EP1125005B1 - Kathode für die elektrolyse von wässrigen lösungen - Google Patents

Kathode für die elektrolyse von wässrigen lösungen Download PDF

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Publication number
EP1125005B1
EP1125005B1 EP00958706A EP00958706A EP1125005B1 EP 1125005 B1 EP1125005 B1 EP 1125005B1 EP 00958706 A EP00958706 A EP 00958706A EP 00958706 A EP00958706 A EP 00958706A EP 1125005 B1 EP1125005 B1 EP 1125005B1
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Prior art keywords
titanium
cathode according
cathode
zirconium
precious metal
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EP00958706A
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English (en)
French (fr)
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EP1125005A1 (de
Inventor
Françoise Andolfatto
Philippe Joubert
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Kem One SAS
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Arkema SA
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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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the present invention relates to a cathode which can be used for electrolysis of aqueous solutions in which a reaction occurs water reduction.
  • the present invention relates to a cathode activated for the electrolysis of alkaline aqueous solutions of chlorides of alkali metals, and especially for the preparation chlorine and sodium hydroxide.
  • chlorine and sodium hydroxide are manufactured in electrolytic cells, each of them comprising several mild steel cathodes and several coated titanium anodes of a mixture of titanium oxides and ruthenium. They are usually fed with electrolytic solution of about 200 to 300 g / l sodium chloride.
  • overvoltage is meant the difference between the thermodynamic potential of the redox couple concerned (H 2 O / H 2 ) with respect to a reference cathode and the potential actually measured in the medium concerned, with respect to the same reference electrode.
  • overvoltage we use the term overvoltage to designate the absolute value of the cathode overvoltage.
  • a cathode whose substrate is a plate made of titanium, zirconium, niobium or alloy essentially consisting of an association of these metals and on which a layer of metal oxide is applied, essentially consisting of an oxide of one or more selected metals among ruthenium, rhodium, palladium, osmium, iridium and platinum and optionally an oxide of one or more metals selected from calcium, magnesium, strontium, barium, zinc, chromium, molybdenum, tungsten, selenium and tellurium.
  • US Pat. No. 4,100,049 discloses a cathode comprising a substrate of iron, nickel, cobalt or an alloy of these metals and a coating of palladium oxide and zirconium oxide.
  • cathode consisting of an electrically conductive nickel substrate, stainless steel or mild steel with a coating consisting of plurality of metal oxide layers, the surface layer being constituted by a valve metal oxide, that is to say a metal chosen from groups 4b, 5b and 6b of the Periodic Table of Elements and the intermediate layer consisting of a precious metal oxide of the group VIII, i.e., ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the intermediate and superficial layers can be formed by the oxide of the only metal concerned or by a mixed oxide of metal concerned and the second metal in a small proportion.
  • a cathode to reduce the overvoltage of the water reduction reaction in an alkaline medium, characterized in that it is constituted by an electroconductive substrate coated with an intermediate layer of oxides based on titanium and a metal Group VIII of the Periodic Table of Elements and an outer layer of metal oxides comprising titanium, zirconium and a precious metal of group VIII of the classification periodic element, the precious metal in the outer layer representing a molar amount of between 30% and 50% relative to the metals used in the composition of this layer.
  • ruthenium By precious metal of group VIII of the Periodic Table elements, ruthenium, rhodium, palladium, osmium, iridium or platinum. Preferably, we will use the ruthenium or iridium and especially ruthenium.
  • the intermediate layer contains oxides of titanium and ruthenium.
  • the outer layer of metal oxides contains oxides of titanium, zirconium and ruthenium.
  • the outer layer consists essentially of ZrTiO 4 accompanied by RuO 2 and optionally ZrO 2 and / or TiO 2 .
  • the material constituting the substrate may be chosen from electrically conductive materials. We will choose it advantageously in the group consisting of titanium, nickel, tantalum, zirconium, nobium, iron and their alloys.
  • titanium, nickel, iron or their alloys Preferably, titanium, nickel, iron or their alloys.
  • the molar ratio of precious metal / titanium in the layer intermediate is preferably between 0.4 and 2.4.
  • the zirconium / titanium molar ratio in the outer layer is generally between 0.25 and 9 and preferably between 0.5 and 2.
  • the precious metal in the outer layer is between 30% and 50% molar with respect to metals used in the composition of this layer.
  • Pretreatment generally involves subjecting the substrate, either to sandblasting followed by acid washing or stripping with an aqueous solution of oxalic acid, hydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of hydrofluoric acid and glycerol, a mixture of hydrofluoric acid, nitric acid and glycerol or a mixture of hydrofluoric acid, nitric acid and hydrogen peroxide, followed by one or more washing (s) with degassed demineralized water.
  • the substrate can be in the form of solid plate, plate perforated, expanded metal or cathode basket made from metal deployed or perforated.
  • Solution A is usually prepared by contacting at at room temperature and with stirring, essentially a mineral salt or organic titanium and a precious metal with water or in a organic solvent, optionally in the presence of a chelating agent.
  • the temperature can be raised above the ambient to facilitate the dissolution of salts.
  • a mineral or organic salt is brought into contact titanium and a precious metal with water or in a solvent organic, optionally in the presence of a chelating agent.
  • Titanium and the precious metal are preferably present in the solution A at a concentration at most equal to 10 mol / l.
  • Solution B is usually prepared by contacting, at at room temperature and with stirring, a mineral or organic salt of titanium, zirconium and a precious metal with water or in a organic solvent, optionally in the presence of a chelating agent.
  • a mineral or organic salt of titanium, zirconium and a precious metal with water or in a organic solvent, optionally in the presence of a chelating agent.
  • an ice bath is used to cool the reaction medium.
  • a mineral or organic salt is brought into contact of titanium, zirconium and a precious metal with water or in a organic solvent, optionally in the presence of a chelating agent.
  • the titanium salts and preferred precious metals are the chlorides, oxychlorides, nitrates, oxynitrates, sulphates and alkoxides.
  • the chlorides of the precious metals, the ruthenium chlorides, titanium chlorides and titanium oxychlorides are used.
  • zirconium salts it is possible to use the chlorides, sulfates, zirconyl chloride, zirconyl nitrate, alkoxides such as than butyl zirconate.
  • Zirconium and zirconyl chlorides are particularly preferred.
  • organic solvent mention may be made of the light alcohols of preferably isopropanol and ethanol, and more preferably isopropanol and absolute ethanol.
  • solvent is absolute ethanol or absolute isopropanol.
  • Titanium and zirconium are usually present in the solution B at a concentration ranging from 0.5 to 5 mol / l.
  • concentration of metal valuable in solution B is usually between 0.05 and 10 mol / l and preferably between 0.1 and 5 mol / l.
  • Solution A can be deposited on the pretreated substrate using different techniques such as sol-gel, electrochemical deposition, electroplating, spraying or coating.
  • the pretreated substrate is coated with solution A, for example with the aid of a brush.
  • the substrate thus coated is then dried in air and / or in a oven at a temperature below 150 ° C.
  • the substrate is calcined under air or under inert gases such as nitrogen, argon or still under inert gases enriched with oxygen at a temperature at less than 300 ° C and preferably between 450 ° C and 550 ° C for a period ranging from 10 minutes to 2 hours.
  • step (c) of the process the same techniques can be used deposition and the same operating conditions for drying and calcination as step (b) except that the deposition is carried out with solution B.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • plasma projection are also suitable for coating the pretreated substrate with intermediate layer and an outer layer.
  • Solution A can be deposited on one of the faces of substrate pretreated only on both sides. We can also drop the solution B on both sides of the substrate coated with the layer intermediate.
  • step (b) Depending on the thickness of the desired intermediate layer, repeat step (b) several times. Similarly, we can repeat several times step (c) of the process.
  • the mass of deposited product is at least equal to 2 g / m 2 , generally between 10 g / m 2 and 60 g / m 2 and, preferably, between 20 g / m 2 and 35 g. / m 2 related to the geometrical surface of the substrate.
  • the concentration of solution A is judiciously chosen from so that this preferred deposited mass can be obtained in repeating step (b) in a reasonable number of times and preferably between 1 and 10 times.
  • the mass of deposited product is at least equal to 5 g / m 2 , generally between 5 g / m 2 and 70 g / m 2 and, preferably, between 25 g / m 2 and 50 g. / m 2 , related to the geometrical surface of the substrate.
  • solution B is prepared so that its concentration makes it possible to obtain a preferred deposited mass by repeating at least 1 time step (c) and preferably between 2 and 10 times.
  • the cathode of the present invention is particularly suitable electrolysis of aqueous solutions of alkali metal chlorides and especially aqueous solutions of NaCl.
  • cathode in combination with an anode allows to electrolytically synthesize the chlorine and hydroxide of a metal alkaline with a high Faraday yield.
  • the DSA anodes (Dimensionally Stable Anode) consisting of a titanium substrate coated with an oxide layer titanium and ruthenium.
  • the molar ratio ruthenium / titanium in this layer is advantageously between 0.4 and 2.4.
  • the cathode of the present invention has the advantage of having a overvoltage lower than the cathodes of the prior art during a operation in electrolysis.
  • the cathode of the present invention does not suffer from modification in the first characterization cycles and presents a greater chemical stability against aggressive alkaline media.
  • a solution A containing ruthenium and titanium in an equimolar quantity, is then prepared by mixing at room temperature with stirring 2.45 g of RuCl 3 , of purity greater than or equal to 98%, 3.64 cm 3 of TiOCl 2 , 2HCl at 127 g / l in Ti and 2.5 cm 3 of absolute isopropanol.
  • the end of one of the faces of the plate is then coated pretreated, representing a surface of 1 cm x 4 cm, with solution A to with a brush, then let it dry for 30 minutes in the open air and ambient temperature.
  • the coated plate is then dried additionally in an oven at 120 ° C for 30 minutes, then calcined in an oven under air at 500 ° C for 30 min.
  • Chloride or oxychloride is mixed with stirring. zirconium, ruthenium chloride and chloride or oxychloride titanium with absolute ethanol. In the case of chlorides, solution B is prepared cold and kept cold by a water / ice bath, under stirring until used.
  • solution B is prepared at 60 ° C. and maintained at this temperature, with stirring, until use.
  • the plate coated with 1.1 is then coated with solution B at using a paintbrush.
  • the coated plate is initially dried 30 minutes in the open air and at room temperature, then in a second time dried additionally in an oven at 120 ° C for 30 minutes, and finally calcined in an oven under air at 500 ° C for 30 minutes.
  • the performances of the cathode, vis-à-vis the reduction of the water, are evaluated from a polarization curve, carried out in a 1M sodium hydroxide solution and at a temperature of between 20 ° C and 25 ° C (room temperature).
  • polarization curve is meant the curve of variation of the measured cathodic potential relative to a reference electrode, by example a saturated calomel electrode (ECS), depending on the density current.
  • ECS saturated calomel electrode
  • the experimental setup consists of the cathode to be evaluated, a platinum counter-electrode (surface 5 cm 2 ) and an ECS reference electrode elongated with a capillary, which is placed in close proximity to the cathode.
  • the whole is immersed in the electrolytic solution (1M NaOH) stirred by magnetic stirring.
  • the three electrodes are connected to the terminals of a potentiostat.
  • the potential of the cathode is imposed by the apparatus and one raises after the equilibrium of the system the value of the current passing through said system.
  • This potential is varied from -0 mV / ECS to -1500 mV / ECS.
  • Solution B is prepared by mixing with stirring in a glass flask 1.07 g of RuCl 3 , 2.59 g of ZrOCl 2 , 8H 2 O, 1.55 ml of TiOCl 2 , 2HCl in 7 ml of absolute ethanol. or a total molar composition of 0.3 Ru-0.7 (Ti, 2Zr).
  • the coated plate of the intermediate layer is then coated with solution B thus prepared, and then dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the deposited mass is 39 g / m 2 relative to the geometric surface of the plate.
  • the cathode thus prepared was evaluated using the procedure described previously.
  • the cathodic potential is -1.375 V / ECS for a current density of -2 kA / m 2 .
  • the cathodic potential of a cathode of nickel is -1.475 V / ECS under the same conditions.
  • Solution B is prepared by mixing with stirring in a glass flask 2.49 g RuCl 3 , 2.59 g of ZrOCl 2 , 8H 2 O, 1.55 ml of TiOCl 2 , 2HCl in 10 ml of absolute ethanol is an overall molar composition of 0.5 Ru-0.5 (Ti, 2Zr).
  • the coated plate of the intermediate layer is then coated with solution B thus prepared, and then dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the external deposited mass is 41 g / m 2 relative to the geometric surface of the plate.
  • the cathode thus prepared was evaluated using the procedure described previously.
  • the cathode potential is -1.195 V / ECS for a current density of -2 kA / m 2 .
  • Solution B is prepared by mixing with stirring in a glass vessel, cooled with an ice bath, 2.49 g of RuCl 3 , 2.80 g of ZrCl 4 , 1.32 ml of TiCl 4. in 10 ml of absolute ethanol, ie a total molar composition of 0.5 Ru-0.5 (Ti, Zr).
  • the coated plate of the intermediate layer is then coated with solution B thus prepared, and then dried and calcined in air as indicated in the general procedure. These operations are repeated 8 times and at the end of the last calcination, the deposited mass is 45 g / m 2 of the plate, relative to the geometric surface of the plate.
  • the cathode thus prepared was evaluated using the procedure described previously.
  • the cathodic potential is -1.190 V / ECS for a current density of -2 kA / m 2 in a 1M NaOH solution.
  • a cathode is prepared according to the patent application EP 209 427 and we evaluate it.
  • the substrate consists of a plate of 4 x 1 x 0.2 cm, which has been welded a round rod of current supply. We perform a surface treatment with corundum.
  • a solution of 2 g of RuCl 3 in 2 ml of ethanol is prepared at ambient temperature.
  • the control plate is coated with this solution. Then, the plate is dried in air at 120 ° C for 30 minutes, followed by calcination in air (500 ° C, 30 minutes).
  • a deposit of 16 mg / m 2 of RuO 2 is obtained.
  • a solution in 2 cm3 of ethanol, 2.6 ml of TiOCl 2 , HCl at 2.5 mol / l of Ti is prepared at ambient temperature. The same treatments are applied coating / steaming / calcination under air. 8.5 g / m 2 of TiO 2 are thus deposited.
  • the cathode potential of this electrode is -1.240 V / ECS for a current density of -2 kA / m 2 evaluated according to the procedure described above.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Kathode für die Elektrolyse von wäßrigen Lösungen, bestehend aus einem elektrisch leitenden Substrat, das mit einer Zwischenschicht aus Oxiden auf Basis von Titan und einem Edelmetall aus der Gruppe VIII des Periodensystems der Elemente und mit einer Außenschicht aus Titan, Zirconium und ein Edelmetall aus der Gruppe VIII des Periodensystems der Elemente enthaltenden Metalloxiden überzogen ist, dadurch gekennzeichnet, daß das Edelmetall in der Außenschicht eine molare Menge zwischen 30 und 50%, bezogen auf die in die Zusammensetzung dieser Schicht eingehenden Metalle, ausmacht.
  2. Kathode nach Anspruch 1, dadurch gekennzeichnet, daß das Substrat aus der Gruppe bestehend aus Titan, Nickel, Tantal, Zirconium, Niob, Eisen und Legierungen davon ausgewählt ist.
  3. Kathode nach Anspruch 2, dadurch gekennzeichnet, daß das Substrat aus Titan, Eisen oder Nickel besteht.
  4. Kathode nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei dem Edelmetall aus der Gruppe VIII des Periodensystems der Elemente um Ruthenium, Rhodium, Palladium, Osmium, Iridium oder Platin handelt.
  5. Kathode nach Anspruch 4, dadurch gekennzeichnet, daß es sich bei dem Edelmetall um Ruthenium oder Iridium handelt.
  6. Kathode nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Zwischenschicht aus Titan- und Rutheniumoxid besteht.
  7. Kathode nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Außenschicht aus Metalloxiden Zirconium-, Titan- und Rutheniumoxid enthält.
  8. Kathode nach Anspruch 7, dadurch gekennzeichnet, daß sie im wesentlichen aus ZrTiO4 mit RuO2 und gegebenenfalls ZrO2 und/oder TiO2 besteht.
  9. Kathode nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Edelmetall/Titan-Molverhältnis in der Zwischenschicht zwischen 0,4 und 2,4 liegt.
  10. Kathode nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Zirconium/Titan-Molverhältnis in der Zwischenschicht zwischen 0,25 und 9 liegt.
  11. Kathode nach Anspruch 10, dadurch gekennzeichnet, daß das Zirconium/Titan-Molverhältnis in der Zwischenschicht zwischen 0,5 und 2 liegt.
  12. Verwendung einer Kathode nach einem der Ansprüche 1 bis 11 zur Elektrolyse von wäßrigen Alkalimetallchloridlösungen.
  13. Verwendung nach Anspruch 12, dadurch gekennzeichnet, daß es sich bei den wäßrigen Alkalimetallchloridlösungen um wäßrige NaCl-Lösungen handelt.
  14. Verfahren zur Herstellung von Chlor und Alkalimetallhydroxid durch Elektrolyse des entsprechenden Chlorids unter Verwendung einer Kathode nach einem der Ansprüche 1 bis 11.
EP00958706A 1999-08-20 2000-08-18 Kathode für die elektrolyse von wässrigen lösungen Expired - Lifetime EP1125005B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9910659 1999-08-20
FR9910659A FR2797646B1 (fr) 1999-08-20 1999-08-20 Cathode utilisable pour l'electrolyse de solutions aqueuses
PCT/FR2000/002341 WO2001014615A1 (fr) 1999-08-20 2000-08-18 Cathode utilisable pour l'electrolyse de solutions aqueuses

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Publication Number Publication Date
EP1125005A1 EP1125005A1 (de) 2001-08-22
EP1125005B1 true EP1125005B1 (de) 2005-04-06

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US (1) US6527924B1 (de)
EP (1) EP1125005B1 (de)
JP (1) JP4464023B2 (de)
KR (1) KR100735588B1 (de)
CN (1) CN1205359C (de)
AT (1) ATE292696T1 (de)
AU (1) AU7014300A (de)
CA (1) CA2347728C (de)
DE (1) DE60019256T2 (de)
ES (1) ES2240152T3 (de)
FR (1) FR2797646B1 (de)
MX (1) MXPA01003960A (de)
NO (1) NO322413B1 (de)
PT (1) PT1125005E (de)
WO (1) WO2001014615A1 (de)

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AU7014300A (en) 2001-03-19
EP1125005A1 (de) 2001-08-22
CA2347728A1 (fr) 2001-03-01
ES2240152T3 (es) 2005-10-16
FR2797646B1 (fr) 2002-07-05
KR20010083919A (ko) 2001-09-03
CN1348510A (zh) 2002-05-08
FR2797646A1 (fr) 2001-02-23
US6527924B1 (en) 2003-03-04
ATE292696T1 (de) 2005-04-15
DE60019256T2 (de) 2006-03-09
JP4464023B2 (ja) 2010-05-19
KR100735588B1 (ko) 2007-07-04
CN1205359C (zh) 2005-06-08
PT1125005E (pt) 2005-08-31
MXPA01003960A (es) 2002-04-24
NO322413B1 (no) 2006-10-02
NO20011931D0 (no) 2001-04-19
CA2347728C (fr) 2010-10-19
NO20011931L (no) 2001-05-28
JP2003507580A (ja) 2003-02-25
DE60019256D1 (de) 2005-05-12
WO2001014615A1 (fr) 2001-03-01

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