EP0274138B1 - Elektrodenanordnung für gasbildende Elektrolyseure mit vertikal angeordneten Plattenelektroden - Google Patents

Elektrodenanordnung für gasbildende Elektrolyseure mit vertikal angeordneten Plattenelektroden Download PDF

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Publication number
EP0274138B1
EP0274138B1 EP87201843A EP87201843A EP0274138B1 EP 0274138 B1 EP0274138 B1 EP 0274138B1 EP 87201843 A EP87201843 A EP 87201843A EP 87201843 A EP87201843 A EP 87201843A EP 0274138 B1 EP0274138 B1 EP 0274138B1
Authority
EP
European Patent Office
Prior art keywords
electrode
plate
electrodes
membrane
ante
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87201843A
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German (de)
English (en)
French (fr)
Other versions
EP0274138A1 (de
Inventor
Karl Lohrberg
Peter Dr. Kohl
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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Filing date
Publication date
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Priority to AT87201843T priority Critical patent/ATE71672T1/de
Publication of EP0274138A1 publication Critical patent/EP0274138A1/de
Application granted granted Critical
Publication of EP0274138B1 publication Critical patent/EP0274138B1/de
Anticipated expiration legal-status Critical
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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
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous

Definitions

  • the invention relates to an electrode arrangement for gas-forming, monopolar membrane electrolysers with a vertically arranged plate electrode and counter electrode and an ion-selective membrane between the plate electrode and counter electrode, the plate electrode consisting of individual strip-shaped sheets separated from one another by a gap, which have a surface on their side facing the counter electrode have activating coating.
  • Electrode arrangement is known from DE-A-31 23 665.
  • the grid-like electrode closest to the membrane is the actually active electrode, behind which there is a perforated support layer.
  • Plate electrodes of a bipolar electrolytic cell are described in EP-A-0 076 747, the electrical field mainly consisting of pre-electrodes, each of which is connected to a plate electrode.
  • Electrodes with openings for the removal of the reaction gases are used, for example perforated electrodes, wire mesh or expanded metal.
  • the disadvantages include in a reduced active surface, lack of mechanical stability and loss of high-quality coating material on the back of the electrode.
  • the electrodes are ideally also to be used as conductors of the electrical current. These Application does not cause any problems in bipolar cells, since the current is transported through the electrode in the direction of the electrolysis current, ie there is in any case a sufficient cross section for the current transport. With monopolar cells, however, the current in the electrode must be transported across the electrolysis current. Flat electrodes can be used for this, but wire mesh and expanded metals cannot be used easily. This applies in particular to those electrolysis cells which, in contrast to the diaphragm cells, operate at current densities above 3 kA / m2. In this case, internal current line elements, such as line rods, are normally used, from which the current is distributed to the active surface of the electrodes (DE-OS 28 21 984).
  • the ion-selective membrane rests on the flat structures of the anode due to the different densities of the alkali hydroxide in the cathode compartment and the acidic aqueous alkali chloride solution in the anode compartment. Since no or only a very weak electrolysis can take place on this contact surface due to the absence or only very slight presence of electrolyte, expanded metal, perforated plates or similar electrode plates made of titanium are used in technical electrolysis for this purpose, in order to flank the holes or the expanded metal and in some cases also to allow the electrolysis process to take place on the back of the electrode sheets. As a result, however, active electrode area is lost. The consequence of this is that the voltage increases undesirably.
  • the invention has for its object to avoid or reduce such voltage losses and to enable high electrolysis currents. At the same time, the current distribution between the plate electrodes be evened out.
  • this is done according to the invention in that the plate electrodes on the side facing the membrane are electrically conductively connected to an areal, perforated, electrically conductive pre-electrode running parallel to the plate electrode, the distance between the plate electrode and the pre-electrode 1 to 5 mm is.
  • the membrane is securely held at a certain distance from the plate-shaped anode and the filling of the space between the membrane and the plate surface with electrolyte is ensured.
  • the pre-electrode carries the ion-selective membrane, while the electrically highly conductive, plate-shaped electrode allows high electrolysis currents and at the same time participates in the electrolysis with its surface facing the pre-electrode.
  • the surface of the membrane that is inactive in conventional arrangements due to the necessary perforation of the usual electrodes is also included in the electrolysis process.
  • particularly effective degassing is brought about in the electrolyte.
  • the vertically arranged plate anode can consist, in a manner known per se, of strip-shaped titanium sheets which are bent in a certain way and have gas discharge lines corresponding to the type described in EP-A-0 102 099.
  • the individual strip-shaped sheets are completely separated from one another by a horizontally continuous gap .
  • the plate electrodes can also be constructed from vertical strips and from vertical strips on the one hand and horizontal strips on the other.
  • Membrane electrolysis cells of such an electrode structure in which the electrodes of one polarity are divided into several horizontal strips and the electrodes of the opposite polarity consist of vertical strips are known from EP-A-0 097 991.
  • the pre-electrode is usually connected to cams or bumps of the plate electrode by spot welding.
  • the distances or number of hump or spot welds are adapted to the requirements with regard to the current load. Of course, all other common connection techniques can also be used.
  • the perforated, electrically conductive metallic pre-electrode which is generally resilient and flexible and has a thickness of about 0.5 to 2 mm, can for example be a perforated plate (screen plate), expanded metal or wire mesh, e.g. a wire mesh or wire mesh.
  • the pre-electrode can also be formed by a system of individual wires, which are aligned in a plane essentially parallel to the plate electrode and are conductively connected to the plate electrode by spot welding. The individual wires can be arranged in parallel or at an angle to one another, so that square or diamond-like structures arise.
  • the construction material for the electrode arrangement according to the invention for monopolar electrolyzers depends in a manner known per se on the use of the electrode arrangement as an anode or cathode. If the electrode arrangement consisting of plate electrodes and pre-electrodes connected to them as anodes is used in the electrolysis of aqueous alkali chloride solutions, the plate and pre-electrodes consist, for example, of titanium, zirconium, niobium, tantalum or their alloys. When used as cathodes, the material is pre and Plate electrode, for example stainless steel, nickel or steel plated with these metals.
  • the electrode arrangement of the invention is firmly installed in a manner known per se in a frame which has connection elements for the supply of the electric current.
  • the plate electrode is only provided with an activating coating on its surface facing the membrane, in a known manner from e.g. Metal oxides and metals from the platinum, iridium, osmium, palladium, rhodium, ruthenium group.
  • the electrode arrangement according to the invention is used in monopolar electrolysers with ion-selective membranes, it being e.g. can be perfluorinated cation exchange membranes.
  • ion-selective membranes it being e.g. can be perfluorinated cation exchange membranes.
  • Such membranes allow the separation of cathodic and anodic products of an electrolysis from one another or from the reactants supplied to the counterelectrode.
  • the electrode arrangement according to the invention has a number of advantages.
  • the ion-selective membrane is kept at the desired constant distance from the plate electrode in a simple and safe manner. Due to the fact that both the perforated pre-electrode works on the flanks of the openings and the plate electrode works on the projected areas of the openings, the current in the membrane is distributed more evenly than when using only perforated electrodes. In the space between the pre-electrode and the plate electrode, a better degassing of the electrolyte and a better electrolyte exchange are achieved due to the geometrical arrangement. Due to the arrangement of the invention, it is also possible to reduce the voltage drop.
  • the K number can be reduced by values of up to 0.05 V.m2 / kA, which corresponds to a voltage gain of 200 mV at a current of 4 kA / m2.
  • a frame (1) carries the plate electrode, which consists of continuously horizontally separated, plate-shaped strips (2), the upper edges (3) of which are angled and thus conduct the evolving gases behind the active electrode surface, cf. 1, 2 and 4.
  • the electrolyte is introduced via a perforated tube, cf. 1 and 4, the tube end (9) is squeezed.
  • the electrolyte enters the cell from the frame (1) via openings (11), cf. Fig. 3.
  • FIG. 10 denotes the outlet opening for the electrolyte, which can be seen in FIG. 1.
  • the frame (1) is extended laterally by the rail (4), which has holes (5) for lines for connection to electrical energy sources.
  • the grid-like, only partially shown pre-electrode (6) is electrically conductively connected to the strips (2) of the plate electrode via a series of welded stitchings (7), cf. in particular Fig. 4.
  • a test cell with an ion-selective membrane (Nafion R 90209 from E.I. du Pont de Nemours & Co. Inc.)
  • comparative measurements were carried out with conventional perforated anode structures and with an electrode arrangement according to the invention.
  • the openwork conventional electrode consisted of expanded metal (titanium, activated with RuO2) with a free area of 20%.
  • the total height of the electrolytic cell was 300 mm, the depth 200 mm.
  • the electrode arrangement according to the invention consisted of a pre-electrode of the same expanded metal (titanium, activated with RuO2) and a triple horizontal plate electrode (titanium, activated with RuO2).
  • the gap between the front and plate electrodes was kept at a distance of 3 mm by vertical titanium wires, which simultaneously made electrical contact between the front and plate electrodes.
  • the counter electrode consisted of non-activated expanded metal made of nickel.
  • the electrode gap between the front electrode and counter electrode was 4 mm.
  • the membrane was in contact with the pre-electrode.
  • the electrolyte temperature was 70 to 80 ° C.
  • the catholyte consisted of 32% sodium hydroxide solution.
  • the brine contained 310 g NaCl / l; the anolyte contained 200 g NaCl / l.

Landscapes

  • 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)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Electroluminescent Light Sources (AREA)
EP87201843A 1986-11-27 1987-09-25 Elektrodenanordnung für gasbildende Elektrolyseure mit vertikal angeordneten Plattenelektroden Expired - Lifetime EP0274138B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87201843T ATE71672T1 (de) 1986-11-27 1987-09-25 Elektrodenanordnung fuer gasbildende elektrolyseure mit vertikal angeordneten plattenelektroden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863640584 DE3640584A1 (de) 1986-11-27 1986-11-27 Elektrodenanordnung fuer gasbildende elektrolyseure mit vertikal angeordneten plattenelektroden
DE3640584 1986-11-27

Publications (2)

Publication Number Publication Date
EP0274138A1 EP0274138A1 (de) 1988-07-13
EP0274138B1 true EP0274138B1 (de) 1992-01-15

Family

ID=6314934

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201843A Expired - Lifetime EP0274138B1 (de) 1986-11-27 1987-09-25 Elektrodenanordnung für gasbildende Elektrolyseure mit vertikal angeordneten Plattenelektroden

Country Status (12)

Country Link
US (1) US4839013A (es)
EP (1) EP0274138B1 (es)
JP (1) JPS63140093A (es)
AT (1) ATE71672T1 (es)
AU (1) AU594214B2 (es)
BR (1) BR8706360A (es)
CA (1) CA1312844C (es)
DE (2) DE3640584A1 (es)
ES (1) ES2029683T3 (es)
FI (1) FI82488C (es)
IN (1) IN165046B (es)
ZA (1) ZA878895B (es)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5221452A (en) * 1990-02-15 1993-06-22 Asahi Glass Company Ltd. Monopolar ion exchange membrane electrolytic cell assembly
US5254233A (en) * 1990-02-15 1993-10-19 Asahi Glass Company Ltd. Monopolar ion exchange membrane electrolytic cell assembly
CN1019590B (zh) * 1990-09-03 1992-12-23 张学明 高效水电解制氢氧装置
DE4306889C1 (de) * 1993-03-05 1994-08-18 Heraeus Elektrochemie Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung
IT1279069B1 (it) * 1995-11-22 1997-12-04 Permelec Spa Nora Migliorato tipo di elettrodo per elettrolizzatori a membrana a scambio ionico
US20030112916A1 (en) * 2000-02-25 2003-06-19 Keeney Franklin W. Cold nuclear fusion under non-equilibrium conditions
US6924049B2 (en) * 2000-09-11 2005-08-02 Joe G. Rich, Sr. Electrolysis fuel cell energy plant
WO2003095705A1 (en) * 2002-05-13 2003-11-20 Kirk Donald W Bifurcated electrode of use in electrolytic cells
EP2343210B1 (en) * 2008-10-31 2018-04-04 Toyota Jidosha Kabushiki Kaisha Power supply system for electric vehicle and control method for the same
US11643739B2 (en) 2014-01-15 2023-05-09 Tosoh Corporation Anode for ion exchange membrane electrolysis vessel, and ion exchange membrane electrolysis vessel using same
NL2032717B1 (en) * 2022-08-10 2024-02-16 Itrec Bv Electrolyser and method for performing electrolysis

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH288156A (de) * 1949-11-03 1953-01-15 Montedison Spa Elektrodensystem für Bipolarelektrolyseure.
US4236989A (en) * 1978-07-07 1980-12-02 Ppg Industries, Inc. Electrolytic cell
DE3123665A1 (de) * 1981-06-15 1982-12-30 Metallgesellschaft Ag, 6000 Frankfurt Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure
FR2513663B1 (fr) * 1981-09-30 1986-02-28 Creusot Loire Electrolyseur du type filtre-presse
DE3228884A1 (de) * 1982-08-03 1984-02-09 Metallgesellschaft Ag, 6000 Frankfurt Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure
US4588483A (en) * 1984-07-02 1986-05-13 Olin Corporation High current density cell
GB8420873D0 (en) * 1984-08-16 1984-09-19 Ici Plc Electrode for electrolytic cell

Also Published As

Publication number Publication date
ZA878895B (en) 1989-07-26
ATE71672T1 (de) 1992-02-15
CA1312844C (en) 1993-01-19
DE3776122D1 (de) 1992-02-27
BR8706360A (pt) 1988-07-26
FI82488C (fi) 1991-03-11
AU594214B2 (en) 1990-03-01
US4839013A (en) 1989-06-13
ES2029683T3 (es) 1992-09-01
FI874376A0 (fi) 1987-10-06
IN165046B (es) 1989-08-05
DE3640584A1 (de) 1988-06-09
FI874376A (fi) 1988-05-28
AU8182087A (en) 1988-06-02
EP0274138A1 (de) 1988-07-13
JPS63140093A (ja) 1988-06-11
FI82488B (fi) 1990-11-30

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