EP2783025B1 - Verfahren zum ablösen einer schicht auf einer elektrode für die elektrolyse - Google Patents

Verfahren zum ablösen einer schicht auf einer elektrode für die elektrolyse Download PDF

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Publication number
EP2783025B1
EP2783025B1 EP12806173.6A EP12806173A EP2783025B1 EP 2783025 B1 EP2783025 B1 EP 2783025B1 EP 12806173 A EP12806173 A EP 12806173A EP 2783025 B1 EP2783025 B1 EP 2783025B1
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Prior art keywords
electrode
thickener
coating layer
alkali
substrate
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English (en)
French (fr)
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EP2783025A2 (de
Inventor
Nobuyuki Kawaguchi
Kenichi Ueno
Tamotsu Hayashi
Miho KAGAMI
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Industrie de Nora SpA
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Industrie de Nora SpA
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

Definitions

  • the present invention relates to a method to effectively exfoliate a coating layer from the surface of the conductive substrate comprising titanium or titanium alloy substrate material of a used electrode for electrolysis comprising an insoluble metal electrode having the coating layer containing electrode substance comprising noble metals and/or their metal oxides on the surface of the electrode substrate comprising valve metals, such as titanium and tantalum or valve metal alloys and then to recover the conductive substrate of noble metals and/or titanium or titanium alloy substrate material for recycling use.
  • This kind of electrode for electrolysis has a problem that in a certain time lapse of use, corrosion is generated in the interface between the electrode substrate comprising valve metals, such as titanium and tantalum or valve metal alloys and the coating layer including the electrode substance comprising noble metals and/or noble metal oxides thereof, which forms a passive layer on the surface of the substrate, leading to a poor reactivation processing. As a result, the substrate has to be shaved off until a new surface appears or an electrode has to be newly manufactured from the electrode material.
  • valve metals such as titanium and tantalum or valve metal alloys
  • the coating layer including the electrode substance comprising noble metals and/or noble metal oxides thereof which forms a passive layer on the surface of the substrate, leading to a poor reactivation processing.
  • the substrate has to be shaved off until a new surface appears or an electrode has to be newly manufactured from the electrode material.
  • electrodes for electrolysis in the case of an electrode for oxygen generation, interface corrosion does not occur between the electrode substrate and the coating layer, when the electrode for electrolysis is applied having a thin film of 0.5 - 3 ⁇ m comprising such metals as tantalum and niobium formed by the vacuum spattering, including ion plating, on the surface of the electrode substrate comprising valve metals, such as titanium and tantalum, or valve metal alloys, and an electrode coating layer containing iridium oxide coated on the surface of the thin film.
  • valve metals such as titanium and tantalum, or valve metal alloys
  • the afore-mentioned electrode for oxygen generation has a defect as an electrode for electrolysis that electric current distribution becomes uneven, causing a poor quality in thickness of copper foil and a long-time, develop continuous service as an electrode for electrolysis is not available.
  • electrode substrate is adequately thick and in plate form
  • the electrode surface is sharpened by manufacturing, and a residual substance is removed by manufacturing after a surface affix was removed by blast processing, and the surface was made to decrease naturally by acid or alkali treatment, a surface residual substance is removed.
  • a method of these has been used alone or in combination.
  • titanium or titanium alloy is used as the substrate may be recycled, but the coating layer containing noble electrode substance cannot be substantially recovered, since such substance is small in amount, compared with processing or by-product materials by machine processing or blast treatment.
  • PTL 1 discloses that the coating is separated by dissolving the surface of the electrode substrate with corrosive acid as an exfoliation method of a coating layer containing electrode substance and the coating and the substrate are recovered.
  • exfoliation of the coating is not easy in reality because it often happens that there is a stable and strong oxide existing between the electrode substrate and the coating, or chemical bonding occurs between the coating layer containing the electrode substance and the substrate metal.
  • PTL 2 shows a method to recover the substrate and the coating in such a manner that highly concentrated alkali aqueous solution is coated on the surface of electrode, followed by heating and dissolving the coating layer containing the electrode substance in an alkali aqueous solution.
  • This method has such problems that considerable depletion of the titanium substrate occurs at the same time in the alkali aqueous solution and the coating dissolves in alkaline matrix, which makes recovery difficult.
  • PTL 3 and PTL 4 disclose a method for recovering the coating layer containing electrode substance after the coating layer containing electrode substance is exfoliated physically and/or chemically.
  • PTLs 3 and 4 indicate acid corrosion or grinding of the substrate, but these methods recover the coating through consumption of the substrate, which may lead to an excessive degree of depletion for recycle of the substrate.
  • PTL 5 discloses a method for exfoliation of the electrode substance through corrosion of the titanium surface by acid treatment after adhesion between the coating layer containing electrode substance and the titanium is physically weakened by applying roll processing to the used electrode. This method is also effective to simultaneously recover the titanium substrate and the coating layer containing electrode substance, but still the titanium cannot be recycled as it is, requiring re-dissolution for recovery.
  • PTL 6 shows a method wherein the electrode is cut into pieces and subjected to barrel polishing in order to separate and recover coating and the substrate titanium. This method is relatively simple and effective, but the substrate cannot be recycled as it is.
  • PTL 7 proposes such processes as (1) caustic alkali aqueous solution is coated on the electrode surface as pre-treatment, (2) retaining it for 10 - 60 min. at 350 - 450 degrees Celsius for reaction, and (3) immersing it in hydrochloric acid, sulfuric acid, and nitric acid, or the mixture thereof.
  • coating substance cannot be separated from the electrode substrate and the electrode substrate cannot be used as it is for recycling, from a point of the keeping of the caustic solution.
  • the conventional methods do not provide a method to recover the coating layer containing electrode substance and the substrate metal at the same time.
  • simultaneous recovery of titanium or titanium alloy of the electrode substrate as substrate as it is and of the coating layer containing electrode substance has not been substantially practiced at all.
  • the present invention aims to provide a method for separating the coating layer containing electrode substance comprising noble metals and/or metal oxides thereof coated on the surface from the surface of the electrode substrate comprising valve metals including titanium and tantalum or valve metal alloys, to recover the electrode substrate comprising valve metals including titanium and tantalum or valve metal alloys in a state enabling recycle use, and to recover the electrode substance efficiently.
  • the present invention provides a method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that in the exfoliation method for the coating layer from the surface of the electrode substrate, wherein the insoluble metal electrode surface having the coating layer containing electrode substance comprising noble metals and/or metal oxides thereof on the surface of the electrode substrate comprising valve metals including titanium and tantalum or valve metal alloys is treated, in succession, with the alkali treatment process using a caustic alkali aqueous solution, the heating and baking process and the acid treatment process, the alkali treatment process is conducted by applying an alkali treatment solution prepared by adding thickener to the caustic alkali aqueous solution, wherein the addition ratio of the thickener in the alkali treatment solution is 0.2 mass% or more but 1 mass% or less.
  • the present invention provides the method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that thickener comprising natural polysaccharide is applied.
  • the present invention provides the method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that thickeners comprising bio gum or guar gum derivatives or cellulose derivatives are applied as the natural polysaccharide thickener.
  • the present invention provides the method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that thickener comprising carboxymethyl cellulose (hereafter called "CMC”) is applied as thickener.
  • CMC carboxymethyl cellulose
  • the present invention provides the method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that xanthan gum (hereafter called "XAG”) is applied as thickener.
  • XAG xanthan gum
  • the present invention provides the method for exfoliating the coating layer from the surface of the electrode substrate, characterized in that the addition ratio of the thickener in the alkali treatment solution is 0.4 mass % or more but 1 mass % or less.
  • the electrode substance can be separated from the electrode substrate effectively and at a high yield.
  • the electrode substrate is not consumed more than required to protects the electrode substrate itself and the stabilized electrode substance does not elute by the molten salt treatment at a relatively low temperature condition and can be separated and recovered as a piece of electrode substance or powder.
  • the substrate metal mainly comprising titanium or electrode substance little flows out into the acid, consumption of acid, which is used only neutralization for residual alkali, can be minimized.
  • the present invention is applicable to various electrodes for electrolyses not being limited to electrodes for oxygen generation.
  • the present invention relates to a separation recovery method of the electrode substance and the electrode substrate which exfoliates the coating layer including the electrode substance comprising noble metals and/or noble metal oxides thereof from the surface of the electrode substrate comprising valve metals including titanium and tantalum or valve metal alloys, and then recovers and re-use the electrode substrates and/or the electrode substance; more in detail, the present invention relates to the recovery method for the insoluble electrode consisting of:
  • the first step is to clean the surface by a suitably applicable method depending on adhering substance.
  • adhering substance usually is little, and therefore, the surface is washed with water or immersed in a dilute hydrochloric acid solution for acid cleaning.
  • the surface is often contaminated with chemical compounds of heavy metals, such as lead sulphate and antimony oxide and acid cleaning is conducted.
  • such compounds can also be removed as alkali salt by 10 - 30 mass % alkali cleaning followed by immersing in an inorganic acid solution.
  • the alkali treatment process is performed with the alkali treatment solution of a caustic alkali aqueous solution.
  • alkali treatment solution is coated, at least, on the surface of the electrode coating.
  • Caustic alkali used for the alkali treatment solution is not specifically specified, but caustic soda is most preferable in view of its high reactivity and easy availability. Mixture of caustic soda and caustic potash is also applicable.
  • the actual reaction in the coating of alkali treatment solution on the surface of the electrode is close to a molten salt reaction, and it is desirable to attach at high concentration.
  • the viscosity of alkali treatment solution is low and it flows relatively easily in case that the alkali treatment solution is coated on the surface of the electrode, and thus, it is not easy for the coated alkali treatment solution to be attached to the surface of the electrode stably. For this reason, in the alkali treatment process, it is necessary to keep the alkali treatment solution to stay on the surface of the electrode stably.
  • the coating for instance, is made with an aqueous solution of caustic soda at 50 - 60 mass% to the electrode to the area where the electrode substance exists. It is also possible that at least the electrode coating surface is immersed for the same purpose in the alkali treatment solution of a similar degree of concentration so that the surface is made acclimated to alkali.
  • the coating should be covered over the entire surface of the electrode and is made impregnated sufficiently.
  • the electrode surface is repellent to caustic solution. It is desirable that the electrode surface is brushed till the surface becomes adequately wet or is immersed in the solution for a certain period of time. But if only caustic alkali is applied, it is hard to achieve expected alkali treatment because caustic alkali does not attach sufficiently to the surface of the electrode to be treated.
  • thickener is added to the caustic alkali solution to prepare the alkali treatment solution.
  • a thickener containing CMC or XAG is applied as thickener.
  • the alkali treatment process is performed using alkali treatment solution prepared by adding the thickener to the caustic alkali solution.
  • the dosage of the thickener is controlled to 0.2 mass% or more, which further increases adhesion of caustic alkali on the coating layer, leading to enhanced exfoliation effect.
  • exfoliation effect is made complete by the dosage of the thickener controlled to 0.4 mass% or more.
  • the dosage of the thickener is preferably 1 mass% or less, because if it exceeds 1 mass%, gelation of caustic alkali immersion liquid proceeds and handling of it becomes difficult.
  • the dosage of the thickener is more preferably controlled to 0.5 mass% or less, and then, the gelation of caustic alkali immersion liquid can be suppressed and the handing of it becomes easier.
  • the thickener substance which represents thickening effect in alkali solution is applied.
  • natural polysaccharide thickener bio gum or guar gum derivativesor cellulose derivatives, etc. are applicable.
  • these thickeners the following are especially preferable.
  • the electrode surface on which the thickener is coated is left for 10 - 30 min. at room temperature, and then dried at 60 - 200 degrees Celsius. By this operation, most of the water in the caustic alkali evaporates and anhydride of caustic alkali deposits on the surface. Drying time is not specifically specified but 10 - 30 min. is preferable. However, the drying process is not essential. In case that alkali solution is uniformly maintained on the electrode surface, the drying process can be eliminated and the following heating process will serve the same function.
  • the electrode surface is heat-treated at a temperature slightly higher than the melting point of caustic alkali.
  • the melting pint is about 330 degrees Celsius and then the preferable temperature is in the range of 350 - 450 degrees Celsius.
  • reaction is made to occur in 10 - 60 min., usually in 30 min.
  • the reaction mechanism is not clear, but later on, the electrode substance being reacted with acid, can be separated.
  • alkali ion in caustic alkali reacts with the electrode substance, the oxide existing between the electrode substance and the substrate, and the surface of the substrate titanium to become alkali complex salt.
  • the electrode thus treated with alkali is immersed in the inorganic acid solution including that of nitric acid, hydrochloric acid or sulfuric acid.
  • the concentration of the inorganic acid is not specifically specified, but usually, diluted acid around 10 - 20 mass % is preferable.
  • the temperature of inorganic acid also is not specified but to expedite the reaction, the inorganic acid solution is preferably heated to 40 degrees Celsius or more.
  • One cycle of treatment can usually separate the electrode substance from the substrate metal sufficiently, but as required, repetition of two to three cycles from the alkali treatment to the baking can separate them completely.
  • the electrode substance at this stage is stabilized by heating and does not dissolve in the acid solution and can be recovered as precipitate.
  • titanium or titanium alloy as substrate metal does not deplete and the electrode substance can be recovered as an oxide solid.
  • any of inorganic acids namely hydrochloric acid, nitric acid and sulfuric acid or mixed acid is applicable.
  • nitric acid or hydrochloric acid is preferable.
  • sulfuric acid caution is needed when it used repeatedly because electrode substrate dissolves slightly or electrode substance may precipitate in the solution as titanium sulfate. But it does not become the problem in particular. But, if such precipitation occurs, it is apparent that operation should be performed so that such precipitation is eliminated because the separation from the electrode substance becomes troublesome.
  • the oxide solid which is separated electrode substance can be recovered under usual conditions. For instance, platinum group metal component in the electrode substance is reduced by hydrogen reduction and metalized for recovery. If the component is ruthenium, it is recovered as ruthenium chloride acid in such a manner that after metallization, it is vaporized as RuO 4 by heat-oxidation in hypochlorite solution, and trapped in hydrochloric acid. If the component is iridium, it is transformed into chloroiridates with chlorine gas together with alkali chloride and then alkali is separated and the iridium component is recovered as hexachloroiridic acid hexahydrate or iridium chloride. For others, recovery is available by dissolving in aqua regia. Also, electrolytic recovery is possible.
  • titanium oxide or tantalum oxide which is the same electrode substance, is not reduced by hydrogen, and therefore, is neither chlorinated nor dissolved; and then complete separation from platinum group metals is possible.
  • Part of electrode substance can be dissolved in acid.
  • recovery is almost completely possible in such a way that it is precipitated as ammonium salt of the platinum group metal through neutralization by adding ammonia to used acid, followed by filtration separation.
  • the recovery can be conducted either separately from the oxide precipitate in the early period, or simultaneously with the oxide precipitate after ammonia treatment by precipitate filtration.
  • the electrode substrate was treated with the cleaning process in such a manner that the surface of titanium plate was subjected to dry blast processing with iron grit (#120 size), followed by acid cleaning for 10 min. in an aqueous solution of 20 mass% sulfuric acid at 90 degrees Celsius.
  • the cleaned electrode substrate is installed to an arc ion plating device to give spattering coating with pure titanium material. Coating conditions are as follows.
  • the X-ray diffraction after the spattering coating shows a sharp crystalline peak belonging to the substrate bulk and a broad pattern belonging to the spattering coating, indicating that the coating was amorphous.
  • the coating solution prepared by dissolving iridium tetrachloride and tantalum pentachloride in a 35 mass% hydrochloric acid solution is applied using a brush on the substrate treated with the spattering coating treatment, followed by drying.
  • the substrate is processed by thermal decomposition coating in an electric furnace of air-circulation type for 20 min. at 550 degrees Celsius to form an electrode coating layer in solid solution comprising iridium oxide and tantalum oxide.
  • the amount of coating is specified so that the thickness of the coating per brush is equivalent to approx. 1.0 g/m 2 as iridium metal.
  • the operation of coating-baking was repeated 12 times.
  • the unused electrode for electrolysis that prepared in this way was cut to 30mm x 30mm and made a sample (hereafter called "The Sample”.)
  • XAG and CMC were selected and observed the state that dissolved this in pure water each for 1 mass% and confirmed a preferable range of concentration.
  • the thickener is preferable to be used at 1.0 mass% or less. If it exceeds 1.0 mass%, XAG becomes muddy white , and when it is left gelated and becomes difficult to stir. On the other hand, the CMC maintains water-clear and slightly thick state, and a higher concentration seems possible, but for both, 1.0 mass% or less is judged to be the optimal concentration.
  • the alkali treatment solution containing thickener was prepared to the following concentration.
  • the 0.2 mass % XAG addition alkali processing solution of condition A) was prepared by the following manner. At first XAG of 0.2g was dissolved in water of 49.8g and prepared 0.4 mass% XAG aqueous solution. Then, NaOH of 25g and KOH of 25g were dissolved in 0.4 mass % XAG aqueous solution and made 100g of 50 mass % NaOH-KOH alkali processing solutions which 0.2 mass% XAG included in.
  • the XAG addition alkali processing solution of condition B) and the CMC addition alkali processing solutions of condition C), D), E), F) were prepared in a similar manner.
  • the sample After having soaked the sample into in the alkali processing solution containing thickener mentioned above, the sample was placed in a crucible with its coating face positioned downward.
  • the Sample was baked for 30 min. at 360 degrees Celsius and the coating was exfoliated with the hydrochloric acid treatment.
  • the state of the alkali processing solution is indicated as follows:
  • the degree of exfoliation is evaluated as follows.
  • the present invention has found that controlling the dosage of thickener to 0.2 mass% or more can improve exfoliation effect and, further, that controlling the addition of thickener to 0.4 mass% or more can achieve complete exfoliation effect.
  • the present invention is applicable in the industrial areas, it can recover and recycle noble metals and/or noble metal oxides belonging to noble, rare metals which constitute the surface coating layer, and electrode substrate of titanium, as well, without deformation from the insoluble metal electrode using electrode substrates mainly of titanium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (6)

  1. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats, dadurch gekennzeichnet, dass bei dem Ablöseverfahren für die Beschichtung von der Oberfläche des Elektrodensubstrats, wobei die unlösliche Metallelektrodenoberfläche die Beschichtung mit einer Elektrodensubstanz aufweist, die Edelmetall und/oder Metalloxid davon umfasst, auf der Oberfläche des Elektrodensubstrats, welches Ventilmetalle einschließlich Titan und Tantal oder Ventilmetalllegierungen umfasst, nacheinander behandelt wird mit dem Alkali-Behandlungsverfahren unter Verwendung einer wässrigen Ätzalkalilösung, dem Erhitzungs- und Backverfahren und dem Säurebehandlungsverfahren, wobei das Alkali-Behandlungsverfahren durch Verwenden einer Alkali-Behandlungslösung durchgeführt wird, die durch Zugabe von Verdickungsmittel zu der wässrigen Ätzalkalilösung hergestellt wird, wobei das Zugabeverhältnis des Verdickungsmittels in der Alkali-Behandlungslösung 0,2 Gew.-% oder mehr, jedoch 1 Gew.-% oder weniger beträgt.
  2. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats gemäß Anspruch 1, dadurch gekennzeichnet, dass ein Verdickungsmittel verwendet wird, das ein natürliches Polysaccharid-Verdickungsmittel umfasst.
  3. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats gemäß Anspruch 2, dadurch gekennzeichnet, dass ein Verdickungsmittel mit Bio-Gummi oder Guar-Gummi-Derivaten oder CelluloseDerivaten als natürliches Polysaccharid-Verdickungsmittel verwendet wird.
  4. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats gemäß einem der Ansprüche 1-3, dadurch gekennzeichnet, dass als Verdickungsmittel ein Carboxymethylcellulose umfassendes Verdickungsmittel verwendet wird.
  5. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats gemäß einem der Ansprüche 1-3, dadurch gekennzeichnet, dass ein Xanthangummi umfassendes Verdickungsmittel als Verdickungsmittel aufgebracht wird.
  6. Verfahren zum Ablösen der Beschichtung von der Oberfläche des Elektrodensubstrats gemäß einem der Ansprüche 1-5, dadurch gekennzeichnet, dass das Zugabeverhältnis des Verdickungsmittels in der Alkali-Behandlungslösung zumindest 0,4 Masse-%, jedoch höchstens 1 Masse-% beträgt.
EP12806173.6A 2011-11-21 2012-11-20 Verfahren zum ablösen einer schicht auf einer elektrode für die elektrolyse Active EP2783025B1 (de)

Priority Applications (1)

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PL12806173T PL2783025T3 (pl) 2011-11-21 2012-11-20 Sposób złuszczania warstwy powłoki elektrody do elektrolizy

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JP2011253772 2011-11-21
PCT/JP2012/080526 WO2013077454A2 (en) 2011-11-21 2012-11-20 Method for exfoliating coating layer of electrode for electrolysis

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EP2783025A2 EP2783025A2 (de) 2014-10-01
EP2783025B1 true EP2783025B1 (de) 2019-02-06

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US (1) US20140305468A1 (de)
EP (1) EP2783025B1 (de)
JP (1) JP5651252B2 (de)
KR (1) KR101583176B1 (de)
CN (1) CN103946424A (de)
MY (1) MY165960A (de)
PL (1) PL2783025T3 (de)
TR (1) TR201904606T4 (de)
WO (1) WO2013077454A2 (de)

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JP7284938B2 (ja) * 2018-11-21 2023-06-01 株式会社大阪ソーダ 鉛化合物の付着した電解用電極から鉛化合物を含む電極表面付着物を除去する方法
CN110016676B (zh) * 2019-04-15 2021-11-02 广州鸿葳科技股份有限公司 一种再生钛阳极及其制备方法
CN110241442B (zh) * 2019-06-14 2021-03-02 中国环境科学研究院 一种高铅阳极泥重金属污染物智能化源削减成套技术方法
CN112680749B (zh) * 2020-12-21 2021-09-28 江苏时代华宜电子科技有限公司 一种基于真空溅射腔室的贵金属回收工艺

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA662524B (de) * 1965-12-28
GB1214579A (en) * 1968-02-28 1970-12-02 Chemner Ag Improvements in or relating to the re-constitution of electrodes
JPS59123730A (ja) 1982-12-28 1984-07-17 Permelec Electrode Ltd 金属電極からイリジウムを回収する方法
GB8813552D0 (en) * 1988-06-08 1988-07-13 Unilever Plc Thickening system
US6337366B1 (en) * 1999-03-25 2002-01-08 Rohm And Haas Method of improving viscosity stability of aqueous compositions
JP4450942B2 (ja) 2000-04-13 2010-04-14 株式会社フルヤ金属 金属電極から貴金属を回収する処理方法
JP4450945B2 (ja) 2000-04-20 2010-04-14 株式会社フルヤ金属 金属電極から貴金属を回収する処理方法
JP4607303B2 (ja) 2000-09-13 2011-01-05 株式会社フルヤ金属 金属電極から白金族金属を回収する方法
JP2002194581A (ja) 2000-12-27 2002-07-10 Furuya Kinzoku:Kk 金属電極からの白金族金属の回収方法
JP4700815B2 (ja) 2001-01-12 2011-06-15 株式会社フルヤ金属 金属電極からの白金族金属の回収方法
US20060089281A1 (en) * 2004-09-01 2006-04-27 Gibson Gregory L Methods and compositions for paint removal
JP4465685B2 (ja) * 2006-09-28 2010-05-19 有限会社シーエス技術研究所 不溶性電極の回収方法
JP5115936B2 (ja) * 2009-07-14 2013-01-09 有限会社シーエス技術研究所 不溶性金属電極の回収方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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US20140305468A1 (en) 2014-10-16
WO2013077454A3 (en) 2013-07-18
KR101583176B1 (ko) 2016-01-07
PL2783025T3 (pl) 2019-08-30
MY165960A (en) 2018-05-18
WO2013077454A2 (en) 2013-05-30
JP2014509347A (ja) 2014-04-17
CN103946424A (zh) 2014-07-23
KR20140098159A (ko) 2014-08-07
JP5651252B2 (ja) 2015-01-07
TR201904606T4 (tr) 2019-04-22
EP2783025A2 (de) 2014-10-01

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