EP0306627A1 - Electrochemical membrane cell with a plain electrode structure disposed at both sides of the membrane - Google Patents

Electrochemical membrane cell with a plain electrode structure disposed at both sides of the membrane Download PDF

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Publication number
EP0306627A1
EP0306627A1 EP88109169A EP88109169A EP0306627A1 EP 0306627 A1 EP0306627 A1 EP 0306627A1 EP 88109169 A EP88109169 A EP 88109169A EP 88109169 A EP88109169 A EP 88109169A EP 0306627 A1 EP0306627 A1 EP 0306627A1
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EP
European Patent Office
Prior art keywords
electrode structure
electrode
carrier
structure according
membrane
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Granted
Application number
EP88109169A
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German (de)
French (fr)
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EP0306627B1 (en
Inventor
Peter Fabian
Helmut Krebs
Heinrich Simon
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De Nora Deutschland GmbH
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Heraeus Elektroden GmbH
Heraeus Elektrochemie GmbH
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections

Definitions

  • the invention relates to an electrode structure for an electrochemical membrane cell with a flat electrode structure arranged on both sides of a membrane, at least the anodic electrode structure being connected via metallic spacers to a support made of sheet metal serving as a current distributor.
  • An electrolytic cell that works according to the membrane method is known from EP-OS 55 930. It is also referred to below as a membrane cell.
  • the actual electrode structure is explained in more detail, for example, in DE-OS 36 25 506, in which a film-like membrane with electrodes on both sides is described.
  • DE-PS 35 19 272 an electrode structure suitable for membrane cells is known, which has a metal plate support serving as a current distributor, on which a plurality of plate-shaped electrode parts form a lamella structure with a flat surface, which is pressed directly onto the membrane.
  • the fixed mechanical connection between the carrier serving as a current distributor and produced by metallic spacers or elevations of the carrier has proven to be problematic made of sheet metal and the plate-shaped active electrode parts, which must be separated from each other in the event of reactivation or repair of the electrodes. This is usually done by mechanical separation processes such as milling, drilling or grinding. After reactivation, the electrode surface is firmly and mechanically connected to the current distributor by means of spacers by welding.
  • the invention has for its object to provide an electrode structure which can be used in membrane cells and which has easily removable active electrode surfaces which can be removed from their supports without any particular mechanical outlay, but nevertheless enable good current transmission in the operating state.
  • At least one bracket serving as a spacer with a U-shaped cross-section with converging legs is arranged on the support serving as a current distributor and is bent apart again in the region of its free ends, the ends of these legs facing away from the support to open; the clip is connected to the carrier in an electrically conductive and mechanically fixed manner.
  • a comb-like elevation of the electrode plate which is perpendicular, engages in this clamp whose plate level is arranged. The comb-like elevation is formed by a bent edge of the electrode plate.
  • the clips have contact surfaces at their ends, which run parallel to the flat electrode surfaces.
  • the electrode surface is fixed and contacted by the clamp holder.
  • the pressure on the cell membrane presses the electrode surface against the contact surfaces of the clamp.
  • the carrier consists of sheet metal with a thickness in the range of 0.4 to 3 mm.
  • the clamp holder consists of a clamp spring 3 with a U-shaped cross section and firmly connected to the carrier 1 by welding points 2 converging legs 4, 5 which are bent apart again in the region of their free ends and end in contact surfaces 14; the contact surfaces 14 run parallel to the plane of the carrier 1.
  • two rows are provided with three such clamp springs each, the central strip 6 arranged between the legs 4 and 5 via strips 7 arranged vertically and fastening webs 8 arranged parallel to the plane of the carrier 1 connected is.
  • the fastening webs 8 are connected to the carrier 1 by welding points 2.
  • Center strip 6, strip 7 and fastening webs 8 form a meandering continuous strip with extensions in the area of the legs 4, 5, which is punched out of elastic metal and bent accordingly.
  • a part of the electrode plate 10 is shown above the carrier 1, which in the present case consists of three partial plates 11, of which the two outer partial plates as well as the underlying carrier 1 are not shown completely or with a gap for a better overview.
  • the partial plates 11 each have at their edges angled edges 12 which are arranged such that the surface of the electrode plate 10 forms a continuous plane.
  • the edges 12 form the rigid part 13 of the releasable clamping bracket in the form of a comb-like elevation.
  • FIG. 1b shows a detail of how the edges of the partial plates 11 combined into a part 13 are inserted into the open end of the clamp spring 3 and are held in place by a non-positive connection between the clamp spring 3 and the rigid part 13.
  • the rigid part 13 of the electrode plate is inserted into the clamp spring 3 until the surfaces 14 of the legs 4, 5 and the underside of the electrode plate are brought up to the stop 1 against the stop.
  • the electrode plate can consist, for example, of a sheet metal slit like a blind. However, it is also possible to use other types of electrodes, such as. B. wire, nets, expanded metal, lamellar arranged flat profiles to provide.
  • the carrier 1 forms a type of electrode trough which, together with the correspondingly designed carrier of the counter electrode, forms a closed space which is divided by the membrane into two electrolyte subspaces, ie into an anolyte space and a catholyte space. Are the two carriers of a cell are electrically separated from each other by the membrane or additional seals.
  • the electrolyte spaces are provided with their own liquid supply and discharge openings, the anolyte space being connected to the brine circuit, while water is supplied to the catholyte space. Means are also provided for removing the chlorine or hydrogen gas generated from the anolyte or catholyte space.
  • Steel or spring-hard nickel alloys are used as materials on the cathode side, while titanium with good spring properties or titanium alloys are used on the anode side.
  • the edges 12 of the partial plates 11 serving as a rigid part 13 of the spring system can have incisions or gaps in order to achieve the best possible contact in the area of the clamp spring despite the tolerances.
  • the number of clip springs essentially depends on the size of the electrode plates. With small electrode plates, it is possible to make do with a single spring clip.
  • FIG 2a another version of the clamp bracket is shown, in which the part connected to the carrier 3 'has a resilient area in the form of a sleeve which is provided with longitudinal slots 15 extending to its opening and is located on the side facing away from the carrier .
  • the sleeve has, on the jacket segments 16 forming its inside, a truncated cone-like taper starting from the opening 17, an annular groove 18 interrupted by the longitudinal slots 15 being provided in the region of the opening 17.
  • the sleeve is connected in an electrically conductive and mechanically fixed manner to the carrier 1, which is only shown in part.
  • a bolt-like region of the rigid part 13' is insertable, which is provided with a frustoconical end 20.
  • the rigid part 13 ' is at its widened end with an electrode plate 10 shown only partially electrically and mechanically firmly connected.
  • a circumferential ring flange 21 which is locked in the circumferential ring groove 18 when the end 20 is inserted into the sleeve.
  • the clamp holder shown in Figure 2a can For example, be designed as a single clamp bracket for small electrode areas. However, it is also possible to use them in a large number in accordance with the example explained with reference to FIGS. 1a and 1b.
  • the part 3 ⁇ connected to the carrier has as a resilient region a sleeve which is provided on its outside with a truncated cone-shaped tapering made of shell segments 16 ⁇ in the direction of its opening 17.
  • the outer edge of the opening 17 is designed as an annular flange 22 interrupted by longitudinal slots 15.
  • the resilient part 3 ⁇ is connected at its end 26 opposite the opening 17 to the support 1, which is only shown in part, in an electrically conductive and mechanically fixed manner.
  • the area of the clamping bracket designed as a rigid part 13 ⁇ is provided with a bolt-like area which can be pushed onto the jacket segments 16 ⁇ .
  • the bolt-like area has on its inside 23 a truncated cone-like taper starting from the open end 24.
  • a circumferential annular groove 25 In the transition area between the tapering of the inside 23 and a hollow cylinder in the rigid part 13 ⁇ there is a circumferential annular groove 25, in which the annular flange 22 can be locked when it is put on.
  • both the sleeve of the rigid part 13 ⁇ and the electrode plate 10 are only shown in fragments in FIG. 2b.
  • connection proves to be extremely stable after the ring flange 22 has been locked in the ring groove 25, the interaction of the two frustoconical surfaces likewise increasing the pressure.
  • the electrode structure i.e. H.
  • the electrode shape of FIGS. 2a, 2b can be designed in accordance with the explanations for FIGS. 1a, 1b; the same applies to the materials used.
  • the locking device must be released by auxiliary tools such as screwdrivers before reactivating the active electrode parts. According to the invention, the follow-up costs in the long-term operation of membrane cells can be considerably reduced, since the detachment and reinstallation of the active electrode surfaces can be carried out quickly, gently and inexpensively without problems.

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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)
  • Hybrid Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

Eine Elektrodenstruktur für Membran-Elektrolysezellen besteht aus einem ebenen Elektrodenteil(11), das über metallische Abstandshalter (3) mit einem als Stromverteiler dienenden Träger (1) aus Metallblech verbunden ist. Die Abstandshalter (3) sind in Form einer Klemmhalterung ausgebildet, die aus einem federnden Teil (4), (5) und einem starren Teil (12) bestehen, wobei jeweils der federnde Teil mit dem Träger unverrückbar verbunden ist, während der starre Teil (12) am Elektrodenteil befestigt ist. Aufgrund der Klemmhalterung sind im Falle einer erfoderlichen Reaktivierung oder einer Reparatur die aktiven Elektrodenteile auf einfache Weise von ihren jeweiligen Trägern zu trennen und können nach der Demontage direkt in die Reaktivierung bzw. Reparatur gegeben werden.An electrode structure for membrane electrolysis cells consists of a flat electrode part (11) which is connected via metallic spacers (3) to a support (1) made of sheet metal serving as a current distributor. The spacers (3) are designed in the form of a clamping bracket, which consist of a resilient part (4), (5) and a rigid part (12), the resilient part in each case being immovably connected to the carrier, while the rigid part ( 12) is attached to the electrode part. Due to the clamp holder, the active electrode parts can be easily separated from their respective supports in the event of a required reactivation or repair and can be put directly into the reactivation or repair after dismantling.

Description

Die Erfindung betrifft eine Elektrodenstruktur für eine elektrochemische Membranzelle mit beiderseits einer Membran angeordneten ebenen Elektroden­struktur, wobei wenigstens die anodische Elektrodenstruktur über metallische Abstandshalter mit einem als Stromverteiler dienenden Träger aus Metallblech verbunden ist.The invention relates to an electrode structure for an electrochemical membrane cell with a flat electrode structure arranged on both sides of a membrane, at least the anodic electrode structure being connected via metallic spacers to a support made of sheet metal serving as a current distributor.

Eine elektrolytische Zelle, die nach dem Membranverfahren arbeitet, ist aus der EP-OS 55 930 bekannt. Sie wird im folgenden auch als Membranzelle bezeich­net. Der eigentliche Elektrodenaufbau ist beispielsweise anhand der DE-OS 36 25 506 näher erläutert, in der eine folienartige Membran mit beid­seitig anliegenden Elektroden beschrieben ist. Weiterhin ist aus der DE-PS 35 19 272 eine für Membranzellen geeignete Elektrodenstruktur bekannt, die einen als Stromverteiler dienenden Träger aus Metallblech aufweist, auf der eine Vielzahl plattenförmiger Elektrodenteile eine Lamellenstruktur mit ebener Oberfläche bilden, die direkt an die Membran gepreßt wird.An electrolytic cell that works according to the membrane method is known from EP-OS 55 930. It is also referred to below as a membrane cell. The actual electrode structure is explained in more detail, for example, in DE-OS 36 25 506, in which a film-like membrane with electrodes on both sides is described. Furthermore, from DE-PS 35 19 272 an electrode structure suitable for membrane cells is known, which has a metal plate support serving as a current distributor, on which a plurality of plate-shaped electrode parts form a lamella structure with a flat surface, which is pressed directly onto the membrane.

Als problematisch erweist sich bei den bekannten Elektrodenstrukturen die durch metallische Abstandshalter bzw. Erhebungen des Trägers hergestellte feste mechanische Verbindung zwischen dem als Stromverteiler dienenden Träger aus Metallblech und den plattenförmigen aktiven Elektrodenteilen, welche im Falle der Reaktivierung oder Reparatur der Elektroden voneinander getrennt werden müssen. Dies erfolgt in der Regel durch mechanische Trennverfahren, wie Fräsen, Bohren oder Schleifen. Nach der Reaktivierung wird die Elektroden­fläche wieder mit dem Stromverteiler über Abstandshalter durch Verschweißen elektrisch und mechanisch fest verbunden.In the known electrode structures, the fixed mechanical connection between the carrier serving as a current distributor and produced by metallic spacers or elevations of the carrier has proven to be problematic made of sheet metal and the plate-shaped active electrode parts, which must be separated from each other in the event of reactivation or repair of the electrodes. This is usually done by mechanical separation processes such as milling, drilling or grinding. After reactivation, the electrode surface is firmly and mechanically connected to the current distributor by means of spacers by welding.

Aufgrund der mit der Reaktivierung oder Reparatur verbundenen aufwendigen mechanischen Arbeiten entstehen verhältnismäßig lange Ausfallzeiten der Elek­trolyse-Anlage sowie verhältnismäßig hohe Transportkosten, da die gesamten Elektrodenstrukturen vom Kunden zum Hersteller zurückgeliefert werden müssen.Due to the complex mechanical work associated with the reactivation or repair, there are comparatively long downtimes of the electrolysis plant and relatively high transport costs, since the entire electrode structures have to be returned from the customer to the manufacturer.

Aus der US-PS 4 149 956 ist eine Anodenstruktur für Elektrolysezellen mit horizontal angeordneten Elektroden bekannt, bei der die aus Ventilmetall bestehenden aktiven Anodenteile mittels ihrer Stromverteiler an Stromzuleitern über eine lösbare Verbindung durch Verschraubung angeschlossen sind.From US Pat. No. 4,149,956 an anode structure for electrolytic cells with horizontally arranged electrodes is known, in which the active anode parts consisting of valve metal are connected by means of their current distributors to current leads via a detachable connection by screwing.

Derartige Verbindungen lassen sich nicht auf Membranzellen übertragen.Such connections cannot be transferred to membrane cells.

Die Erfindung stellt sich die Aufgabe, eine bei Membranzellen einsetzbare Elektrodenstruktur zu schaffen, die leicht abnehmbare aktive Elektrodenflächen aufweist, die ohne besonderen mechanischen Aufwand von ihren Trägern demontierbar sind, aber dennoch im Betriebszustand eine gute Stromübertragung ermöglichen.The invention has for its object to provide an electrode structure which can be used in membrane cells and which has easily removable active electrode surfaces which can be removed from their supports without any particular mechanical outlay, but nevertheless enable good current transmission in the operating state.

Die Aufgabe wird erfindungsgemäß durch die kennzeichnenden Merkmale des An­spruchs 1 gelöst.The object is achieved by the characterizing features of claim 1.

Weitere vorteilhafte Ausgestaltungen des Gegenstandes der Erfindung sind den Unteransprüchen zu entnehmen.Further advantageous refinements of the subject matter of the invention can be found in the subclaims.

In einer bevorzugten Ausführungsform ist auf dem als Stromverteiler dienenden Träger wenigstens eine als Abstandshalter dienende Klammer mit einem U-för­migen Querschnitt mit zusammenlaufenden Schenkeln angeordnet, die im Bereich ihrer freien Enden wieder auseinandergebogen sind, wobei die Enden dieser Schenkel sich auf der dem Träger abgewandten Seite öffnen; die Klammer ist mit dem Träger elektrisch leitend und mechanisch fest verbunden. In diese Klammer greift eine kammartige Erhebung der Elektrodenplatte ein, die senk- recht zu deren Plattenebene angeordnet ist. Die kammartige Erhebung wird durch eine umgebogene Kante der Elektrodenplatte gebildet.In a preferred embodiment, at least one bracket serving as a spacer with a U-shaped cross-section with converging legs is arranged on the support serving as a current distributor and is bent apart again in the region of its free ends, the ends of these legs facing away from the support to open; the clip is connected to the carrier in an electrically conductive and mechanically fixed manner. A comb-like elevation of the electrode plate, which is perpendicular, engages in this clamp whose plate level is arranged. The comb-like elevation is formed by a bent edge of the electrode plate.

Die Klammern weisen an ihren Enden Kontaktflächen auf, die parallel zu den ebenen Elektrodenflächen verlaufen. Beim Betrieb einer solchen Elektrodenan­ordnung wird die Elektrodenfläche durch die Klemmhalterung fixiert und kontak­tiert. Zusätzlich wird durch den Druck über die Zellenmembran die Elektroden­fläche gegen die Kontaktflächen der Klemmhalterung angedrückt. Der Träger be­steht aus Metallblech mit einer Dicke im Bereich von 0,4 bis 3 mm.The clips have contact surfaces at their ends, which run parallel to the flat electrode surfaces. When operating such an electrode arrangement, the electrode surface is fixed and contacted by the clamp holder. In addition, the pressure on the cell membrane presses the electrode surface against the contact surfaces of the clamp. The carrier consists of sheet metal with a thickness in the range of 0.4 to 3 mm.

Als besonders vorteilhaft erweist sich die Möglichkeit, bei Reaktivierung oder Reparatur von Elektrodenteilen diese vor Ort von dem Träger durch Heraus­ziehen zu trennen und mittels vorliegender Reserveelektrodenteile den Träger erneut zu bestücken, so daß keine längeren Ausfallzeiten der Elektrolyseanlage durch Entnahme zu reaktivierender Elektroden bzw. Elektrodenteile entstehen können. Da nur noch die aktiven Elektrodensegmente zu behandeln sind, redu­zieren sich die üblichen Lager- und Transportkosten auf ein Minimum.It has proven particularly advantageous to reactivate or repair electrode parts on site by pulling them out of the carrier by pulling them out, and to re-equip them using existing spare electrode parts, so that no longer downtimes of the electrolysis system result from removal of electrodes or electrode parts to be reactivated can. Since only the active electrode segments have to be treated, the usual storage and transport costs are reduced to a minimum.

Im folgenden ist der Gegenstand der Erfindung anhand der Figuren 1a, 1b, 2a und 2b näher erläutert.

  • Figur 1a zeigt Träger- und Elektrodenteil vor dem Zusammenfügen in der Klemm­halterung,
  • Figur 1b zeigt eine zusammengefügte Klemmhalterung mit ausschnittsweise darge­stellter Elektrodenplatte und Träger,
  • Figur 2a zeigt eine lösbare Klemmhalterung aus einer zylindersymmetrischen Hülse mit Längsschlitzen, die auf ihrer Innenseite eine kegelstumpf­artige Verjüngung zur Aufnahme eines kegelstumpfförmigen Endes eines als starres Teil ausgebildeten Bolzens aufweist,
  • Figur 2b zeigt als weiteres Element, eine ebenfalls mit Längsschlitzen ausge­bildete Hülse, deren äußere Fläche kegelstumpfartig ausgebildet ist und auf die eine starre Hülse mit ebenfalls kegelstumpartig ausgebil­deter Innenfläche aufschiebbar ist.
The subject matter of the invention is explained in more detail below with reference to FIGS. 1a, 1b, 2a and 2b.
  • FIG. 1a shows the carrier and electrode part before being assembled in the clamp holder,
  • FIG. 1b shows an assembled clamp holder with an electrode plate and carrier shown in sections,
  • FIG. 2a shows a releasable clamping holder made of a cylindrical symmetrical sleeve with longitudinal slots, which has on its inside a truncated cone for receiving a truncated cone-shaped end of a bolt designed as a rigid part,
  • FIG. 2b shows, as a further element, a sleeve which is also formed with longitudinal slots, the outer surface of which is frustoconical and onto which a rigid sleeve with an inner surface which is also conical part can be pushed.

Gemäß Figur 1a besteht die Klemmhalterung aus einer mit dem Träger 1 durch Schweißpunkte 2 fest verbundenen Klammerfeder 3 mit U-förmigem Querschnitt und zusammenlaufenden Schenkeln 4, 5, die im Bereich ihrer freien Enden wieder auseinandergebogen sind und in Kontaktflächen 14 enden; die Kontaktflächen 14 verlaufen parallel zur Ebene des Trägers 1. Gemäß Figur 1a sind zwei Reihen mit jeweils drei solcher Klammerfedern versehen, wobei der zwischen den Schen­keln 4 und 5 angeordnete Mittelstreifen 6 über senkrecht angeordnete Streifen 7 und parallel zur Ebene des Trägers 1 angeordnete Befestigungsstege 8 verbunden ist. Die Befestigungsstege 8 sind durch Schweißpunkte 2 mit dem Träger 1 verbunden. Mittelstreifen 6, Streifen 7 und Befestigungsstege 8 bilden einen mäanderförmig durchlaufenden Streifen mit Erweiterungen im Bereich der Schenkel 4, 5, der aus elastischem Metall gestanzt und entsprechend gebogen ist.According to FIG. 1 a, the clamp holder consists of a clamp spring 3 with a U-shaped cross section and firmly connected to the carrier 1 by welding points 2 converging legs 4, 5 which are bent apart again in the region of their free ends and end in contact surfaces 14; the contact surfaces 14 run parallel to the plane of the carrier 1. According to FIG. 1a, two rows are provided with three such clamp springs each, the central strip 6 arranged between the legs 4 and 5 via strips 7 arranged vertically and fastening webs 8 arranged parallel to the plane of the carrier 1 connected is. The fastening webs 8 are connected to the carrier 1 by welding points 2. Center strip 6, strip 7 and fastening webs 8 form a meandering continuous strip with extensions in the area of the legs 4, 5, which is punched out of elastic metal and bent accordingly.

Oberhalb des Trägers 1 ist ein Teil der Elektrodenplatte 10 dargestellt, die im vorliegenden Fall aus drei Teilplatten 11 besteht, von denen die beiden äußeren Teilplatten ebenso wie der darunter liegende Träger 1 zwecks besserer Übersicht nicht vollständig bzw. mit einer Lücke dargestellt sind. Die Teil­platten 11 weisen an ihren Rändern jeweils rechtwinklig abgewinkelte Kanten 12 auf, die so angeordnet sind, daß die Oberfläche der Elektrodenplatte 10 eine durchgehende Ebene bildet. Die Kanten 12 bilden in Form einer kammartigen Er­hebung den starren Teil 13 der lösbaren Klemmhalterung.A part of the electrode plate 10 is shown above the carrier 1, which in the present case consists of three partial plates 11, of which the two outer partial plates as well as the underlying carrier 1 are not shown completely or with a gap for a better overview. The partial plates 11 each have at their edges angled edges 12 which are arranged such that the surface of the electrode plate 10 forms a continuous plane. The edges 12 form the rigid part 13 of the releasable clamping bracket in the form of a comb-like elevation.

Figur 1b zeigt in einer ausschnittsweisen Darstellung, wie die zu einem Teil 13 zusammengefaßten Kanten der Teilplatten 11 in das offene Ende der Klammer­feder 3 eingeführt sind und durch eine kraftschlüssige Verbindung zwischen Klammerfeder 3 und starrem Teil 13 festgehalten werden. In der Praxis wird der starre Teil 13 der Elektrodenplatte soweit in die Klammerfeder 3 eingeführt, bis die Flächen 14 der Schenkel 4, 5 und die Unterseite der Elektrodenplatte bis zum Anschlag an den Träger 1 herangeführt ist.FIG. 1b shows a detail of how the edges of the partial plates 11 combined into a part 13 are inserted into the open end of the clamp spring 3 and are held in place by a non-positive connection between the clamp spring 3 and the rigid part 13. In practice, the rigid part 13 of the electrode plate is inserted into the clamp spring 3 until the surfaces 14 of the legs 4, 5 and the underside of the electrode plate are brought up to the stop 1 against the stop.

Die Elektrodenplatte kann beispielsweise aus einem jalousieartig aufgeschlitz­ten Blech bestehen. Es ist jedoch auch möglich, andere Elektrodenarten, wie z. B. Draht, Netze, Streckmetall, lamellenartig angeordnete Flachprofile, vorzu­sehen. Der Träger 1 bildet dabei in der Praxis eine Art Elektrodenwanne, die zusammen mit dem entsprechend ausgeführten Träger der Gegenelektrode einen abgeschlossenen Raum bildet, der durch die Membran in zwei Elektrolyt-Teil­räume, d. h. in einen Anolytraum und Katholytraum aufgeteilt wird. Dabei sind die beiden Träger jeweils einer Zelle durch die Membran bzw. zusätzliche Dich­tungen elektrisch voneinander getrennt. Die Elektrolyträume sind mit eigenen Flüssigkeitszufuhr- und -abfuhröffnungen versehen, wobei der Anolytraum an den Solekreislauf angeschlossen ist,während dem Katholytraum Wasser zugeführt wird. Weiterhin sind Mittel zur Abführung des erzeugten Chlor- bzw. Wasserstoffgases aus Anolyt- bzw. Katholytraum vorgesehen. Als Materialien dienen auf der Kathodenseite Stahl- bzw. federharte Nickellegie- rungen, während auf der Anodenseite Titan mit guten Federeigenschaften bzw. Titanlegierungen eingesetzt werden. Die als starrer Teil 13 des Federsystems dienenden Kanten 12 der Teilplatten 11 können dabei Einschnitte bzw. Zwischen­räume aufweisen, um trotz der Toleranzen eine möglichst gute Kontaktierung im Bereich der Klammerfeder zu erzielen. Die Zahl der Klammerfedern hängt dabei im wesentlichen von der Größe der Elektrodenplatten ab. Bei kleinen Elektro­denplatten ist es möglich, mit einer einzigen Klammerfeder auszukommen.The electrode plate can consist, for example, of a sheet metal slit like a blind. However, it is also possible to use other types of electrodes, such as. B. wire, nets, expanded metal, lamellar arranged flat profiles to provide. In practice, the carrier 1 forms a type of electrode trough which, together with the correspondingly designed carrier of the counter electrode, forms a closed space which is divided by the membrane into two electrolyte subspaces, ie into an anolyte space and a catholyte space. Are the two carriers of a cell are electrically separated from each other by the membrane or additional seals. The electrolyte spaces are provided with their own liquid supply and discharge openings, the anolyte space being connected to the brine circuit, while water is supplied to the catholyte space. Means are also provided for removing the chlorine or hydrogen gas generated from the anolyte or catholyte space. Steel or spring-hard nickel alloys are used as materials on the cathode side, while titanium with good spring properties or titanium alloys are used on the anode side. The edges 12 of the partial plates 11 serving as a rigid part 13 of the spring system can have incisions or gaps in order to achieve the best possible contact in the area of the clamp spring despite the tolerances. The number of clip springs essentially depends on the size of the electrode plates. With small electrode plates, it is possible to make do with a single spring clip.

In Figur 2a ist eine weitere Version der Klemmhalterung dargestellt, in der der mit dem Träger verbundene Teil 3′ einen federnden Bereich in Form einer Hülse aufweist, welche mit bis an ihre Öffnung reichenden Längsschlitzen 15 versehen ist und sich auf der dem Träger abgewandten Seite befindet. Die Hülse weist auf den ihre Innenseite bildenden Mantelsegmenten 16 eine von der Öff­nung 17 ausgehende kegelstumpfartige Verjüngung auf, wobei im Bereich der Öff­nung 17 eine durch die Längsschlitze 15 unterbrochene Ringnut 18 vorgesehen ist. Die Hülse ist mit dem nur ausschnittsweise dargestellten Träger 1 elek­trisch leitend und mechanisch fest verbunden.In Figure 2a, another version of the clamp bracket is shown, in which the part connected to the carrier 3 'has a resilient area in the form of a sleeve which is provided with longitudinal slots 15 extending to its opening and is located on the side facing away from the carrier . The sleeve has, on the jacket segments 16 forming its inside, a truncated cone-like taper starting from the opening 17, an annular groove 18 interrupted by the longitudinal slots 15 being provided in the region of the opening 17. The sleeve is connected in an electrically conductive and mechanically fixed manner to the carrier 1, which is only shown in part.

In die Hülse des mit dem Träger verbundenen Teils 3′ der Klemmhalterung ist ein bolzenartiger Bereich des starren Teils 13′ einführbar, der mit einem kegelstumpfförmig verjüngten Ende 20 versehen ist. Der starre Teil 13′ ist an seinem erweiterten Ende mit einer nur ausschnittsweise dargestellten Elektrodenplatte 10 elektrisch leitend und mechanisch fest verbunden. Im Übergangsbereich zwischen dem kegelstumpfförmigen Ende 20 und dem zylindrischen Teil des starren Teils 13′ befindet sich ein umlaufender Ringflansch 21, welcher bei Einführung des Endes 20 in die Hülse in der umlaufenden Ringnut 18 arretiert wird. Nach der Arretierung ist aufgrund der Wechselwirkung zwischen den beiden kegelstumpfförmigen Flächen von starren und federndem Teil die Verbindung äußerst stabil und beispielsweise durch Zugkraft kaum mehr zu lösen. Die in Figur 2a dargestellte Klemmhalterung kann beispielsweise bei kleinen Elektrodenflächen als einzige Klemmhalterung ausgeführt sein. Es ist jedoch auch möglich, sie entsprechend dem anhand der Figuren 1a und 1b erläuterten Beispiel in einer Vielzahl einzusetzen.In the sleeve of the part connected to the carrier 3 'of the clamping bracket, a bolt-like region of the rigid part 13' is insertable, which is provided with a frustoconical end 20. The rigid part 13 'is at its widened end with an electrode plate 10 shown only partially electrically and mechanically firmly connected. In the transition region between the frustoconical end 20 and the cylindrical part of the rigid part 13 'there is a circumferential ring flange 21 which is locked in the circumferential ring groove 18 when the end 20 is inserted into the sleeve. After locking, the connection is extremely stable due to the interaction between the two frustoconical surfaces of the rigid and resilient part and can hardly be released, for example by tensile force. The clamp holder shown in Figure 2a can For example, be designed as a single clamp bracket for small electrode areas. However, it is also possible to use them in a large number in accordance with the example explained with reference to FIGS. 1a and 1b.

Eine weitere Ausführungsform des erfindungsgemäßen Gegenstandes ist anhand der Figur 2b erläutert. In dieser Ausführungsform weist der mit dem Träger ver­bundene Teil 3˝ als federnder Bereich eine Hülse auf, die auf ihrer Außen­seite mit einer in Richtung ihrer Öffnung 17 verlaufenden kegelstumpfartigen Verjüngung aus Mantelsegmenten 16˝ versehen ist. Der äußere Rand der Öffnung 17 ist als ein durch Längsschlitze 15 unterbrochener Ringflansch 22 ausgebildet. Der federnde Teil 3˝ ist mit seinem der Öffnung 17 entgegenge­setzten Ende 26 mit dem nur ausschnittsweise dargestellten Träger 1 elektrisch leitend und mechanisch fest verbunden.Another embodiment of the subject matter of the invention is explained with reference to Figure 2b. In this embodiment, the part 3˝ connected to the carrier has as a resilient region a sleeve which is provided on its outside with a truncated cone-shaped tapering made of shell segments 16˝ in the direction of its opening 17. The outer edge of the opening 17 is designed as an annular flange 22 interrupted by longitudinal slots 15. The resilient part 3˝ is connected at its end 26 opposite the opening 17 to the support 1, which is only shown in part, in an electrically conductive and mechanically fixed manner.

Der als starrer Teil 13˝ ausgebildete Bereich der Klemmhalterung ist mit einem bolzenartigen Bereich versehen, der auf die Mantelsegmente 16˝ auf­schiebbar ist. Der bolzenartige Bereich weist auf seiner Innenseite 23 eine vom offenen Ende 24 ausgehende kegelstumpfartige Verjüngung auf. Im Übergangs­bereich zwischen der Verjüngung der Innenseite 23 und einem Hohlzylinder im starren Teil 13˝ befindet sich eine umlaufende Ringnut 25, in welcher der Ringflansch 22 beim Aufsetzen arretierbar ist. Zur besseren Übersicht sind in Figur 2b sowohl die Hülse des starren Teils 13˝ als auch die Elektroden­platte 10 nur bruchstücksweise dargestellt.The area of the clamping bracket designed as a rigid part 13˝ is provided with a bolt-like area which can be pushed onto the jacket segments 16˝. The bolt-like area has on its inside 23 a truncated cone-like taper starting from the open end 24. In the transition area between the tapering of the inside 23 and a hollow cylinder in the rigid part 13˝ there is a circumferential annular groove 25, in which the annular flange 22 can be locked when it is put on. For a better overview, both the sleeve of the rigid part 13˝ and the electrode plate 10 are only shown in fragments in FIG. 2b.

Auch bei dieser Anordnung erweist sich die Verbindung nach Arretierung des Ringflansches 22 in der Ringnut 25 als äußerst stabil, wobei ebenfalls die Wechselwirkung der beiden kegelstumpfförmigen Flächen die Pressung verstärkt. Die Elektrodenstruktur, d. h. Elektrodenform der Figuren 2a, 2b können ent­sprechend den Ausführungen zu den Figuren 1a, 1b gestaltet werden; das gleiche trifft für die eingesetzten Materialien zu. Die Arretierung ist vor der Reak­tivierung der aktiven Elektrodenteile durch Hilfswerkzeuge, wie beispielsweise Schraubenzieher zu lösen. Nach der Erfindung lassen sich die Folgekosten im langfristigen Betrieb von Membranzellen erheblich senken, da das Lösen und Wiedereinbauen der aktiven Elektrodenflächen ohne Probleme schnell, schonend und kosten- günstig durchgeführt werden kann.In this arrangement, too, the connection proves to be extremely stable after the ring flange 22 has been locked in the ring groove 25, the interaction of the two frustoconical surfaces likewise increasing the pressure. The electrode structure, i.e. H. The electrode shape of FIGS. 2a, 2b can be designed in accordance with the explanations for FIGS. 1a, 1b; the same applies to the materials used. The locking device must be released by auxiliary tools such as screwdrivers before reactivating the active electrode parts. According to the invention, the follow-up costs in the long-term operation of membrane cells can be considerably reduced, since the detachment and reinstallation of the active electrode surfaces can be carried out quickly, gently and inexpensively without problems.

Claims (7)

1. Elektrodenstruktur für eine elektrochemische Membranzelle mit beiderseits einer Membran angeordneten ebenen Elektrodenstruktur, wobei wenigstens die anodische Elektrodenstruktur über metallische Abstandshalter mit einem als Stromverteiler dienenden Träger aus Metallblech verbunden ist, dadurch gekennzeichnet, daß die Abstandshalter in Form einer Klemmhalterung ausgebildet sind, die aus einem federnden Teil (3, 3′, 3˝) und einem im wesentlichen starren Teil (13, 13′, 13˝) besteht, wobei jeweils der federnde Teil mit dem Träger (1) unverrückbar verbunden ist.1. Electrode structure for an electrochemical membrane cell with a flat electrode structure arranged on both sides of a membrane, wherein at least the anodic electrode structure is connected via metallic spacers to a metal sheet carrier serving as a current distributor, characterized in that the spacers are designed in the form of a clamping bracket which consists of a resilient part (3, 3 ', 3˝) and a substantially rigid part (13, 13', 13˝), the respective resilient part being immovably connected to the carrier (1). 2. Elektrodenstruktur nach Anspruch 1, dadurch gekennzeichnet, daß der mit dem Träger verbundene Teil eine Klammerfeder (3) mit u-förmigem Quer­schnitt aufweist, wobei die freien Endbereiche ihrer Schenkel (4, 5) zu einer Kontaktfläche (14) umgebogen sind.2. Electrode structure according to claim 1, characterized in that the part connected to the carrier has a clip spring (3) with a U-shaped cross section, the free end regions of its legs (4, 5) being bent over to form a contact surface (14). 3. Elektrodenstruktur nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der starre Teil (13) in Form einer kammartigenn Erhebung vom ebenen Elektro­denteil absteht.3. Electrode structure according to claim 1 or 2, characterized in that the rigid part (13) protrudes from the flat electrode part in the form of a comb-like elevation. 4. Elektrodenstruktur nach Anspruch 3, dadurch gekennzeichnet, daß das ebene Elektrodenteil als Elektrodenplatte (10) ausgebildet ist und die kammar­tige Erhebung aus wenigstens einer umgebogenen Kante (12) einer Elek­trodenplatte besteht, die bis zum Anschlag auf die Kontaktflächen (14) in die Klammerhaltung eingeschoben ist.4. Electrode structure according to claim 3, characterized in that the flat electrode part is designed as an electrode plate (10) and the comb-like elevation consists of at least one bent edge (12) of an electrode plate, which up to the stop on the contact surfaces (14) in the bracket is inserted. 5. Elektrodenstruktur nach Anspruch 4, dadurch gekennzeichnet, daß die Elek­trodenplatte (10) aus mehreren Teilplatten (11) besteht, deren einander benachbarte Kanten (12) die kammartige Erhebung bilden, welche in die Klemmhalterung eingeführt ist.5. Electrode structure according to claim 4, characterized in that the electrode plate (10) consists of several partial plates (11), the mutually adjacent edges (12) of which form the comb-like elevation which is inserted into the clamping bracket. 6. Elektrodenstruktur nach Anspruch 1, dadurch gekennzeichnet, daß der mit dem Träger (1) verbundene Teil (3′,3˝) einen federnden Bereich in Form einer Hülse aufweist, die mit Längsschlitzen (15) versehen ist und sich auf der dem Träger (1) abgewandten Seite befindet.6. Electrode structure according to claim 1, characterized in that the part (3 ', 3˝) connected to the carrier (1) has a resilient region in the form of a sleeve which is provided with longitudinal slots (15) and on which the carrier (1) facing away. 7. Elektrodenstruktur nach Anspruch 6, dadurch gekennzeichnet, daß der starre Teil einen bolzenartigen Bereich aufweist, der in die Hülse eingreift.7. Electrode structure according to claim 6, characterized in that the rigid part has a bolt-like area which engages in the sleeve.
EP88109169A 1987-08-11 1988-06-09 Electrochemical membrane cell with a plain electrode structure disposed at both sides of the membrane Expired - Lifetime EP0306627B1 (en)

Applications Claiming Priority (2)

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DE19873726674 DE3726674A1 (en) 1987-08-11 1987-08-11 ELECTRODE STRUCTURE FOR ELECTROCHEMICAL CELLS
DE3726674 1987-08-11

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EP0306627A1 true EP0306627A1 (en) 1989-03-15
EP0306627B1 EP0306627B1 (en) 1992-05-06

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EP0713932A1 (en) * 1994-11-29 1996-05-29 Heraeus Elektrochemie GmbH Electrode with platelike electrode body
EP0892086A1 (en) * 1997-07-11 1999-01-20 Magneto-Chemie B.V. Anode on a basis of lead
WO1999045174A1 (en) * 1998-03-05 1999-09-10 Permascand Ab Clamping device for electrochemical cell

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JP3110551B2 (en) * 1992-04-30 2000-11-20 クロリンエンジニアズ株式会社 Electrolytic cell
US5322560A (en) * 1993-08-31 1994-06-21 Basf Corporation Aluminum flake pigment treated with time release corrosion inhibiting compounds and coatings containing the same
IT1279069B1 (en) * 1995-11-22 1997-12-04 Permelec Spa Nora IMPROVED ELECTRODE TYPE FOR ION EXCHANGE MEMBRANE ELECTROLYZERS
JP7289077B2 (en) * 2018-07-13 2023-06-09 パナソニックＩｐマネジメント株式会社 Electrolyzed water generator
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Also Published As

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JP2607278B2 (en) 1997-05-07
ES2031178T3 (en) 1992-12-01
EP0306627B1 (en) 1992-05-06
US4855032A (en) 1989-08-08
JPS6455392A (en) 1989-03-02
KR890004461A (en) 1989-04-22
DE3870771D1 (en) 1992-06-11
DE3726674A1 (en) 1989-02-23

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