EP2655693B1 - Électrode pour cellule électrolytique - Google Patents

Électrode pour cellule électrolytique Download PDF

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Publication number
EP2655693B1
EP2655693B1 EP11802731.7A EP11802731A EP2655693B1 EP 2655693 B1 EP2655693 B1 EP 2655693B1 EP 11802731 A EP11802731 A EP 11802731A EP 2655693 B1 EP2655693 B1 EP 2655693B1
Authority
EP
European Patent Office
Prior art keywords
catalytic composition
electrode according
electrode
metals
noble metal
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.)
Not-in-force
Application number
EP11802731.7A
Other languages
German (de)
English (en)
Other versions
EP2655693A2 (fr
Inventor
Christian Urgeghe
Antonio Lorenzo Antozzi
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.)
Industrie de Nora SpA
Original Assignee
Industrie de Nora SpA
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Filing date
Publication date
Application filed by Industrie de Nora SpA filed Critical Industrie de Nora SpA
Priority to EP16186150.5A priority Critical patent/EP3118351A1/fr
Publication of EP2655693A2 publication Critical patent/EP2655693A2/fr
Application granted granted Critical
Publication of EP2655693B1 publication Critical patent/EP2655693B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/046—Alloys
    • 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
    • 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
    • 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
    • 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
    • C25B11/097—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 comprising two or more noble metals or noble metal alloys

Definitions

  • the invention relates to an electrode suitable for operating as anode in electrolysis cells, for instance as chlorine-evolving anode in chlor-alkali cells.
  • electrodes consisting of a metal substrate equipped with a coating based on noble metals or oxides thereof are for instance utilised as cathodes for hydrogen evolution in water or alkali chloride electrolysis processes, as anodes for oxygen evolution in electrometallurgical processes of various kinds or for chlorine evolution in alkali chloride electrolysis. Electrodes of such kind can be produced via thermal route, i.e. by suitable thermal decomposition of solutions containing the precursors of metals to be deposited; by galvanic electrodeposition from suitable electrolytic baths; by direct metallisation via flame or plasma spraying processes or chemical or physical phase vapour deposition.
  • the electrolysis of sodium chloride brine directed to the production of chlorine and caustic soda is often carried out with anodes consisting of a titanium or other valve metal substrate activated with a superficial layer or ruthenium dioxide (RuO 2 ) in order to lower the overvoltage of the anodic chorine evolution reaction.
  • anodes consisting of a titanium or other valve metal substrate activated with a superficial layer or ruthenium dioxide (RuO 2 ) in order to lower the overvoltage of the anodic chorine evolution reaction.
  • RuO 2 ruthenium dioxide
  • catalyst formulations based on mixtures of oxides of ruthenium, iridium and titanium are also known, all capable of lowering the overvoltage of the anodic chorine evolution reaction.
  • Electrodes of such kind are generally produced via thermal route.
  • Catalytic formulations can be deposited on the substrate by phase vapour deposition techniques, having the advantage of allowing an extremely accurate control of coating deposition parameters.
  • these are fundamentally characterised by being batch-type processes, requiring the loading of the substrate in a suitable deposition chamber, which has to undergo a slow depressurisation process, lasting several hours, in order to be able to treat a single piece.
  • the remarkable duration of the process severed hours being usually necessary, depending on the required noble metal loading
  • the application of high amounts of catalytic coatings leads to coatings having a very limited lifetime.
  • an electrode for evolution of gaseous products in electrochemical cells comprising an outer catalytic composition deposited by a plasma spray technique, wherein the amount of noble metal in said outer catalytic composition is comprised between 5 and 100 g/m 2 .
  • an electrode for evolution of gaseous products in electrochemical cells comprising an intermediate activating layer and an outer protection layer deposited by thermal decomposition, in which the weight ratio of valve metals to noble metals is higher in the outer layer than in the intermediate activating layer.
  • the present invention relates to an electrode for evolution of gaseous products in electrolysis cells consisting of a valve metal substrate coated with at least one first catalytic composition and with an outer catalytic composition, said at least one first catalytic composition comprising a mixture of oxides of a valve metal or of tin and of noble metals selected from the group of platinum metals (PM) or oxides thereof taken alone or in admixture, said at least one first catalytic composition obtained by thermal decomposition of precursors, said outer catalytic composition comprising noble metals selected from the group of platinum metals or oxides thereof taken alone or in admixture, said outer catalytic composition being deposited by means of a chemical or physical phase vapour deposition technique, the amount of noble metal on said first catalytic composition being higher than 5 g/m 2 of surface and the amount of noble metal in said outer catalytic composition ranging between 0.1 and 3.0 g/m 2 of surface.
  • the inventors have surprisingly found out that the deposition of one last catalytic layer, with the specified characteristics, through chemical or physical phase vapour allows obtaining an electrode with unexpected features both in terms of duration and of potential decrease.
  • the first catalytic composition of the electrode according to the invention comprises titanium, iridium, ruthenium in form of metals or oxides.
  • the outer catalytic composition comprises ruthenium and/or iridium in form of metals or oxides.
  • the specific noble metal loading in the first catalytic composition ranges between 6 and 8 g/m 2 and the specific metal loading in the outer catalytic composition ranges between 1.5 and 2.5 g/m 2 .
  • the invention relates to a method of manufacturing an electrode comprising the deposition of an outer catalytic composition by chemical or physical phase vapour deposition, preferably by reactive sputtering of noble metals selected in the group of platinum metals.
  • a used electrode can be re-activated by chemical or physical phase vapour deposition of an outer catalytic composition including noble metals selected from the group of platinum metals or oxides thereof taken alone or in admixture.
  • the invention relates to an electrolysis cell of alkali chloride solutions, for instance a sodium chloride brine electrolysis cell directed to producing chlorine and caustic soda, which effects the anodic evolution of chlorine on an electrode as hereinbefore described.
  • a sample of titanium mesh of 10 cm x 10 cm size was blasted with corundum, cleaning the residues with a jet of compressed air.
  • the sample was then degreased using acetone in a ultrasonic bath for about 10 minutes. After drying, the sample was dipped into an aqueous solution containing 250 g/l of NaOH and 50 g/l of KNO 3 at about 100°C for 1 hour. After the alkaline treatment, the sample was rinsed in deionised water at 60°C for three times, changing the liquid every time. The last rinse was carried out adding a small quantity of HCl (about 1 ml per litre of solution).
  • the solution was applied to the sample of titanium mesh by brushing in five coats; after each coat, a drying at 100-110°C for about 10 minutes was carried out, followed by a thermal treatment of 15 minutes at 450°C.
  • the sample was cooled in air each time prior to applying the subsequent coat.
  • a sample of titanium mesh of 10 cm x 10 cm size was blasted with corundum, cleaning the residues with a jet of compressed air.
  • the sample was then degreased using acetone in a ultrasonic bath for about 10 minutes. After drying, the sample was dipped into an aqueous solution containing 250 g/l of NaOH and 50 g/l of KNO 3 at about 100°C for 1 hour. After the alkaline treatment, the sample was rinsed in deionised water at 60°C for three times, changing the liquid every time. The last rinse was carried out adding a small quantity of HCl (about 1 ml per litre of solution). An air drying was effected, observing the formation of a brown hue due to the growth of a thin film of TiO x .
  • the mesh sample was then introduced into the vacuum chamber of the reactive sputtering equipment.
  • the sputtering targets were polarised at the following powers: ruthenium 35 W, iridium 24 W, titanium 250 W.
  • the target-electrode substrate gap was about 10 centimetres.
  • the process of deposition was carried out, at the same conditions, alternatively on the two sides of the titanium mesh for an overall duration of 220 minutes.
  • the thus obtained electrode presented a catalytic coating of about 1 micron and a total noble metal loading of about 9 g/m 2 , expressed as the sum of Ru and Ir referred to the metals.
  • a sample of titanium mesh of 10 cm x 10 cm size was blasted with corundum, cleaning the residues with a jet of compressed air.
  • the sample was then degreased using acetone in a ultrasonic bath for about 10 minutes. After drying, the sample was dipped into an aqueous solution containing 250 g/l of NaOH and 50 g/l of KNO 3 at about 100°C for 1 hour. After the alkaline treatment, the sample was rinsed in deionised water at 60°C for three times, changing the liquid every time. The last rinse was carried out adding a small quantity of HCl (about 1 ml per litre of solution). An air drying was effected, observing the formation of a brown hue due to the growth of a thin film of TiO x .
  • the solution was applied to the sample of titanium mesh by brushing in five coats; after each coat, a drying at 100-110°C for about 10 minutes was carried out, followed by a thermal treatment of 15 minutes at 450°C.
  • the sample was cooled in air each time prior to applying the subsequent coat.
  • the sputtering targets were polarised at the following powers: ruthenium 30 W, iridium 35 W.
  • the target-electrode substrate gap was about 10 centimetres.
  • the substrate was also subjected to a residual polarisation of about 150 V.
  • the process of deposition was carried out, at the same conditions, alternatively on the two sides of the electrode for an overall duration of 40 minutes.
  • the thus obtained electrode had an outer catalytic coating about 0.1 ⁇ m thick and a total noble metal loading of about 9 g/m 2 , expressed as the sum of Ru and Ir referred to the metals.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Inert Electrodes (AREA)

Claims (7)

  1. Électrode de dégagement de produits gazeux dans des cellules électrochimiques, composée d'un substrat métallique pour valve enrobé d'au moins une première composition catalytique et d'une composition catalytique externe, ladite première composition catalytique, au moins au nombre de une, comprenant un mélange de métal pour valve ou d'étain ou d'un oxyde de celui-ci et de métaux nobles sélectionnés parmi les métaux du groupe du platine et leurs oxydes, pris seuls ou en mélange, ladite première composition catalytique, au moins au nombre de une, étant obtenue par décomposition thermique de précurseurs, ladite composition catalytique externe étant déposée par une technique de dépôt chimique ou dépôt physique en phase vapeur, la quantité de métal noble dans ladite première composition catalytique, au moins au nombre de une, étant supérieure à 5 g/m2, et la quantité de métal noble dans ladite composition catalytique externe allant de 0,1 à 3,0 g/m2.
  2. Électrode selon la revendication 1, dans laquelle ledit mélange de ladite première composition catalytique, au moins au nombre de une, comprend du titane, de l'iridium et du ruthérium.
  3. Électrode selon la revendication 1, dans laquelle ladite composition catalytique externe comprend du ruthénium et/ou de l'iridium.
  4. Électrode selon l'une quelconque des revendications 1 à 3, dans laquelle la charge spécifique en métal noble de ladite première composition catalytique, au moins au nombre de une, est de 6 à 8 g/m2, et la charge spécifique en métal noble de ladite composition catalytique externe est de 1,5 à 2,5 g/m2.
  5. Procédé de fabrication d'une électrode selon l'une quelconque des revendications 1 à 4, comprenant le dépôt de ladite composition catalytique externe par une technique de dépôt chimique ou physique en phase vapeur.
  6. Procédé de fabrication d'une électrode selon la revendication 5, comprenant le dépôt de ladite composition catalytique externe sous la forme d'un mélange d'oxydes par pulvérisation réactive de métaux nobles sélectionnés dans le groupe des métaux du platine.
  7. Cellule d'électrolyse comprenant un compartiment cathodique qui contient une cathode et un compartiment anodique qui contient une anode séparée par une membrane ou un diaphragme, ledit compartiment anodique étant alimenté par une saumure de chlorure alcalin, ladite anode dudit compartiment anodique étant une électrode selon l'une quelconque des revendications 1 à 4.
EP11802731.7A 2010-12-22 2011-12-21 Électrode pour cellule électrolytique Not-in-force EP2655693B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16186150.5A EP3118351A1 (fr) 2010-12-22 2011-12-21 Réactivation d'une électrode épuisée

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT002354A ITMI20102354A1 (it) 2010-12-22 2010-12-22 Elettrodo per cella elettrolitica
PCT/EP2011/073605 WO2012085095A2 (fr) 2010-12-22 2011-12-21 Électrode pour cellule électrolytique

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP16186150.5A Division-Into EP3118351A1 (fr) 2010-12-22 2011-12-21 Réactivation d'une électrode épuisée
EP16186150.5A Division EP3118351A1 (fr) 2010-12-22 2011-12-21 Réactivation d'une électrode épuisée

Publications (2)

Publication Number Publication Date
EP2655693A2 EP2655693A2 (fr) 2013-10-30
EP2655693B1 true EP2655693B1 (fr) 2016-11-16

Family

ID=43737007

Family Applications (2)

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EP16186150.5A Ceased EP3118351A1 (fr) 2010-12-22 2011-12-21 Réactivation d'une électrode épuisée
EP11802731.7A Not-in-force EP2655693B1 (fr) 2010-12-22 2011-12-21 Électrode pour cellule électrolytique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP16186150.5A Ceased EP3118351A1 (fr) 2010-12-22 2011-12-21 Réactivation d'une électrode épuisée

Country Status (20)

Country Link
US (1) US20130228450A1 (fr)
EP (2) EP3118351A1 (fr)
JP (1) JP6247535B2 (fr)
KR (2) KR101886032B1 (fr)
CN (1) CN103249872B (fr)
AR (1) AR083989A1 (fr)
AU (1) AU2011347262B2 (fr)
BR (1) BR112013014015B1 (fr)
CA (1) CA2815137C (fr)
CL (1) CL2013001620A1 (fr)
CO (1) CO6741167A2 (fr)
DK (1) DK2655693T3 (fr)
EA (1) EA024356B1 (fr)
IL (1) IL225905A (fr)
IT (1) ITMI20102354A1 (fr)
MX (1) MX354730B (fr)
SG (1) SG190951A1 (fr)
TW (1) TW201226631A (fr)
WO (1) WO2012085095A2 (fr)
ZA (1) ZA201302944B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6920998B2 (ja) * 2014-11-24 2021-08-18 インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ 塩素の電解発生のためのアノード
JP6670948B2 (ja) * 2016-11-22 2020-03-25 旭化成株式会社 電解用電極

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US20050211553A1 (en) * 2002-05-24 2005-09-29 Corrado Mojana Electrode for gas evolution and method for its production

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Also Published As

Publication number Publication date
AR083989A1 (es) 2013-04-10
CA2815137A1 (fr) 2012-06-28
SG190951A1 (en) 2013-07-31
KR101886032B1 (ko) 2018-08-07
US20130228450A1 (en) 2013-09-05
EA024356B1 (ru) 2016-09-30
EA201390927A1 (ru) 2013-11-29
WO2012085095A3 (fr) 2012-10-04
JP6247535B2 (ja) 2017-12-13
BR112013014015A2 (pt) 2016-09-13
TW201226631A (en) 2012-07-01
MX354730B (es) 2018-03-15
CA2815137C (fr) 2019-03-05
AU2011347262A1 (en) 2013-05-23
CN103249872B (zh) 2016-08-10
BR112013014015B1 (pt) 2020-05-12
ITMI20102354A1 (it) 2012-06-23
JP2014505166A (ja) 2014-02-27
EP2655693A2 (fr) 2013-10-30
ZA201302944B (en) 2014-06-25
WO2012085095A2 (fr) 2012-06-28
CL2013001620A1 (es) 2013-11-08
KR20130143624A (ko) 2013-12-31
MX2013006271A (es) 2013-08-01
AU2011347262B2 (en) 2016-03-31
CN103249872A (zh) 2013-08-14
IL225905A (en) 2015-08-31
KR20180043398A (ko) 2018-04-27
DK2655693T3 (en) 2017-02-20
CO6741167A2 (es) 2013-08-30
EP3118351A1 (fr) 2017-01-18
IL225905A0 (en) 2013-07-31

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