EP0022445A1 - Electrolytic apparatus for the production of chlorine from aqueous alkali halogenide solutions - Google Patents

Electrolytic apparatus for the production of chlorine from aqueous alkali halogenide solutions Download PDF

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Publication number
EP0022445A1
EP0022445A1 EP80101139A EP80101139A EP0022445A1 EP 0022445 A1 EP0022445 A1 EP 0022445A1 EP 80101139 A EP80101139 A EP 80101139A EP 80101139 A EP80101139 A EP 80101139A EP 0022445 A1 EP0022445 A1 EP 0022445A1
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EP
European Patent Office
Prior art keywords
electrolysis
shells
electrolysis apparatus
electrodes
chlorine
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EP80101139A
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German (de)
French (fr)
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EP0022445B1 (en
Inventor
Dieter Dr. Bergner
Kurt Hannesen
Wilfried Schulte
Peter Steinmetz
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Hoechst AG
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Hoechst AG
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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
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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 an electrolysis apparatus for the production of chlorine from aqueous alkali halide solution, in which the anode and cathode compartments are separated from one another by a partition, for example a diaphragm or an ion exchange membrane.
  • a partition for example a diaphragm or an ion exchange membrane.
  • DT-OS 25 38 414 an electrolysis cell is described which is operable as a single element, but is combined into a multiple electrolysis cell in a suitable device.
  • One element of this electrolyser is characterized in that the housing consists of two half-shells, the electrodes are connected to the half-shells by means of electrically conductive bolts, the bolts projecting through the wall of the half-shells and on their protruding end face current leads and devices for compressing the current leads, Half-shells, electrodes and partition lie on and the partition between electrically insulating spacers, which are arranged in the extension of the bolts on the electrolytically active side of the electrodes and is clamped between the edges of the half-shells by means of sealing elements.
  • the housings have openings through which the current leads are led to the electrodes, which is disadvantageous since leaks can occur at these bushings, which can only be eliminated by decommissioning the entire electrolyser and replacing the leaky element.
  • Another disadvantage is that elements that are built for economic reasons using thin steel and titanium sheets are bulged by the hydrostatic pressure of the liquid column in the cell and are therefore difficult to remove from the electrolyzer in the liquid-filled state the pressing device are to be removed.
  • a further disadvantage of the existing multiple electrolysis cells is that considerable amounts of current as leakage or leakage currents can flow off both through the supply lines for the electrolyte solutions and through the discharge lines for the products. This can lead to
  • the tasks are accomplished by electrolysis Apparatus for the production of chlorine from an aqueous alkali halide solution, which has at least one electrolysis cell, the anode and cathode of which are separated from one another by a partition in a housing made of two half-shells, the housing being provided with devices for supplying the electrolysis starting materials and for removing the electrolysis products and the partition is clamped between the edges of the half-shells by means of sealing elements and is held between power transmission elements made of electrically non-conductive material and extending in each case up to the electrodes and which is characterized in that the electrodes are attached via spacers which are fastened to the inside of the half-shells are, and are mechanically and electrically connected via their edges to the half-shells.
  • the half-shells of the electrolysis cells can be provided with stiffeners and at least one of the half-shells of an electrolysis cell can have electrically conductive force transmission elements on the outside and in an extension of the force transmission elements and spacers.
  • at least one tube of electrically non-conductive material running in the vertical direction and passing through the half-shells near the edge can be arranged in the interior of the half-shells to supply the electrolysis starting materials and / or to remove the electrolysis products.
  • the cathodes can consist of iron, cobalt, nickel or chromium or one of their alloys and the anodes can consist of titanium, niobium or tantalum or an alloy of these metals or of a metal or oxide ceramic material.
  • the anodes are provided with an electrically conductive, catalytically active coating which contains metals or compounds from the group of platinum metals. Due to the shape of the electrodes, which are made of perforated material such as perforated sheets, expanded metal, wickerwork or constructions made of thin round rods, and their arrangement in the electrolysis cell can be used in the Electrolysis gases easily enter the space behind the electrodes. This gas discharge from the electrode gap leads to a reduction in the gas bubble resistance between the electrodes and thus a reduction in the cell voltage.
  • the half-shells on the cathode side can be made of iron or iron alloys. If the cathode and the cathode-side half-shell are to be welded to one another, they preferably consist of the same material, preferably steel.
  • the anode-side half-shell must consist of a chlorine-resistant material such as titanium, niobium or tantalum, or an alloy of these metals, or of a metal or oxide ceramic material. If the half-shell and anode are to be connected to one another by welding, the same material, preferably titanium, is selected for both parts.
  • Half-shell and electrodes can also be firmly connected to each other by screwing. In this case, half-shells and electrodes can be made of different materials.
  • the diaphragms or ion exchange membranes customary in alkali metal chloride electrolysis come into consideration as the partition.
  • Membranes with terminal sulfonamide groups (-S0 3 NHR) are also used as ion exchange groups.
  • the equivalent weights of such ion exchangers are between 800 and 1600, preferably between 1100 and 1500.
  • the ion exchange membrane is usually reinforced with a support fabric made of polytetrafluoroethylene.
  • these ion exchange membranes prevent diaphragms mix hydrogen and chlorine, but because of their selective permeability they allow the passage of alkali metal ions into the cathode compartment. They largely prevent the transition of halide into the cathode compartment and the passage of hydroxyl ions into the anode compartment. This results in a practically salt-free lye, whereas the salt must first be removed from the catholyte of the diaphragm cells in a complex process.
  • the ion exchange membranes represent dimensionally stable partition walls which are also more resistant to the aggressive media of alkali halide electrolysis and therefore have a longer service life than asbestos diaphragms.
  • the electrolysis apparatus can consist of an electrolysis cell, but also of a large number of cells connected in series, the electrical contact between adjacent cells taking place directly via the contacting half-shells of adjacent electrolysis cells or via the electrically conductive force transmission elements.
  • the housing of an electrolytic cell consists of an anode-side and a cathode-side half-shell.
  • the anode-side half-shell 1 is formed from sheet metal and has a loose flange 2 while the half-shell of the cathode side consists of a wall 9 which is connected to a fixed flange 10.
  • an integral flange or at the cathode-side half-shell a loose flange can also be used for the anode-side half-shell '.
  • the partition 7 is clamped between the sealing elements 12.
  • the electrodes 4 and 8 are firmly connected to the half-shells 1 and 9 via the spacers (for example bolts) 5.
  • the electrolysis current is supplied to the anode and cathode either directly by contact with the half-shell wall of the adjacent electrolytic cell or by a force transmission element (for example bolts) 3 which is firmly connected to the half-shell 1 for example by screws 11.
  • the disks 6 are used for power transmission for the power supply.
  • the electrode spacing and the distance between the electrodes and the partition can be adjusted by the choice of the pane thickness. To stiffen the half-shells, they are provided with beads 13 a).
  • stiffeners 13 a and 13 b Two versions of these stiffeners 13 a and 13 b are shown in Figures 2, 3, 4 and 6. The same or different stiffeners are also used in the cathode-side half-shell.
  • FIG. 4 also shows a discharge pipe 14 for the electrolyte solutions in connection with a bead 13 b.
  • the pipe is held with a bracket 18.
  • Figure 5 shows the supply of the electrolyte to the cell via the pipe socket 15, which is firmly connected to the half-shell.
  • the arrangement is also valid for the fixed flange half shell 9.
  • the derivation of the electrolyte is shown in FIG.
  • the long tube 14 made of insulating material leads the electrolyte solution and the electrolysis gases out of the cell and reduces leakage currents due to the length of the tube part located inside the cell. It is through pushed the pipe socket 16 into the cell.
  • the transition piece 17 enables the transition to a subsequent hose line (not shown).
  • the pipe connection shown in FIG. 6 can of course also be used in this form for the supply of the electrolytes.
  • the anode and cathode of adjacent cells can be connected to one another in an electrically conductive manner via force transmission elements 3 made of electrically conductive material.
  • the arrangement thus represents a bipolar electrolysis apparatus.
  • the series connection of such cells results in high voltages and relatively low currents.
  • the series connection has the advantage of better utilization of the capacity of the rectifier elements, lower copper consumption and lower voltage losses in the busbars.

Abstract

Der Elektrolyseapparat zur Herstellung von Chlor aus wäßrigen Alkalihalogenidlösungen soll mindestens eine Elektrolysezelle aufweisen, deren Elektroden (4, 8) durch eine Trennwand (7) voneinander getrennt in einem Gehäuse aus zwei Halbschalen (1, 9) angeordnet sind. Das Gehäuse ist ferner mit Einrichtungen (15) zum Zuführen der Elektrolyseausgangsstoffe und Einrichtungen (14) zum Abführen der Elektrolyseprodukte versehen. Die Trennwand (7) ist mittels Dichtelementen (12) zwischen den Rändern der Halbschalen (1, 9) eingeklemmt und wird außerdem durch Kraftübertragungselemente (6) aus elektrisch nichtleitendem Material gehalten. Die Elektroden (4, 8) sind über Distanzstücke (5) in den Innenseiten der Halbschalen befestigt und über ihre Ränder mit den Halbschalen mechanisch und elektrisch leitend verbunden.The electrolysis apparatus for the production of chlorine from aqueous alkali halide solutions should have at least one electrolysis cell, the electrodes (4, 8) of which are separated from one another by a partition (7) in a housing made of two half-shells (1, 9). The housing is further provided with devices (15) for supplying the electrolysis starting materials and devices (14) for discharging the electrolysis products. The partition (7) is clamped between the edges of the half-shells (1, 9) by means of sealing elements (12) and is also held by electrically non-conductive material by means of force transmission elements (6). The electrodes (4, 8) are fastened in the inner sides of the half-shells via spacers (5) and mechanically and electrically conductively connected to the half-shells via their edges.

Description

Gegenstand der Erfindung ist ein Elektrolyseapparat zur Herstellung von Chlor aus wässriger Alkalihalogenidlösung, bei dem Anoden- und Kathodenraum durch eine Trennwand, zum Beispiel ein Diaphragma oder eine Ionenaustauschermembran, voneinander getrennt sind.The invention relates to an electrolysis apparatus for the production of chlorine from aqueous alkali halide solution, in which the anode and cathode compartments are separated from one another by a partition, for example a diaphragm or an ion exchange membrane.

In der DT-OS 25 38 414 wird eine Elektrolysezelle beschrieben, die als einzelnes Element betriebsfähig ist, jedoch in einer geeigneten Vorrichtung zu einer Mehrfachelektrolysezelle zusammengefaßt wird. Ein Element dieses Elektrolyseurs ist dadurch gekennzeichnet, daß das Gehäuse aus zwei Halbschalen besteht, die Elektroden über elektrisch leitende Bolzen mit den Halbschalen verbunden sind, wobei die Bolzen durch die Wandung der Halbschalen hindurchragen und auf ihrer hindurchragenden Stirnseite Stromzuführungen und Einrichtungen zum Zusammenpressen der Stromzuführungen, Halbschalen, Elektroden und Trennwand aufliegen und die Trennwand zwischen elektrisch isolierenden Distanzstücken, die in der Verlängerung der Bolzen auf der elektrolytisch aktiven Seite der Elektroden angeordnet sind und mittels Dichtelementen zwischen den Rändern der Halbschalen eingeklemmt ist.In DT-OS 25 38 414 an electrolysis cell is described which is operable as a single element, but is combined into a multiple electrolysis cell in a suitable device. One element of this electrolyser is characterized in that the housing consists of two half-shells, the electrodes are connected to the half-shells by means of electrically conductive bolts, the bolts projecting through the wall of the half-shells and on their protruding end face current leads and devices for compressing the current leads, Half-shells, electrodes and partition lie on and the partition between electrically insulating spacers, which are arranged in the extension of the bolts on the electrolytically active side of the electrodes and is clamped between the edges of the half-shells by means of sealing elements.

Bei den bekannten Mehrfachelektrolysezellen weisen die Gehäuse Durchbrüche auf, durch die die Stromzuführungen an die Elektroden geführt werden, was nachteilig ist, da an diesen Durchführungen Leckagen auftreten können, die nur durch Ausserbetriebsetzen des gesamten Elektrolyseurs und Auswechseln des undichten Elements zu beseitigen sind.In the case of the known multiple electrolysis cells, the housings have openings through which the current leads are led to the electrodes, which is disadvantageous since leaks can occur at these bushings, which can only be eliminated by decommissioning the entire electrolyser and replacing the leaky element.

Ein weiterer Nachteil ist darin zu sehen, daß Elemente, die aus wirtschaftlichen Gründen unter Verwendung von dünnen Stahl- und Titanblechen gebaut sind, durch den hydrostatischen Druck der Flüssigkeitssäule in der Zelle ausgebeult werden und daher bei der Entnahme aus dem Elektrolyseur in flüssigkeitsgefülltem Zustand schwierig aus der Preßvorrichtung zu entfernen sind.Another disadvantage is that elements that are built for economic reasons using thin steel and titanium sheets are bulged by the hydrostatic pressure of the liquid column in the cell and are therefore difficult to remove from the electrolyzer in the liquid-filled state the pressing device are to be removed.

Ferner ist bei den bestehenden Mehrfachelektrolysezellen von Nachteil, daß sowohl über die Zuführungsleitungen für die Elektrolytlösungen als auch durch die Abführungsleitungen für die Produkte beträchtliche Stromanteile als Kriech-oder Leckströme abfließen können. Es kann hierdurch zuA further disadvantage of the existing multiple electrolysis cells is that considerable amounts of current as leakage or leakage currents can flow off both through the supply lines for the electrolyte solutions and through the discharge lines for the products. This can lead to

Korrosionsschäden an den aus Metall gefertigten Zellenteilen kommen.Corrosion damage to the cell parts made of metal.

Es war daher die Aufgabe zu lösen, einen Elektrolyseapparat zu schaffen, der die oben gezeigten Nachteile nicht aufweist. Darüber hinaus bestand die Aufgabe, den Elektrolyseapparat aus Einzelzellen so aufzubauen, daß die Dichtigkeit der einzelnen Zellen, der Zustand der elektrischen Kontakte und die Stromverteilung ohne weiteres überwacht werden können. Ferner sollen die Einzelzellen für für sich allein funktionsfähig sein. Im Reparaturfall sollen die defekten Zellen in gefülltem Zustand leicht entfernt oder ausgetauscht werden können ohne daß damit Demontage des gesamten Elektrolyseapparates erforderlich wird und der Betrieb langfristig unterbrochen wird.It was therefore the task to solve an electrolysis apparatus that does not have the disadvantages shown above. In addition, there was the task of constructing the electrolysis apparatus from individual cells in such a way that the tightness of the individual cells, the condition of the electrical contacts and the current distribution can be easily monitored. Furthermore, the individual cells should be functional on their own. In the event of repairs, the defective cells should be easily removed or replaced when full, without the need to dismantle the entire electrolysis apparatus and to interrupt operation in the long term.

Die Aufgaben werden erfindungsgemäß durch einen Elektrolyseapparat zur Herstellung von Chlor aus wässriger Alkalihalogenidlösung gelöst, der mindestens eine Elektrolysezelle aufweist, deren Anode und Kathode durch eine Trennwand voneinander getrennt in einem Gehäuse aus zwei Halbschalen angeordnet sind, wobei das Gehäuse mit Einrichtungen zum zum Zuführen der Elektrolyseausgangsstoffe und zum Abführen der Elektrolyseprodukte versehen ist, und die Trennwand mittels Dichtelementen zwischen den Rändern der Halbschalen eingeklemmt und zwischen sich jeweils bis zu den Elektroden erstreckenden Kraftübertragungselementen aus elektrisch nicht leitendem Material gehalten ist und der dadurch gekennzeichnet ist, daß die Elektroden über Distanzstücke, die an der Innenseite der.Halbschalen befestigt sind, und über ihre Ränder mit den Halbschalen mechanisch und elektrisch leitend verbunden sind.According to the invention, the tasks are accomplished by electrolysis Apparatus for the production of chlorine from an aqueous alkali halide solution, which has at least one electrolysis cell, the anode and cathode of which are separated from one another by a partition in a housing made of two half-shells, the housing being provided with devices for supplying the electrolysis starting materials and for removing the electrolysis products and the partition is clamped between the edges of the half-shells by means of sealing elements and is held between power transmission elements made of electrically non-conductive material and extending in each case up to the electrodes and which is characterized in that the electrodes are attached via spacers which are fastened to the inside of the half-shells are, and are mechanically and electrically connected via their edges to the half-shells.

Die Halbschalen der Elektrolysezellen können mit Versteifungen versehen sein und es kann mindestens eine der Halbschalen einer Elektrolysezelle auf ihrer Außenseite und in Verlängerung der Kraftübertragungselemente und Distanzstücke elektrisch leitende Kraftübertragungselemente aufweisen. Um Kriechströme zu vermeiden, können zum Zuführen der Elektrolyseausgangsstoffe und/oder zum Abführen der Elektrolyseprodukte im Innern der Halbschalen mindestens ein in vertikaler Richtung verlaufendes und in der Nähe des Randes durch die Halbschalen hindurchtretendes Rohr aus elektrisch nicht leitendem Material angeordnet sein. Die Kathoden können aus Eisen, Kobalt, Nickel oder Chrom oder einer ihrer Legierungen und die Anoden aus Titan, Niob oder Tantal oder einer Legierung dieser Metalle oder aus einem metall- oder oxidkeramischen Material bestehen. Darüberhinaus sind die Anoden mit einem elektrisch leitfähigen katalytisch wirksamen Überzug versehen, der Metalle oder Verbindungen der Gruppe der Platinmetalle enthält. Durch die Form der Elektroden, die aus durchbrochenem Material wie Lochbleche, Streckmetall, Flechtwerk oder Konstruktionen aus dünnen Rundstäben bestehen, und ihre Anordnung in der Elektrolysezelle können die bei der Elektrolyse gebildeten Gase leicht in den Raum hinter den Elektroden eintreten. Durch diesen Gasabzug aus dem Elektrodenspalt erreicht man eine Verminderung des Gasblasenwiderstandes zwischen den Elektroden und damit einer Verminderung der Zellenspannung.The half-shells of the electrolysis cells can be provided with stiffeners and at least one of the half-shells of an electrolysis cell can have electrically conductive force transmission elements on the outside and in an extension of the force transmission elements and spacers. In order to avoid leakage currents, at least one tube of electrically non-conductive material running in the vertical direction and passing through the half-shells near the edge can be arranged in the interior of the half-shells to supply the electrolysis starting materials and / or to remove the electrolysis products. The cathodes can consist of iron, cobalt, nickel or chromium or one of their alloys and the anodes can consist of titanium, niobium or tantalum or an alloy of these metals or of a metal or oxide ceramic material. In addition, the anodes are provided with an electrically conductive, catalytically active coating which contains metals or compounds from the group of platinum metals. Due to the shape of the electrodes, which are made of perforated material such as perforated sheets, expanded metal, wickerwork or constructions made of thin round rods, and their arrangement in the electrolysis cell can be used in the Electrolysis gases easily enter the space behind the electrodes. This gas discharge from the electrode gap leads to a reduction in the gas bubble resistance between the electrodes and thus a reduction in the cell voltage.

Die kathodenseitigen Halbschalen können aus Eisen oder Eisenlegierungen bestehen. Falls Kathoden und kathodenseitige Halbschale miteinander verschweißt werden sollen, bestehen sie möglichst aus dem gleichen Material, vorzugsweise aus Stahl. Die anodenseitige Halbschale muß aus einem gegen Chlor beständigen Material wie Titan, Niob oder Tantal .oder einer Legierung dieser Metalle oder aus einem metall-oder oxidkeramischen Material bestehen. Falls Halbschale und Anode durch Schweißen miteinander verbunden werden sollen, wählt man für beide Teile den gleichen Werkstoff, vorzugsweise Titan. Halbschale und Elektroden können aber auch miteinander durch Verschrauben fest miteinander verbunden werden. In diesem Fall können Halbschalen und Elektroden aus unterschiedlichen Werkstoffen bestehen.The half-shells on the cathode side can be made of iron or iron alloys. If the cathode and the cathode-side half-shell are to be welded to one another, they preferably consist of the same material, preferably steel. The anode-side half-shell must consist of a chlorine-resistant material such as titanium, niobium or tantalum, or an alloy of these metals, or of a metal or oxide ceramic material. If the half-shell and anode are to be connected to one another by welding, the same material, preferably titanium, is selected for both parts. Half-shell and electrodes can also be firmly connected to each other by screwing. In this case, half-shells and electrodes can be made of different materials.

Als Trennwand kommen die in der Alkalichlorid-Elektrolyse üblichen Diaphragmen oder Ionenaustauschermembranen in Betracht. Die Ionenaustauschermembranen bestehen im wesentlichen aus einem Copolymerisat aus Tetrafluoräthylen und Perfluorvinylverbindungen wie CF2=CF2-O-CF2-CF(CF3)-O-CF2-CF2-SO3H oder CF2=CF2-O-CF2-CF(CF3)-O-CF2-CF2-COOH. Ebenso sind Membranen mit endständigen Sulfonamidgruppen (-S03NHR) als Ionenaustauschergruppen in Gebrauch. Die Äquivalentgewichte solcher Ionenaustauscher liegen zwischen 800 und 1600, vorzugsweise zwischen 1100 und 1500. Zur Erhöhung der mechanischen Festigkeit ist die Ionenaustauschmembran meistens mit einem Stützgewebe aus Polytetrafluoräthylen verstärkt.The diaphragms or ion exchange membranes customary in alkali metal chloride electrolysis come into consideration as the partition. The ion exchange membranes essentially consist of a copolymer of tetrafluoroethylene and perfluorovinyl compounds such as CF 2 = CF 2 -O-CF 2 -CF (CF 3 ) -O-CF 2 -CF 2 -SO 3 H or CF 2 = CF 2 -O- CF 2 -CF (CF 3 ) -O-CF 2 -CF 2 -COOH. Membranes with terminal sulfonamide groups (-S0 3 NHR) are also used as ion exchange groups. The equivalent weights of such ion exchangers are between 800 and 1600, preferably between 1100 and 1500. To increase the mechanical strength, the ion exchange membrane is usually reinforced with a support fabric made of polytetrafluoroethylene.

Diese Ionenaustauschermembranen verhindern wie die Asbestdiaphragmen die Vermischung von Wasserstoff und Chlor, erlauben aber wegen ihrer selektiven Permeabilität den Durchgang von Alkalimetallionen in den Kathodenraum. Sie verhindern also weitgehend den Übergang von Halogenid in den Kathodenraum und den Durchtritt von Hydroxylionen in den Anodenraum. Dadurch erhält man eine praktisch salzfreie Lauge, wogegen aus dem Katholyten der Diaphragmazellen das Salz erst in einem aufwendigen Verfahren entfernt werden muß. Dazu kommt, daß im Gegensatz zu Asbestdiaphragmen die Ionenaustauschermembranen dimensionsstabile Trennwände darstellen, die auch beständiger sind gegen die aggresiven Medien der Alkalihalogenid-Elektrolyse und daher eine höhere Lebensdauer besitzen als Asbestdiaphragmen.Like the asbestos, these ion exchange membranes prevent diaphragms mix hydrogen and chlorine, but because of their selective permeability they allow the passage of alkali metal ions into the cathode compartment. They largely prevent the transition of halide into the cathode compartment and the passage of hydroxyl ions into the anode compartment. This results in a practically salt-free lye, whereas the salt must first be removed from the catholyte of the diaphragm cells in a complex process. In addition, in contrast to asbestos diaphragms, the ion exchange membranes represent dimensionally stable partition walls which are also more resistant to the aggressive media of alkali halide electrolysis and therefore have a longer service life than asbestos diaphragms.

Der Elektrolyseapparat kann aus einer Elektrolysezelle, aber auch aus einer Vielzahl hintereinandergeschalteter Zellen, wobei der elektrische Kontakt-benachbarter Zellen jeweils direkt über die einander berührenden Halbschalen benachbarter Elektrolysezellen oder über die elektrisch leitenden Kraftübertragungselemente erfolgt, bestehen.The electrolysis apparatus can consist of an electrolysis cell, but also of a large number of cells connected in series, the electrical contact between adjacent cells taking place directly via the contacting half-shells of adjacent electrolysis cells or via the electrically conductive force transmission elements.

Der erfindungsgemäße Elektrolyseapparat wird anhand der Figuren in beispielsweiser Ausführung erläutert.

  • Figur 1 zeigt einen Schnitt durch eine Elektrolysezelle und Figur 2 einen Schnitt durch zwei benachbarte Elektrolysezellen.
  • Figur 3 zeigt eine Halbschale in Ansicht,
  • Figur 4 zeigt den Schnitt IV - IV in der Figur 3;
  • Figuren 5 und 6 zeigen Möglichkeiten zur Zu- und Abfuhr von Gasen und Flüssigkeiten aus der Elektrolysezelle und
  • Figuren 7 und 8 zeigen zwei Möglichkeiten zur elektrischen Schaltung der erfindungsgemäßen Elektrolysezellen.
The electrolysis apparatus according to the invention is explained with reference to the figures in an exemplary embodiment.
  • Figure 1 shows a section through an electrolytic cell and Figure 2 shows a section through two adjacent electrolytic cells.
  • FIG. 3 shows a half-shell in view,
  • Figure 4 shows the section IV - IV in Figure 3;
  • Figures 5 and 6 show possibilities for supplying and removing gases and liquids from the electrolytic cell and
  • FIGS. 7 and 8 show two possibilities for the electrical switching of the electrolysis cells according to the invention.

Das Gehäuse einer Elektrolysezelle besteht aus einer anodenseitigen und einer kathodenseitigen Halbschale. Die anodenseitige Halbschale 1 wird aus Blech geformt und besitzt einen losen Flansch 2 während die Halbschale der Kathodenseite aus einer Wand 9 besteht, die mit einem festen Flansch 10 verbunden ist. Selbstverständlich kann auch bei der anodenseitigen Halbschale ein fester Flansch oder bei der kathodenseitigen Halbschale ein loser Flansch eingesetzt werden'. Zwischen den Dichtelementen 12 ist die Trennwand 7 eingespannt. Der Elektroden 4 und 8 sind über die Distanzstücke (z.B. Bolzen) 5 mit den Halbschalen 1 und 9 fest verbunden. Die Zufuhr des Elektrolysestroms zu Anode und Kathode erfolgt entweder direkt durch Kontakt mit der Halbschalenwand der benachbarten Elektrolysezelle oder durch ein Kraftübertragungselement (z.B. Bolzen) 3, das z.B. durch Schrauben 11 mit der Halbschale 1 fest verbunden ist. Die Scheiben 6 dienen zur Kraftübertragung für die Stromzuführung. Durch die Wahl der Scheibendicke kann der Elektrodenabstand als auch der Abstand der Elektroden zur Trennwand eingestellt werden. Zur Versteifung der Halbschalen sind diese mit Sicken 13 a) versehen.The housing of an electrolytic cell consists of an anode-side and a cathode-side half-shell. The anode-side half-shell 1 is formed from sheet metal and has a loose flange 2 while the half-shell of the cathode side consists of a wall 9 which is connected to a fixed flange 10. Of course, an integral flange or at the cathode-side half-shell a loose flange can also be used for the anode-side half-shell '. The partition 7 is clamped between the sealing elements 12. The electrodes 4 and 8 are firmly connected to the half-shells 1 and 9 via the spacers (for example bolts) 5. The electrolysis current is supplied to the anode and cathode either directly by contact with the half-shell wall of the adjacent electrolytic cell or by a force transmission element (for example bolts) 3 which is firmly connected to the half-shell 1 for example by screws 11. The disks 6 are used for power transmission for the power supply. The electrode spacing and the distance between the electrodes and the partition can be adjusted by the choice of the pane thickness. To stiffen the half-shells, they are provided with beads 13 a).

Zwei Ausführungen dieser Versteifungen 13 a und 13 b sind in Figuren 2, 3, 4 und 6 dargestellt. Die gleichen oder andere Versteifungen werden auch bei der kathodenseitigen Halbschale eingesetzt.Two versions of these stiffeners 13 a and 13 b are shown in Figures 2, 3, 4 and 6. The same or different stiffeners are also used in the cathode-side half-shell.

In Figur 4 ist ferner ein Ableitungsrohr 14 für die Elektrolytlösungen in Verbindung mit einer Sicke 13 b dargestellt. Die Halterung des Rohres erfolgt.mit Bügel 18.FIG. 4 also shows a discharge pipe 14 for the electrolyte solutions in connection with a bead 13 b. The pipe is held with a bracket 18.

Figur 5 zeigt die Zuführung des Elektrolyten zur Zelle über den Rohrstutzen 15, der mit der Halbschale fest verbunden ist. Die Anordnung ist auch für die Festflanschhalbschale 9 gültig.Figure 5 shows the supply of the electrolyte to the cell via the pipe socket 15, which is firmly connected to the half-shell. The arrangement is also valid for the fixed flange half shell 9.

In Figur 6 wird die Ableitung des Elektrolyten dargestellt. Das lange, aus isolierendem Material hergestellte Rohr 14 leitet die Elektrolytlösung und die Elektrolysegase aus der Zelle ab und reduziert durch die Länge des innerhalb der Zelle gelegenen Rohrteiles Kriechströme. Es wird durch den Rohrstutzen 16 in die Zelle geschoben. Das Übergangsstück 17 ermöglicht den Übergang auf eine anschließende Schlauchleitung (nicht dargestellt). Der in Figur 6 dargestellte Rohranschluß kann selbstverständlich auch in dieser Form für die Zuleitung der Elektrolyten angewendet werden.The derivation of the electrolyte is shown in FIG. The long tube 14 made of insulating material leads the electrolyte solution and the electrolysis gases out of the cell and reduces leakage currents due to the length of the tube part located inside the cell. It is through pushed the pipe socket 16 into the cell. The transition piece 17 enables the transition to a subsequent hose line (not shown). The pipe connection shown in FIG. 6 can of course also be used in this form for the supply of the electrolytes.

Wie Figur 2 zeigt,können bei Elektrolyseapparaten mit mehreren Elektrolysezellen Anode und Kathode benachbarter Zellen über Kraftübertragungselemente3 aus elektrisch leitfähigem Material elektrisch leitend miteinander verbunden sein. Damit stellt die Anordnung einen bipolaren Elektrolyseapparat dar. Die Reihenschaltung solcher Zellen ergibt hohe Spannungen und'relativ geringe Ströme. Dafür hat die Serienschaltung den Vorteil der besseren Ausnutzung der Kapazität der Gleichrichterelemente, des geringeren Kupferverbrauchs und geringerer Spannungsverluste in den Stromschienen.- In manchen Fällen, insbesondere bei Verwendung von vorgegebenen Gleichrichtern mit relativ niedriger Spannung und hoher Stromstärke, kann es vorteilhaft sein, die bipolaren Elemente in monopolarer Anordnung, das heißt in Parallelschaltung, zu betreiben. Dies ist mit den erfin-- dungsgemäßen Zellen möglich, vorteilhaft ist jedoch Reihen- 'und Parallelschaltung nebeneinander zu verwenden. Durch geeignete Wahl der Größe seriengeschalteter Gruppen von Zellen, die ihrerseits parallel geschaltet werden, kann jede beliebige Strom/Spannung-Kombination erreicht werden.As shown in FIG. 2, in the case of electrolysis apparatuses having a plurality of electrolysis cells, the anode and cathode of adjacent cells can be connected to one another in an electrically conductive manner via force transmission elements 3 made of electrically conductive material. The arrangement thus represents a bipolar electrolysis apparatus. The series connection of such cells results in high voltages and relatively low currents. For this, the series connection has the advantage of better utilization of the capacity of the rectifier elements, lower copper consumption and lower voltage losses in the busbars. In some cases, in particular when using specified rectifiers with a relatively low voltage and high current intensity, it can be advantageous to use the bipolar ones To operate elements in a monopolar arrangement, that is to say in parallel connection. This is possible with the cells according to the invention, but it is advantageous to use series and parallel connection next to one another. By suitable choice of the size of series-connected groups of cells, which in turn are connected in parallel, any current / voltage combination can be achieved.

Um dieses zu verdeutlichen, sollen wie in Fig. 7 dargestellt 32 Elemente20 eines Elektrolyseurs in Reihe geschaltet werden. Am Gleichrichter19 liegt bei einem Spannungsabfall von 4 V je Element eine Spannung von 128 V an, wenn ein Strom von 8 kA fließt.To illustrate this, 32 elements 20 of an electrolyser are to be connected in series, as shown in FIG. 7. With a voltage drop of 4 V per element, a voltage of 128 V is present at the rectifier 19 when a current of 8 kA flows.

Schaltet man dagegen nach Fig.8 die Elemente 20 des Elektrolyseurs parallel, so liegen am Gleichrichter 19 4V an, wenn bei gleicher Stromdichte wie im Fall nach Fig. 7 ein Gesamtstrom von 256 kA fließt. Dem Fachmann ist damit ohne weiteres verständlich, wie durch Variation der Anzahl der Elemente pro Elektrolyseur und der Anzahl der zusammengeschalteten Elektrolyseure jedes gewünschte Strom-/Spannungsverhältnis erreicht werden kann.If, however, the elements 20 of the electrolyser are connected in parallel according to FIG. 8, 4V are present at the rectifier 19, if a total with the same current density as in the case of FIG current of 256 kA flows. The person skilled in the art can thus easily understand how any desired current / voltage ratio can be achieved by varying the number of elements per electrolyzer and the number of interconnected electrolyzers.

Claims (9)

1. Elektrolyseapparat zur Herstellung von Chlor aus wässrigen Alkalihalogenidlösungen, der mindestens eine Elektrolysezelle aufweist, deren Anode und Kathode durch eine Trennwand voneinander getrennt in einem Gehäuse aus zwei Halbschalen angeordnet sind, wobei das Gehäuse mit Einrichtungen zum Zuführen der Elektrolyseausgangsstoffe und zum Abführen der Elektrolyseprodukte versehen ist, und die Trennwand mittels Dichtelementen zwischen den Rändern der Halbschalen eingeklemmt und zwischen sich jeweils bis zu den Elektroden erstreckenden Kraftübertragungselementen aus elektrisch nicht leitendem Material gehalten ist, dadurch gekennzeichnet, daß die Elektroden--(4, 8) über Distanzstücke (5), die an der Innenseite der Halbschalen (1, 9) befestigt sind, und über ihre Ränder mit den Halbschalen mechanisch und elektrisch leitend verbunden sind.1. Electrolysis apparatus for the production of chlorine from aqueous alkali halide solutions, which has at least one electrolysis cell, the anode and cathode of which are separated from one another by a partition in a housing made of two half-shells, the housing being provided with devices for supplying the electrolysis starting materials and for removing the electrolysis products is, and the partition is clamped between the edges of the half-shells by means of sealing elements and is held between power transmission elements made of electrically non-conductive material and extending up to the electrodes, characterized in that the electrodes (4, 8) are spaced (5), which are attached to the inside of the half-shells (1, 9) and are mechanically and electrically conductively connected to the half-shells via their edges. 2. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnet, daß die Halbschalen (1, 9) der Elektrolysezellen mit Versteifungen (13a, 13b) versehen sind.2. Electrolysis apparatus according to claim 1, characterized in that the half-shells (1, 9) of the electrolysis cells are provided with stiffeners (13a, 13b). 3. Elektrolyseapparat nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß zum Zuführen der Elektrolyseausgangsstoffe und/oder zum Abführen der Elektrolyseprodukte im Innern der Halbschalen (1, 9)'mindestens ein in vertikaler Richtung verlaufendes und in der Nähe des Randes durch die Halbschale hindurchtretendes Rohr (14) aus elektrisch nicht leitendem Material angeordnet ist.3. Electrolysis apparatus according to claims 1 and 2, characterized in that for supplying the electrolysis starting materials and / or for removing the electrolysis products inside the half-shells (1, 9) 'at least one running in the vertical direction and near the edge through the half-shell tube (14) passing through and made of electrically non-conductive material. 4. Elektrolyseapparat nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß mindestens eine der Halbschalen (1, 9) einer Elektrolysezelle auf ihrer Außenseite und in Verlängerung der Kraftübertragungselemente (6) und Distanzstücke (5) elektrisch leitende Kraftübertragungselemente (3) aufweist.4. Electrolysis apparatus according to claims 1 and 2, characterized in that at least one of the half-shells (1, 9) of an electrolysis cell on its outside and in extension of the force transmission elements (6) and spacers (5) has electrically conductive force transmission elements (3). 5. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnet, daß die Kathoden aus Eisen, Kobalt, Nickel oder Chrom oder einer ihrer Legierungen bestehen.5. Electrolysis apparatus according to claim 1, characterized in that the cathodes consist of iron, cobalt, nickel or chromium or one of their alloys. 6. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnet, daß die Anoden aus Titan, Niob, Tantal oder einer Legierung dieser Metalle oder aus einem metall- oder oxidkeramischen Material bestehen und mit einem elektrisch leitfähigen, elektrokatalytisch wirksamen Überzug versehen sind, der Metall oder Verbindungen der Metalle der Platingruppe enthält.6. Electrolysis apparatus according to claim 1, characterized in that the anodes consist of titanium, niobium, tantalum or an alloy of these metals or of a metal or oxide ceramic material and are provided with an electrically conductive, electrocatalytically active coating, the metal or compounds of Contains platinum group metals. 7. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnet, daß die Halbschalen der Anodenseiten aus einem gegen Chlor beständigen Metall bestehen wie Titan, Niob, Tantal oder einer Legierung dieser Metalle.7. Electrolysis apparatus according to claim 1, characterized in that the half-shells of the anode sides consist of a chlorine-resistant metal such as titanium, niobium, tantalum or an alloy of these metals. 8. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnet, daß die Halbschalen der Kathodenseiten aus Eisen, Kobalt, Nickel, Chrom oder einer ihrer Legierungen bestehen.8. Electrolysis apparatus according to claim 1, characterized in that the half-shells of the cathode sides consist of iron, cobalt, nickel, chromium or one of their alloys. 9. Elektrolyseapparat nach Anspruch 1, dadurch gekennzeichnat, daß als Trennwände Ionenaustauschermembranen verwendet werden.9. Electrolysis apparatus according to claim 1, characterized gekennzeichnat that ion exchange membranes are used as partitions.
EP80101139A 1979-03-12 1980-03-06 Electrolytic apparatus for the production of chlorine from aqueous alkali halogenide solutions Expired EP0022445B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80101139T ATE4820T1 (en) 1979-03-12 1980-03-06 ELECTROLYZER FOR THE PRODUCTION OF CHLORINE FROM AQUEOUS ALKALI HALOGENIDE SOLUTIONS.

Applications Claiming Priority (2)

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DE19792909640 DE2909640A1 (en) 1979-03-12 1979-03-12 ELECTROLYSIS
DE2909640 1979-03-12

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EP0022445B1 EP0022445B1 (en) 1983-09-28

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US (1) US4420387A (en)
EP (1) EP0022445B1 (en)
JP (1) JPS55125285A (en)
AR (1) AR220821A1 (en)
AT (1) ATE4820T1 (en)
AU (1) AU532940B2 (en)
BR (1) BR8001430A (en)
CA (1) CA1146910A (en)
DE (2) DE2909640A1 (en)
ES (1) ES489266A1 (en)
FI (1) FI67575C (en)
IN (1) IN152756B (en)
MX (1) MX147698A (en)
NO (1) NO153613C (en)
ZA (1) ZA801406B (en)

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EP0168600A3 (en) * 1984-06-01 1986-03-19 Hoechst Aktiengesellschaft Bipolar apparatus for electrolysis using a gas diffusion cathode
EP0565836A1 (en) * 1992-04-16 1993-10-20 Heraeus Elektrochemie Gmbh Electrochemical membrane cell

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JPS57174479A (en) * 1981-04-20 1982-10-27 Tokuyama Soda Co Ltd Unit electrolytic cell
DE3439265A1 (en) * 1984-10-26 1986-05-07 Hoechst Ag, 6230 Frankfurt ELECTROLYSIS APPARATUS WITH HORIZONTALLY ARRANGED ELECTRODES
JP3213213B2 (en) * 1995-09-06 2001-10-02 ホシザキ電機株式会社 Electrolytic cell
US5766431A (en) * 1996-07-24 1998-06-16 Hosizaki Denki Kabushiki Kaisha Electrolyzer
US20040035696A1 (en) * 2002-08-21 2004-02-26 Reinhard Fred P. Apparatus and method for membrane electrolysis for process chemical recycling
DE102005003527A1 (en) * 2005-01-25 2006-07-27 Uhdenora S.P.A. An electrolytic cell for the production of chlorine has an anode and a cathode separated from each other by electrically conductive spacers on either side of the ion exchange membrane
FR2919617B1 (en) * 2007-08-02 2009-11-20 Commissariat Energie Atomique HIGH TEMPERATURE AND HIGH PRESSURE ELECTROLYSIS WITH ALLOTHERMIC OPERATION

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GB1523045A (en) * 1975-06-04 1978-08-31 Asahi Chemical Ind Multi-electrode electrolytic cell
AT346863B (en) * 1975-08-29 1978-11-27 Hoechst Ag ELECTROLYSIS DEVICE FOR THE PRODUCTION OF CHLORINE FROM AQUATIC ALKALICHLORIDE SOLUTION

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EP0168600A3 (en) * 1984-06-01 1986-03-19 Hoechst Aktiengesellschaft Bipolar apparatus for electrolysis using a gas diffusion cathode
EP0565836A1 (en) * 1992-04-16 1993-10-20 Heraeus Elektrochemie Gmbh Electrochemical membrane cell

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IN152756B (en) 1984-03-31
ATE4820T1 (en) 1983-10-15
JPS55125285A (en) 1980-09-26
FI800730A (en) 1980-09-13
NO153613B (en) 1986-01-13
US4420387A (en) 1983-12-13
JPS6246638B2 (en) 1987-10-02
MX147698A (en) 1983-01-05
AR220821A1 (en) 1980-11-28
EP0022445B1 (en) 1983-09-28
ES489266A1 (en) 1980-08-16
AU532940B2 (en) 1983-10-20
AU5631880A (en) 1980-09-18
CA1146910A (en) 1983-05-24
DE2909640A1 (en) 1980-09-25
FI67575C (en) 1985-04-10
ZA801406B (en) 1981-04-29
NO153613C (en) 1986-04-23
NO800690L (en) 1980-09-15
FI67575B (en) 1984-12-31
DE3065000D1 (en) 1983-11-03
BR8001430A (en) 1980-11-11

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