US20020139689A1 - Electrode coating and method of use in a reverse polarity electrolytic cell - Google Patents

Electrode coating and method of use in a reverse polarity electrolytic cell Download PDF

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Publication number
US20020139689A1
US20020139689A1 US09/776,035 US77603501A US2002139689A1 US 20020139689 A1 US20020139689 A1 US 20020139689A1 US 77603501 A US77603501 A US 77603501A US 2002139689 A1 US2002139689 A1 US 2002139689A1
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mixture
electrolytic cell
electrode
electrodes
oxide
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US09/776,035
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Vadim Zolotarsky
Irina Ivanter
Mark Geusic
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Water Applications and Systems Corp
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Assigned to UNITED STATES FILTER CORPORATION reassignment UNITED STATES FILTER CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GEUSIC, MARK J., IVANTER, IRINA A., ZOLOTARSKY, VADIM
Priority to PCT/US2002/000261 priority patent/WO2002061182A2/fr
Publication of US20020139689A1 publication Critical patent/US20020139689A1/en
Abandoned legal-status Critical Current

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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or 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
    • 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
    • C25B11/073—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
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes

Definitions

  • the invention relates to an electrode coating for use in reverse polarity electrolytic cells and, more particularly, to an electrode coating comprising iridium oxide for use in reverse polarity electrolytic cells for producing a hypohalite.
  • An electrolytic cell is an electrochemical device that may be used to overcome a positive free energy and force a chemical reaction in the desired direction.
  • Stillman in U.S. Pat. No. 4,790,923, and Silveri, in U.S. Pat. No. 5,885,426, describe an electrolytic cell for producing a halogen.
  • Electrolytic cells The design of electrolytic cells depends on several factors including, for example, construction and operating costs, desired product, electrical, chemical and transport properties, electrode materials, shapes and surface properties, electrolyte pH and temperature, competing undesirable reactions and undesirable by-products.
  • Some efforts have focused on developing electrode coatings. For example, Beer et al., in U.S. Pat. Nos. 3,751,296, 3,864,163 and 4,528,084 teach of an electrode coating and method of preparation thereof.
  • Chisholm in U.S. Pat. No. 3,770,613, Franks et al., in U.S. Pat. No. 3,875,043, Ohe et al., in U.S. Pat. No.
  • an electrochemical device may produce a desired chemical product; in particular, an electrolytic cell may produce an alkali metal hypohalite, for example, potassium hypochlorite, lithium hypobromite, sodium hypochlorite and sodium hypobromite.
  • an electrolytic cell may produce an alkali metal hypohalite, for example, potassium hypochlorite, lithium hypobromite, sodium hypochlorite and sodium hypobromite.
  • a sodium hypochlorite electrolytic cell will find use where there is a need to treat or disinfect water sources such as in drinking and service water treatment, sewage treatment, in-land and offshore installations, swimming pools and spas.
  • Sodium hypochlorite cells also may find use in pulp and textile bleaching operations.
  • the brine electrolyte used in such cells typically has impurities that interfere with the electrolysis of the electrolyte.
  • the brine may have hardness ions.
  • the invention provides a reversible polarity electrolytic cell comprising an electrolyte in a cell compartment, electrodes immersed in the electrolyte, a power source for applying a current to the electrodes at a first polarity and means for reversing the polarity of the current.
  • the electrodes are coated with a mixture comprising iridium oxide.
  • the invention also provides a method of producing a hypohalite comprising the steps of immersing electrodes in an electrolyte, supplying a current to the electrodes at a first polarity and reversing the polarity of the current.
  • the electrodes are coated with a mixture comprising iridium oxide.
  • the invention provides a method of producing an electrolytic product comprising the steps of immersing a first electrode and a second electrode in an electrolyte, applying a current at a first polarity to the first electrode and the second electrode to populate the first electrode with electron donors and populate the second electrode with electron acceptors and changing the first polarity to populate the first electrode with electron acceptors and populate the second electrode with electron donors.
  • the first and second electrodes are coated with a mixture comprising iridium oxide.
  • FIG. 1 is a schematic diagram of one embodiment of a reverse polarity electrolytic apparatus of the present invention
  • FIG. 2 is a graph of the measured current across the electrodes used in the apparatus of FIG. 1 for a period of over 28 days;
  • FIG. 3 is a graph of the measured sodium hypochlorite concentration in the electrolyte of the apparatus used in FIG. 1 for a period of over 28 days.
  • the invention is directed to an electrolytic cell for producing alkali metal hypohalites and, more particularly, to using an electrode with an electrocatalytic surface in a reversible polarity electrolytic cell to electrolyze a brine electrolyte made with hard water to produce sodium hypochlorite or sodium hypobromite.
  • the electrode has an electrocatalytic surface or coat composed of a mixture having iridium oxide.
  • the mixture may comprise another electrocatalyst, for example a platinum group metal or its oxide, and a binder to maintain the structural stability of the surface.
  • the binder is a valve metal or its oxide.
  • the electrocatalyst is ruthenium oxide and the binder is titanium oxide.
  • the mixture exhibits surprising stability and selectivity because those practicing the art seek to avoid the use of iridium oxide mixtures because of their known instability in reverse polarity systems.
  • an “electrolytic cell” generally refers to an apparatus that converts electrical energy into chemical energy or produces a chemical products or an electrocatalytic product through a chemical reaction.
  • the electrolytic cell may have “electrodes” or surfaces which are electrically conductive. “Current density” is the current passing through an electrode per unit area of the electrode. Typically, the current is a direct current which is a continuous unidirectional current flow rather an alternating current which is an oscillating current flow. Notably, reversing the polarity of the potential or voltage involves changing the direction of applied current flowing through the electrolytic cell.
  • the reactions in the electrolytic cell typically involve at least one oxidation reaction and at least one reduction reaction where the material or compound loosing an electron or electrons is being oxidized and the material gaining an electron or electrons is being reduced.
  • An “anode” is a surface around which oxidation reactions occur and is typically the positive electrode in an electrolytic cell.
  • a “cathode” is a surface around which reduction reactions typically occur and is typically the negative electrode.
  • Electrocatalysis is the phenomena of increasing the rate of an electrochemical reaction. Hence, an electrocatalytic material increases the rate of an electrochemical reaction.
  • passivation is the process whereby a material looses its active properties including, for example, its electrocatalytic properties.
  • Dissolved polyvalent metal ions typically cations, cause water “hardness” and frequently interfere with the preferred electrochemical reaction.
  • “hard water” is water with dissolved polyvalent metal ions. These ions typically precipitate on a surface as calcium and magnesium hydroxides or carbonates.
  • applying an electrical current on a surface may promote the chemical reduction, hence precipitation, of hardness ions.
  • applying a current of reverse polarity promotes dissolution of the precipitated hardness ions. This technique of reversing the polarity of the applied voltage is well-known in the art, and incorporated herein, as one way to extend the operating life of electrodes.
  • “Selectivity” is the degree to which a material prefers one property to others or the degree to which a material promotes one reaction over others. “Stability” refers to the ability of a material to resist degradation or to maintain its desired operative properties.
  • Platinum group metals are those metals, typically in the Group VIII of the periodic table, including ruthenium (Ru), rhodium, palladium, osmium, iridium, and platinum.
  • “Valve metals” are any of the transition metals of Group IV and V of the periodic table including titanium (Ti), vanadium, zirconium, niobium, hafnium and tantalum.
  • FIG. 1 is a schematic diagram of an electrolytic apparatus, specifically a reverse polarity electrolytic cell 10 .
  • the cell has electrodes 12 immersed in an electrolyte 14 contained in a cell compartment 16 .
  • the embodiment shown in FIG. 1 also shows a power source 18 for supplying a current through electrodes 12 .
  • the electrodes have a surface 20 , and optionally a coating 22 , where electrochemical reactions may occur.
  • surface 20 and coating 22 are electrocatalytic. Effectively, surface 20 and coating 22 perform as the electrocatalytic site where electrochemical reduction and oxidation reactions may be catalyzed.
  • the electrolytic cell having electrodes coated with an electrocatalytic coating 22 comprising a mixture comprising iridium oxide, electrolyzes brine made from hard water to produce sodium hypohalite, for example, hypochlorite, hypoiodite and hypobromite.
  • the mixture also has a binder comprising a valve metal, a valve metal oxide or a combination of a valve metal and a valve metal oxide.
  • the mixture has another electrocatalyst comprising a precious metal, a precious metal oxide, a platinum group metal, a platinum group metal oxide or a combination thereof.
  • the binder is titanium oxide and the electrocatalyst is ruthenium oxide.
  • the iridium oxide in the mixture is between about 0.5 to about 10 mole percent.
  • the electrolytic cell may have meters, voltmeter 24 and ammeter 26 for example, measuring the applied voltage potential and the amount and direction of flowing current respectively.
  • the electrolytic cell has a timer 28 controlling the closing and opening of contact switches 30 thereby dictating the direction of current flow.
  • one electrode performs as an anode while the other performs as a cathode, depending on the polarity of the applied current.
  • the polarity or direction of the applied current from power source 18 changes so that the electrode formerly performing as the anode now performs as the cathode and the electrode formerly performing as the cathode now performs as the anode.
  • a first region of surface 20 or coating 22 of one electrode may populate with electron donors, or charge donors, and a second region of surface 20 or coating 22 of another electrode may populate with electron acceptors, or charge acceptors.
  • surface 20 or coating 22 may be cation-rich in the first region and may be anion-rich in the second region.
  • the first region of surface 20 or coating 22 may electrocatalyze an oxidation reaction while the second region of surface 20 or coating 22 may electrocatalyze the corresponding reduction reaction.
  • the first region formerly populated with electron donors may populate with electron acceptors while the second region formerly populated with electron acceptors may become populated with electron donors.
  • the first region formerly electrocatalyzing the oxidation reaction now electrocatalyzes the reduction reaction and the second region now electrocatalyzes the corresponding oxidation reaction.
  • the first region which may have an electron donor
  • the second region which may have an electron acceptor, may have an electron donor.
  • the electrolytic cells may be used in electrochlorination systems for treatment of sea, fresh and municipal water systems such as in cooling systems and fire protection systems.
  • the design and operation of these systems are influenced by, among other things, the extent of hardness in the electrolyte.
  • the system may include a narrow gap between the electrodes and an electrolyte flowing through the electrode gap at a high rate. In this way, deposition or precipitation of scale is inhibited especially around the electrode surfaces.
  • such electrochlorination systems may be operated using brine made from softer water and thus require only occasional cleaning.
  • the scale deposited on electrodes are cleaned in an acid wash. Consequently, the entire system must be placed out of service. This leads to reduced capacity and higher maintenance cost.
  • reverse polarity may be used to clean or remove any precipitated scale at significantly lower maintenance costs.
  • the electrolytic cell may be used in industrial systems where the current density is at least 1,000 amperes/m 2 (A/m 2 ).
  • reverse polarity operation may be performed at a lower current density, at about less than 500 A/m 2 for example, in order to remove or dissolve precipitated scale.
  • the cells may be switched back to a normal operation mode at higher current density.
  • the current applied at the low density and reverse direction is sufficient to dissolve at least a portion of any precipitated scale without damaging the iridium comprising coating.
  • the electrochemical device may further include other process sensing elements, as is well known in the art, measuring any of the electrolytic cell operating parameters including, for example, the concentration of a species in the electrolyte, the voltage, the cell resistance, the pH and the current flow.
  • the sensing element may be a combination of sensors measuring the cell operating parameters in addition to those noted.
  • the sensing elements and may be controlled or triggered to change the polarity of the current when a predetermined condition has been satisfied.
  • the electrolytic cell may have a control system that changes the polarity of the current according to a predetermined sequence or when the concentration of a particular species, the desired product for example, has reached a predetermined level.
  • the predetermined sequence may be set by an operator according to empirical or other information.
  • the control system may include a control loop incorporating, for example, a computer with a control loop around a set-point.
  • the set-point may be set by the operator or may be set according to other requirements.
  • the control system typically includes such systems well-known control in the art such as a control loop incorporating any of proportional, integral and derivative control, or a combination thereof, or may be based on, for example, fuzzy logic or artificial intelligence control.
  • the substrate preferably an electrically conductive substrate and more preferably a titanium substrate
  • a cleaning bath apparatus to remove or minimize contaminants that may hinder proper adhesion of the coating to the substrate surface.
  • the substrate may be placed in an alkaline bath for at least 20 minutes at a temperature of at least 50° C.
  • the substrate surface may then be rinsed with deionized (DI) water and air dried.
  • DI deionized
  • the substrate surface is further treated by grit blasting with aluminum oxide grit or by chemical etching.
  • the chemical etching may comprise washing the substrate surface with an acid, such as oxalic, sulfuric, hydrochloric or a combination thereof, at a temperature of at least about 40° C. for several minutes, preferably several hours, depending on the desired substrate surface characteristics.
  • the chemical etch may be followed by one or several DI water rinses.
  • an iridium salt may be dissolved in an alcohol to produce a homogeneous alcohol salt mixture which may be applied to the substrate surface.
  • the alcoholic salt mixture is prepared by dissolving iridium chloride salt in n-butanol or other suitable solvent known in the art such as ethanol, n-propanol and isopropanol.
  • the alcoholic salt mixture may further comprise salts of a valve metal, preferably, titanium and a platinum group metal, preferably ruthenium. This mixture may be applied to the cleaned substrate surface. Typically, each application produces a coat of about 1 to 6 g/m 2 (dry basis). The wet coated substrates are typically allowed to air dry before being heat-treated.
  • the heat treatment may involve placing the air-dried substrate in a furnace for at least about 20 minutes at a temperature of at least about 400° C.
  • the alcoholic salt mixture may be reapplied several times to obtain a total coating loading of at least 10 and preferably, at least 20 g/m 2 .
  • the coated substrate is typically exposed to a final thermal treatment at a temperature sufficient to convert the salts to their corresponding oxides.
  • the final thermal treatment is performed at a temperature of at least 400° C.
  • An electrode with an electrocatalytic surface embodying features of the invention was prepared by coating a substrate of commercial Grade 2 titanium.
  • the titanium substrate was cleaned in a commercially available alkaline cleaning bath for 20 minutes at a temperature of 50° C. and then rinsed with DI water. After air drying, the substrate was grit blasted with aluminum oxide grit.
  • a mixture was prepared by dissolving 0.7 g of chloroiridic acid (H 2 IrCl 6 .4H 2 O) with ruthenium chloride (RuCl 3 .3H 2 O) and titanium tetraorthobutanate (Ti(C 4 H 9 O) 4 ) in 1.0 ml of DI water and 73 ml of n-butanol.
  • This mixture was applied to the cleaned substrate to achieve a loading of about 1 to 6 g/m 2 per coat on a dry basis.
  • the wet coated substrate was allowed to air dry before being placed in a furnace where it was heat treated for 20 minutes at a temperature of about 450° C.
  • the mixture was reapplied several times to obtain a total coating loading of at least 10 g/cm 2 .
  • the coated substrate was thermally treated for at least 10 minutes at a temperature of about 450° C. to oxidize the salts.
  • the resultant coating had about 1.5 mole percent iridium oxide.
  • Example 1 The electrodes as prepared Example 1 were evaluated in a reverse polarity electrolytic cell similar to one shown in the schematic of FIG. 1.
  • Example 2 summarizes the results of an accelerated test designed to test the electrodes at the conditions more sever than a real application. In particular, the tests were performed at low sodium chloride concentrations, which promotes an undesirable oxygen producing side reaction.
  • a plastic tank was filled with 40 liters of tap water. To the water, 80 grams of sodium chloride was added to produce a 2,000 ppm NaCl solution. Two electrochemical cells were submersed into the tank. The cell with electrodes with the coating prepared in Example 1 was designated as “A.” The other cell had electrodes with a similar coating, designated as “B.” Notably, the “B” coating was prepared similarly as in the coating of Example 1 except that no iridium was added.
  • Each cell had two electrodes each with a 1-inch ⁇ 3-inch electrocatalytic coating on either one or both sides.
  • the gap between electrodes, the interelectrode gap, was 1 ⁇ 4 inch.
  • Each cell had a separate current power supply and a control panel.
  • each cell was operated at constant cell voltage and at a current sufficient to provide a required current density of approximately 2,500 A/m 2 .
  • the measured current began to decline as illustrated in FIG. 2.
  • the absolute value of the current falls from approximately 2.3-2.5 A to about 1 A
  • the anode is considered to have failed.
  • the time from the start of the test to the anode failure is called the anode's lifetime.
  • Anode lifetime is one measure of the stability of the anode.
  • FIG. 2 shows two test runs for each of A and B. In both sets of test runs, the A coating significantly outlasted the B coating. Thus, the coating of Example 1 out performed the coating typically used in sodium hypochlorite production.
  • FIG. 3 shows the sodium hypochlorite concentration in the electrolyte during the test runs.
  • the data shows that the hypochlorite production of the A coating compared favorably with the B coating.
  • the coating of the invention as prepared in the embodiment of Example 1, showed improved stability with little or no reduction in electrolytic efficiency.
  • An electrochlorination system was designed to use the electrodes as coated in Example 1.
  • the electrochlorination system was designed to provide hypochlorite continuously at a level sufficient to disinfect an industrial seawater system.
  • the design considerations for such a system included: Salt concentration: about 30,000 ppm Operating temperture: 10° to 35° C. Normal current density: at least 1,300 A/m 2 (high density)
  • this electrochlorination system further included a control system for reversing the polarity of the applied current.
  • the electrochlorination system was designed such that a normal applied current would be applied for a predetermined period, typically several weeks, at a high current density. At the end of the normal current period, the current would be reversed and would be applied at a low current density, typically at less than about 500 A/m 2 , for several hours. The system would then be switched back to normal operation at high current density.
  • the expected operating life of the coated electrodes is at least five years with none or minimal cleaning. This reverse current is expected to be sufficient to dissolve any deposited scale without damaging or shortening the operating life of the electrode coatings.

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  • Metallurgy (AREA)
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PCT/US2002/000261 WO2002061182A2 (fr) 2001-02-01 2002-01-04 Revetement d'electrode et procede d'utilisation dans une cellule electrolytique a polarite inversee

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US20080017519A1 (en) * 2005-01-21 2008-01-24 Andreas Siemer Method and device for producing an alkali metal hypochlorite solution
US20090159460A1 (en) * 2007-12-25 2009-06-25 General Electric Company Electrodialysis device and process
US20090229992A1 (en) * 2006-11-28 2009-09-17 Miox Corporation Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US20100096260A1 (en) * 2008-10-16 2010-04-22 Finnchem Usa Inc Water chlorinator having dual functioning electrodes
US20110079520A1 (en) * 2009-10-02 2011-04-07 Tretheway James A Method and Apparatus for the Electrochemical Treatment of Liquids Using Frequent Polarity Reversal
US20130087450A1 (en) * 2010-06-17 2013-04-11 Industrie De Nora S.P.A. Electrode for electrochlorination
TWI418371B (zh) * 2007-01-25 2013-12-11 Hercules Inc 產生鹵胺殺生物劑之方法及裝置及所產生之鹵胺殺生物劑之用途
CN104988530A (zh) * 2015-08-12 2015-10-21 海南金海浆纸业有限公司 一种复合涂层电极及其制备方法和电解槽
US20180282882A1 (en) * 2015-10-06 2018-10-04 Johnson Matthey Public Limited Company Electrolytic production of halogen based disinfectant solutions from halide containing waters and uses thereof
US10400349B2 (en) 2006-11-28 2019-09-03 De Nora Holdings Us, Inc. Electrolytic on-site generator
US10597313B2 (en) 2017-02-16 2020-03-24 Saudi Arabian Oil Company Chlorination-assisted coagulation processes for water purification
EP3593401A4 (fr) * 2017-03-06 2021-01-13 Evoqua Water Technologies LLC Mise en uvre d'une commande de rétroaction en vue d'une conception améliorée de système électrochimique
US11668017B2 (en) 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes
EP4284569A4 (fr) * 2021-01-28 2024-09-11 De Nora Water Tech Llc Cellule tubulaire autonettoyante à polarité inverse

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080017519A1 (en) * 2005-01-21 2008-01-24 Andreas Siemer Method and device for producing an alkali metal hypochlorite solution
US20090229992A1 (en) * 2006-11-28 2009-09-17 Miox Corporation Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US10400349B2 (en) 2006-11-28 2019-09-03 De Nora Holdings Us, Inc. Electrolytic on-site generator
US11421337B2 (en) 2006-11-28 2022-08-23 De Nora Holdings Us, Inc. Electrolytic on-site generator
US8747740B2 (en) * 2007-01-25 2014-06-10 Hercules Incorporated Process and apparatus for generating haloamine biocide
TWI418371B (zh) * 2007-01-25 2013-12-11 Hercules Inc 產生鹵胺殺生物劑之方法及裝置及所產生之鹵胺殺生物劑之用途
US20090159460A1 (en) * 2007-12-25 2009-06-25 General Electric Company Electrodialysis device and process
US8038867B2 (en) * 2007-12-25 2011-10-18 General Electric Company Electrodialysis device and process
KR101573092B1 (ko) 2007-12-25 2015-12-01 제너럴 일렉트릭 캄파니 전기투석 방법 및 장치
US20100096260A1 (en) * 2008-10-16 2010-04-22 Finnchem Usa Inc Water chlorinator having dual functioning electrodes
US8075751B2 (en) * 2008-10-16 2011-12-13 Finnchem Usa, Inc. Water chlorinator having dual functioning electrodes
US20110079520A1 (en) * 2009-10-02 2011-04-07 Tretheway James A Method and Apparatus for the Electrochemical Treatment of Liquids Using Frequent Polarity Reversal
US20130087450A1 (en) * 2010-06-17 2013-04-11 Industrie De Nora S.P.A. Electrode for electrochlorination
KR101769279B1 (ko) * 2010-06-17 2017-08-18 인두스트리에 데 노라 에스.피.에이. 염소전해용 전극
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