EP0004236B1 - Elektrode für Elektrolyse - Google Patents

Elektrode für Elektrolyse Download PDF

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Publication number
EP0004236B1
EP0004236B1 EP79400139A EP79400139A EP0004236B1 EP 0004236 B1 EP0004236 B1 EP 0004236B1 EP 79400139 A EP79400139 A EP 79400139A EP 79400139 A EP79400139 A EP 79400139A EP 0004236 B1 EP0004236 B1 EP 0004236B1
Authority
EP
European Patent Office
Prior art keywords
titanium
electrode according
oxide
cobalt oxide
cobalt
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
EP79400139A
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English (en)
French (fr)
Other versions
EP0004236A2 (de
EP0004236A3 (en
Inventor
Pierre Bouy
Dominique Ravier
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.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
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
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Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Publication of EP0004236A2 publication Critical patent/EP0004236A2/de
Publication of EP0004236A3 publication Critical patent/EP0004236A3/xx
Application granted granted Critical
Publication of EP0004236B1 publication Critical patent/EP0004236B1/de
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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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

Definitions

  • the invention relates to electrodes for electrolysis, in particular of sodium chloride, the coating of which consists of cobalt and titanium compounds.
  • the anodes used industrially generally comprise a substrate, generally of titanium, covered with metals of the platinum group or their oxides in mixture optionally with oxides of other metals and in particular of titanium in rutile form; which oxide is also formed in situ during electrolysis.
  • the use of precious metals leads to high investments when setting up factories; in addition, the consumption of these metals, although low in weight, reaches a non-negligible value compared to the value of the products of electrolysis.
  • the invention relates to an electrode for electrolysis, in particular sodium chloride, consisting of a valve metal substrate and a coating comprising cobalt oxide, characterized in that the cobalt oxide corresponds to formula C 03 _ X O 4 wherein x is between 10- 1 and 10- 2 and in that the coating also comprises a titanium compound and at least one of the group consisting of oxygen and hydrogen , the average valence of titanium in this compound being less than 3.
  • the titanium compound can be an oxide of formula TiO x in which formula x is between 0.45 and 1.2 and preferably between 0.9 and 1.1. It can also be a hydride of formula TiH x in which formula x is between 0.1 and 2 and preferably between 1.8 and 2. These compounds, in which the titanium has a valence lower than its maximum valence, reveal a better conductivity.
  • Cobalt oxide is preferably obtained by thermal decomposition of cobalt nitrate in particular (N0 3 ) z Co6 H 2 0, under air sweeping at a temperature of 200 to 600 ° C but preferably between 300 and 400 ° C .
  • the substrate is a valve metal, that is to say titanium, tantalum, molybdenum, zirconium, niobium or tungsten. Titanium is the preferred substrate; it can be in the form of a smooth metal plate, of canvas or obtained by powder sintering.
  • the titanium oxide or hydride can be deposited beforehand on the substrate in direct contact with it. These titanium compounds can also be deposited on the substrate at the same time as the cobalt oxide; they are then dispersed in the layer of this oxide.
  • the amount of cobalt oxide deposited is preferably 15 to 40 milligrams per square centimeter. More may be used, but this has no beneficial effect.
  • a prior deposition of titanium oxide or hydride it is necessary, for satisfactory operation of the electrode, that at least one face of the substrate is covered on at least 5 % of its surface by this compound; the thickness of the titanium compound layer is greater than 0.5 microns.
  • the atomic ratio Ti / Co must be between 0.6 and 20 and preferably between 6 and 11. These latter values are therefore not imperative but it turns out that for a ratio less than 6, there is a voltage drift after a few hundred hours of electrolysis of sodium chloride under the usual industrial conditions, using these electrodes, while that the adhesion of the coating is poor when the ratio exceeds 11.
  • the prior deposition of titanium sub-oxide on a titanium substrate is described in the published French patent application No. 2 259 921.
  • the hydride can also be formed in situ by hydriding solid or porous titanium.
  • the deposition of these compounds at the same time as that of the titanium oxide can advantageously be carried out by suspending the sub-oxide or the titanium hydride previously prepared, in a solution of cobalt salt.
  • the substrate is coated with this suspension then dried and finally heated to a temperature allowing the decomposition of the salt into oxide. This operation is repeated several times until the desired weight of cobalt and titanium is obtained: the proportion of titanium compound in the salt solution.
  • cobalt is obviously chosen accordingly.
  • the preferred cobalt salt is nitrate which is decomposed at a temperature of 200 to 600 ° C and preferably 300 to 400 ° C under air sweep, whether it is deposited alone or with the titanium compound.
  • Titanium oxide the particle size of which is preferably 0.5 to 20 microns, can be prepared separately, or deposited directly on the substrate previously pickled and washed, using a plasma torch either from the dioxide. with, as carrier gas and plasma-forming agent, a mixture of hydrogen and argon, either from titanium powder with a mixture of oxygen and argon, or from a mixture of titanium dioxide and / or hydride with an argon plasma.
  • a plasma torch either from the dioxide.
  • a mixture of hydrogen and argon either from titanium powder with a mixture of oxygen and argon, or from a mixture of titanium dioxide and / or hydride with an argon plasma.
  • the method described in the French patent application cited above for forming the sub-oxide on the substrate can be used to form it separately.
  • Titanium hydride can be prepared and deposited by a wide variety of methods such as those described in US Patents 2,401,326 and 3,732,157. Hydride can also be formed chemically in a hydrochloric acid solution from 4 to 13 N or electrochemically. Titanium dioxide can also be reduced by elements such as magnesium or carbon in the presence of hydrogen or by a hydride such as calcium.
  • the analyzes carried out in particular by X-rays have shown that the coatings of the invention were in fact a mixture of cobalt oxide of composition close to C 03 0 4 and of sub-oxide or of titanium hydride; the significant presence of a mixed compound of these two metals has never been observed.
  • a substrate consisting of a sintered titanium plate covered with titanium sub-oxide over a thickness of approximately 1 mm, as described in the French application published under No. 2 259 921, is coated on the oxide layer, using a brush, a solution of cobalt nitrate obtained by dissolving 1 g of Co (N0 3 ) 2 6 H 2 0 in 2 cm 3 of mixture with equal volume of water and isopropyl alcohol .
  • This substrate thus coated is dried in an oven and then heated for 10 minutes at 350 ° C. in an oven with air sweeping. This sequence of operations is repeated until 37 mg of cobalt oxide per cm 2 is obtained .
  • the plate thus coated is used as an anode in a diaphragm electrolysis cell containing a NaCl brine at 300 g / i of which the pH is 4.5 and the temperature 85 ° C.
  • the voltage compared to a saturated calomel electrode (DHW voltage) measured after 3000 hours of operation is 1077 mV, at a current density of 25 A / dm 2 .
  • DHW voltage saturated calomel electrode
  • the treatment of the coated plate is carried out according to the process described in Example 1 and this plate is used as an electrode also under the same conditions as those indicated in the previous example (current density 25 A / dm 2 ).
  • the amount of cobalt oxide deposited is 27 mg / cm 2 .
  • the DHW voltage measured after 957 hours of operation is 1090 mV.
  • the weight of cobalt oxide is 37 mg / cm 2 .

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)
  • Electrolytic Production Of Metals (AREA)

Claims (8)

1. Elektrode ohne Edelmetall zur Elektrolyse, insbesondere von Natriumchlorid, bestehend aus einer Schicht eines Ventilmetalls und einem Kobaltoxid enthaltenden Überzug, dadurch gekennzeichnet, daß das Kobaltoxid der Formel CO3-x04 entspricht, in der x zwischen 0,1 und 0,01 liegt und daß der Überzug im wesentlichen aus Kobaltoxid und einer Verbindung aus Titan und einem Element aus der durch Wasserstoff und Sauerstoff gebildeten Gruppe besteht, wobei die mittlere Valenz des Titans in dieser Verbindung kleiner 3 ist.
2. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß die Titanverbindung ein Oxid der Formel TiOx ist, in der x zwischen 0,45 und 1,2, vorzugsweise zwischen 0,9 und 1,1 liegt.
3. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß die Titanverbindung ein Hydrid der Formel TiHx ist, in der x zwischen 0,1 und 2, vorzugsweise zwischen 1,8 und 2 liegt.
4. Elektrode nach Anspruch 1, dadurch gekennzeichnet, daß die Menge an Kobaltoxid zwischen 15 und 40 mg/cm2 beträgt.
5. Elektrode nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das verwendete Kobaltoxid das durch thermische Zersetzung von Kobaltnitrat erhaltene Produkt ist.
6. Elektrode nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Titanverbindung eine Schicht mit direktem Kontakt zur Schicht des Ventilmetalls bildet.
7. Elektrode nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Titanverbindung in der Kobaltoxidschicht dispergiert ist.
8. Elektrode nach Anspruch 7 in der das Verhältnis der Zahl der Titanatome gegenüber der von Kobalt im Überzug zwischen 0,6 und 20, vorzugsweise zwischen 6 und 11 liegt.
EP79400139A 1978-03-13 1979-03-06 Elektrode für Elektrolyse Expired EP0004236B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7807093 1978-03-13
FR7807093A FR2419985A1 (fr) 1978-03-13 1978-03-13 Electrode pour electrolyse du chlorure de sodium

Publications (3)

Publication Number Publication Date
EP0004236A2 EP0004236A2 (de) 1979-09-19
EP0004236A3 EP0004236A3 (en) 1979-10-31
EP0004236B1 true EP0004236B1 (de) 1982-09-01

Family

ID=9205665

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79400139A Expired EP0004236B1 (de) 1978-03-13 1979-03-06 Elektrode für Elektrolyse

Country Status (14)

Country Link
US (1) US4222842A (de)
EP (1) EP0004236B1 (de)
JP (1) JPS54130498A (de)
AR (1) AR217508A1 (de)
AT (1) AT360560B (de)
AU (1) AU521561B2 (de)
BR (1) BR7901475A (de)
CA (1) CA1103204A (de)
DE (1) DE2963595D1 (de)
ES (1) ES478528A1 (de)
FR (1) FR2419985A1 (de)
GR (1) GR66977B (de)
IL (1) IL56840A (de)
NO (1) NO152258C (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5004626A (en) * 1986-10-27 1991-04-02 Huron Technologies, Inc. Anodes and method of making
US4912286A (en) * 1988-08-16 1990-03-27 Ebonex Technologies Inc. Electrical conductors formed of sub-oxides of titanium
EP1489200A1 (de) * 2003-06-19 2004-12-22 Akzo Nobel N.V. Elektrode
CN111041508A (zh) * 2018-10-12 2020-04-21 丰田自动车株式会社 四氧化三钴阵列/钛网分解水制氧电极及其制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2401326A (en) * 1943-03-12 1946-06-04 Metal Hydrides Inc Production of metal hydrides
US3399966A (en) * 1964-05-18 1968-09-03 Trurumi Soda Company Ltd Novel cobalt oxide and an electrode having the cobalt oxide coating
US3617462A (en) * 1968-05-06 1971-11-02 Ppg Industries Inc Platinum titanium hydride bipolar electrodes
SU431900A1 (de) * 1972-11-28 1974-06-15
DE2300422C3 (de) * 1973-01-05 1981-10-15 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung einer Elektrode
US3977958A (en) * 1973-12-17 1976-08-31 The Dow Chemical Company Insoluble electrode for electrolysis
DE2405010C3 (de) * 1974-02-02 1982-08-05 Sigri Elektrographit Gmbh, 8901 Meitingen Sinter-Elektrode für elektrochemische Prozesse und Verfahren zum Herstellen der Elektrode
US4078988A (en) * 1974-02-02 1978-03-14 Sigri Elektrographit Gmbh Electrode for electrochemical processes and method of producing the same
US4080278A (en) * 1975-07-08 1978-03-21 Rhone-Poulenc Industries Cathode for electrolytic cell
US4061549A (en) * 1976-07-02 1977-12-06 The Dow Chemical Company Electrolytic cell anode structures containing cobalt spinels

Also Published As

Publication number Publication date
IL56840A (en) 1982-04-30
AU4504979A (en) 1979-09-20
NO790826L (no) 1979-09-14
AR217508A1 (es) 1980-03-31
BR7901475A (pt) 1979-10-09
AT360560B (de) 1981-01-26
IL56840A0 (en) 1979-05-31
NO152258C (no) 1985-08-28
JPS54130498A (en) 1979-10-09
GR66977B (de) 1981-05-15
ATA184579A (de) 1980-06-15
FR2419985B1 (de) 1982-10-01
EP0004236A2 (de) 1979-09-19
EP0004236A3 (en) 1979-10-31
JPS578193B2 (de) 1982-02-15
DE2963595D1 (en) 1982-10-28
NO152258B (no) 1985-05-20
AU521561B2 (en) 1982-04-08
CA1103204A (fr) 1981-06-16
US4222842A (en) 1980-09-16
FR2419985A1 (fr) 1979-10-12
ES478528A1 (es) 1979-06-01

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