WO2017171113A1 - Bain électrolytique et procédé d'électrolyse - Google Patents

Bain électrolytique et procédé d'électrolyse Download PDF

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Publication number
WO2017171113A1
WO2017171113A1 PCT/KR2016/003230 KR2016003230W WO2017171113A1 WO 2017171113 A1 WO2017171113 A1 WO 2017171113A1 KR 2016003230 W KR2016003230 W KR 2016003230W WO 2017171113 A1 WO2017171113 A1 WO 2017171113A1
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Prior art keywords
electrolytic
cathode
electrolytic cell
solute
chamber
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PCT/KR2016/003230
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English (en)
Korean (ko)
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정붕익
김정식
신현수
현순택
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(주) 테크윈
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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
    • C25B1/28—Per-compounds
    • 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
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • 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
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to an electrolytic cell and a method, and more particularly, to an electrolytic cell and an electrolytic method capable of simultaneously producing an oxidant and a chemical product by simultaneously carrying out an anode reaction and a cathode reaction in one electrolyzer.
  • the oxidation reaction occurring in the anode chamber of the electrolyzer and the reduction reaction occurring in the cathode chamber of the electrolyzer occur simultaneously.
  • the desired product is prepared through anodic or cathodic reaction, and the opposite electrode produces acid or base through electrochemical reaction of water, a solvent in solution, and these reactants are produced as by-products. It can be used for waste treatment or for separate purposes.
  • Korean Patent No. 10-1525340 discloses a "conductive diamond electrode, a sulfuric acid electrolysis method and a sulfuric acid electrolysis apparatus using the same".
  • the conductive diamond anode 10 is accommodated by the porous PTFE diaphragm 9, and the anode chamber 3 and the conductive diamond cathode 12 filled with the electrolyte solution containing the sulfate ion are accommodated.
  • the anode chamber 3 is partitioned into a cathode chamber 4 filled with sulfuric acid at the same concentration.
  • An anolyte solution supply port 7 is connected to the anode chamber 3, and sulfuric acid, which is an anolyte solution, is supplied to the anode chamber 3 through the anolyte solution supply port 7.
  • a catholyte supply port 8 is connected to the cathode chamber 4, and the catholyte is supplied to the cathode chamber 4 through this catholyte supply port 8.
  • the oxidizing substance solution produced in the anode chamber 3 is discharged to the anolyte outlet 1.
  • hydrogen and residual sulfuric acid solution generated in the cathode chamber 4 are discharged to the cathode liquid outlet 2.
  • FIG. 1 is an exemplary view showing an electrochemical conversion process of carbon dioxide under a solution condition containing potassium sulfate according to the prior art.
  • H + hydrogen ions
  • Carbon dioxide is converted to formate (HCOOK) by the electrode reaction in the cathode portion.
  • KOH is continuously supplied to the oxidation reaction part to balance the ions.
  • one equivalent of potassium sulfate is produced when two equivalents of formic acid are produced using sulfuric acid (H 2 SO 4 ).
  • formic acid is distilled and potassium sulfate is precipitated to separate formic acid and potassium sulfate.
  • the reactant carbon dioxide is dissolved in gas or electrolyte and injected into the cathode chamber, and generates formic acid ions through the cathode reaction.
  • O 2 is generated through the H 2 O decomposition reaction as a solvent, and the generated O 2 is mainly diluted.
  • chloro-alkali process is an electrochemical process used in traditional chemical processes.
  • the electrochemical reaction by the ion exchange membrane method is divided into a positive electrode and a negative electrode using an ion exchange membrane as a diaphragm as in the above example, an electrolyte solution containing chloride as a solute is supplied to the positive electrode, and a negative electrode. Water is supplied.
  • the cation in the chloride solute at the anode eg, potassium chloride (K + ) in the potassium chloride (KCl) chloride solute, or sodium cation (Na + ) in the sodium chloride (NaCl) chloride solute
  • K + potassium chloride
  • Na + sodium cation
  • Na + sodium chloride
  • the generated chlorine (Cl 2 ) is used as a raw material of a chemical process for producing PVC, or the produced alkaline solution (KOH or NaOH) as a chemical product to the user, or generated from chlorine (Cl 2 ) and the negative electrode React with an alkaline solution (KOH or NaOH, etc.) to generate hypochlorite (KOCl or NaOCl, etc.) to use as a disinfectant disinfectant, or by reacting chlorine (Cl 2 ) and hydrogen (H 2 ) to produce hydrochloric acid (HCl) It is used for various purposes such as using. However, all these by-products are merely a means to efficiently handle the by-products that are inevitably produced in the electrochemical reaction.
  • the electrochemical decomposition reaction generates an effective chemical by electrolyzing a solute of a solution supplied to an electrolyte in only one of redox reactions to an anode or a cathode, and in another, water, which is a solvent of an electrolyte solution.
  • Decomposition is accompanied by side reactions that generate acids or alkaline ions and hydrogen or oxygen gas.
  • An object of the present invention is to provide an electrolytic cell capable of simultaneously producing two high value-added chemicals and an electrolytic method using the same.
  • Another object of the present invention is to provide an electrolytic cell that can lower the amount of power and by-products used in the process and an electrolytic method using the same.
  • An electrolytic cell according to the present invention for achieving the above objects is a diaphragm electrolytic cell composed of a diaphragm that is disposed between the anode and the cathode facing each other, the anode chamber and the cathode chamber in which the anode is located, the anode chamber and In the cathode chamber is characterized by supplying an electrolyte solution containing a solute to be made different electrode reactions, each of the positive electrode and the negative electrode is characterized by producing different electrolytic products at the same time through the electrolytic reaction of different solutes.
  • Supplying an electrolyte solution containing a solute containing oxo acid ions to the anode chamber of the electrolytic cell according to the present invention may be characterized in that to produce a peroxo acid compound through the anodic reaction.
  • the electrolyte solution including the chloride solute may be supplied to the cathode chamber of the electrolytic cell according to another embodiment of the present invention to generate chlorine through an anode reaction.
  • the gas may be solute to the cathode chamber of the electrolytic cell according to the present invention to supply a gas or an electrolyte solution in which the gas is dissolved, thereby producing a chemical through a cathode reaction.
  • the cathode chamber of the electrolytic cell according to another embodiment of the present invention may be characterized by generating a metal reducing material through a cathode reaction by supplying an electrolyte solution containing a solute of a metal oxide or a metal salt.
  • the solute containing oxo acid ions provided to the anode chamber may be selected from the group consisting of sulfuric acid, carbonic acid, acetic acid, boric acid, phosphoric acid and such salts.
  • the gas solute is carbon dioxide
  • the chemical product produced in the cathode chamber is composed of a liquid product selected from the group consisting of formic acid, formate, ethylene, and ethanol, and hydrogen, carbon monoxide, syngas, and methane. It may be characterized in that any one of the gaseous products selected from the group.
  • the gas solute according to another embodiment of the present invention may be oxygen, and the chemical product produced in the cathode chamber may be hydrogen peroxide.
  • an electrode manufactured using any one material selected from the group consisting of boron-doped diamond (BDD), diamond like carbon (DLC), platinum (Pt), platinum plating, and DSA is used. It is desirable to.
  • Examples of the cathode of the electrolytic cell according to the present invention include boron-doped diamond (BDD), diamond like carbon (DLC), lead (Pb), mercury (Hg), titanium (Ti), indium (In), tin (Sn), and gold.
  • the diaphragm of the electrolytic cell according to the present invention is a cation exchange membrane, more preferably a fluorine-based cation exchange membrane.
  • the electrolytic method according to the present invention includes a solute through which a different electrode reaction is performed in each of the anode chamber and the cathode chamber by using a diaphragm electrolytic cell in which an anode chamber in which an anode is embedded and an anode chamber incorporating a cathode are disposed opposite to each other.
  • An electrolyte solution is supplied, and different electrolytic products are produced simultaneously through electrolytic reactions of different solutes of the positive electrode and the negative electrode.
  • the electrolytic method according to the present invention may be characterized in that a peroxoic acid compound is produced through an anodic reaction by receiving an electrolyte solution containing a solute containing oxo acid ions into the anode chamber.
  • the electrolytic method according to another embodiment of the present invention may be characterized in that chlorine is generated through an anodic reaction by receiving an electrolyte solution containing chloride solute into the anode chamber.
  • the electrolytic method according to the present invention may be characterized by generating a chemical through a cathodic reaction by receiving a gas or an electrolyte solution in which gas is dissolved using gas as a solute into a cathode chamber.
  • the electrolytic method according to another embodiment of the present invention may be characterized by generating a metal reducing material by receiving an electrolyte solution containing a solute of a metal oxide or a metal salt into a cathode chamber.
  • the electrolytic cell and the electrolytic method according to the present invention have the following effects.
  • the greenhouse gas reduction effect can be expected by using carbon dioxide.
  • FIG. 1 is an exemplary view schematically showing the configuration of an electrolytic cell using the anode reaction according to the prior art.
  • FIG. 2 is an exemplary view schematically showing a configuration of an electrolytic cell using a cathode reaction according to the prior art.
  • FIG 3 is an exemplary view showing a configuration of an electrolytic cell according to an embodiment of the present invention.
  • FIG. 4 is a flowchart illustrating a process of an electrolytic method according to the embodiment of FIG. 3 of the present invention.
  • the electrolytic cell 10 includes a diaphragm 15 and an anode chamber 13 and a cathode chamber 14 which are disposed opposite the diaphragm 15.
  • the positive electrode 11 is configured in the negative electrode chamber 14 so that the negative electrode 12 is opposed to each other.
  • an electrolyte solution containing different solutes is supplied from the anode chamber and the cathode chamber.
  • the solute is a substance in which an electrolysis reaction is performed at the positive electrode and the negative electrode and is limited to being dissolved or contained in water as a solvent.
  • the electrolyte solution including the solute containing the oxo acid ions may be supplied to the anode chamber 13 of the electrolytic cell 10.
  • Oxoic acid also called oxyacid or oxyacid, refers to an acid having a group in which an element other than oxygen has an oxygen or hydroxy group, which includes sulfuric acid, carbonate, acetic acid, boric acid, phosphoric acid, oxalic acid, citric acid, nitric acid, and the like.
  • the solute containing ions can be selected from the group consisting of oxoacid or oxoacid salt.
  • peroxo acid is also referred to as peroxide and is an acid that distributes a peroxo (O 2 ) group in place of an oxygen atom among oxygen acids, for example, disulfide peroxide, sulfur peroxide, and peroxide.
  • the electrolyte solution including the chloride solute may be supplied to the anode chamber 13 of the electrolytic cell 10.
  • the chloride solute is a solute containing chlorine ions, such as potassium chloride (KCl), sodium chloride (NaCl), hydrochloric acid (HCl).
  • KCl potassium chloride
  • NaCl sodium chloride
  • HCl hydrochloric acid
  • the chloride electrolyte solution is supplied to the anode chamber 13, the electrolysis reaction is completed, a positive electrode 11, the solute of the chloride ion (Cl -), the oxidation reaction (2Cl - Cl 2 + 2e - ) of chlorine gas (Cl through 2 ).
  • the gas solute or the electrolyte solution in which the gas is dissolved may be supplied to the cathode chamber 14 of the electrolytic cell 10.
  • the electrolyte solution is composed of an ionic component, a gas or a dissolved gas component, and water, which is a solvent, but the solute is defined as a material that participates in the electrode reaction at the cathode.
  • the gas supplied to the solute carbon dioxide (CO 2) may be a carbon dioxide (CO 2) is a gas phase or negative electrolyte is a solution state supplied to the cathode chamber 14 to dissolve in the electrolytic reaction in the cathode 12
  • formic acid or formic acid salts HCOOH, HCOONa, HCOOK, HCOONH 4, etc.
  • the gas solute supplied to the cathode chamber 14 may be oxygen (O 2 ).
  • Oxygen (O 2 ) is supplied to the cathode chamber 14 dissolved in a gaseous or cathodic electrolyte solution, and hydrogen peroxide through the electrolytic reaction (O 2 + 2H + + 2e - H 2 O 2 ) of the cathode 12. Will produce (H 2 O 2 ).
  • Carbon gas and oxygen have been described as examples of the gas solute, but the present invention is not limited thereto.
  • the solute supplied to the cathode chamber 14 may be a metal oxide or a metal salt, and the electrolyte may be supplied to the cathode chamber 14 to generate a metal reducing material through an electrolytic reaction.
  • the electrolyte may be supplied to the cathode chamber 14 to generate a metal reducing material through an electrolytic reaction.
  • CuSO 4 copper sulfate
  • Cu 2 + copper ions
  • Cu 2 + + 2e - Cu copper ions
  • This example is not limited in the present invention, there may be a reaction to produce a variety of metal reduction.
  • the electrode reaction of various solutes as in the above embodiment it is possible to produce useful chemicals in the positive electrode and the negative electrode.
  • peroxate is produced from oxoate and at the same time, formate is produced from formic acid from carbon dioxide, and at the same time, peroxate and formate, which are useful chemicals at the positive and negative electrodes, can be produced simultaneously.
  • the reaction of generating chlorine from chloride at the anode and hydrogen peroxide from oxygen at the cathode may be simultaneously performed to simultaneously generate chlorine and hydrogen peroxide, which are useful chemicals at the anode and cathode, respectively.
  • This combination may be various, and the present invention is not limited to the above-described embodiment.
  • the anode chamber 13 may be configured to supply an electrolyte solution using sodium sulfate (Na 2 SO 4 ), which is one of oxoates, as a solute, and carbon dioxide (CO 2 ) dissolved in the electrolyte solution into the cathode chamber 14.
  • Na 2 SO 4 sodium sulfate
  • CO 2 carbon dioxide
  • the electrolyte solution supplied to the cathode chamber is configured to additionally supply some electrolyte to reduce electrical resistance during the electrolytic reaction.
  • solutes Na 2 SO 4 and CO 2
  • the solute (Na 2 SO 4 ) supplied as the anode in the anode 11 is peroxate sodium persulfate, as shown in Equation (1) below. Is converted to (Na 2 S 2 O 8 ).
  • the remaining sodium ions (Na + ) is moved from the anode chamber 13 to the cathode chamber 14 through the diaphragm, the formic acid ion (HCOO ⁇ ) through the electrolytic reaction of carbon dioxide (CO 2 ) in the cathode 12. ) And meets sodium ions (Na + ) moved in the anode chamber 13 to produce sodium formate (HCOONa) as shown in the general scheme of Equation (2) below.
  • an electrolyte solution of sodium sulfate (Na 2 SO 4 ) solute is supplied to the anode chamber 13, and an electrolyte solution of carbon dioxide (CO 2 ) solute is supplied to the cathode chamber 14, and sodium persulfate ( Na 2 S 2 O 8 ) at the cathode to produce sodium formate (HCOONa) at the same time.
  • Na 2 SO 4 sodium sulfate
  • CO 2 carbon dioxide
  • the persulfate produced as a cathode product is a powerful oxidizing agent and is used in synthetic resin polymerization catalysts, fiber stimulators, metal surface treatment agents, analytical reagents, chemical decomposition treatment agents, and the like.
  • Chemicals decomposed by persulfate are chemicals that cause contamination of soil, groundwater, drainage, and waste, and are regulated by the Soil Contamination Measure Act such as volatile organic compounds, cyanide, and metal cyano complexes, or oil films.
  • Soil Contamination Measure Act such as volatile organic compounds, cyanide, and metal cyano complexes, or oil films.
  • Objects containing chemicals that are degraded by persulfates may take the form of solids, liquids or slurries.
  • the formic acid produced at the cathode is used in leather treatment agents, rubber coagulants, dyeing aids, hair dyes, leather tanning, medicine, epoxy plasticizers, plating, sterilizers, fragrances, organic synthetic raw materials, etc., and is recently used as fuel for fuel cells.
  • an electrode manufactured using any one or more materials selected from a group consisting of boron-doped diamond (BDD), diamond like carbon (DLC), platinum (Pt), platinum plating, and DSA may be used.
  • BDD boron-doped diamond
  • DLC diamond like carbon
  • Pt platinum
  • platinum plating and DSA
  • the anode 11 used is supplied to the anode chamber 13 so that the overvoltage at which the electrolytic reaction of the solute is performed is lowered, and the decomposition overvoltage of water, which is a solvent, is raised to the maximum so that the electrolytic reaction of the solute is further increased. It is desirable to select the kind and material which is advantageous.
  • the cathode 12 of the electrolyzer is boron-doped diamond (BDD), diamond like carbon (DLC), lead (Pb), mercury (Hg), titanium (Ti), indium (In), tin (Sn), gold.
  • the negative electrode 12 used is supplied to the cathode chamber 14 to reduce the overvoltage at which the electrolytic reaction of the solute is performed, and the decomposition overvoltage of water as a solvent is maximized to increase the electrolytic reaction of the solute. It is desirable to select the kind and material which is advantageous.
  • the diaphragm 15 of the said electrolytic cell is a cation exchange membrane. More preferably, it is a fluorine-type cation exchange membrane.
  • Electrolytic method according to the present invention comprises the steps of supplying an electrolyte solution containing a solute to each different electrode reaction to the anode chamber 13 and the cathode chamber 14 as in the above embodiment; Each of the different solutes may be supplied to produce different electrolytic products simultaneously through electrolysis.
  • the reaction is performed at the same time the oxidation reaction in the anode chamber and the reduction reaction in the cathode chamber at the same time, the following description of the electrolytic process does not indicate the progress of the electrolytic process.
  • sulfuric acid or sulfate is supplied to the anode chamber, and carbon dioxide and cathode electrolyte are respectively supplied to the cathode chamber. This is for explaining an embodiment of the present invention and does not mean that the present invention is limited thereto.
  • Sulfuric acid (H 2 SO 4 ) or sulfate is supplied to the anode chamber as a cathode electrolyte.
  • sodium sulfate (Na 2 SO 4 ) is taken as an example, and various sulfates such as potassium sulfate (K 2 SO 4 ) or ammonium sulfate ((NH 4 ) 2 SO 4 ) may be provided (S401). .
  • the remaining sodium ions (Na + ) after the reaction moves to the cathode chamber through the diaphragm, and the produced sodium persulfate (Na 2 S 2 O 8 ) is discharged through the anode outlet to be used according to the intended use.
  • carbon dioxide supplied from the carbon dioxide supply unit 18 is dissolved in the cathode electrolyte provided from the cathode electrolyte supply unit 17 by the carbon dioxide dissolving means 19 and supplied to the cathode chamber (S403).
  • the produced sodium formate is converted to formic acid either directly or through a conversion process to formic acid at a later stage, and then used according to the purpose of use.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un bain électrolytique à diaphragme, qui comporte une anode et une cathode se faisant face et un diaphragme servant à séparer une chambre d'anode, dans laquelle est placée l'anode, et une chambre de cathode, dans laquelle est placée la cathode. L'invention concerne également un procédé d'électrolyse pour produire des produits chimiques dans la chambre d'anode et la chambre de cathode simultanément au moyen du bain électrolytique. Le bain électrolytique est caractérisé en ce qu'il comprend la fourniture d'une solution électrolytique, qui comprend des solutés qui doivent présenter des réactions d'électrode variées, à une chambre d'anode et à une chambre de cathode d'un bain électrolytique à membrane; et en ce que des produits d'électrolyse variés sont produits simultanément par des réactions électrolytiques des différents solutés à l'anode et à la cathode, respectivement.
PCT/KR2016/003230 2016-03-29 2016-03-30 Bain électrolytique et procédé d'électrolyse WO2017171113A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950006502B1 (ko) * 1986-10-14 1995-06-16 알라이드 코오포레이션 산 및 염을 함유한 물질로부터 산을 회수하는 방법
KR20010071074A (ko) * 1998-07-30 2001-07-28 추후제출 알칼리성 아연 니켈 배드
KR20020040768A (ko) * 1999-08-05 2002-05-30 스테리스 인코퍼레이티드 과아세트산의 전기분해 합성
JP2009511740A (ja) * 2005-10-13 2009-03-19 マントラ エナジー オールターナティヴス リミテッド 二酸化炭素の連続並流電気化学還元
KR20140005003A (ko) * 2012-07-04 2014-01-14 문학수 자동 불판 세척장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950006502B1 (ko) * 1986-10-14 1995-06-16 알라이드 코오포레이션 산 및 염을 함유한 물질로부터 산을 회수하는 방법
KR20010071074A (ko) * 1998-07-30 2001-07-28 추후제출 알칼리성 아연 니켈 배드
KR20020040768A (ko) * 1999-08-05 2002-05-30 스테리스 인코퍼레이티드 과아세트산의 전기분해 합성
JP2009511740A (ja) * 2005-10-13 2009-03-19 マントラ エナジー オールターナティヴス リミテッド 二酸化炭素の連続並流電気化学還元
KR20140005003A (ko) * 2012-07-04 2014-01-14 문학수 자동 불판 세척장치

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