EP0135687B1 - Electrode métallique pour dégagement gazeux - Google Patents

Electrode métallique pour dégagement gazeux Download PDF

Info

Publication number
EP0135687B1
EP0135687B1 EP84107873A EP84107873A EP0135687B1 EP 0135687 B1 EP0135687 B1 EP 0135687B1 EP 84107873 A EP84107873 A EP 84107873A EP 84107873 A EP84107873 A EP 84107873A EP 0135687 B1 EP0135687 B1 EP 0135687B1
Authority
EP
European Patent Office
Prior art keywords
profiles
electrode
curvature
gas
metal electrode
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
Application number
EP84107873A
Other languages
German (de)
English (en)
Other versions
EP0135687A1 (fr
Inventor
Hans Dr. Roos
Dieter Dr. Schlaefer
Hugo Boehn
Knut Dr. Bittler
Heinz Kilthau
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.)
BASF SE
Original Assignee
BASF SE
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
Priority claimed from DE19833325187 external-priority patent/DE3325187A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP0135687A1 publication Critical patent/EP0135687A1/fr
Application granted granted Critical
Publication of EP0135687B1 publication Critical patent/EP0135687B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a gas-evolving metal electrode, e.g. can be used in particular as an anode in amalgam cells for chlor-alkali electrolysis.
  • the use of titanium as the electrode base material allows a large number of different geometrical designs in comparison to graphite in order to fulfill the required function as a gas-generating electrode.
  • the production of very flat electrode surfaces (+ 1 mm difference / m 2 electrode surface) has become possible. This in turn allows the distance from the anode to the cathode to be significantly reduced.
  • the electrolyte solution in the case of chloralkali electrolysis the NaCI solution, has an electrical resistance, the aim is to reduce the voltage or energy losses caused thereby to a minimum by keeping the distance between the electrodes as small as possible.
  • OE-AS 20 41 250 an electrode construction is described in which the working electrode surface, that of the cathode, e.g. in chlorine production using the amalgam process, the mercury cathode, made of expanded metal, perforated sheet metal, wire mesh or the like. is formed.
  • a U-shaped conductor rail is used for uniform current distribution, which must also give the expanded metal the necessary mechanical rigidity in order to achieve the required planarity. It is easy to see that the production of such a conductor rail is very problematic, since titanium sheets have to be pressed into a U-shape and titanium tends to “spring back” after such a pressing process.
  • notches have to be incorporated into this conductor rail , which reduce the stresses that occur when the expanded metal is welded to the rail, and also allow subsequent correction of the working surface of the anode in order to achieve a better planarity of the electrode surface
  • the gas bubbles formed are now discharged upwards through the openings in the expanded metal, perforated plate, etc.
  • openings must therefore also be worked into the relatively large conductor rail
  • Conductor rails can also be fixed with stable cross struts.
  • the titanium sheathing of the aluminum must be absolutely tight at all points, in particular also at the weld seams, since with the slightest damage to the titanium sheath, the electrode is rapidly destroyed by the anodic dissolution of the aluminum which takes place in the presence of chloride.
  • US Pat. No. 4,055,847 describes a complicated structure for achieving the necessary strength of the electrode surface and for achieving a good current distribution. It consists of a spider-shaped power distribution system, in which additional support ribs are required. As stated in the patent specification, melting and casting processes are necessary to produce the corresponding structures. However, as is generally known, these are complex and expensive in the processing of metals, in particular titanium or valve metals, since valve metals can only be melted in an argon atmosphere with a strict exclusion of air for metallurgical reasons. Another possible solution is shown in DE-OS 29 49 495. However, this construction also requires a primary and secondary power distribution system, which - analogous to that of DE-OS 1814 567 - require high manufacturing and material costs. Due to the relatively open construction of this system from flat profiles, however, gas bubble tearing and mass transfer on the electrode surface are to be improved.
  • DE-OS 30 08 116 describes an electrode construction which has only a primary distribution system, but which is also relatively complex.
  • the oval profiles used here are created by flattening the round bars. This should achieve a ratio of working to projected electrode area of> 1.
  • no attention is paid here cf. J. Cramer, Chem. Ing. Techn. 52, 1980, pp. 48-51 that the solution to be electrolyzed opposes the passage of the electric current, so that the electrode surfaces are all the less to the course of the electrolysis reaction, ie Gas evolution contribute the further away they are from the counter electrode.
  • the reason for this is the fact that the streamlines are looking for the shortest possible route as they pass through the solution to be electrolyzed.
  • German utility model 72 07 894 describes a gas-developing electrode which consists of a plate which is interspersed with channels which widen near and to a surface of the electrode. These channels can be continuously conical or venturi-like. This is intended to achieve an improved electrolyte circulation. Apart from the fact that this electrode can only be produced with complex manufacturing technology, this electrode has not found any technical use, since plate-shaped electrodes in particular have disadvantages with regard to gas removal.
  • a gas-developing metal electrode for electrolysis cells in particular anode for amalgam cells for chloralkali electrolysis, which consists of profiles arranged parallel to one another in a horizontal plane, the effective electrode surface facing the counterelectrode being curved and the profiles having a transverse profile with it a power supply provided power supply are connected to each other, which is characterized in that the curvature of the effective electrode surface in the area of the gaps into one with a smaller radius (r) passes, the radius (R) determining the curvature of the effective electrode surface being from 7 to 180 mm and the smaller radius (r) being 0.5 to 4 mm, and the profiles being closed off at the top by two side surfaces which emerge tangentially from the curvature (22, 25), which form an angle (alpha) of 20 to 120 ° at their intersection.
  • Solid or hollow profiles can be used as profiles for the electrodes according to the invention.
  • full profiles more titanium is required than with hollow profiles, but this disadvantage is offset by the advantage that the resistance is reduced and the voltage drop is reduced.
  • full profiles are easier to process.
  • the effective electrode area i.e. the surface which can be projected onto the counterelectrode is curved in such a way that the curvature increases from the center towards the edges.
  • FIG. 1 is a perspective view
  • FIG. 2 in which two profiles are shown enlarged from viewing direction X.
  • the effective electrode surface consists of profiles arranged parallel to each other.
  • the mechanical and electrical connection of these electrode profiles to one another is carried out by welding with one or more titanium webs (2) which have a shape specially developed for the purpose described. Titanium bodies (5) with an internal thread are attached to these webs.
  • the internal thread serves to receive a power supply (4), e.g. a copper bolt. If necessary, this can be protected from the electrolyte solution (and thus anodic dissolution) by a welded-on titanium tube (5).
  • the power supply to the individual electrode profiles takes place exclusively through a simple primary conductor system made of titanium webs (2). This is easy to manufacture from commercially available titanium sheets of appropriate thickness (matched to the current load) by simply punching them out.
  • FIG. 2 two hollow electrode profiles according to the invention, according to viewing direction X from FIG. 1, are shown schematically, enlarged compared to FIG.
  • the work surface 21, i.e. the surface which can be projected onto the counterelectrode is curved according to the invention in such a way that the curvature on the sides, i.e. to the neighboring profile or to the cell wall becomes stronger.
  • the curvature is determined by the radius R and the two smaller radii r.
  • the hollow profile is closed at the top by the two meeting side surfaces 22 and 25, which are continued tangentially from the curved working surface.
  • the cross section of the gap zone between two profiles is given the profile of a nozzle-shaped rounded inlet zone and a calming zone which widens upward like a diffuser.
  • the gas bubbles formed on the work surface move towards the edges of the profiles and, due to the intensifying curvature, experience a desired uniform acceleration in contrast to an abrupt tearing off of the gas bubbles on an edge-shaped profile, which results in a higher pressure loss connected is.
  • the gas is brought to the speed required to pass the narrowest point of the gap between two profiles with a minimal pressure loss. Due to the lower pressure drop, the gas bubbles reach a higher speed, which entrains a larger amount of liquid.
  • the profiles should have certain geometric dimensions have, which are selected depending on the cell conditions.
  • the work surface has less curvature in the middle than at the edges.
  • the curvature in the central part is determined by a circular line whose radius R is 7-180 mm, preferably 15 to 25 mm, while on both sides the curvature becomes stronger and in a circular line with a radius r of 0.5 to 4 mm passes.
  • the two radii should be chosen so that R / r i: 5.
  • the inventive design of the work surface ensures that, due to the relatively large radius of the circular line in the central region, an almost optimal, uniform distance of the work surface from the counter-cathode is ensured, the relatively small curvature of which, however, is already sufficient for rapid removal of the gas bubbles formed. Due to the stronger rounding at the transition of the work surface into the tangential side surfaces, edges are avoided at this point, which, as is known, are subject to increased wear.
  • the height of the circular arc results (ie the greatest distance between the web width S and the working surface 21), which, however, should meet the condition that is from 5 to 1800.
  • the inclination of the side surfaces can also be varied within wide limits. This inclination is determined by the angle with which they meet and which can expediently be from 20 ° to 120 °.
  • the technical outlay for producing the metal electrodes according to the invention is low.
  • the individual electrode profiles (5) need only be welded continuously to the distributor webs (2). Notches into which the profiles are inserted can be incorporated into these webs for better fixation.
  • the relatively long weld seam ensures good current transfer from the distributor web to the profiles.
  • the electrode construction according to the invention is characterized by an extraordinarily simple structure, its mechanical strength is excellent, essentially also due to the cross-sectional shape of the profiles according to the invention.
  • the electrodes are also very easy to repair. If a profile is damaged, e.g. by short-circuiting, the respective electrode profiles can easily be exchanged individually or brought to the required planarity by corresponding messages.
  • the claimed electrode From the description of the claimed electrode it also follows that only the actually effective surface of the electrode base body has to be provided with an active layer, since here there is a construction in which different partial areas of the profiles are each optimized with regard to the task to be performed.
  • the side opposite the counterelectrode is so designed that the working electrode surface can optimally fulfill its function in the electrolysis process.
  • the other sections of the electrode profile are optimized according to hydrodynamic criteria and simple manufacture.
  • the construction is therefore very suitable for applying the activation solution by dipping, rolling or brushing. Since it is relatively easy to coat only the working electrode surface (which is desirable but not a requirement), the amount of activation solution required is reduced to a minimum. This is particularly advantageous when using activation solutions which contain expensive noble metals or noble metal compounds, for example in the case of the known Ru0 2- containing active layers for anodic chlorine deposition.
  • this construction can be coated very well with the aid of spraying processes - in particular thermal spraying processes - since the working electrode surface has no sharp edges and since it is not necessary to coat side surfaces which are difficult to access.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Claims (4)

1.- Electrode métallique à dégagement de gaz, pour cellules d'électrolyse, en particulier anode pour cellules à amalgame pour l'électrolyse de chlorure alcalin, qui est constituée de profllés disposés, parallèlement les uns aux autres, dans un plan horizontal, la surface d'électrode active tournée vers la contre-électrode étant courbe et les profilés étant reliés entre eux par des répartiteurs de courant munis d'une amenée de courant et orientés transversalement par rapport auxdits profilés, caractérisé par le fait que la courbure de la surface d'électrode active passe, dans la zone de l'interstice entre profilés, à un rayon plus petit (r), le rayon (R) qui détermine la courbure de la surface d'électrode active étant de 7 à 180 mm et le plus petit rayon (r) étant de 0,5 à 4 mm, et les profilés sont délimités vers le haut par deux surfaces latérales (22, 23) partant tangentiellement de la partie courbe et faisant entre elles, à leur ligne de rencontre un angle (a) de 20 à 120°.
2.- Electrode métallique à dégagement de gaz selon la revendication 1, caractérisé par le fait que R/r est supérieur ou égal à 5.
3.- Electrode métallique à dégagement de gaz selon les revendications 1 à 2, caractérisé par le fait que la différence de hauteur hs, déterminée par la courbure de la surface de travail, entre la largeur d'âme S et le point le plus rapproché de la contre-électrode, satisfait aux conditions
Figure imgb0005
1800.
4.- Electrode métallique à dégagement de gaz selon les revendications 1 à 3, caractérisé par le fait que les profilés sont des profilés pleins.
EP84107873A 1983-07-13 1984-07-05 Electrode métallique pour dégagement gazeux Expired EP0135687B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19833325187 DE3325187A1 (de) 1983-07-13 1983-07-13 Gasentwickelnde metallelektrode
DE3325187 1983-07-13
DE19833345530 DE3345530A1 (de) 1983-07-13 1983-12-16 Gasentwickelnde metallelektrode fuer elektrolysezellen
DE3345530 1983-12-16

Publications (2)

Publication Number Publication Date
EP0135687A1 EP0135687A1 (fr) 1985-04-03
EP0135687B1 true EP0135687B1 (fr) 1986-10-15

Family

ID=25812249

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107873A Expired EP0135687B1 (fr) 1983-07-13 1984-07-05 Electrode métallique pour dégagement gazeux

Country Status (3)

Country Link
US (1) US4557818A (fr)
EP (1) EP0135687B1 (fr)
DE (2) DE3345530A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087344A (en) * 1990-09-26 1992-02-11 Heraeus Elektroden Gmbh Electrolysis cell for gas-evolving electrolytic processes
DE4306889C1 (de) * 1993-03-05 1994-08-18 Heraeus Elektrochemie Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung
DE4419277C2 (de) * 1994-06-01 1998-07-02 Heraeus Elektrochemie Elektrolysezellen-Elektrode
KR970064007U (ko) * 1996-05-28 1997-12-11 카 오디오의 탈거 구조
US5849164A (en) * 1996-06-27 1998-12-15 Eltech Systems Corporation Cell with blade electrodes and recirculation chamber
ES2215603T3 (es) * 1999-01-08 2004-10-16 Moltech Invent S.A. Celda para electrolisis de aluminio con anodos generadores de oxigeno.
ATE382722T1 (de) * 2001-07-13 2008-01-15 Moltech Invent Sa Anodenstrukturen auf der basis von legierungen für die herstellung von aluminium
US20080041729A1 (en) * 2004-11-05 2008-02-21 Vittorio De Nora Aluminium Electrowinning With Enhanced Electrolyte Circulation
DE102006054442A1 (de) * 2006-11-16 2008-05-21 Hydrodivide Ag Elektrode und ihre Verwendung

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3409533A (en) * 1964-03-23 1968-11-05 Asahi Chemical Ind Mercury-method cell for alkali chloride electrolysis
GB1068992A (en) * 1964-03-31 1967-05-17 Asahi Chemical Ind Anode assembly
US3616445A (en) * 1967-12-14 1971-10-26 Electronor Corp Titanium or tantalum base electrodes with applied titanium or tantalum oxide face activated with noble metals or noble metal oxides
BE754741A (fr) * 1969-08-14 1971-01-18 Burndy Corp Amortisseur de cable pour des lignes de transmission
BE755592A (fr) * 1969-09-02 1971-03-02 Ici Ltd Assemblage anodique
US3795603A (en) * 1971-08-26 1974-03-05 Uhde Gmbh Apparatus for the electrolysis of alkali metal chloride solutions with mercury cathode
DE7207894U (de) * 1972-03-02 1972-11-30 Metallges Ag Elektrode, insbesondere anode
US4033847A (en) * 1973-11-05 1977-07-05 Olin Corporation Metal anode assembly
SU567771A1 (ru) * 1975-04-14 1977-08-05 Предприятие П/Я В-2287 Диафрагменный электролизер дл получени хлора и щелочи
DE2721958A1 (de) * 1977-05-14 1978-11-16 Hoechst Ag Metallelektrode fuer elektrolyseapparate zum elektrolytischen herstellen von chlor
DE3008116A1 (de) * 1980-03-03 1981-09-17 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach Gasentwickelnde metallelektrode fuer elektrochemische prozesse

Also Published As

Publication number Publication date
DE3460986D1 (en) 1986-11-20
US4557818A (en) 1985-12-10
EP0135687A1 (fr) 1985-04-03
DE3345530A1 (de) 1985-06-27

Similar Documents

Publication Publication Date Title
DD243516A5 (de) Monopolare und bipolara chlorzellen und elektrodenstrukturen fuer diese
DE2262173C3 (fr)
DE2231196A1 (de) Anodensatz fuer elektrolytische zellen
EP0135687B1 (fr) Electrode métallique pour dégagement gazeux
DE69213362T2 (de) Elektrolyseur und Herstellung davon
DE2135873B2 (de) Zellenoberteil für Amalgamhochlastzellen
EP0089475A1 (fr) Anode revêtue à base de métal soupape pour l'obtention électrolytique de métaux ou oxydes de métaux
DE2923818C2 (fr)
EP0479840A1 (fr) Cellule electrolytique pour processus electrolytiques degageant du gaz.
DE3808495C2 (fr)
DE2125941C3 (de) Bipolare Einheit und damit aufgebaute elektrolytische Zelle
DE1467075B2 (de) Anode zur elektrolytischen Herstellung von Chlor
EP0035131B1 (fr) Electrode métallique dégageant du gaz pour procédés électrochimiques
EP0753604B1 (fr) Anode pour l'obtention électrolytique de métaux
EP0274138A1 (fr) Agencement d'électrode, pour électrolyseurs produisant des gaz, présentant des plaques d'électrode disposées verticalement
DE2845832A1 (de) Vorrichtung zur diaphragma-elektrolyse
DE2949495A1 (de) Elektrode fuer elektrolysezellen
DE2909640A1 (de) Elektrolyseapparat
DE3239535C2 (de) Verfahren zur Herstellung einer bipolaren Elektrode
DE3406797A1 (de) Beschichtete ventilmetallanode zur elektrolytischen gewinnung von metallen oder metalloxiden
DD242641A5 (de) Vollstaendig aus teilen zusammengesetzte elektrochemische zelle
DE3325187A1 (de) Gasentwickelnde metallelektrode
DE3005795C2 (de) Beschichtete Metallanode zur elektrolytischen Gewinnung von Metallen
DE69203267T2 (de) Elektrischer Leiter, Verfahren zur Herstellung eines elektrischen Leiters und Elektrode für Elektrolysezelle.
DE3941056C2 (de) Verfahren zur Herstellung einer elektrisch gutleitenden Verbindung durch Reibschweißung und Stromleiter

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19850329

17Q First examination report despatched

Effective date: 19860227

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL SE

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3460986

Country of ref document: DE

Date of ref document: 19861120

ET Fr: translation filed
R20 Corrections of a patent specification

Effective date: 19870119

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 84107873.6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000626

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000627

Year of fee payment: 17

Ref country code: NL

Payment date: 20000627

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000703

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000714

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000817

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010705

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010706

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 20010714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010731

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 20010731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010705

EUG Se: european patent has lapsed

Ref document number: 84107873.6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020329

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST