EP1841901B1 - High efficiency hypochlorite anode coating - Google Patents

High efficiency hypochlorite anode coating Download PDF

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Publication number
EP1841901B1
EP1841901B1 EP05722638A EP05722638A EP1841901B1 EP 1841901 B1 EP1841901 B1 EP 1841901B1 EP 05722638 A EP05722638 A EP 05722638A EP 05722638 A EP05722638 A EP 05722638A EP 1841901 B1 EP1841901 B1 EP 1841901B1
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EP
European Patent Office
Prior art keywords
coating
titanium
oxide
anode
valve metal
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Not-in-force
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EP05722638A
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German (de)
English (en)
French (fr)
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EP1841901A1 (en
Inventor
Richard C. Carlson
Michael S. Moats
Kenneth L. Hardee
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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
    • 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
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25B11/091—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 invention is directed to an electrolytic electrode and a mixed metal oxide coating thereon for the generation of hypochlorite.
  • hypochlorite is manufactured through the electrolysis of brine, however, the available chlorine concentration of the hypochlorite product can be as low as 1 weight percent (wt%) or less. Additionally, current efficiency and electrode lifetimes diminish where brine feed solutions are less concentrated (i.e., 10-30 g/l) and the desired hypochlorite concentrations exceed 8 g/l.
  • an electrode especially for chlorine and hypochlorite production, comprises an electrocatalyst consisting of 22-44 mol% ruthenium oxide, 0.2-22 mol% palladium oxide and 44-77.8 mol% titanium oxide.
  • the electrocatalyst may form a coating on a valve metal substrate and may be topcoated with a porous layer of titanium or tantalum oxide.
  • a method for manufacturing hypochlorite efficiently using an anode having a coating of palladium oxide by 10 to 45 weight%, ruthenium oxide by 15 to 45 weight %, titanium dioxide by 10 to 40 weight % and platinum by 10 to 20 weight %, as well as an oxide of at least one metal selected from cobalt, lanthanum, cerium or yttrium by 2 to 10 weight % is described in U.S. Patent 5,622,613 .
  • Hirakata et al. have described an anode for the electrolysis of dilute brine, which achieves a current efficiency of 90% and reaches a hypochlorite concentration of 21.000 ppm.
  • the anode is made of a titanium substrate and a coating composition containing 3-42 wt% Pt, 3-34 wt% PdO, 42-94 wt% RuO 2 and 20-40 wt% TiO 2 based on the total weight of the precious metal components ( Hirakata K. et al., extended abstracts, electrochemical society. Princeton, New Jersey, US, vol. 89/1, 7 may 1989, pp. 565-566 ).
  • EP 0 174 413 demonstrates the effect of iridium in a coating containing ruthenium-titanium oxide and palladium oxide for increasing the resistance of a titanium electrode.
  • an electrode having an electrocatalytic coating thereon which is capable of providing improved electrode lifetimes and operating efficiencies in electrolyte environments used for the generation of hypochlorite from 15-30 grams per liter (g/l) NaCl or KCl feed solutions and where desired hypochlorite concentrations exceed 8 g/l. It would be further desirable to provide such an electrode at reduced costs as compared to platinum based formulations.
  • the coating is a mixed metal oxide coating consisting of combinations of the oxides of palladium, iridium, ruthenium and titanium.
  • the invention is directed to an electrode for use in the electrolysis of an aqueous solution for the production of hypochlorite, the electrode having an electrocatalytic coating thereon, with the electrode comprising a valve metal electrode base; a coating layer of an electrochemically active coating on the valve metal electrode base, the coating comprising a mixed metal oxide coating of platinum group metal oxides and a valve metal oxide of titanium, the mixed metal oxide coating consisting essentially of platinum group metal oxides of ruthenium, palladium, and iridium; wherein
  • the invention is directed to a process for the electrolysis of an aqueous solution in an electrolytic cell having at least one anode therein, the anode having an electrocatalytic coating thereon, the process comprising the steps of providing an unseparated electrolytic cell, establishing in the cell an electrolyte containing chloride, providing the anode in the cell in contact with the electrolyte, the anode having the electrocatalytic coating comprising a mixed metal oxide coating of platinum group metal oxides and a valve metal oxide of titanium, the mixed metal oxide coating consisting essentially of platinum group metal oxides of ruthenium, palladium, and iridium, wherein
  • an electrode having an electrocatalytic coating having a high current efficiency at high hypochlorite concentrations e.g., > 8 gpl (grams per liter) and having a low electrode potential and improved lifetimes.
  • the current efficiency will be from about 90% to about 100% over a hypochlorite concentration of from 16 to 0 grams per liter (g/l).
  • the electrode having the electrocatalytic coating described herein will virtually always find service as an anode.
  • the word "anode” is often used herein when referring to the electrode, but this is simply for convenience and should not be construed as limiting the invention.
  • the electrode used in the present invention comprises an electrocatalytically active film on a conductive base.
  • the conductive base may be a metal such as nickel or manganese or a sheet of any film-forming metal such as titanium, tantalum, zirconium, niobium, tungsten and silicon, and alloys containing one or more of these metals, with titanium being preferred for cost reasons.
  • film-forming metal it is meant a metal or alloy which has the property that when connected as an anode in the electrolyte in which the coated anode is subsequently to operate, there rapidly forms a passivating oxide film which protects the underlying metal from corrosion by electrolyte, i.e., those metals and alloys which are frequently referred to as “valve metals", as well as alloys containing valve metal (e.g., Ti-Ni, Ti-Co, Ti-Fe and Ti-Cu), but which in the same conditions form a non-passivating anodic surface oxide film.
  • valve metals e.g., Ti-Ni, Ti-Co, Ti-Fe and Ti-Cu
  • Plates, rods, tubes, wires or knitted wires and expanded meshes of titanium or other film-forming metals can be used as the electrode base. Titanium or other film-forming metal clad on a conducting core can also be used. It is also possible to surface treat porous sintered titanium with dilute paint solutions
  • titanium Of particular interest for its ruggedness, corrosion resistance and availability is titanium.
  • the suitable metals of the substrate include metal alloys and intermetallic mixtures, as well as ceramics and cermets such as contain one or more valve metals.
  • titanium may be alloyed with nickel, cobalt, iron, manganese or copper.
  • grade 5 titanium may include up to 6.75 weight percent aluminum and 4.5 weight percent vanadium, grade 6 up to 6 percent aluminum and 3 percent tin, grade 7 up to 0.25 weight percent palladium, grade 10, from 10 to 13 weight percent plus 4.5 to 7.5 weight percent zirconium and so on.
  • elemental metals By use of elemental metals, it is most particularly meant the metals in their normally available condition, i.e., having minor amounts of impurities.
  • metal of particular interest i.e., titanium
  • various grades of the metal are available including those in which other constituents may be alloys or alloys plus impurities. Grades of titanium have been more specifically set forth in the standard specifications for titanium detailed in ASTM B 265-79. Because it is a metal of particular interest, titanium will often be referred to herein for convenience when referring to metal for the electrode base.
  • the electrode base is advantageously a cleaned surface. This may be obtained by any of the treatments used to achieve a clean metal surface, including mechanical cleaning. The usual cleaning procedures of degreasing, either chemical or electrolytic, or other chemical cleaning operation may also be used to advantage.
  • the base preparation includes annealing, and the metal is grade 1 titanium
  • the titanium can be annealed at a temperature of at least about 450°C for a time of at least about 15 minutes, but most often a more elevated annealing temperature, e.g., 600°C to 875°C is advantageous.
  • a base with a surface roughness For most applications, it is advantageous to obtain a base with a surface roughness. This will be achieved by means which can include intergranular etching of the metal, plasma spray application, which spray application can be of particulate valve metal or of ceramic oxide particles, or both, etching and sharp grit blasting of the metal surface, optionally followed by surface treatment to remove embedded grit and/or clean the surface, or combinations thereof.
  • the base can simply be cleaned, and this gives a very smooth substrate surface.
  • the film-forming conductive base can have a pre-applied surface film of film-forming metal oxide which, during application of the active coating, can be attacked by an agent in the coating solution (e.g. HCI) and reconstituted as a part of the integral surface film.
  • Etching will be with a sufficiently active etch solution to develop a surface roughness and/or surface morphology, including possible aggressive grain boundary attack.
  • Typical etch solutions are acid solutions. These can be provided by hydrochloric, sulfuric, perchloric, nitric, oxalic, tartaric, and phosphoric acids as well as mixtures thereof, e.g., aqua regia.
  • Other etchants that may be utilized include caustic etchants such as a solution of potassium hydroxide/hydrogen peroxide, or a melt of potassium hydroxide with potassium nitrate.
  • the etched metal surface can then be subjected to rinsing and drying steps.
  • the suitable preparation of the surface by etching has been more fully discussed in U.S. Pat. No. 5,167,788 , which patent is incorporated herein by reference.
  • plasma spraying for a suitably roughened metal surface, the material will be applied in particulate form such as droplets of molten metal.
  • the metal is melted and sprayed in a plasma stream generated by heating with an electric arc to high temperatures in inert gas, such as argon or nitrogen, optionally containing a minor amount of hydrogen.
  • inert gas such as argon or nitrogen
  • the particulate material employed may be a valve metal or oxides thereof, e.g., titanium oxide, tantalum oxide and niobium oxide. It is also contemplated to melt spray titanates, spinels, magnetite, tin oxide, lead oxide, manganese oxide and perovskites. It is also contemplated that the oxide being sprayed can be doped with various additives including dopants in ion form such as of niobium or tin or indium.
  • plasma spray application may be used in combination with etching of the substrate metal surface.
  • the electrode base may be first prepared by grit blasting, as discussed hereinabove, which may or may not be followed by etching.
  • a suitably roughened metal surface can be obtained by special grit blasting with sharp grit, optionally followed by removal of surface embedded grit.
  • the grit which will usually contain angular particles, will cut the metal surface as opposed to peening the surface.
  • Serviceable grit for such purpose can include sand, aluminum oxide, steel and silicon carbide. Etching, or other treatment such as water blasting, following grit blasting can be used to remove embedded grit and/or clean the surface.
  • the surface may then proceed through various operations, providing a pretreatment before coating, e.g., the above-described plasma spraying of a valve metal oxide coating.
  • Other pretreatments may also be useful.
  • the surface be subjected to a hydriding or nitriding treatment.
  • an electrochemically active material Prior to coating with an electrochemically active material, it has been proposed to provide an oxide layer by heating the substrate in air or by anodic oxidation of the substrate as described in U.S. Patent 3,234,110 .
  • Various proposals have also been made in which an outer layer of electrochemically active material is deposited on a sublayer, which primarily serves as a protective and conductive intermediate.
  • Various tin oxide based underlayers are disclosed in U.S. Patent Nos. 4,272,354 , 3,882,002 and 3,950,240 . It is also contemplated that the surface may be prepared as with an antipassivation layer.
  • an electrochemically active coating layer is applied to the substrate member.
  • the electrochemically active coatings are those provided from active oxide coatings such as platinum group metal oxides, magnetite, ferrite, cobalt spinel or mixed metal oxide coatings. They may be water based, such as aqueous solutions, or solvent based, e.g., using alcohol solvent.
  • the preferred coating composition solutions are typically those consisting of a mixed metal oxide coating of platinum group metal oxides and a valve metal oxide.
  • the platinum group metal oxides of the present invention preferably comprise, RuCl 3 , PdCl 2 , IrCl 3 , and hydrochloric acid, all in alcohol solution, in combination with a valve metal oxide.
  • RuCl 3 , PdCl 2 , IrCl 3 may be utilized in a form such as RuCl 3 xH 2 O, PdCl 2 xH 2 O and IrCl 3 ⁇ xH 2 O.
  • RuCl 3 , PdCl 2 and IrCl 3 will generally be referred to herein simply as RuCl 3 , PdCl 2 and IrCl 3 .
  • the metal salts will be dissolved in an alcohol such as either isopropanol or butanol, all combined with or with out small additions of hydrochloric acid, with n-butanol being preferred. It will be understood that the constituents are substantially present as their oxides in the finished coating, and the reference to the metals is for convenience, particularly when referring to proportions.
  • valve metal component will be present in the coating composition in order to further stabilize the coating and/or alter the anode efficiency.
  • Various valve metals can be utilized including titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum, and tungsten, with titanium being preferred.
  • the valve metal component can be formed from a valve metal alchoxide in an alcohol solvent, with or without the presence of an acid.
  • Such valve metal alchoxides which are contemplated for use in the present invention include methoxides, ethoxides, isopropoxides and butoxides.
  • titanium ethoxide, titanium propoxide, titanium butoxide, tantalum ethoxide, tantalum isopropoxide or tantalum butoxide may be useful, with titanium butoxide being preferred.
  • the mixed metal oxide coating of the present invention will contain a molar ratio of titanium to platinum group metal oxides of from about 90:10 to about 40:60, a molar ratio of ruthenium to iridium of about 90:10 to about 50:50 and a molar ratio of Pd:(Ru+Ir) of about 5:95 to about 40:60.
  • a particularly preferred composition of the mixed metal oxide coating of the present invention will contain a molar ratio of titanium to precious metal oxides of about 70:30 on a metals basis and a molar ratio of Pd:(Ru+Ir) of about 20:80.
  • the mixed metal oxide coating layers utilized herein will be applied by any of those means which are useful for applying a liquid coating composition to a metal substrate. Such methods include dip spin and dip drain techniques, brush application, roller coating and spray application such as electrostatic spray. Moreover, spray application and combination techniques, e.g., dip drain with spray application can be utilized. With the above-mentioned coating compositions for providing an electrochemically active coating, a roller coating operation can be most serviceable.
  • the amount of coating applied will be sufficient to provide in the range of from about 0.05 g/m 2 (gram per square meter) to about 6 g/m 2 , and preferably, from about 1 g/m 2 to about 4 g/m 2 based on ruthenium content, as metal, per side of the electrode base.
  • the applied composition will be heated to prepare the resulting mixed oxide coating by thermal decomposition of the precursors present in the coating composition.
  • This prepares the mixed oxide coating containing the mixed oxides in the molar proportions, basis the metals of the oxides, as above discussed.
  • Such heating for the thermal decomposition will be conducted at a temperature of about 450°C to about 550°C for a time of from about 3 minutes to about 15 minutes per coat. More typically, the applied coating will be heated at a more elevated temperature of up to about 490-525°C for a time of not more than about 20 minutes per coat.
  • Suitable conditions can include heating in air or oxygen.
  • the heating technique employed can be any of those that may be used for curing a coating on a metal substrate.
  • oven coating including conveyor ovens may be utilized.
  • infrared cure techniques can be useful.
  • the heated and coated substrate will usually be permitted to cool to at least substantially ambient temperature.
  • postbaking can be employed. Typical postbake conditions for coatings can include temperatures of from about 450°C up to about 550°C. Baking times may vary from about 1 hour up to as long as about 6 hours.
  • Coating compositions as set forth in Table 1 were applied to separate samples measuring 10 cm x 15 cm x 0.15 cm of Grade 1 titanium which was prepared by grit blasting with 54 grit alumina.
  • the coating solutions A-D were prepared by dissolving sufficient amount of metals, as chloride salts, to achieve the concentrations listed in the table to a solution of n-butanol and 4.2 vol% concentrated HCI.
  • the compounds used were RuCl 3 , IrCl 3 , and PdCl 2 (all hydrated) and titanium orthobutyl titanate. After mixing to dissolve all of the salts, the solutions were applied to individual samples of prepared titanium plates.
  • the coatings were applied in layers by brushing, with each coat being applied separately and allowed to dry at 110°C for 3 minutes, followed by heating in air to 500°C for 6 minutes. A total of 5 coats was applied to each sample.
  • Sample A is in accordance with the present invention.
  • Samples B, C, D, E are considered comparative examples.
  • hypochlorite efficiency of the samples was measured in a beaker-cell by immersing an area of 26 cm 2 into a solution of 28 gpl NaCl with 1 gpl Na 2 Cr 2 O 7 and applying an anodic current of 4.86 amps (0.186A/cm 2 ). A titanium cathode was used, spaced 3 mm from the anode. A sample was pulled every 8 minutes and titrated for hypochlorite.
  • the current efficiencies for the production of hypochlorite as a function of hypochlorite concentrations are plotted in Figure 1 and Table II.
  • the set of samples, A-E, were then operated as anodes in an accelerated test as an oxygen-evolving anode at a current density of 10 kA/m 2 in an electrochemical cell containing 150 g/l H 2 SO 4 at 65°C.
  • Cell voltage versus time data was collected every 30 minutes and the lifetime taken as the inflexion point at which the voltage began to increase rapidly.
  • the results are summarized in Figure 2 and Table II, normalized for the amount of platinum group metal. Normalization was done by measuring the x-ray fluorescence count for the metal peaks using a Jordan Valley EX-300 spectrometer with a Rh tube and a 0.15 mm Sn filter. The applied voltage was 40kV (kilovolts) and current was 25 ⁇ A.
  • the peaks measured were the Ru K-alpha, Pd K-alpha and Ir L-beta. The total counts of the Ru, Pd and/or Ir were used to normalize the lifetimes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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EP05722638A 2005-01-27 2005-01-27 High efficiency hypochlorite anode coating Not-in-force EP1841901B1 (en)

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Application Number Priority Date Filing Date Title
PCT/US2005/003046 WO2006080926A1 (en) 2005-01-27 2005-01-27 High efficiency hypochlorite anode coating

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EP1841901A1 EP1841901A1 (en) 2007-10-10
EP1841901B1 true EP1841901B1 (en) 2010-01-20

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EP (1) EP1841901B1 (zh)
JP (1) JP4560089B2 (zh)
KR (1) KR101135887B1 (zh)
CN (1) CN101111631B (zh)
AT (1) ATE455878T1 (zh)
AU (1) AU2005325733B2 (zh)
BR (1) BRPI0519878A2 (zh)
DE (1) DE602005019105D1 (zh)
ES (1) ES2337271T3 (zh)
IL (1) IL184290A0 (zh)
MX (1) MX2007009129A (zh)
WO (1) WO2006080926A1 (zh)

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CN114232018A (zh) * 2021-11-22 2022-03-25 宝鸡永吉泰金属科技股份有限公司 一种涂层钛电极的制备方法

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AU2005325733A1 (en) 2006-08-03
MX2007009129A (es) 2008-02-12
CN101111631A (zh) 2008-01-23
JP4560089B2 (ja) 2010-10-13
CN101111631B (zh) 2011-05-25
ATE455878T1 (de) 2010-02-15
BRPI0519878A2 (pt) 2009-03-24
KR101135887B1 (ko) 2012-04-13
AU2005325733B2 (en) 2010-06-10
JP2008528804A (ja) 2008-07-31
IL184290A0 (en) 2007-10-31
DE602005019105D1 (de) 2010-03-11
WO2006080926A1 (en) 2006-08-03
EP1841901A1 (en) 2007-10-10
KR20070099667A (ko) 2007-10-09
ES2337271T3 (es) 2010-04-22

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