber 13.
  • An internal electrolyte circulation is thus established in the chamber 13: the electrolyte entering the chamber via the channel 16 is driven in an upward movement between the sheets 6, a fraction of it is removed with the chlorine by the channel 17 and another fraction is recycled at the bottom of the chamber 13 via the chimneys 12.
  • the internal circulation of electrolyte in the chamber 13 is favorable for better homogenization and, therefore, for optimum energy efficiency of the electrolysis operation.
  • the chlorine separates from the aqueous sodium chloride solution and is evacuated via the tube 19.
  • the aqueous solution overflows above the threshold 21 and passes into the vertical channel 18, from where it is evacuated by tubing 20.
  • the invention has been applied to a chassis of an anode chamber of the electrolyser.
  • the uprights 2 and 3 and the side members 4 and 5 of the frame 1 are made of nickel
  • the sheets 6 form a cathode and are made of nickel (and possibly carry a conductive coating with low overvoltage for proton reduction)
  • the bars 7 are made of nickel or include a copper core lined with a nickel casing and the profiles 8 and the plates 11 are made of nickel.
  • intermediate pieces 22 are interposed between the sheets 6 and the middle part 9 of each of the profiles 8.
  • These intermediate pieces 22 are made of an electrically conductive material and are welded to the sheets 6 and to the sections 8. They can either be rods which extend over the entire height of the sections 8, or regularly spaced studs. They have the function of ensuring a substantial spacing between the sheets 6 and the sections 8, so as to allow an electrolyte passage between the sheets and the sections.
  • This embodiment of the chassis according to the invention is specially intended for membrane electrolysers, in which it is necessary to ensure effective wetting of the membrane by the electrolyte located in the electrolysis chamber 13.
  • FIG. 6 shows another embodiment of the chassis according to the invention, also designed to ensure effective wetting of the membrane by the electrolyte.
  • the middle part 9 of the sections 8 is pierced with holes 31; a vertical partition 32 joining the two wings 33 of the profile isolates the chimney 12 from a vertical channel 34.
  • the part of the wings 33, located between the middle part 9 and the partition 32 can optionally be perforated to facilitate communication between the chamber 13 and channel 34.
  • the openings 14 of the upper spar 4 of the chassis 1 have their edge 23 chamfered in the direction for which the cross section of the opening goes decreasing in bottom up. This embodiment of the invention accelerates the passage of gas from the chamber 13 to the channel 17, during the electrolysis.
  • the electrolyser shown in FIG. 8 is formed by a stack of vertical frames, alternately anodic 25 and cathodic 25 ′.
  • the anode frames 25 are similar to those described above, with reference to FIGS. 1 to 7.
  • the cathode frames 25 ′ are analogous to the anode frames 25, in which the constituent elements in titanium have been replaced by similar elements in nickel.
  • These nickel elements of chassis 25 ′ have the same reference numbers as their respective counterparts of chassis 25, but are assigned a prime index (′).
  • the frames 25 and 25 ′ are separated by cationic membranes 26, which thus delimit alternately anodic and cathodic electrolysis chambers
  • the stacking of the frames 25 and 25 ′ and membranes 26 is retained between end flanges 27, connected by tie rods not shown, seals 28 ensuring sealing.
  • the vertical junction bars 24 (FIG. 1) of the anode frames 25 are coupled to a bus bar connected to the positive terminal of a direct current source, the junction bars, the bus bar and the current source not being visible in Figure 7.
  • the cathode frames 25 ' are connected to a common bus bar, connected to the negative terminal of the DC source.
  • the pipes 15 of the anode frames 25 ( Figures 1 and 5) open into a common manifold for the admission of an aqueous sodium chloride solution, this manifold and the pipes 15 not being visible in FIG. 7.
  • the corresponding pipes of the cathode frames 25 ′ open into a common manifold of admission of water or a dilute aqueous solution of sodium hydroxide.
  • the pipes 19 and 20 of the anode frames 25 open respectively into two general collectors 29 and 30, the collector 29 serving for the evacuation of the chlorine produced in the anode chambers 13 and the collector 30 serving for the evacuation of the dilute chloride solution. sodium.
  • the pipes 19 ′ and 20 ′ of the cathode frames 25 ′ open respectively into two general collectors 29 ′ and 30 ′, the manifold 29 ′ serving for the evacuation of the hydrogen produced in the cathode chambers 13 ′ and the collector 30 ′ used for the discharge of a concentrated aqueous solution of sodium hydroxide.
  • the hydrostatic pressure prevailing in the electrolysis chambers 13 of the anode frames 25 is usually lower than that prevailing in the chambers 13 ′ of the cathode frames 25 ′. It follows that the membranes 26 are pushed against the sheets 6 of the anodes. Because of their convex cross section, the vertical profiles 8 effectively oppose bending of the sheets 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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

Framework for an electrolyser of the filter-press type, comprising a vertical frame (1) defining an electrolysis chamber (13), an electrode in the electrolysis chamber, comprising a pair of vertical metal sheets (6) arranged facing each other, horizontal or oblique metal bars (7) arranged between the sheets (6) and U- or V-shaped vertical metal beams (8) placed between the bars and the sheets, the beams (8) being arranged in pairs symmetrically on either side of the bars (7) and being connected to each other by vertical plates (11) which join the bars (7) so as to form vertical shafts (12) in the chamber 13. <IMAGE>

Description

L'invention concerne des électrolyseurs du type filtre-­presse pour la production électrolytique d'un gaz et des châssis entrant dans la construction de ces électrolyseurs.The invention relates to electrolysers of the filter press type for the electrolytic production of a gas and chassis used in the construction of these electrolysers.

Les électrolyseurs du type filtre-presse sont généralement formés d'un empilage de châssis verticaux qui délimitent des chambres d'électrolyse alternativement anodiques et cathodiques, dans lesquelles des électrodes sont disposées verticalement. Des membranes à perméabilité sélective ou des diaphragmes perméables aux électrolytes peuvent être insérés entre les châssis, pour séparer les chambres d'électrolyse.Electrolysers of the filter press type are generally formed by a stack of vertical frames which delimit alternately anodic and cathodic electrolysis chambers, in which electrodes are arranged vertically. Selectively permeable membranes or electrolyte permeable diaphragms can be inserted between the frames to separate the electrolysis chambers.

L'invention concerne principalement des châssis entrant dans la construction d'électrolyseurs de ce type, ces châssis compre­nant chacun un cadre vertical délimitant une chambre d'électro­lyse; celle-ci contient une électrode formée d'une paire de tôles métalliques, verticales, ajourées, se faisant face; des barreaux métalliques horizontaux sont insérés entre les tôles et fixés à celles-ci par des éléments de jonction adéquats. Dans les châssis de ce type, les barreaux métalliques et les éléments de jonction servent à soutenir les tôles de l'électrode dans la chambre d'électrolyse et participent à leur connexion à une source de courant. Ils doivent être conçus pour permettre une circulation verticale de l'électrolyte et des produits de l'électrolyse entre les tôles de l'électrode. A cet effet, on a proposé de donner aux barreaux une section transversale inférieure à l'écartement entre les tôles et d'utiliser, pour les éléments de jonction des barres verticales, insérées entre les barreaux horizontaux et les tôles de l'électrode. Les barres verticales peuvent avoir des profils très divers (DE-A-2821984; JP-A-58-123885). Dans le document JP-A-58-123885, on propose d'utiliser, pour les barres verticales, des feuillards cintrés en forme de gouttière. Dans ces châssis connus, les barreaux horizontaux et les barres verticales forment un assemblage en treillis dans la chambre d'électrolyse, qui nuit à une uniformisation des conditions de l'électrolyse. Ce désavantage est spécialement sensible dans le cas où un gaz est généré sur l'électrode pendant l'électrolyse, l'assemblage en treillis constituant un obstacle à une circula­tion du gaz et de l'électrolyte dans la chambre d'électrolyse.The invention relates mainly to chassis used in the construction of electrolysers of this type, these chassis each comprising a vertical frame delimiting an electrolysis chamber; this contains an electrode formed by a pair of metal sheets, vertical, perforated, facing each other; horizontal metal bars are inserted between the sheets and fixed to them by suitable joining elements. In chassis of this type, the metal bars and the junction elements serve to support the sheets of the electrode in the electrolysis chamber and participate in their connection to a current source. They must be designed to allow vertical circulation of the electrolyte and the products of electrolysis between the plates of the electrode. To this end, it has been proposed to give the bars a cross section less than the spacing between the sheets and to use, for the junction elements of the vertical bars, inserted between the horizontal bars and the sheets of the electrode. The vertical bars can have very diverse profiles (DE-A-2821984; JP-A-58-123885). In document JP-A-58-123885, it is proposed to use, for the vertical bars, curved strips in the shape of a gutter. In these known frames, the horizontal bars and the vertical bars form a lattice assembly in the electrolysis chamber, which harms the standardization of the conditions of electrolysis. This disadvantage is especially noticeable in the case where a gas is generated on the electrode during electrolysis, the trellis assembly constituting an obstacle to a circulation of the gas and the electrolyte in the electrolysis chamber.

L'invention remédie à cet inconvénient des châssis connus décrits ci-dessus, en fournissant un châssis de conception nouvelle qui facilite la circulation naturelle du gaz et de l'électrolyte pendant l'électrolyse et uniformise les conditions d'électrolyse au sein de la chambre d'électrolyse.The invention overcomes this disadvantage of the known chassis described above, by providing a chassis of new design which facilitates the natural circulation of the gas and the electrolyte during electrolysis and standardizes the conditions of electrolysis within the chamber. electrolysis.

En conséquence, l'invention concerne un châssis pour un électrolyseur du type filtre-presse, ledit châssis comprenant :
- un cadre vertical délimitant une chambre d'électrolyse,
- une électrode dans la chambre d'électrolyse, comprenant une paire de tôles métalliques, verticales, ajourées, disposées vis-à-vis l'une de l'autre, et
- une amenée de courant à l'électrode, ladite amenée de courant comprenant des barreaux métalliques horizontaux ou obliques, disposés entre les tôles et des éléments de jonction des barreaux aux tôles, les éléments de jonction comprenant, conformément à l'invention, des paires de profilés verticaux en U ou en V, disposés symétriquement de part et d'autre des barreaux et raccordés l'un à l'autre par des plaques verticales joignant les barreaux en sorte de former des cheminées verticales dans la chambre d'électrolyse.Consequently, the invention relates to a chassis for an electrolyser of the filter press type, said chassis comprising:
- a vertical frame delimiting an electrolysis chamber,
- an electrode in the electrolysis chamber, comprising a pair of metal, vertical, perforated sheets, arranged opposite one another, and
a current supply to the electrode, said current supply comprising horizontal or oblique metal bars, disposed between the sheets and elements for joining the bars to the sheets, the joining elements comprising, in accordance with the invention, pairs vertical profiles in U or V, arranged symmetrically on either side of the bars and connected to each other by vertical plates joining the bars so as to form vertical chimneys in the electrolysis chamber.

Dans le châssis selon l'invention, le cadre peut avoir tout profil compatible avec la construction d'un électrolyseur du type filtre-presse. Il peut indifféremment avoir un profil circulaire ou polygonal, par exemple carré, trapézoïdal ou rectangulaire. Il doit être réalisé en un matériau qui résiste chimiquement aux conditions de l'électrolyse. On peut par exemple le réaliser en titane ou en nickel, selon qu'il est destiné à former une chambre anodique ou une chambre cathodique dans un électrolyseur pour l'électrolyse de solutions aqueuses de chlorure de sodium.In the frame according to the invention, the frame can have any profile compatible with the construction of an electrolyser of the filter press type. It can either have a circular or polygonal profile, for example square, trapezoidal or rectangular. It must be made of a material which chemically withstands the conditions of electrolysis. It can for example be made of titanium or nickel, depending on whether it is intended to form an anode chamber or a cathode chamber in an electrolyser for the electrolysis of aqueous solutions of sodium chloride.

Les tôles métalliques formant l'électrode peuvent être, par exemple, des tôles métalliques percées d'ouvertures, des tôles en métal déployé ou des treillis.The metal sheets forming the electrode can be, for example, metal sheets pierced with openings, expanded metal sheets or lattices.

Le choix du matériau des tôles dépend de la destination de l'électrode. Par exemple, dans le cas où l'électrode est destinée à fonctionner comme cathode pour la production d'hydrogène dans une cellule d'électrolyse de l'eau ou de solutions aqueuses, les tôles peuvent être en fer, en acier, en nickel ou en tout autre matériau conducteur, actif pour la production électrolytique d'hydrogène, tel que, par exemple, ceux décrits dans les brevets EP-A-8476, FR-A-2460343, EP-A-113931, EP-A-131978 (SOLVAY & Cie). Dans le cas où l'électrode est destinée à fonctionner comme anode pour la génération de chlore dans une cellule d'électrolyse d'une solution aqueuse de chlorure de sodium, les tôles peuvent avanta­geusement être en un matériau conducteur filmogène sélectionné parmi le titane, le tantale, le niobium, le zirconium, le tungstène et les alliages de ces métaux, portant un revêtement conducteur actif en un matériau sélectionné parmi le platine, le ruthénium, le rhodium, le palladium, l'osmium, l'iridium et les alliages et composés de ces métaux, notamment leurs oxydes. Des électrodes spécialement adaptées à la production de chlore par électrolyse de solutions aqueuses de chlorure de sodium sont celles dans lesquelles le matériau du revêtement actif comprend un mélange d'oxyde de ruthénium et de dioxyde de titane ou l'un des composés décrits dans les brevets BE-A-769677, BE-A-769678, BE-A-769679, BE-A-776709, BE-A-785605 (SOLVAY & Cie).The choice of sheet material depends on the destination of the electrode. For example, in the case where the electrode is intended to function as a cathode for the production of hydrogen in a cell for the electrolysis of water or aqueous solutions, the sheets may be of iron, steel, nickel or in any other conductive material, active for the electrolytic production of hydrogen, such as, for example, those described in patents EP-A-8476, FR-A-2460343, EP-A-113931, EP-A-131978 ( SOLVAY & Cie). In the case where the electrode is intended to function as an anode for the generation of chlorine in an electrolysis cell of an aqueous solution of sodium chloride, the sheets can advantageously be made of a film-forming conductive material selected from titanium, the tantalum, niobium, zirconium, tungsten and the alloys of these metals, carrying an active conductive coating of a material selected from platinum, ruthenium, rhodium, palladium, osmium, iridium and alloys and compounds of these metals, especially their oxides. Electrodes specially adapted for the production of chlorine by electrolysis of aqueous sodium chloride solutions are those in which the material of the active coating comprises a mixture of ruthenium oxide and titanium dioxide or one of the compounds described in the patents BE-A-769677, BE-A-769678, BE-A-769679, BE-A-776709, BE-A-785605 (SOLVAY & Cie).

Les barreaux métalliques ont une épaisseur inférieure à l'écartement entre les deux tôles formant l'électrode. Ils sont disposés horizontalement ou obliquement entre les tôles auxquelles ils sont reliés par les profilés métalliques verticaux en U.The metal bars have a thickness less than the spacing between the two sheets forming the electrode. They are arranged horizontally or obliquely between the sheets to which they are connected by vertical metal U-shaped profiles.

On entend désigner par l'expression "profilés en U ou en V" des profilés de section transversale convexe, présentant la configuration d'une gouttière. Conformément à l'invention, les profilés peuvent dès lors avoir ne section transversale semi-circulaire, semi-ovale, ou semi-polygonale.The expression “U or V sections” is intended to denote profiles of convex cross section, having the configuration of a gutter. According to the invention, the profiles can therefore have a semi-circular, semi-oval, or semi-polygonal cross section.

Les barreaux et les profilés coopèrent pour véhiculer le courant électrique entre une source de courant et les tôles de l'électrode pendant une opération d'électrolyse. En variante, ils peuvent également coopérer pour supporter les tôles de l élec­trode dans le cadre. Leur section transversale convexe confère par ailleurs aux profilés une bonne résistance à la flexion, de sorte que ceux-ci servent également de raidisseurs pour les tôles de l'électrode. Les barreaux et les profilés doivent être en un matériau conducteur de l'électricité et capable de résister à l'environnement chimique pendant l'électrolyse. On utilise avan­tageusement des barreaux composites, comprenant une âme en un métal ou alliage bon conducteur de l'électricité (par exemple en cuivre ou en aluminium) dans une gaine en titane ou en nickel. De tels barreaux composites peuvent par exemple être obtenus par une opération métallurgique de cofilage. Les profilés verticaux peuvent consister en des feuillards métalliques, par exemple en titane ou en nickel, pliés pour leur conférer le profil requis en U ou en V défini plus haut. Les plaques verticales peuvent être en tous matériaux capables de supporter les sollicitations de nature mécanique, thermique et chimique régnant normalement dans les électrolyseurs. Elles peuvent être en métal ou en un matériau polymérique.The bars and the profiles cooperate to convey the electric current between a current source and the sheets of the electrode during an electrolysis operation. Alternatively, they can also cooperate to support the sheets of the electrode in the frame. Their convex cross section also gives the profiles good resistance to bending, so that they also serve as stiffeners for the electrode sheets. Bars and profiles must be made of an electrically conductive material capable of withstanding the chemical environment during electrolysis. Advantageously, composite bars are used, comprising a core made of a metal or alloy that is a good conductor of electricity (for example copper or aluminum) in a titanium or nickel sheath. Such composite bars can for example be obtained by a metallurgical operation of cofiling. The vertical profiles can consist of metal strips, for example made of titanium or nickel, folded to give them the required U or V profile defined above. The vertical plates can be made of any material capable of withstanding the stresses of a mechanical, thermal and chemical nature normally prevailing in electrolysers. They can be made of metal or of a polymeric material.

Les profilés en U ou en V sont disposés symétriquement, par paires, de part et d'autre des barreaux. Les deux profilés de chaque paire sont raccordés l'un à l'autre par les plaques verti­cales joignant les barreaux, de manière à former une cheminée verticale. Celle-ci débouche dans la chambre d'électrolyse à ses deux extrémités, de préférence au voisinage du cadre. Dans le châssis selon l'invention, l'espace délimité entre les deux tôles de l'électrode est ainsi cloisonné par des cheminées, de sorte que, pendant l'électrolyse, l'électrolyte est soumis à un dépla­cement ascendant entre les cheminées, sous l'action du gaz généré à l'électrode et à un déplacement descendant dans ces cheminées Il s'ensuit une circulation interne de l'électrolyte à l'inté­rieur de la chambre d'électrolyse, ce qui est favorable à une uniformisation des conditions de l'électrolyse. Il est dès lors nécessaire, conformément à l'invention, que l'espace interne des cheminées ne soit pas le siège d'un dégagement de gaz. A cet effet, l'espace interne des cheminées doit être isolé des électrodes; en outre, les faces des profilés et des plaques, qui sont orientées vers l'intérieur des cheminées doivent être en un matériau qui ne participe pas à la réaction d'électrolyse pendant le fontionnement de l'électrolyseur.The U or V profiles are arranged symmetrically, in pairs, on either side of the bars. The two profiles of each pair are connected to each other by the vertical plates joining the bars, so as to form a vertical chimney. This opens into the electrolysis chamber at its two ends, preferably in the vicinity of the frame. In the chassis according to the invention, the space delimited between the two sheets of the electrode is thus partitioned by chimneys, so that, during the electrolysis, the electrolyte is subjected to an upward movement between the chimneys, under the action of the gas generated at the electrode and a downward movement in these chimneys. There follows an internal circulation of the electrolyte inside the electrolysis chamber, which is favorable to a standardization of the conditions of electrolysis. It is therefore necessary, in accordance with the invention, that the internal space of the chimneys is not the seat of a gas release. For this purpose, the internal space of the chimneys must be isolated from the electrodes; in addition, the faces of the profiles and plates, which are oriented towards the inside of the chimneys must be made of a material which does not participate in the electrolysis reaction during the operation of the electrolyser.

Dans une forme de réalisation particulière du châssis selon l'invention, le cadre comprend deux montants verticaux reliés par deux longerons horizontaux, et les deux longerons sont conçus pour former deux canaux internes qui sont percés d'ouvertures sur leurs parois respectives qui se font face dans la chambre d'élec­trolyse; l'un des canaux est raccordé à un conduit d'admission d'un électrolyte et l'autre canal est raccordé à un conduit d évacuation des produits de l'électrolyse. Dans cette forme de réalisation du châssis selon l'invention, les canaux des longe­rons servent à distribuer l'électrolyte dans la chambre d'élec­trolyse et à en évacuer les produits résultant de l'électrolyse. C'est de préférence le canal du longeron inférieur qui est raccordé au conduit d'admission de l'électrolyte, le canal du longeron supérieur étant raccordé au conduit d'évacuation des produits de l'électrolyse.In a particular embodiment of the chassis according to the invention, the frame comprises two vertical uprights connected by two horizontal beams, and the two beams are designed to form two internal channels which are pierced with openings on their respective walls which face each other in the electrolysis chamber; one of the channels is connected to an electrolyte intake duct and the other channel is connected to a duct for discharging the electrolysis products. In this embodiment of the chassis according to the invention, the channels of the side members serve to distribute the electrolyte in the electrolysis chamber and to evacuate the products resulting from the electrolysis. It is preferably the channel of the lower beam which is connected to the electrolyte intake duct, the channel of the upper beam being connected to the duct for discharging the electrolysis products.

Le châssis selon l'invention est destiné à être intégré dans un électrolyseur du type monopolaire.The chassis according to the invention is intended to be integrated into an electrolyser of the monopolar type.

L'invention concerne dès lors également un électrolyseur du type monopolaire, filtre-presse, comprenant un empilage de châssis conformes à l'invention, délimitant des chambres d'élec­trolyse alternativement anodiques et cathodiques. L'invention s'applique tout spécialement à des électrolyseurs de ce type, dans lesquels les chambres d'électrolyse sont séparées par des séparateurs perméables aux ions. Les séparateurs sont des feuilles interposées entre les châssis successifs de l'empilage et réalisées en un matériau susceptible d'être traversé par un courant ionique pendant le fonctionnement de l'électrolyseur. Ils peuvent être indifféremment des diaphragmes perméables aux électrolytes aqueux ou des membranes à perméabilité sélective.The invention therefore also relates to an electrolyser of the monopolar type, filter press, comprising a stack of frames in accordance with the invention, delimiting electrolysis chambers alternately anodic and cathodic. The invention applies especially to electrolysers of this type, in which the electrolysis chambers are separated by separators permeable to ions. The separators are sheets interposed between the successive frames of the stack and made of a material capable of being traversed by an ion current during the operation of the electrolyser. They can be either diaphragms permeable to aqueous electrolytes or membranes with selective permeability.

Des exemples de diaphragmes utilisables dans les électro­lyseurs selon l'invention sont des diaphragmes en amiante, tels que ceux décrits dans le brevet US-A-1855497 (STUART) et dans les brevets FR-A-2400569, EP-A-1644 et EP-A-18034 (SOLVAY & Cie) et des diaphragmes en polymères organiques, tels que ceux décrits dans les brevets FR-A-2170247 (IMPERIAL CHEMICAL INDUSTRIES PLC) et dans les brevets EP-A-7674 et EP-A-37140 (SOLVAY & Cie).Examples of diaphragms which can be used in the electrolysers according to the invention are asbestos diaphragms, such as those described in patent US-A-1855497 (STUART) and in patents FR-A-2400569, EP-A-1644 and EP -A-18034 (SOLVAY & Cie) and diaphragms made of organic polymers, such as those described in patents FR-A-2170247 (IMPERIAL CHEMICAL INDUSTRIES PLC) and in patents EP-A-7674 and EP-A-37140 ( SOLVAY & Cie).

On entend, par membranes à perméabilité sélective, des membranes minces, non poreuses, comprenant une matière échangeuse d'ions. Le choix du matériau constituant les membranes et de la matière échangeuse d'ions va dépendre de la nature des électro­lytes soumis à l'électrolyse et des produits que l'on cherche à obtenir. En règle générale, le matériau des membranes est choisi parmi ceux qui sont capables de résister aux conditions thermiques et chimiques régnant normalement dans l'électrolyseur pendant l'électrolyse, la matière échangeuse d'ions étant choisie parmi les matières échangeuses d'anions ou les matières échan­geuses de cations, en fonction des opérations d'électrolyse auxquelles l'électrolyseur est destiné.The term “membranes with selective permeability” is understood to mean thin, non-porous membranes comprising an ion-exchange material. The choice of the material constituting the membranes and of the ion exchange material will depend on the nature of the electrolytes subjected to the electrolysis and on the products which it is sought to obtain. As a general rule, the material of the membranes is chosen from those which are capable of withstanding the thermal and chemical conditions normally prevailing in the electrolyser during electrolysis, the ion-exchange material being chosen from anion-exchange materials or cation exchange materials, depending on the electrolysis operations for which the electrolyser is intended.

Par exemple, dans le cas d'électrolyseurs destinés à l'élec­trolyse de solutions aqueuses de chlorure de sodium pour la production de chlore, d'hydrogène et de solutions aqueuses d'hydroxyde de sodium, des membranes qui conviennent bien sont des membranes cationiques en polymère fluoré, de préférence perfluoré, contenant des groupements fonctionnels cationiques dérivés d'acides sulfoniques, d'acides carboxyliques ou d'acides phosphoniques ou des mélanges de tels groupements fonctionnels. Des exemples de membranes de ce type sont celles décrites dans les brevets GB-A-1497748 et GB-A-1497749 (ASAHI KASEI KOGYO K.K.), GB-A-1518387, GB-A-1522877 et US-A-4126588 (ASAHI GLASS COMPANY LTD) et GB-A-1402920 (DIAMOND SHAMROCK CORP.). Des membranes particulièrement adaptées à cette application de la cellule selon l'invention sont celles connues sous les noms "NAFION" (DU PONT DE NEMOURS & Co) et "FLEMION" (ASAHI GLASS COMPANY LTD).For example, in the case of electrolysers intended for the electrolysis of aqueous solutions of sodium chloride for the production of chlorine, hydrogen and aqueous solutions of sodium hydroxide, membranes which are well suited are cationic membranes in fluorinated polymer, preferably perfluorinated, containing cationic functional groups derived from sulfonic acids, carboxylic acids or phosphonic acids or mixtures of such functional groups. Examples of membranes of this type are those described in patents GB-A-1497748 and GB-A-1497749 (ASAHI KASEI KOGYO KK), GB-A-1518387, GB-A-1522877 and US-A-4126588 (ASAHI GLASS COMPANY LTD) and GB-A-1402920 (DIAMOND SHAMROCK CORP.). Membranes particularly suitable for this application of the cell according to the invention are those known under the names "NAFION" (DU PONT DE NEMOURS & Co) and "FLEMION" (ASAHI GLASS COMPANY LTD).

Les électrolyseurs selon l'invention trouvent une application spécialement avantageuse pour la production de chlore et de solutions aqueuses d'hydroxyde de sodium par électrolyse de solutions aqueuses de chlorure de sodium.The electrolysers according to the invention find a especially advantageous application for the production of chlorine and aqueous solutions of sodium hydroxide by electrolysis of aqueous solutions of sodium chloride.

Des particularités et détails de l'invention vont ressortir de la description qui suit, en référence aux dessins annexés.

  • La figure 1 est une vue en élévation, avec arrachement, d'une forme de réalisation particulière du châssis selon l'invention;
  • La figure 2 est une coupe horizontale selon le plan II-II des figures 1 et 3;
  • La figure 3 est une coupe verticale selon le plan III-III des figures 1 et 2;
  • La figure 4 est une vue à grande échelle d'un détail de la figure 2;
  • La figure 5 est une vue du cadre du châssis des figures 1 à 3, en coupe selon le plan vertical médian V-V des figures 2 et 3;
  • La figure 6 est une vue à grande échelle d'une forme de réalisation particulière d'un détail de la figure 5;
  • La figure 7 montre en section verticale longitudinale, une forme de réalisation particulière de l'électrolyseur selon l'invention.
Special features and details of the invention will emerge from the description which follows, with reference to the accompanying drawings.
  • Figure 1 is an elevational view, broken away, of a particular embodiment of the chassis according to the invention;
  • Figure 2 is a horizontal section along the plane II-II of Figures 1 and 3;
  • Figure 3 is a vertical section along the plane III-III of Figures 1 and 2;
  • Figure 4 is an enlarged view of a detail of Figure 2;
  • Figure 5 is a view of the frame of the chassis of Figures 1 to 3, in section along the median vertical plane VV of Figures 2 and 3;
  • Figure 6 is an enlarged view of a particular embodiment of a detail of Figure 5;
  • FIG. 7 shows in longitudinal vertical section, a particular embodiment of the electrolyser according to the invention.

Dans ces figures, des mêmes notations de référence désignent des éléments identiques.In these figures, the same reference notations designate identical elements.

Dans la description qui suit, l'invention est spécifiquement appliquée aux électrolyseurs monopolaires du type filtre-presse à membranes cationiques, pour la production de chlore, d'hydrogène et de solutions aqueuses d'hydroxyde de sodium par électrolyse de solutions aqueuses de chlorure de sodium.In the description which follows, the invention is specifically applied to monopolar electrolysers of the filter press type with cationic membranes, for the production of chlorine, hydrogen and aqueous solutions of sodium hydroxide by electrolysis of aqueous solutions of chloride of sodium.

Le châssis conforme à l'invention, représenté aux figures 1 à 5, est destiné à former une chambre anodique de l'électroly­seur. Il comprend un cadre vertical désigné de manière générale par la notation de référence 1, présentant une section trans­versale approximativement carrée. Le cadre 1 comprend deux montants verticaux 2 et 3 en titane, soudés à deux longerons 4 et 5 également en titane.The chassis according to the invention, shown in Figures 1 to 5, is intended to form an anode chamber of the electrolyser. It comprises a vertical frame generally designated by the reference notation 1, having an approximately square cross section. The frame 1 comprises two vertical uprights 2 and 3 made of titanium, welded to two longitudinal members 4 and 5 also made of titanium.

L'espace 13 circonscrit par le cadre 1 constitue une chambre d'électrolyse anodique. Celle-ci contient une anode formée d'une paire de tôles verticales 6 en métal déployé, disposées de part et d'autre de plusieurs barreaux métalliques horizontaux 7. Les tôles 6 sont soudées à des proiilés verticaux 8 qui sont par ailleurs soudés aux barreaux horizontaux 7. Les barreaux 7 sont soudés aux montants 2 et 3 du cadre, qu'ils traversent. Ils sont fixés ensemble à une barre de jonction 24, destinée à être couplée à une source de courant. Les barreaux 6 et les profilés 8 coopérent ainsi au couplage des tôles 6 à la source de courant et au support de ces tôles à l'intérieur du cadre 1.The space 13 circumscribed by the frame 1 constitutes a room anodic electrolysis. This contains an anode formed by a pair of vertical sheets 6 of expanded metal, arranged on either side of several horizontal metal bars 7. The sheets 6 are welded to vertical profiles 8 which are also welded to the bars horizontal 7. The bars 7 are welded to the uprights 2 and 3 of the frame, which they pass through. They are fixed together to a junction bar 24, intended to be coupled to a current source. The bars 6 and the profiles 8 thus cooperate in the coupling of the sheets 6 to the current source and to the support of these sheets inside the frame 1.

Les tôles 6 sont des tôles en titane, portant un revêtement conducteur de l'électricité, à faible surtension pour l'oxydation électrochimique des ions chlorure. De tels revêtements sont bien connus dans la technique de l'électrolyse. Les barreaux 7 comprennent une âme en cuivre chemisée dans une enveloppe en titane. Les profilés verticaux 8, mieux visibles aux figures 2, 3 et 4, sont formés chacun d'un feuillard vertical en titane, plié en forme de U ou de Ω, de manière à présenter la forme d'une gouttière. Ils sont fixés aux tôles 6 le long de la partie médiane axiale 9 du U et aux barreaux 7 le long de leurs bandes marginales 10 (figure 4).The sheets 6 are titanium sheets, carrying an electrically conductive coating, with low overvoltage for the electrochemical oxidation of chloride ions. Such coatings are well known in the art of electrolysis. The bars 7 include a copper core lined in a titanium casing. The vertical sections 8, better visible in Figures 2, 3 and 4, are each formed of a vertical strip of titanium, folded in the form of U or Ω, so as to have the shape of a gutter. They are fixed to the sheets 6 along the axial middle part 9 of the U and to the bars 7 along their marginal strips 10 (Figure 4).

Les profilés verticaux 8 sont disposés symétriquement, par paires, de part et d'autre des barreaux 7. Les deux profilés 8 de chaque paire sont joints par des plaques verticales 11, s'éten­dant entre les barreaux successifs 7, de manière à former une cheminée verticale 12 entre les deux tôles 6. Les plaques verticales 11 sont des feuilles en titane, soudées aux bandes marginales 10 des barreaux 8 (figure 4). Chaque cheminée 12 est ainsi isolée des tôles 6 formant l'anode, de sorte qu'elle n'est pas le siège d'une formation de chlore pendant l'électrolyse d'une solution aqueuse de chlorure de sodium au contact des tôles 6. Les extrémités supérieure et inférieure des profilés 8 sont maintenues écartées des longerons 4 et 5 du cadre 1, de manière que les cheminées 12 débouchent dans la chambre d'électrolyse à leurs deux extrémités.The vertical profiles 8 are arranged symmetrically, in pairs, on either side of the bars 7. The two profiles 8 of each pair are joined by vertical plates 11, extending between the successive bars 7, so as to form a vertical chimney 12 between the two sheets 6. The vertical plates 11 are titanium sheets, welded to the marginal strips 10 of the bars 8 (Figure 4). Each chimney 12 is thus isolated from the sheets 6 forming the anode, so that it is not the site of chlorine formation during the electrolysis of an aqueous solution of sodium chloride in contact with the sheets 6. The upper and lower ends of the profiles 8 are kept apart from the side members 4 and 5 of the frame 1, so that the chimneys 12 open into the electrolysis chamber at their two ends.

Les longerons 5 et 4 et le montant 3 du cadre 1 sont conçus pour former des canaux internes de section carrée ou rectangu­laire qui vont servir respectivement à introduire une solution aqueuse de chlorure de sodium dans la chambre d'électrolyse 13 et à en évacuer les produits résultant de l'électrolyse (du chlore et une solution aqueuse diluée de chlorure de sodium). A cet effet, les longerons 4 et 5 sont percés d'ouvertures 14 réguliè­rement réparties sur leurs parois qui se font face dans la chambre 13. Le longeron inférieur 5 est muni d'une tubulure 15 pour l'admission dans son canal 16, de la solution aqueuse de chlorure de sodium à électrolyser. Le canal 17 délimité dans le longeron supérieur 4 sert de chambre de dégazage, pour séparer le chlore de la solution aqueuse diluée de chlorure de sodium sortant de la chambre d'électrolyse 13. Il débouche dans le canal 18 formé dans le montant 3, muni d'une tubulure 19 pour l'extraction du chlore et d'une tubulure 20 pour l'extraction de la solution diluée de chlorure de sodium. Un seuil 21 séparant les canaux 17 et 18 sert à maintenir un niveau constant de solution dans le canal 17.The longitudinal members 5 and 4 and the upright 3 of the frame 1 are designed to form internal channels of square or rectangular section which will respectively serve to introduce an aqueous solution of sodium chloride into the electrolysis chamber 13 and to evacuate the products thereof resulting from the electrolysis (chlorine and a dilute aqueous solution of sodium chloride). To this end, the side members 4 and 5 are pierced with openings 14 regularly distributed on their walls which face each other in the chamber 13. The lower side member 5 is provided with a tube 15 for admission into its channel 16, of the aqueous sodium chloride solution to be electrolyzed. The channel 17 delimited in the upper beam 4 serves as a degassing chamber, for separating the chlorine from the dilute aqueous solution of sodium chloride leaving the electrolysis chamber 13. It opens into the channel 18 formed in the upright 3, provided a tube 19 for the extraction of chlorine and a tube 20 for the extraction of the dilute sodium chloride solution. A threshold 21 separating the channels 17 and 18 is used to maintain a constant level of solution in the channel 17.

Lorsque le châssis représenté aux figures 1 à 5 est en exploitation dans un électrolyseur, la chambre d'électrolyse 13 est remplie d'une solution aqueuse de chlorure de sodium jusqu'au niveau supérieur de seuil 21. Une solution aqueuse de chlorure de sodium est introduite de manière continue dans le canal 16, via la tubulure 15, pénètre dans la chambre d'électrolyse 13 en traversant les ouvertures 14 et est entraînée de bas en haut dans celle-ci par le chlore qui est généré sur les tôles 6 de l'anode. Dans la chambre 13, les cheminées verticales 12 ne sont pas le siège d'un dégagement de chlore, de sorte que la masse volumique de la solution qui s'y trouve est supérieure à celle de l'émul­sion dans la partie restante de la chambre 13. Il s'établit ainsi une circulation interne d'électrolyte dans la chambre 13 : l'électrolyte entrant dans la chambre via le canal 16 est entraîné en un mouvement ascendant entre les tôles 6, une fraction en est évacuée avec le chlore par le canal 17 et une autre fraction est recyclée au bas de la chambre 13 via les cheminées 12. La circulation interne d'électrolyte dans la chambre 13 est favorable à une meilleure homogénéisation et, dès lors, à un rendement énergétique optimum de l'opération d'électrolyse.When the chassis shown in FIGS. 1 to 5 is in operation in an electrolyser, the electrolysis chamber 13 is filled with an aqueous solution of sodium chloride up to the upper threshold level 21. An aqueous solution of sodium chloride is introduced continuously into the channel 16, via the tubing 15, enters the electrolysis chamber 13 through the openings 14 and is driven from bottom to top therein by the chlorine which is generated on the sheets 6 of l 'anode. In the chamber 13, the vertical chimneys 12 are not the seat of a release of chlorine, so that the density of the solution which is there is greater than that of the emulsion in the remaining part of the chamber 13. An internal electrolyte circulation is thus established in the chamber 13: the electrolyte entering the chamber via the channel 16 is driven in an upward movement between the sheets 6, a fraction of it is removed with the chlorine by the channel 17 and another fraction is recycled at the bottom of the chamber 13 via the chimneys 12. The internal circulation of electrolyte in the chamber 13 is favorable for better homogenization and, therefore, for optimum energy efficiency of the electrolysis operation.

Dans le canal 17, le chlore se sépare de la solution aqueuse de chlorure de sodium et est évacué par la tubulure 19. La solu­tion aqueuse déborde au-dessus du seuil 21 et passe dans le canal vertical 18, d'où elle est évacuée par la tubulure 20.In channel 17, the chlorine separates from the aqueous sodium chloride solution and is evacuated via the tube 19. The aqueous solution overflows above the threshold 21 and passes into the vertical channel 18, from where it is evacuated by tubing 20.

Dans la description qui précède des figures 1 à 5, l'inven­tion a été appliquée à un châssis d'une chambre anodique de l'électrolyseur. Dans le cas d'un châssis destiné à une chambre cathodique de l'électrolyseur, les montants 2 et 3 et les longe­rons 4 et 5 du cadre 1 sont en nickel, les tôles 6 forment une cathode et sont en nickel (et portent éventuellement un revête­ment conducteur à faible surtension pour la réduction des protons), les barreaux 7 sont en nickel ou comprennent une âme en cuivre chemisée d'une enveloppe en nickel et les profilés 8 et les plaques 11 sont en nickel.In the foregoing description of Figures 1 to 5, the invention has been applied to a chassis of an anode chamber of the electrolyser. In the case of a chassis intended for a cathode chamber of the electrolyser, the uprights 2 and 3 and the side members 4 and 5 of the frame 1 are made of nickel, the sheets 6 form a cathode and are made of nickel (and possibly carry a conductive coating with low overvoltage for proton reduction), the bars 7 are made of nickel or include a copper core lined with a nickel casing and the profiles 8 and the plates 11 are made of nickel.

Dans une forme de réalisation modifiée du châssis, représen­tée à la figure 4, des pièces intercalaires 22 sont interposées entre les tôles 6 et la partie médiane 9 de chacun des profilés 8. Ces pièces intercalaires 22 sont en un matériau conducteur de l'électricité et sont soudées aux tôles 6 et aux profilés 8. Elles peuvent indifféremment être des tiges qui s'étendent sur toute la hauteur des profilés 8, ou des plots régulièrement espacés. Elles ont pour fonction d'assurer un écartement substantiel entre les tôles 6 et les profilés 8, de manière à permettre un passage d'électrolyte entre les tôles et les profilés.In a modified embodiment of the chassis, shown in FIG. 4, intermediate pieces 22 are interposed between the sheets 6 and the middle part 9 of each of the profiles 8. These intermediate pieces 22 are made of an electrically conductive material and are welded to the sheets 6 and to the sections 8. They can either be rods which extend over the entire height of the sections 8, or regularly spaced studs. They have the function of ensuring a substantial spacing between the sheets 6 and the sections 8, so as to allow an electrolyte passage between the sheets and the sections.

Cette forme de réalisation du châssis selon l'invention est spécialement destinée aux électrolyseurs à membranes, dans lesquels il s'avère nécessaire d'assurer un mouillage efficace de la membrane par l'électrolyte se trouvant dans la chambre d'électrolyse 13.This embodiment of the chassis according to the invention is specially intended for membrane electrolysers, in which it is necessary to ensure effective wetting of the membrane by the electrolyte located in the electrolysis chamber 13.

La figure 6 montre une autre forme de réalisation du châssis selon l'invention, également conçue pour assurer un mouillage efficace de la membrane par l'électrolyte. Dans cette forme de réalisation, la partie médiane 9 des profilés 8 est percée de trous 31; une cloison verticale 32 joignant les deux ailes 33 du profilé isole la cheminée 12, d'un canal vertical 34. La partie des ailes 33, située entre la partie médiane 9 et la cloison 32 peut éventuellement être ajourée pour faciliter la communication entre la chambre 13 et le canal 34.FIG. 6 shows another embodiment of the chassis according to the invention, also designed to ensure effective wetting of the membrane by the electrolyte. In this form of embodiment, the middle part 9 of the sections 8 is pierced with holes 31; a vertical partition 32 joining the two wings 33 of the profile isolates the chimney 12 from a vertical channel 34. The part of the wings 33, located between the middle part 9 and the partition 32 can optionally be perforated to facilitate communication between the chamber 13 and channel 34.

Dans une forme de réalisation supplémentaire du châssis selon l'invention, représentée à la figure 7, les ouvertures 14 du longeron supérieur 4 du châssis 1 ont leur bord 23 chanfreiné dans le sens pour lequel la section transversale de l'ouverture aille en diminuant du bas vers le haut. Cette forme de réalisa­tion de l'invention accélère le passage du gaz de la chambre 13 vers le canal 17, pendant l'électrolyse.In an additional embodiment of the chassis according to the invention, shown in FIG. 7, the openings 14 of the upper spar 4 of the chassis 1 have their edge 23 chamfered in the direction for which the cross section of the opening goes decreasing in bottom up. This embodiment of the invention accelerates the passage of gas from the chamber 13 to the channel 17, during the electrolysis.

L'électrolyseur représenté à la figure 8 est formé d'un empilage de châssis verticaux, alternativement anodiques 25 et cathodiques 25′. Les châssis anodiques 25 sont analogues à ceux décrits plus haut, en référence aux figures 1 à 7. Les châssis cathodiques 25′ sont analogues aux châssis anodiques 25, dans lesquels les éléments constitutifs en titane ont été remplacés par des éléments similaires en nickel. Ces éléments en nickel des châssis 25′ portent les mêmes numéros de référence que leurs homologues respectifs des châssis 25, mais sont affectés d'un indice prime (′). Les châssis 25 et 25′ sont séparés par des membranes cationiques 26, qui délimitent ainsi des chambres d'électrolyse alternativement anodiques et cathodiques L'empilage des châssis 25 et 25′ et des membranes 26 est retenu entre des flasques d'extrémités 27, reliés par des tirants non représentés, des joints 28 assurant l'étanchéité. Les barreaux verticaux de jonction 24 (figure 1) des châssis anodiques 25 sont couplés à une barre omnibus reliée à la borne positive d'une source de courant continu, les barreaux de jonction, la barre omnibus et la source de courant n'étant pas visible à la figure 7. D'une manière similaire, les châssis cathodiques 25′ sont raccordés à une barre omnibus commune, reliée à la borne négative de la source de courant continu. Par ailleurs, les tubulures 15 des châssis anodiques 25 (figures 1 et 5) débouchent dans un collecteur commun d'admission d'une solution aqueuse de chlorure de sodium, ce collecteur ainsi que les tubulures 15 n'étant pas visibles à la figure 7. Par analogie, les tubulures correspon­dantes des châssis cathodiques 25′ débouchent dans un collecteur commun d'admission d'eau ou d'une solution aqueuse diluée d'hydroxyde de sodium. Les tubulures 19 et 20 des châssis anodiques 25 débouchent respectivement dans deux collecteurs généraux 29 et 30, le collecteur 29 servant à l'évacuation du chlore produit dans les chambres anodiques 13 et le collecteur 30 servant à l'évacuation de la solution diluée de chlorure de sodium. De manière similaire, les tubulures 19′ et 20′ des châssis cathodiques 25′ débouchent respectivement dans deux collecteurs généraux 29′ et 30′, le collecteur 29′ servant à l'évacuation de l'hydrogène produit dans les chambres cathodiques 13′ et le collecteur 30′ servant à l'évacuation d'une solution aqueuse concentrée d'hydroxyde de sodium.The electrolyser shown in FIG. 8 is formed by a stack of vertical frames, alternately anodic 25 and cathodic 25 ′. The anode frames 25 are similar to those described above, with reference to FIGS. 1 to 7. The cathode frames 25 ′ are analogous to the anode frames 25, in which the constituent elements in titanium have been replaced by similar elements in nickel. These nickel elements of chassis 25 ′ have the same reference numbers as their respective counterparts of chassis 25, but are assigned a prime index (′). The frames 25 and 25 ′ are separated by cationic membranes 26, which thus delimit alternately anodic and cathodic electrolysis chambers The stacking of the frames 25 and 25 ′ and membranes 26 is retained between end flanges 27, connected by tie rods not shown, seals 28 ensuring sealing. The vertical junction bars 24 (FIG. 1) of the anode frames 25 are coupled to a bus bar connected to the positive terminal of a direct current source, the junction bars, the bus bar and the current source not being visible in Figure 7. Similarly, the cathode frames 25 'are connected to a common bus bar, connected to the negative terminal of the DC source. Furthermore, the pipes 15 of the anode frames 25 (Figures 1 and 5) open into a common manifold for the admission of an aqueous sodium chloride solution, this manifold and the pipes 15 not being visible in FIG. 7. By analogy, the corresponding pipes of the cathode frames 25 ′ open into a common manifold of admission of water or a dilute aqueous solution of sodium hydroxide. The pipes 19 and 20 of the anode frames 25 open respectively into two general collectors 29 and 30, the collector 29 serving for the evacuation of the chlorine produced in the anode chambers 13 and the collector 30 serving for the evacuation of the dilute chloride solution. sodium. Similarly, the pipes 19 ′ and 20 ′ of the cathode frames 25 ′ open respectively into two general collectors 29 ′ and 30 ′, the manifold 29 ′ serving for the evacuation of the hydrogen produced in the cathode chambers 13 ′ and the collector 30 ′ used for the discharge of a concentrated aqueous solution of sodium hydroxide.

Pendant le fonctionnement de l'électrolyseur, la pression hydrostatique régnant dans les chambres d'électrolyse 13 des châssis anodiques 25 est habituellement inférieure de celle régnant dans les chambres 13′ des châssis cathodiques 25′. Il s'ensuit que les membranes 26 sont repoussées contre les tôles 6 des anodes. Du fait de leur section transversale convexe, les profilés verticaux 8 s'opposent efficacement à une flexion des tôles 6.During the operation of the electrolyser, the hydrostatic pressure prevailing in the electrolysis chambers 13 of the anode frames 25 is usually lower than that prevailing in the chambers 13 ′ of the cathode frames 25 ′. It follows that the membranes 26 are pushed against the sheets 6 of the anodes. Because of their convex cross section, the vertical profiles 8 effectively oppose bending of the sheets 6.

Inversément, dans le cas d'un électrolyseur fonctionnant avec une différence positive de pression hydrostatique entre les chambres anodiques 13 et les chambres cathodiques 13′, les profilés verticaux 8′ des châssis 25′ s'opposent à une flexion des tôles 6′ des cathodes.Conversely, in the case of an electrolyser operating with a positive difference in hydrostatic pressure between the anode chambers 13 and the cathode chambers 13 ′, the vertical profiles 8 ′ of the frames 25 ′ oppose bending of the sheets 6 ′ of the cathodes .

Claims (10)

1 - Châssis pour électrolyseur du type filtre-presse, comprenant :
- un cadre vertical (1) délimitant une chambre d'électrolyse (13);
- une électrode dans la chambre d'électrolyse, comprenant une paire de tôles métalliques, verticales, ajourées (6), disposées vis-à-vis l'une de l'autre;
- une amenée de courant à l'électrode, comprenant des barreaux métalliques horizontaux ou obliques (7), disposés entre les tôles (6) et des éléments de jonction des barreaux aux tôles;
caractérisé en ce que les éléments de jonction comprennent des paires de profilés métalliques verticaux en U ou en V (8), disposés symétriquement de part et d'autre des barreaux (7) et raccordés l'un à l'autre par des plaques verticales (11) joignant les barreaux (7) en sorte de former des cheminées verticales (12) dans la chambre d'électrolyse (13).1 - Chassis for an electrolyser of the filter press type, comprising:
- a vertical frame (1) delimiting an electrolysis chamber (13);
- an electrode in the electrolysis chamber, comprising a pair of metal, vertical, perforated (6) metal sheets, arranged opposite one another;
- a current supply to the electrode, comprising horizontal or oblique metal bars (7), disposed between the sheets (6) and elements for joining the bars to the sheets;
characterized in that the joining elements comprise pairs of vertical metal profiles in U or V (8), arranged symmetrically on either side of the bars (7) and connected to each other by vertical plates (11) joining the bars (7) so as to form vertical chimneys (12) in the electrolysis chamber (13). 2 - Châssis selon la revendication 1, caractérisé en ce que les profilés verticaux (8) sont soudés par leurs ailes longitudi­nales (33, 10) aux barreaux (7) et dans leur partie médiane (9) aux tôles (6).2 - Chassis according to claim 1, characterized in that the vertical profiles (8) are welded by their longitudinal wings (33, 10) to the bars (7) and in their middle part (9) to the sheets (6). 3 - Châssis selon la revendication 1 ou 2, caractérisé en ce que les faces des profilés (8) et des plaques (11), qui sont orientées à l'intérieur des cheminées (12) sont en un matériau qui ne participe pas à la réaction d'électrolyse.3 - Chassis according to claim 1 or 2, characterized in that the faces of the profiles (8) and plates (11), which are oriented inside the chimneys (12) are made of a material which does not participate in the electrolysis reaction. 4 - Châssis selon la revendication 2 ou 3, caractérisé en ce que la partie médiane (9) des profilés (8) est percée de trous (31) et une cloison verticale (32) joignant les deux ailes (33) du profilé (8) isole la cheminée verticale (12), d'un canal vertical (34) s'étendant le long de la partie médiane (9) du profilé (8).4 - Chassis according to claim 2 or 3, characterized in that the middle part (9) of the profiles (8) is pierced with holes (31) and a vertical partition (32) joining the two wings (33) of the profile (8 ) isolates the vertical chimney (12) from a vertical channel (34) extending along the middle part (9) of the profile (8). 5 - Châssis selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le cadre (1) comprend deux montants verti­caux (2, 3) reliés par deux longerons horizontaux (4, 5).5 - Chassis according to any one of claims 1 to 4, characterized in that the frame (1) comprises two vertical uprights (2, 3) connected by two horizontal beams (4, 5). 6 - Châssis selon la revendication 5, caractérisé en ce que les longerons (5, 4) forment des canaux internes (16, 17) qui sont percés d'ouvertures (14) sur leurs parois respectives qui se font face dans la chambre d'électrolyse (13), les canaux (16, 17) étant en communication avec des conduits pour l'admission et pour l'évacuation d'un électrolyte.6 - Chassis according to claim 5, characterized in that the side members (5, 4) form internal channels (16, 17) which are pierced with openings (14) on their respective walls which face each other in the chamber electrolysis (13), the channels (16, 17) being in communication with conduits for the admission and for the evacuation of an electrolyte. 7 - Châssis selon la revendication 6, caractérisé en ce que le canal (16) du longeron inférieur (5) est raccordé au conduit d'admission de l'électrolyte et le canal (17) du longeron supé­rieur (4) est raccordé au conduit d'évacuation de l'électrolyte.7 - Chassis according to claim 6, characterized in that the channel (16) of the lower beam (5) is connected to the electrolyte intake duct and the channel (17) of the upper beam (4) is connected to the duct electrolyte discharge. 8 - Châssis selon la revendication 7, caractérisé en ce que le conduit d'évacuation de l'électrolyte comprend un canal interne (18) d'un montant (3) du châssis (1).8 - Chassis according to claim 7, characterized in that the electrolyte discharge conduit comprises an internal channel (18) of an amount (3) of the chassis (1). 9 - Electrolyseur du type monopolaire, filtre-presse, comprenant un empilage de châssis (25, 25′) délimitant des chambres d'électrolyse alternativement anodiques (13) et cathodiques (13′), contenant des électrodes verticales, caracté­risé en ce qu'il comprend des châssis conformes à l'une quelconque des revendications 1 à 8.9 - Monopolar type electrolyser, filter press, comprising a stack of frames (25, 25 ′) delimiting alternately anodic (13) and cathodic (13 ′) electrolysis chambers, containing vertical electrodes, characterized in that it comprises frames according to any one of claims 1 to 8. 10 - Electrolyseur selon la revendication 9, caractérisé en ce qu'il comprend des membranes à perméabilité selective (26), alternant avec les châssis (25, 25′).10 - An electrolyser according to claim 9, characterized in that it comprises membranes with selective permeability (26), alternating with the frames (25, 25 ′).
EP90202084A 1989-08-11 1990-07-31 Frame for electrolyzer of the filterpress type and monopolar electrolyzer of the filterpress type Expired - Lifetime EP0412600B1 (en)

Priority Applications (1)

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AT90202084T ATE102661T1 (en) 1989-08-11 1990-07-31 FRAME FOR ELECTROLYSER OF FILTER PRESS TYPE AND MONOPOLAR ELECTROLYSER OF FILTER PRESS TYPE.

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BE8900867 1989-08-11
BE8900867A BE1004364A3 (en) 1989-08-11 1989-08-11 Chassis for electrolyser type filter press and electrolyser monopolar type of filter press.

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EP0412600B1 EP0412600B1 (en) 1994-03-09

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AT (1) ATE102661T1 (en)
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Publication number Publication date
NO903526L (en) 1991-02-12
HUT57288A (en) 1991-11-28
TR24979A (en) 1992-09-01
DD297191A5 (en) 1992-01-02
CN1049875A (en) 1991-03-13
ZA906097B (en) 1991-05-29
BE1004364A3 (en) 1992-11-10
HU904977D0 (en) 1991-01-28
US5130008A (en) 1992-07-14
ES2050937T3 (en) 1994-06-01
ATE102661T1 (en) 1994-03-15
DE69007205D1 (en) 1994-04-14
CA2023126A1 (en) 1991-02-12
JPH03177593A (en) 1991-08-01
PL164675B1 (en) 1994-09-30
PT94871A (en) 1991-04-18
AU6086690A (en) 1991-02-14
NO903526D0 (en) 1990-08-10
HRP920972A2 (en) 1994-04-30
PL286433A1 (en) 1991-02-25
BR9003960A (en) 1991-09-03
AU623032B2 (en) 1992-04-30
JP3053199B2 (en) 2000-06-19
PT94871B (en) 1997-11-28
DE69007205T2 (en) 1994-06-30
EP0412600B1 (en) 1994-03-09
NO302486B1 (en) 1998-03-09
CA2023126C (en) 2000-11-28
AR242998A1 (en) 1993-06-30

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