EP0565836A1 - Cellule électrochimique à membrane - Google Patents

Cellule électrochimique à membrane Download PDF

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Publication number
EP0565836A1
EP0565836A1 EP93103012A EP93103012A EP0565836A1 EP 0565836 A1 EP0565836 A1 EP 0565836A1 EP 93103012 A EP93103012 A EP 93103012A EP 93103012 A EP93103012 A EP 93103012A EP 0565836 A1 EP0565836 A1 EP 0565836A1
Authority
EP
European Patent Office
Prior art keywords
cell according
membrane cell
electrochemical membrane
cathode
supply structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93103012A
Other languages
German (de)
English (en)
Inventor
Bernd Dr. Busse
Michael Holzapfel
Antonius Fischer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektrochemie GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Heraeus Elektrochemie GmbH filed Critical Heraeus Elektrochemie GmbH
Publication of EP0565836A1 publication Critical patent/EP0565836A1/fr
Withdrawn legal-status Critical Current

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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 an electrochemical membrane cell with electrodes arranged on both sides of a membrane, with both anodic and cathodic electrodes being connected via an electrically conductive current supply structure serving as a spacer to a metal sheet support and at least one for the purpose of uniform current distribution Power supply structure of the cell is releasably connected to the associated electrode via flat parts.
  • EP-OS 55 930 An electrolytic cell operating according to the membrane method is described in EP-OS 55 930; it is also referred to as a membrane cell.
  • the electrode arrangement located on both sides of the membrane is explained in more detail, for example, by means of DE-OS 36 25 506, in which a film-like membrane with electrodes closely fitting on both sides is described.
  • an electrode structure for membrane or diaphragm cells which has a metal plate carrier 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.
  • a metal plate carrier serving as a current distributor
  • the coatings on the cathodes in membrane cells have a shorter operating time compared to coatings on the anode.
  • To re-coat the electrodes it is necessary to remove the complete membrane cell elements, the electrodes being separated from the cell elements, re-coated and re-installed, and possibly welded.
  • an electrode structure for membrane electrolysis cells with a flat electrode part is known, which is connected via metallic spacers to a metal plate carrier serving as a current distributor.
  • the spacers are designed in the form of a clamping bracket, which consist of a resilient part and a rigid part, the resilient part in each case being immovably connected to the carrier, while the rigid part is connected to the electrode part. If reactivation is required, the active electrode parts can thus be separated from their respective carriers and, after disassembly, sent directly to the reactivation.
  • the comparatively complex clamping bracket proves to be problematic here, the current transfer between the clamping brackets being crucially dependent on the respective spring tension and cannot easily be subsequently strengthened. The contact resistance can thus prove to increase resistance due to the relatively small contacting areas between the elements of the spring holder. Furthermore, uniform redistribution is difficult with the contact spring elements arranged in series.
  • the object of the invention is to create a detachable connection between the electrode and the respective cell element, the contact resistance of which is practically negligible, and in addition a uniform power supply via the electrode surface is to be achieved.
  • the power supply structure is mechanically pressed against the flat parts of the associated electrode via a clamping structure, which acts on the outer sides of the metal sheets, forming an electrical surface contact.
  • the simple construction of the cathode results in a reduction in manufacturing costs; furthermore, it proves to be advantageous that the installation and removal of the cathodes on site (i.e. at the user) is possible and thus an expensive transport of complete cells for the purpose of reactivating the cathodes can be avoided. By stocking replacement cathodes on site, immediate restart is possible.
  • the contact surfaces between the electrode structure of the cathode and cell element are centered by interlocking interlocking locking elements, so that the optimum position is always obtained.
  • the locking elements each consist of a recess and a projection protruding into the recess, and this arrangement can also serve for electrical contacting in addition to the very important two-dimensional contact.
  • the reactivated electrodes can be installed or removed again in a relatively simple manner by the user of the system in the cell elements, without the need for associated specialist personnel; it is also possible to convert older cell elements with welded cathodes into cell elements according to the invention in a simple manner.
  • the cell element 1 consists of two half-shells 2 and 3, which each enclose an anode 4 with an anodic current supply structure 5 and a cathode 6 with a cathodic current supply structure 7.
  • a membrane 8 is clamped between the anode 4 and the cathode 6 and encloses the interior of the cell element 1 in an anolyte space 9 and a catholyte space 10 divided.
  • Anodic and cathodic power supply structures 5 and 7 are designed in the form of corrugated strips, which are each connected to the inside of the respective half-shells 2 and 3 in an electrically conductive and mechanically fixed manner by welded connections 16, 19.
  • contact strips 13 are provided for the purpose of contacting the adjacent, but not shown, cathode, which consist of a diffusion or explosion-welded titanium-nickel strip, the titanium surface 14 of which is welded to the half-shell 2 made of titanium is connected and the nickel surface 15 represents the external contact to the adjacent cathode element.
  • the symbolically represented welding spots 26 between contact strips 13 and half-shell 2 are produced by resistance welding.
  • the anode structure 5 consisting of wavebands is likewise connected to the activated surface of the anode 4 by welding points 17 by resistance welding.
  • Electrically insulating, anolyte-resistant spacers 18 are provided between the anode 4 and the membrane 8, which support the anode 4 against the membrane.
  • the half-shell 3 is also connected in an electrically conductive and mechanically fixed manner by resistance welding using the welding points 19 to the wave band used as the cathodic power supply structure 7.
  • Half-shell 3 as well as the waveband serving as cathodic power supply structure 7 and the cathode 6 essentially consist of nickel.
  • a cation exchange membrane is used as membrane 8.
  • FIG. 1 a which is directed to section A according to FIG. 1 a, spacers 23 made of catholyte-resistant, electrically insulating, elastic material are inserted between the cathode 6 and the membrane 8.
  • openings 21, 22, one above the other are provided in the contacting areas both in the cathode 6 and in the waveband, through which a fixing pin 38 is guided with its shaft, while the broadened one Head 39 of the pin comes to lie on the outside of the cathode; the pins 38 consist essentially of nickel, but it is also possible to use fixing pins made of another material, e.g. Use plastic.
  • the electrical contacting takes place essentially via the contact areas of the cathodic power supply structure 7 and the cathode 6 which are pressed onto one another in a planar manner.
  • An expedient embodiment consists in that the heads 39 of the fixing pins 38 are simultaneously used for locking the spacers 23 arranged between the cathode and the membrane.
  • the arrangement consisting of membrane 8, spacers 18, 23, anode, anodic power supply structure, cathode, cathodic power supply structure and half-shells 2 and 3 is pressed perpendicularly to the surface of the membrane by an external force and held in the locked position and thus against lateral Shift protected.
  • the pressing force is released and the sealing elements 12 pressing the sealing elements 12 are released; then the half-shell serving as the carrier 3 is removed from the half-shell as the carrier 2, so that the cathode 6 can be removed from the cathodic power supply structure 7.
  • the fixing pins 38 projecting into the recesses 21, 22 of the cathode 6 and the power supply structure 7, so that the contact pins are used to lock them against lateral displacements.
  • the current supply structures 7 have the shape of a corrugated strip, the surfaces facing the cathode 6 each having an opening 22 for receiving the fixing pin 38 guided through the opening 21 of the cathode.
  • bands 40 possibly also spacers with a pin structure, instead of individual fixing pins, the respective shaft-shaped shaft 41 protruding through both openings 21, 22 as a fixing pin.
  • the spacers are applied to the openings 21 and, for better locking, are also provided with a recess into which the heads 39 of the pins 38 protrude.
  • FIG. 1 d shows the cell structure already described with reference to FIG. 1 a with a large number of cells, the individual cells being shown schematically in different production states and the pressing force F acting on the two outer cells being shown symbolically.
  • the manufacturing state can be seen from the cell 45, in which the fixing pins 38 are located before being inserted into the openings of the cathode 6 and the cathodic power supply structure 7, the heads 39 of the fixing pins each being oriented toward the membrane.
  • the anode 4 and the anodic current supply structure 5 are firmly and electrically connected to one another in the areas in contact with one another by spot welding; the cell 46 is located directly in front of the assembly, the pins 38 having already been inserted into the overlapping openings 21, 22 of the cathode 6 and the current supply structure 7, while the spacers and membrane are not yet resting on the heads 39.
  • the cells 47, 48, 49 already show cells that have been finally assembled, the associated sealing and closure elements on the edge not being shown for the sake of a better overview.
  • Figure 1 e shows in detail an enlargement of section B according to Figure 1 d.
  • the contact transition area between two adjacent cells 47, 48 can be seen on the basis of FIG. 1e, contacting being made between the contact strip 13 and the outside of the cathodic half-shell 3 using the acting pressure.
  • FIG. 1 f shows an enlargement of section C according to FIG. 1 d, the diaphragm 8 being shown at a distance from the cathode 6 with its current supply structure 7 partially shown being pulled apart for a better overview.
  • the fixing pin 38 projects through the openings 21 and 22 of the cathode 6 and the current supply structure 7 for the purpose of locking.
  • FIG. 2 a The longitudinal section shown in Figure 2 a shows the series connection of several cell elements together with the two end plates, via which the contact is made and the spring force is exerted; For a better overview, however, only three cells are shown here in a relaxed state, i.e. that no pressing force is exerted according to Figure 2a.
  • Each of the three cell elements 1 each has an anode and cathode structure 5, 7, each of which consists of a plurality of corrugated bands arranged in parallel, which are shown here in a side view.
  • three wavebands are shown, but it is also possible, depending on the size of the electrode surface, to increase the number of wavebands.
  • the cross section of the contact strip 13, which consists of a titanium-nickel strip, is visible on the anode side, titanium and nickel being connected to one another by diffusion welding or explosion welding, and the contact strip 13 on the titanium side on the outside of the anodic half-shell 2 Resistance welding is applied. Due to the series connection, the nickel part 15 contacts the outside of the adjacent cathodic half-shell 3, which essentially also consists of nickel.
  • the cathode and anode of the two outer cells are each connected to the cathode end plate 24 and the anode end plate 25, both end plates having an inelastic structure for the purpose of transmitting the spring force and each having contact elements 34, 35 on the side facing the cell elements, which predominantly are made of nickel.
  • the two end plates 24, 25 are pressed together by the partially shown bolts 30 and nuts 31, 32 along the axis 33, so that the anode-side half-shells are each electrically connected to the cathode-sensitive half-shells of adjacent cell elements due to the pressing action between contact strips 13 half-shell 3 with low electrical resistance are, the contact between the two outer end plates 24, 25 and the adjacent half-shells 2 and 3 also has a low contact resistance.
  • bolts 30 and nuts 31, 32 are insulated from end plates 24, 25 by electrically insulating bushings 28, 29.
  • the screw bolts are arranged in one of the four corners; for a better overview only a screw bolt 30 of a lower corner is shown here.
  • the power connections of the cathode end plate 24 and the anode end plate 25 are designated by the reference numbers 36, 37.
  • FIG. 2 c shows a membrane cell under construction, cell elements being arranged between the two end plates 24, 25, which are held together at their four corners with the aid of the screw bolts 30; the cell elements are switched such that the cathode of one cell element is electrically connected to the anode of the adjacent cell element.
  • the nuts 31 and 32 of the two end plates are tightened, so that there is only a very low contact resistance between adjacent cells.
  • the external power supply is supplied via the current connections 36 and 37 to the cathode end plate 24 and the anode end plate 25.
  • the cells hanging vertically parallel to one another in a frame construction the individual cells, starting from their edge region, having support elements lying in the extension of the membrane surface, which rest on a horizontally running support of the frame construction; the two outer cells, with their respective outward-facing supports or half-shells, are in electrical and mechanical contact with one end plate, of which at least one of these end plates can be moved by pressing elements, for example spindle screws, in the direction of the other end plate for the purpose of applying the required contact pressure by pressing is.
  • pressing elements for example spindle screws
  • the current density is in the range from 2 kA to 5 kA per m2.
  • the cells are particularly suitable for chlor-alkali electrolysis, with the gas and liquid removal not shown for the sake of clarity.

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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)
EP93103012A 1992-04-16 1993-02-26 Cellule électrochimique à membrane Withdrawn EP0565836A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4212678A DE4212678A1 (de) 1992-04-16 1992-04-16 Elektrochemische Membran-Zelle
DE4212678 1992-04-16

Publications (1)

Publication Number Publication Date
EP0565836A1 true EP0565836A1 (fr) 1993-10-20

Family

ID=6456904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93103012A Withdrawn EP0565836A1 (fr) 1992-04-16 1993-02-26 Cellule électrochimique à membrane

Country Status (4)

Country Link
EP (1) EP0565836A1 (fr)
JP (1) JPH0641777A (fr)
CA (1) CA2091943A1 (fr)
DE (1) DE4212678A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000039361A2 (fr) * 1998-12-23 2000-07-06 Krupp Uhde Gmbh Cellule a membrane echangeuse d'ions a fort debit de produit
EP3464683A4 (fr) * 2016-05-26 2020-04-01 Calera Corporation Ensemble anode, bandes de contact, cellule électrochimique, et leurs procédés d'utilisation et de fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5493787B2 (ja) * 2009-12-04 2014-05-14 東ソー株式会社 イオン交換膜法電解槽

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2322215A1 (fr) * 1975-08-29 1977-03-25 Hoechst Ag Appareil d'electrolyse
EP0022445A1 (fr) * 1979-03-12 1981-01-21 Hoechst Aktiengesellschaft Appareil d'électrolyse pour la production de chlore à partir de solutions aqueuses d'halogénures de métaux alcalins
EP0189535A1 (fr) * 1985-01-16 1986-08-06 Uhde GmbH Appareil d'électrolyse
EP0456295A1 (fr) * 1990-05-09 1991-11-13 Metallgesellschaft Aktiengesellschaft Electrolyseur

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2914869A1 (de) * 1979-04-12 1980-10-30 Hoechst Ag Elektrolyseapparat
US4368109A (en) * 1980-11-05 1983-01-11 Olin Corporation Electrolytic cell with inter-electrode spacer means
DE3519272C1 (de) * 1985-05-30 1986-12-18 Heraeus Elektroden GmbH, 6450 Hanau Elektrodenstruktur fuer elektrochemische Zellen
NL8601906A (nl) * 1985-07-29 1987-02-16 Permelec Electrode Ltd Electrode voor electrolyse bij toepassing van een diafragma.
DE3726674A1 (de) * 1987-08-11 1989-02-23 Heraeus Elektroden Elektrodenstruktur fuer elektrochemische zellen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2322215A1 (fr) * 1975-08-29 1977-03-25 Hoechst Ag Appareil d'electrolyse
EP0022445A1 (fr) * 1979-03-12 1981-01-21 Hoechst Aktiengesellschaft Appareil d'électrolyse pour la production de chlore à partir de solutions aqueuses d'halogénures de métaux alcalins
EP0189535A1 (fr) * 1985-01-16 1986-08-06 Uhde GmbH Appareil d'électrolyse
EP0456295A1 (fr) * 1990-05-09 1991-11-13 Metallgesellschaft Aktiengesellschaft Electrolyseur

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000039361A2 (fr) * 1998-12-23 2000-07-06 Krupp Uhde Gmbh Cellule a membrane echangeuse d'ions a fort debit de produit
WO2000039361A3 (fr) * 1998-12-23 2001-08-09 Krupp Uhde Gmbh Cellule a membrane echangeuse d'ions a fort debit de produit
EP3464683A4 (fr) * 2016-05-26 2020-04-01 Calera Corporation Ensemble anode, bandes de contact, cellule électrochimique, et leurs procédés d'utilisation et de fabrication
US11142834B2 (en) 2016-05-26 2021-10-12 Calera Corporation Anode assembly, contact strips, electrochemical cell, and methods to use and manufacture thereof

Also Published As

Publication number Publication date
CA2091943A1 (fr) 1993-10-17
DE4212678A1 (de) 1993-10-21
JPH0641777A (ja) 1994-02-15

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