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WO2017213413A1 - Procédé de séparation de dioxyde de carbone et système de séparation de dioxyde de carbone - Google Patents

Procédé de séparation de dioxyde de carbone et système de séparation de dioxyde de carbone Download PDF

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Publication number
WO2017213413A1
WO2017213413A1 PCT/KR2017/005904 KR2017005904W WO2017213413A1 WO 2017213413 A1 WO2017213413 A1 WO 2017213413A1 KR 2017005904 W KR2017005904 W KR 2017005904W WO 2017213413 A1 WO2017213413 A1 WO 2017213413A1
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Prior art keywords
carbon dioxide
compartment
cathode
anode
ions
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English (en)
Korean (ko)
Inventor
한종인
정재인
정욱
이예린
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Korea Advanced Institute of Science and Technology KAIST
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Korea Advanced Institute of Science and Technology KAIST
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • 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
    • C25B1/22—Inorganic acids
    • 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
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a method and system capable of selectively separating carbon dioxide from industrial waste gases and the like.
  • Carbon dioxide (C0 2 ) is known as a representative greenhouse gas causing global warming, and has recently been reported as a material that adversely affects the ecosystem by causing acidification of seawater and rainwater. It is also known to cause respiratory disease and asphyxiation when the concentration of carbon dioxide in the atmosphere exceeds the reference value (0.038% v / v). Therefore, countries around the world are aware of the problems that occur when the concentration of carbon dioxide in the atmosphere exceeds the threshold and specify as a joint obligation to reduce the emissions of carbon dioxide. Beginning with the Vienna Convention in 1985, the CO2 emissions were restricted by country through the Montreal Protocol (1987), the climate Change Convention (1992), the Kyoto Protocol (1997), and the Paris Agreement (2015). I try to reduce.
  • Carbon dioxide is a gas produced in large quantities in the combustion process of fossil fuels such as coal and oil. Due to the positive correlation between fossil fuel use and GDP, population growth and industrial development have accelerated the generation of carbon dioxide and are still increasing. Currently, 80 million tons of carbon dioxide is generated annually.
  • Carbon Capture Ut il izat ion and Storage (CCUS) technology, which combines Carbon Capture and Storage (CCS), which captures and stores carbon dioxide, and Carbon Capture and Ut izat ion (CCU), which captures and recycles carbon dioxide. This is getting attention.
  • CCUS technology encompasses all technologies for selectively separating, transporting, storing and utilizing carbon dioxide in exhaust gases. Ecus is currently commercialized Since the process incremental capture stage accounts for 50 to ⁇ of the total cost, a low-cost and efficient collection method is needed to reduce the processing cost.
  • Post-combustion capture is a method of separating carbon dioxide from a mixed gas generated after fuel combustion
  • pre-combustion capture is a method of separating carbon dioxide from a mixed gas of carbon dioxide and hydrogen in fuel through oxygen. It is a method of separating carbon dioxide with water through high concentration of oxygen.
  • Each collection method is based on the conversion of carbon dioxide into the gas form after absorption, adsorption, and separation by membrane. Different separation methods are applied according to the type of fuel demand.
  • absorption is the most effective method, and the carbon dioxide in the exhaust gas is selectively collected through chemical bonding with carbon dioxide using an amine-based material as an absorbent.
  • carbon dioxide ionized by chemical bonds has a disadvantage in that it is difficult to reverse the gas form to be easily recycled, and an additional step is required to recycle the used absorbent.
  • the present invention is to provide a method and system capable of selectively separating carbon dioxide from industrial waste gas and the like.
  • a method of separating carbon dioxide is provided that includes a second step of reconversion.
  • the carbon dioxide separation system in a mixed gas containing carbon dioxide, the anode (anode); Cathode; A cathode compartment in which hydroxide ions are generated when a voltage is applied to the anode and the cathode, and carbon dioxide is trapped in a mixed gas including carbon dioxide to generate carbonic acid-based ions or salts thereof; An anode compartment for generating hydrogen ions when a voltage is applied to the anode and the cathode and reconverting the carbonate-based ions or salts thereof transferred to the carbon dioxide; And an ion exchange membrane separating the anode compartment and the cathode compartment.
  • the first electrode Second electrode;
  • a cation exchange membrane positioned between the first electrode and the second electrode; And a pair of first and second compartments separated by the cation exchange membrane, the first compartment located on the first electrode side and the second compartment located on the second electrode side.
  • carbonic acid-based ions or salts thereof In order to generate carbonic acid-based ions or salts thereof by applying a voltage such that the first electrode becomes an anode and the second electrode becomes a cathode, carbon dioxide in a mixed gas containing carbon dioxide is collected in a second section in which hydroxide ions are generated. Stage 1 ; And converting the carbonate-based ions or salts thereof into carbon dioxide in a second section in which hydrogen ions are generated by applying a voltage such that the first electrode becomes a cathode and the second electrode becomes an anode.
  • the carbon dioxide separation system in a mixed gas containing carbon dioxide, the first electrode; Second electrode; A cation exchange membrane positioned between the first and second electrodes; A pair of crabs 1 and a second compartment separated by the cation exchange membrane, the first compartment located on the first electrode side and the second compartment located on the second electrode side; And a power supply for applying a voltage such that the first electrode becomes the anode and the second electrode becomes the cathode, and then applies the voltage such that the first electrode becomes the cathode and the second electrode becomes the anode.
  • a system is provided.
  • FIG. 1 is a view schematically showing an electrolysis apparatus including a pair of anode compartments and cathode compartments separated by one ion exchange membrane.
  • FIG. 2 is a diagram schematically illustrating an electrolysis apparatus including a pair of anode compartments, an intermediate compartment and a cathode compartment separated by two ion exchange membranes.
  • 3 is a diagram schematically illustrating an electrolysis apparatus including two pairs of anode and cathode sections, including one bipolar membrane.
  • FIG. 4 is a diagram schematically showing an electrolysis device including two bipolar membranes and three pairs of anode compartments and cathode compartments.
  • FIG. 5 and 6 are diagrams schematically showing an electrolysis apparatus including four or more bipolar membranes and five or more anode and cathode compartments
  • FIG. 5 is a carbonate-based black containing a salt thereof
  • 6 is a view showing the movement to the anode compartment paired with the cathode compartment
  • Figure 6 is a view showing the movement of the carbonic acid-based ions or salts thereof to the anode compartment not paired with the cathode compartment including the same.
  • FIG. 7 is a view showing a method for implementing a method of separating carbon dioxide using two electrolysis devices.
  • FIG. 8 is a view showing a method for implementing a method of separating carbon dioxide using three or more electrolysis devices.
  • FIG. 9 is a schematic view of the first stage (10) and the second stage (20) using an electrolysis device comprising a pair of first and second compartments separated by a bilateral exchange membrane. .
  • Figure 1 schematically shows the state (10) of the first step, the state (20) of the second step and the state (10 ') of the first step after the second step using an electrolysis device comprising.
  • FIG. 11 is a view schematically showing a first stage view 10 and a second stage view 20 using an electrolysis device including two pairs of first and second compartments, including one bipolar membrane. .
  • FIG. 12 is a diagram schematically illustrating an electrolysis apparatus including five pairs of first and second compartments, including four bipolar membranes.
  • FIG. 13 is a graph showing pH over time of the cathode compartment in separating carbon dioxide according to Examples 1 and 2.
  • FIG. 13 is a graph showing pH over time of the cathode compartment in separating carbon dioxide according to Examples 1 and 2.
  • FIG. 14 is a graph showing pH over time of the anode compartment in separating carbon dioxide according to Examples 1 and 2.
  • FIG. 14 is a graph showing pH over time of the anode compartment in separating carbon dioxide according to Examples 1 and 2.
  • FIG. 15 is a graph showing the content of pure carbon dioxide (pure C0 2 ), the content of H 2 S0 4 and the pH of the positive electrode compartment obtained in the positive electrode compartment of Example 1.
  • FIG. 16 shows the first and second electrodes in Example 1 2. When the voltage of 5 V and 3 is applied, it is a graph showing the change of concentration of inorganic carbon in the second compartment with time.
  • Carbon dioxide separation method is an electrochemical system Based on the low energy, carbon dioxide can be selectively separated from industrial waste gas. Accordingly, the carbon dioxide separation method can provide an economical CCUS technology by replacing the capture process that occupies 50 to 70% of the total cost of the existing carbon capture technology (CCUS) technology, thereby Carbon dioxide, a representative greenhouse gas, can be efficiently removed from industrial waste gas.
  • CCUS carbon capture technology
  • Separation method of carbon dioxide according to the embodiment may provide a high purity concentrated carbon dioxide. Therefore, the method of separating carbon dioxide according to the embodiment is expected to provide carbon dioxide useful in fields requiring ultra-high purity carbon dioxide, for example, chemical reaction processes in which carbon dioxide is used as a precursor.
  • the method for separating carbon dioxide uses a hydroxide ion generated by electrolysis of water instead of an amine-based collector or ammonia, which is a representative collector for carbon dioxide, so that it is regenerated to recycle the collector after carbon dioxide capture.
  • a hydroxide ion generated by electrolysis of water instead of an amine-based collector or ammonia, which is a representative collector for carbon dioxide, so that it is regenerated to recycle the collector after carbon dioxide capture.
  • the carbon dioxide separation method is an anode (anode); Cathode; An ion exchange membrane (I EM) positioned between the anode and the cathode; And a pair of anode compartments (AC) and cathode compartments (CC) separated by the ion exchange membrane.
  • the device may be referred to as an electrolysis device.
  • the 'anode' When voltage is applied to the anode and the cathode in the electrolysis device, an oxidation reaction may occur in the anode compartment and a reduction reaction may occur in the cathode compartment. Accordingly, the 'anode' may be referred to as an 'oxide electrode' and the 'cathode' may be referred to as a 'reduction electrode'.
  • hydrogen silver When voltage is applied to the anode and the cathode, hydrogen silver may be generated in the anode compartment, and hydroxide ions may be generated in the cathode compartment.
  • hydroxide ions For example, if an anode is installed in the anode compartment, hydrogen ions may be generated due to an oxidation reaction as shown in Equation 1 or 2 below.
  • hydroxide ions may be generated due to the reduction reaction as shown in Equation 3 below.
  • the electrolysis apparatus includes a bipolar membrane (see FIGS. 3 to 6)
  • at least one anode compartment and the cathode compartment may be in contact with the bipolar membrane.
  • voltage is applied to the anode and the cathode
  • water is separated into hydrogen ions and silver hydroxide by the bipolar membrane.
  • the hydrogen ions and the hydroxide ions are moved by the electrical attraction, so that hydrogen ions are supplied to the anode compartment in contact with the bipolar membrane and hydroxide ions are supplied to the cathode compartment in contact with the bipolar membrane.
  • a region where hydrogen ions are generated by applying voltage to the anode and the cathode is defined as a cathode compartment, and a region where hydroxide ions are generated is defined as a cathode compartment.
  • the anode compartment and the cathode compartment may be filled with a solvent in which the electrolyte is dissolved.
  • the solvent may be water
  • the electrolyte may be various salts that can be dissolved in water and dissociated into cations and anions.
  • Non-limiting examples of electrolytes include hydrochloride, sulfate, nitrate, carbonate, hydroxide, oxide black.
  • the electrolyte is sodium chloride, potassium chloride, lithium chloride, rubidium chloride : , calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, lithium sulfate, rubidium sulfate : , calcium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, Lithium nitrate, rubidium nitrate, calcium nitrate, magnesium nitrate, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate : Calcium carbonate, magnesium carbonate, Sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide, sodium potassium oxide, lithium oxide, rubidium oxide, calcium oxide, magnesium oxide, aluminum oxide, or a combination thereof.
  • a voltage may be applied to the anode and the cathode such that hydrogen ions are generated in the anode compartment and hydroxide ions are generated in the cathode compartment.
  • the applied voltage may be adjusted according to the type and concentration of the electrolyte contained in the positive electrode compartment and the negative electrode compartment, the type of oxidation reaction occurring in the positive electrode compartment, the type of reduction reaction occurring in the black negative electrode compartment, and the like.
  • the positive electrode and the negative electrode are 0.42 V or more, 0.83 V or more, 1.03 V or more, black is 2.06 V or more, 10 V or less, 7 V or less, 5 V or less, 4 V or less, 3 V or less, and black is 2 V or less.
  • the voltage of can be applied. Within this range, carbon dioxide in the mixed gas can be efficiently separated with little energy.
  • the mixed gas may be directly supplied to the negative electrode compartment to collect carbon dioxide in the mixed gas in the negative electrode compartment. Accordingly, the method of separating carbon dioxide has the advantage that it is not necessary to provide a separate collecting device such as a scrubber to collect carbon dioxide in the mixed gas.
  • the mixed gas may be supplied to the cathode compartment before the voltage is applied to the anode and the cathode, at the same time as the voltage is applied to the anode and the cathode, and after the voltage is applied to the black anode and the cathode.
  • the mixed gas may be supplied to a cathode compartment after applying a voltage to the anode and the cathode to generate hydroxide ions in abundance.
  • the mixed gas has a pH of the cathode compartment of about 10 to 14, about 11 to 14, about 12 to 14, about 13 to 14, and about 10 as the hydroxide ions are generated by applying voltage to the anode and the cathode.
  • To 13 about 11 to 13, about 12 to 13, about 10 to 12, about 11 to 12, or about 10 to 11, may be supplied to the cathode compartment.
  • the mixed gas may be continuously supplied to the cathode compartment or black may be periodically supplied.
  • the mixed gas has a pH of the cathode compartment It may be supplied periodically when the above range is reached.
  • the carbon dioxide separation method is capable of separating pure carbon dioxide from various mixed gases containing carbon dioxide.
  • a mixed gas include a mixed gas requiring separation of carbon dioxide, industrial waste gas discharged from a natural gas power generation facility, a cement refining plant, and an exhaust gas discharged from a combustion process of fuel.
  • the ratio of carbon dioxide in the mixed gas is not particularly limited, but at least 2% by volume, at least 5% by volume, at least 10% by volume, at least 15% by volume, at least 20% by volume, at least 30% by volume, at least 40% by volume, It may be at least 50% by volume. In this range, more pure and concentrated carbon dioxide can be obtained.
  • the upper limit of the ratio of carbon dioxide contained in the mixed gas is not particularly limited, 100 vol% or less, 90 vol% or less, 80 vol% or less, 70 vol% or less, 60 vol% or less 50 vol% or less, 40 vol% Or less, 30 volume% or less, black may be 20 volume% or less.
  • the cathode compartment is a region where hydroxide ions are generated when a voltage is applied to the anode and the cathode. Therefore, in the first step, carbon dioxide in the mixed gas supplied to the cathode compartment may be collected as hydroxide ions present in the cathode compartment according to Equation 4 below.
  • carbon dioxide in the mixed gas may be collected under normal pressure. Atmospheric pressure means natural pressure that is not pressurized or depressurized. Specifically, the carbon dioxide in the mixed gas may be collected in a pressure range of about 100. 0 to 100. 102 MPa. In addition, the carbon dioxide in the mixed gas in the method for producing carbon dioxide according to the embodiment may be collected at a temperature of about 15 to 80 ° C black or about 15 to 60 ° C. As a result, the industrial waste gas black can be supplied directly to the cathode compartment without notice of a mixed gas such as exhaust gas, and carbon dioxide can be collected from the mixed gas.
  • Atmospheric pressure means natural pressure that is not pressurized or depressurized.
  • the carbon dioxide in the mixed gas may be collected in a pressure range of about 100. 0 to 100. 102 MPa.
  • the carbon dioxide in the mixed gas in the method for producing carbon dioxide according to the embodiment may be collected at a temperature of about 15 to 80 ° C black or about 15 to 60 ° C
  • the pH of the cathode compartment in which carbon dioxide is collected in the mixed gas is about 4 Or more, about 5 or more, about 6 or more, about 7 or more, about 8 or more, about 9 or more, about 10 or more, about 11 or more, or about 12 or more, about 14 or less, about 13 or less, and black may be about 12 or less.
  • the pH of the cathode compartment is about 10 to 14, about 11 to 14, about 12 to 14, about 13 to 14, about 10 to 13, about 11 to 13, about 12 to 13, and about 10 for the selective collection of carbon dioxide. 12 to 12, about 11 to 12 black may be adjusted to about 10 to 11.
  • carbon dioxide in the mixed gas is selectively collected by hydroxide ions to generate hydrogen carbonate ions (HC0 3 _).
  • the hydrogen carbonate (HCCV) is changed to carbonate (C0 3 2 ) as the pH is higher.
  • carbon dioxide in the mixed gas supplied to the cathode compartment may be collected by hydroxide ions to generate hydrogen carbonate ions and / or carbonate ions.
  • the term 'carbonate-based ion' is used to collectively refer to a mixture of hydrogen carbonate ions, black hydrogen carbonate ions, and carbonate ions.
  • the negative electrode compartment may include a carbonate, hydroxide black or a combination thereof among the above-mentioned electrolytes. More specifically, the negative electrode compartment includes electrolytes such as sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, calcium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide lithium hydroxide, rubidium hydroxide, calcium hydroxide, and magnesium hydroxide black. can do.
  • the carbonate supplied as an electrolyte to the cathode compartment is dissociated into cations and silver carbonate (C0 3 2 ), and the carbonate ions may collect carbon dioxide in a mixed gas to generate hydrogen carbonate ions as shown in Equation 5 below.
  • the hydroxide supplied as an electrolyte to the cathode compartment is also dissociated into cations and hydroxide ions, and the hydroxide ions may collect carbon dioxide in a mixed gas as in Formula 4 to generate hydrogen carbonate ions.
  • carbonate and hydroxide black supplied as electrolyte to the cathode compartment can stably capture carbon dioxide in the initial mixed gas.
  • carbon dioxide in the mixed gas may be continuously collected by the hydroxide ions generated by applying voltage to the anode and the cathode.
  • Carbonate ions dissociated from the carbonate supplied to the electrolyte and hydroxide ions dissociated from the hydroxide supplied to the electrolyte or generated by applying voltage to the black anode and cathode have the advantage of selectively trapping carbon dioxide in the mixed gas, and then into carbon dioxide.
  • carbon dioxide can be regenerated without a separate energy supply.
  • concentration of carbonates, hydroxide blacks, and mixtures thereof supplied to the electrolyte may be appropriately adjusted in consideration of carbon dioxide capture efficiency and economic efficiency.
  • the electrolyte may be supplied to the negative electrode compartment at a concentration below the saturation concentration of the electrolyte, and more specifically, the electrolyte is 1% to 50%, 1% to 30% black silver 22% to 28% relative to the saturation concentration Can be supplied.
  • the saturated concentration of sodium carbonate at 15 ° C is 1.55 M. Therefore, in the case of using sodium carbonate as the electrolyte, sodium carbonate may be supplied so that the concentration of sodium carbonate in the negative electrode compartment is 0.0155 to 0.775 M, 0.0155 to 0.465 M, or 0.341 to 0.434 M based on 15 ° C. Within this range, carbon dioxide can be captured economically and efficiently.
  • the carbonate-based silver or salts thereof may be moved from the cathode compartment to the anode compartment.
  • the time point when carbon dioxide is collected and the carbonic acid-based salts or salts thereof are generated can be confirmed by the pH of the anode compartment or the cathode compartment, the concentration of carbonate ions in the electrolyte of the cathode compartment, the electrical conductivity of the black cathode compartment, and the like.
  • the pH of the anode compartment or the cathode compartment the concentration of carbonate ions in the electrolyte of the cathode compartment, the electrical conductivity of the black cathode compartment, and the like.
  • a voltage is applied to the anode and the cathode
  • hydroxide ions are generated in the cathode compartment, so that the cathode compartment exhibits a high pH
  • black is the above.
  • Carbonate, hydroxide black, or a mixture thereof is supplied to the cathode compartment as an electrolyte so that the cathode compartment can exhibit high pH.
  • the concentration of carbonate ions in the cathode compartment is measured directly or indirectly, if the carbonate ions are produced above the saturation concentration, for example, above the saturation concentration, the carbonate ions or salts thereof are added to the cathode compartment. Can be moved to the anode compartment.
  • the electrical conductivity of the cathode compartment is measured to increase the electrical conductivity from 0 mS / cm to 50 mS / cm, 10 mS / cm to 50 mS / cm, 20 mS / cm to 50 mS / cm, and 30 mS / cm to When 50 mS / cm, black is 40 mS / cm to 50 mS / cm, carbonate-based ions or salts thereof can be moved from the cathode compartment to the anode compartment.
  • the method for transferring the carbonate-based ions or salts thereof into the anode compartment is not particularly limited, and the electrolyte solution contained in the cathode compartment may be anode by using a method of supplying an electrolyte solution or the like from the reservoir to the cathode compartment or the anode compartment. Can be moved to a compartment Accordingly, carbonic acid ions Alternatively, a moving path and a fluid flow rate regulating device may be installed between the cathode compartment in which the salt thereof is formed and the anode compartment in which the carbonate-based ion or the salt thereof is supplied.
  • the carbonate-based ions or salts thereof in the cathode compartment may be periodically moved to the anode compartment.
  • the content of the carbonate-based ions or salts thereof transferred to the anode compartment may be adjusted according to the amount of carbon dioxide to be obtained in the anode compartment.
  • Carbonic acid ions or salts thereof supplied from the cathode compartment are reconverted to carbon dioxide in the anode compartment.
  • the anode compartment is a region in which hydrogen is generated when a voltage is applied to the anode and the cathode, and when a carbonate-based ion or a salt thereof is supplied to the anode compartment, according to the equation of pH equilibrium as shown in Equations 6 and 7 below.
  • the carbonate dissociated from the carbonate or black carbonate dissolved in the electrolyte may be converted to hydrogen carbonate ions as shown in Equation 6 below, and the hydrogen carbonate ions may be converted to carbon dioxide as shown in Equation 7 below.
  • the collected carbon dioxide may be reconverted into carbon dioxide without adding an additive or supplying energy.
  • carbonic acid-based ions or salts thereof may be converted into carbon dioxide under normal pressure.
  • the carbonate-based ions or salts thereof may be reconverted to carbon dioxide at a pressure in the range of about 0.1 to 100 MPa.
  • the carbonate-based ions or salts thereof may be reconverted to carbon dioxide at a temperature of about 15 to 80 ° C. black or about 15 to 60 ° C. Accordingly, even if the industrial waste gas black or the mixed gas such as the exhaust gas is used immediately without notice, carbon dioxide can be separated from the mixed gas with excellent efficiency.
  • the pH of the anode compartment in which the carbonic acid ion or salt thereof is reconverted to carbon dioxide may be about 7 or less, about 6 or less, about 5 or less, about 4 or less, about 3 or less, and black may be about 2 or less, about 0 or more, or about One or more blacks may be about two or more.
  • the pH of the anode compartment is about 0 to 6, about 0 to 5, about 0 to 4, about 0 to 3, about 0 to 2, about 0 to 1, about 1 to 6, for efficient reconversion to carbon dioxide.
  • About 1 to 5, about 1 to 4, about 1 to 3, about 2 to 6, about 2 to 5, about 2 to 4 black may be adjusted to about 2 to 3.
  • a voltage of 0.83 V to 2 V is applied to the anode and the cathode.
  • Applying a voltage in this range can significantly reduce the energy required to separate carbon dioxide.
  • the theoretical voltage for oxidizing water to generate hydrogen ions and oxygen gas is 2.06V. Therefore, the purity of carbon dioxide can be improved by suppressing generation of oxygen gas in the anode compartment by adjusting the voltage range as described above.
  • the method of separating carbon dioxide according to the embodiment may pretreat the mixed gas before the first step.
  • the mixed gas may be contacted with a solvent to remove other gases other than carbon dioxide from the mixed gas.
  • the mixed gas may include gases such as S0 X) HF, HC1, NH 3 , Cl 2 , SiF 4) 0 2 , N 2 , CO, N0 X , SH 2 in addition to carbon dioxide. It may include.
  • C3 ⁇ 4 may be a pH of 3.5 to 5.5 which is not very soluble in water, S0 X, HF, HC1, NH 3, Cl 2, SiF 4 and so on is smoothly dissolved.
  • the heunhap gas a pH in water of about 3.5 to 7, 3.5 to 6, from about 3.5 to 5.5, the pH range than C0 2 from the gas mixture about 3.5 to 5 black is brought into contact with from about 3.5 to 4 water
  • a gas with high solubility in water, for example, S0 X , HF, HC1, N3 ⁇ 4, Cl 2) SiF 4, etc., can be removed in advance.
  • the mixed gas is passed through a container, a black tube, or the like, containing the water in the pH range, or the black is sprayed with the water in the pH range to the flow of the mixed gas passes in advance to other gases other than ⁇ 2 in the mixed gas in advance. Can be removed
  • the pretreatment of the mixed gas may be performed using a scrubber.
  • the pretreated mixed gas may be obtained by filling the scrubber with water in the pH range and dispersing the mixed gas under a high pressure through a sparger.
  • water of the pH range may be injected into the flow of the mixed gas to obtain a pretreated mixed gas from the outlet of the scrubber.
  • gases other than C0 2 not removed in this pretreatment step may not be dissolved in the high pH electrolyte in the cathode compartment and may be removed naturally.
  • the gas such as 0 2 , N 2 , CO, N0 X , SH 2 in the mixed gas does not dissolve in the high pH electrolyte of the cathode compartment, and thus the mixed gas containing such gas is supplied from the mixed gas even if the mixed gas containing the gas is supplied to the cathode compartment.
  • the inventors have found that after a lot of research, when the mixed gas contains C0 2 and S0 2 , SO 2 improves the capture efficiency and reconversion efficiency of CO 2 .
  • the mixed gas contains ⁇ 2 and so 2 , carbon dioxide can be separated from the mixed gas more efficiently even if the pretreatment step is omitted.
  • sulfate ions SO 4 2 —
  • SO 4 2 — sulfate ions
  • carbon dioxide in the mixed gas is collected by the hydroxide ions present in the cathode compartment as shown in Equation 4 above.
  • sulfur dioxide in the mixed gas may be collected by hydroxide ions present in the cathode compartment as shown in Equation 8.
  • the mixed gas may not be pretreated so that the mixed gas may contain NO x .
  • ⁇ 0 ⁇ is not dissolved in an electrolytic solution of high ⁇ the cathode compartment.
  • ⁇ 0 ⁇ can be removed not to enter the melt electrolyte to supply the gas to the cathode compartment heunhap.
  • sulfur dioxide is continuously collected by the hydroxide ions as shown in Equation 8, the concentration of sulfite ions (sul fite s0 3 2 ⁇ ) in the cathode compartment is increased, similar to the carbonate ions, and some sulfite ions are electrolytes. It may be precipitated as a salt in combination with a cation derived from and the like. Therefore, when a voltage is applied to the anode and the cathode and a mixed gas is supplied to the cathode compartment in which hydroxide ions are generated, carbon dioxide in the mixed gas is trapped to form carbonate ions, black carbonate ions and salts thereof, and salts of black carbonate ions. And sulfur dioxide in the mixed gas may be collected to form sulfite ions, sulfite ions and salts thereof, and salts of black sulfite ions.
  • the sulfite ions or salts thereof along with the carbonate ions or salts thereof are moved from the cathode compartment to the anode compartment to reconvert the carbonate ions or salts thereof to carbon dioxide in the anode compartment and from the sulfite ions or salts thereof.
  • Sulfate ions or salts thereof can be produced.
  • the second step can be carried out as described above, except that the disulfide or sulfite along with the carbonate ions or salts thereof is moved from the cathode compartment to the anode compartment, unless otherwise noted.
  • the sulfite ions dissociated from the sulfite ions or salts thereof supplied to the anode compartment may react with water to generate hydrogen ions as shown in Equation 9 below.
  • hydrogen ions are required to reconvert carbon dioxide from carbonate-based ions or salts thereof, and the hydrogen ions are subjected to oxidation reaction of sulfite ions or salts thereof according to Equation 9 rather than electrolysis of water according to Equation 1 above. If so, it is possible to prevent the generation of oxygen gas in the anode compartment to provide high purity carbon dioxide. Specifically, a voltage of 1.03 V to 2 V may be applied to the anode and the cathode to minimize the oxygen gas generated in the anode compartment. Since the theoretical voltage for oxidizing water to generate hydrogen ions and oxygen gas is 2.06 V, it is possible to suppress the generation of oxygen gas by adjusting the voltage range as described above. have.
  • the anode compartment may further improve the purity of carbon dioxide by further including a catalyst to promote the reaction of the formula (10).
  • a catalyst any catalyst capable of promoting the reaction of oxidizing sulfite ions (S3 ⁇ 4 2 —) to sulfate ions (S0 4 2 —) may be used.
  • the catalyst is composed of a compound containing Co 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Zn 2+ , Au 2+ or Cu 2+ and a compound containing Au, kg, Ru or Ir It may be one or more compounds selected from the group.
  • a voltage optimized for capture and reconversion of carbon dioxide may be applied to the anode and the cathode regardless of generation of oxygen gas.
  • a voltage of 0.83 V to 20 V, 0.83 V to 15 V, or 0.83 V to 10 V may be applied to the anode and the cathode.
  • the carbon dioxide separation method according to the embodiment may repeat the first step after the second step. Thereby, high purity and high concentration of carbon dioxide can be separated continuously from the mixed gas.
  • the first and second steps described above may be performed using the electrolysis device described above.
  • the electrolysis device used in the carbon dioxide separation method according to the embodiment will be described in detail.
  • the electrolysis device includes an anode; Cathode; An ion exchange membrane (IEM) positioned between the anode and the cathode; And a pair of anode compartments (AC) and cathode compartments (CC) separated by the ion exchange membrane.
  • IEM ion exchange membrane
  • the ion exchange membrane may be a cat ion exchange membrane (CEM) or an anion exchange membrane (AEM).
  • CEM cat ion exchange membrane
  • AEM anion exchange membrane
  • the degree of reduction in the efficiency of carbon dioxide trapping by the migration of hydroxide ions by the anion exchange membrane is greater than the degree of reduction of the conversion efficiency of carbon dioxide by the movement of hydrogen ions by the cation exchange membrane.
  • hydrogen ions are supplied in many routes as compared with hydroxide ions.
  • hydrogen ions can be obtained from hydrogen gas supplied from the cathode compartment, and the collection of sulfur dioxide together with carbon dioxide generates additional hydrogen ions with the formation of disulfide sulphate from sulfite ions. Therefore, when the pair of anode and cathode compartments are separated by one ion exchange membrane, a different exchange membrane may be employed as the ion exchange membrane.
  • the separation method of carbon dioxide may further include a step of regenerating the electrolyte after the second step.
  • Regenerating the electrolyte may be performed by mixing the electrolyte solution in the positive electrode compartment and the negative electrode compartment, and supplying a uniformly mixed electrolyte solution to the positive electrode compartment and the negative electrode compartment.
  • regenerating the electrolyte may be performed by applying a voltage to the positive electrode and the negative electrode to adjust the pH of the positive electrode compartment to 3 to 5, and to adjust the pH of the negative electrode compartment to 11 to 12, the electrolyte solution of the positive electrode compartment and the negative electrode compartment It can be carried out by producing an electrolyte solution of pH 8 to 10 by mixing. The electrolyte of pH 8 to 10 thus produced can be supplied to the positive electrode compartment and the negative electrode compartment again.
  • both a cation exchange membrane (CEM) and an anion exchange membrane (AEM) may be employed as the ion exchange membrane.
  • this electrolysis device is intermediate between a pair of anode compartments (AC) and cathode compartments (CC).
  • Anion exchange membrane (AEM) separating the anode compartment (AC) and the intermediate compartment (MC) so that a middle compartment (MC) is present and a cation exchange membrane (CEM) separating the middle compartment (MC) and the cathode compartment (CC) It may include.
  • the intermediate compartment (MC) may unexpectedly prevent the cation exchange membrane from passing through the cation exchange membrane or the anion exchange membrane from the anode compartment black cathode compartment due to chemical black physical defects of the cation exchange membrane black anion exchange membrane so that the anion does not cross over to the opposite compartment. Play a role
  • the electrolyte in the intermediate compartment can be desalted by moving to. Accordingly, the desalination may be supplied to the intermediate compartment MC to desalination.
  • the middle compartment may be desalted by supplying water resources including salts such as seawater, sewage, wastewater, and industrial water or their mixtures. Accordingly, by continuously supplying a water resource including a salt to the intermediate compartment as an electrolyte solution to obtain desalted fresh water continuously, it is possible to simultaneously perform a separation process and a desalination process of carbon dioxide.
  • the type of electrolyte supplied to the intermediate compartment is not limited thereto, and artificial brine may be supplied or black artificial brine may be supplied in combination with the water resource.
  • the artificial saline may be a solvent in which the above-described electrolyte is dissolved.
  • the electrolysis device may include two or more pairs of anode compartments and cathode compartments using a bipolar membrane.
  • a bipolar membrane When voltage is applied to the positive and negative poles, Water is separated into hydrogen ions and hydroxide ions by a bipolar membrane, and the hydrogen ions and hydroxide ions can be moved by electrical attraction.
  • the bipolar membrane may be replaced with a water migration passage whose sidewall is composed of the bipolar membrane.
  • the water is flowed into the water passage and voltage is applied to the anode and the cathode, the water is separated into hydrogen hydride and hydroxide ions in the bipolar membrane where the water is the sidewall, and hydrogen ions are supplied to the anode compartment by electrical attraction.
  • the compartment may be supplied with hydroxide ions.
  • the electrolysis device includes an anode; Cathode; A bipol membrane (BM) positioned between the anode and the cathode; Two ion exchange membranes IEM positioned between the anode and the bipolar membrane BM and between the bipolar membrane BM and the cathode; Each ear may comprise two pairs of anode compartments AC and cathode compartments CC separated by an exchange membrane IEM.
  • the electrolysis device includes an anode; Cathode; Two or more bipolar membranes (BM) positioned between the anode and the cathode; between the anode and the bipolar membrane (BM), between the bipolar membrane and the bipolar membrane, and between the bipolar membrane (BM) and the cathode (cathode)
  • BM bipolar membrane
  • IEMs ion exchange membranes located in the; It may include three or more pairs of anode compartments AC and cathode compartments CC separated by respective ion exchange membranes IEM.
  • 5 and 6 are diagrams schematically showing an electrolysis apparatus including four or more bipolar membranes.
  • a region in which a voltage is applied to the anode and a cathode to generate hydroxide ions is a cathode section
  • a region in which a voltage is applied to the anode and the cathode to generate hydrogen ions is a cathode section.
  • a mixed gas may be supplied to each of two or more cathode compartments.
  • the carbonate-based ions or salts thereof generated in each cathode compartment may be moved to the anode compartment paired with the corresponding cathode compartment as shown in FIG. 5, or moved to the anode compartment paired with another cathode compartment as shown in FIG. 6. .
  • the carbon dioxide separation method according to the embodiment is two or more It can be implemented using an electrolysis device.
  • each electrolysis device is represented as a device including a pair of anode compartments and a cathode compartment separated by one silver exchange membrane, but each electrolysis unit is represented by two ions schematically shown in FIG. 2.
  • the device may include a pair of anode compartments, an intermediate compartment and a cathode compartment by means of an exchange membrane, or black may be a device including two or more pairs of anode compartments and cathode compartments including the bipolar membrane shown in FIGS. 3 to 6.
  • the method for separating carbon dioxide according to one embodiment may be implemented using three or more electrolysis devices.
  • the electrolysis device may be configured as known in the art. Hereinafter, the components constituting the electrolysis device will be described in detail.
  • cation exchange membrane and the negative exchange membrane all kinds of ion exchange membranes applied to an electrolysis device or a fuel cell may be used.
  • a cation exchange membrane commercially available Nafion from Dupont or CMX of Tokuyama, Japan can be used.
  • CMX commercially available Nafion from Dupont or CMX of Tokuyama, Japan
  • an anion exchange membrane for example, Tokuyama, Japan AMX, AHA, ACS, etc. can be used.
  • the positive electrode and the negative electrode may be installed at an appropriate position to exert an electrical attraction to the ionic species contained in the positive electrode compartment and the negative electrode compartment.
  • the shape of the positive electrode and the negative electrode is not particularly limited, and may be variously modified as known in the art.
  • anode and the cathode various kinds of electrodes applied to an electrolysis device or a fuel cell may be used.
  • the anode and As the cathode various kinds of conductors may be used, or an electrode including an electrode substrate and a catalyst applied to the electrode substrate may be used.
  • the above conductors include titanium (Ti), stainless steel, nickel (Ni), nickel / chromium (Ni / Cr) alloys, platinum (Pt), gold (Au), palladium (Pd), iridium (Ir) and rhodium ( Rh), ruthenium (Ru) or those selected from the group consisting of these oxides can be used.
  • an electrode including a catalyst coated on the electrode substrate carbon cloth or the like may be used as the electrode substrate, and platinum (Pt), ruthenium (Ru), osmium (0s), or palladium may be used as the catalyst. (Pd), iridium (Ir), carbon (other transition metals and mixtures thereof) may be used.
  • the positive electrode and the negative electrode may be connected to a power supply.
  • the power supply device any of those known in the art to which the present invention pertains may be used as long as the voltage can be applied to the positive electrode and the negative electrode.
  • the electrolysis device may include a movement path connecting the anode compartment and the cathode compartment to allow fluid to move between the anode compartment and the cathode compartment.
  • the material forming the moving path is not particularly limited as long as it is not corroded or damaged by the fluid and can withstand the flow of the fluid.
  • the moving path may be formed of various materials such as SUS (steel use stainless), acrylic polymer, Teflon, nylon.
  • the flow path may be further provided with a fluid flow rate control device.
  • the electrolysis device may be connected to one or more reservoirs so as to continuously supply a mixed gas and an electrolyte to the electrolysis device, and collect carbon dioxide and fresh water obtained from the electrolysis device.
  • the electrolysis device includes a fluid flow rate adjusting device capable of adjusting a flow rate of a fluid or the like; A sensor for monitoring the status of the anode compartment, the cathode compartment, and optionally an intermediate compartment; And a recording device capable of recording an electrical signal related to the electrolysis device and a change in solution properties of each compartment.
  • the electrolysis device further includes a configuration commonly employed in addition to the above-described configuration, such as an electrolysis device known in the art. Black may be employed as part of a larger facility in connection with other device components.
  • the carbon dioxide separation system in a mixed gas containing carbon dioxide, the anode (anode); Cathode; A cathode compartment in which hydroxide ions are generated when a voltage is applied to the anode and the cathode, and carbon dioxide is trapped in a mixed gas including carbon dioxide to generate carbonic acid-based ions or salts thereof; An anode compartment for generating hydrogen ions when a voltage is applied to the anode and the cathode and reconverting the carbonate-based ions or salts thereof transferred to the carbon dioxide; And an ion exchange membrane separating the anode compartment and the cathode compartment.
  • the carbon dioxide separation system is a system capable of performing the above-described method of separating carbon dioxide, which has been described in detail above, and thus, a detailed description thereof will be omitted.
  • the method for separating carbon dioxide according to one embodiment of the present invention is capable of purely separating carbon dioxide from a mixed gas discharged during combustion, it is expected to be applicable to various technical fields for separating, using, or treating carbon dioxide.
  • the carbon dioxide separation method is useful for reducing the cost of the ecus technology, it is expected to provide carbon dioxide useful in fields requiring ultra-high purity carbon dioxide, for example, chemical reaction process.
  • the first electrode may be a cathode
  • the second electrode may be applied with a voltage to collect carbon dioxide in a mixed gas including carbon dioxide in a second compartment in which hydroxide ions are generated, thereby generating carbonic acid-based silver or a salt thereof.
  • Stage 1 ; And generating a hydrogen ion by applying a voltage such that the first electrode becomes a cathode and the second electrode becomes an anode.
  • a method for separating carbon dioxide comprising a second step of reconverting the carbonate-based ions or salts thereof to carbon dioxide in two compartments.
  • the method for separating carbon dioxide according to the embodiment may selectively separate carbon dioxide from industrial waste gas and the like with low energy based on an electrochemical system. Accordingly, the carbon dioxide separation method can provide an economical CCUS technology by replacing the capture process that occupies 50 to 70% of the total cost of the existing Carbon Capture Ut ion ion and Storage (CCUS) technology, thereby Carbon dioxide, a representative greenhouse gas, can be efficiently removed from industrial waste gas.
  • CCUS Carbon Capture Ut ion ion and Storage
  • Separation method of carbon dioxide according to the embodiment may provide a high purity concentrated carbon dioxide. Therefore, the carbon dioxide separation method according to the embodiment is expected to provide a carbon dioxide useful in the field requiring ultra-high purity carbon dioxide, for example, chemical reaction process using carbon dioxide as a precursor.
  • the method for separating carbon dioxide uses a hydroxide ion generated by electrolysis of water instead of amine-based collector black or ammonia, which is a representative collector for carbon dioxide, so that it is regenerated to recycle the collector after carbon dioxide capture. There is an advantage that no separate process is required.
  • the carbon dioxide separation method may include a first electrode (f irst electrode; 1st EL); Second electrode (2nd EL); A cat ion exchange membrane (CEM) positioned between the first electrode and the second electrode; And a pair of first and second compartments separated by the cation exchange membrane, the first compartment located on the first electrode side and the second compartment located on the second electrode side. compartment (2nd CP).
  • the device may be referred to as an electrolysis device.
  • the first electrode becomes the anode and the second electrode becomes the cathode.
  • an oxidation reaction may occur in the first compartment located on the first electrode side based on the cation exchange membrane, and a reduction reaction may occur in the second compartment located on the second electrode side based on the cation exchange membrane. That is, in the present specification, 'anode' means 'oxidizing electrode', and 'cathode' means 'reducing electrode'.
  • the first step when a voltage is applied such that the first electrode becomes the anode and the second electrode becomes the cathode, hydrogen ions may be generated in the first compartment, and hydroxide ions may be generated in the second compartment (see FIG. 9 10). .
  • hydrogen ions may be generated due to oxidation reaction as shown in Equation 1 or 2 below.
  • hydroxide ions may be generated due to the reduction reaction as shown in Equation 3 below.
  • the electrolysis apparatus includes a bipolar membrane as described below (see FIGS. 11 and 12)
  • at least one of the first and second compartments may be in contact with the bipolar membrane.
  • voltage is applied to the first and second electrodes
  • water is separated into hydrogen ions and hydroxide ions by the bipolar membrane.
  • the hydrogen ions and the hydroxide ions are moved by electrical attraction.
  • a voltage is applied to the first and second electrodes such that the first electrode becomes the anode and the second electrode becomes the cathode, hydrogen is added to the first compartment adjacent to the bipolar membrane. Hydrogen ions are supplied to the second compartment in which the ions are supplied and in contact with the bipolar membrane.
  • the reduction reaction occurs in the first compartment of the second stage as in Equation 3 to generate hydroxide ions
  • an oxidation reaction may occur as in Equation 1 or Equation 2 to generate hydrogen ions (see 20 in FIG. 9).
  • the electrolysis device includes a bipolar membrane (see FIGS. 11 and 12), and according to the second step, the first electrode and the second electrode become the anode according to the second step.
  • a voltage is applied to the electrode, hydroxide ions are supplied to the first compartment in contact with the bipolar membrane and hydrogen ions are supplied to the second compartment in contact with the bipolar membrane (Fig.
  • the type of ions generated in the first and second compartments may be determined depending on which of the first and second electrodes is applied with a voltage such that the anode is the anode black or the cathode.
  • the first and second compartments may be filled with a solvent in which an electrolyte is dissolved for stable driving of the electrolysis device, high capture efficiency and reconversion efficiency of carbon dioxide.
  • the solvent may be water
  • the electrolyte may be various salts that can be dissolved in water and dissociated into cations and anions.
  • the electrolyte may be a hydrochloride, sulfate, nitrate, carbonate, hydroxide, oxide black or a combination thereof.
  • the electrolyte is sodium chloride, lithium chloride, rubidium chloride, calcium chloride, magnesium chloride, sodium sulfate sulfate, lithium sulfate, rubidium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, Calcium nitrate, magnesium nitrate, sodium carbonate potassium carbonate, lithium carbonate, rubidium carbonate, calcium carbonate, magnesium carbonate, sodium hydroxide potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, magnesium hydroxide sodium oxide, potassium oxide, lithium oxide, rubidium oxide, Calcium oxide, magnesium oxide or oxides thereof.
  • hydrogen ions are generated in one of the first and second compartments, and in the other of the first and second compartments.
  • a voltage may be applied to the first and second electrodes to generate hydroxide ions.
  • the applied voltage is the kind and concentration of the electrolyte contained in the first and second compartments, the type of oxidation reaction occurring in one compartment of the first and second compartments, and the reduction occurring in the other compartment of the black and the first and second compartments. It can be adjusted according to the type of reaction.
  • the first and second electrodes are 0.42 V or more, 0.83 V or more, 1.03 V or more, and 2.06 V or more, and 10 V or less, 7 V or less, 5 V or less, 4 V or less, 3 V or less.
  • a voltage of 2 V or less can be applied. Within this range, carbon dioxide in the mixed gas can be efficiently separated with little energy.
  • the mixed gas may be directly supplied to any one of the first and second compartments to collect carbon dioxide in the mixed gas in any one of the compartments.
  • the mixed gas in the first step, the mixed gas is directly supplied to the second compartment to collect carbon dioxide in the mixed gas, and in the second step, the mixed gas is directly supplied to the first compartment to capture the carbon dioxide in the mixed gas, and again.
  • the mixed gas may be directly supplied to the second compartment to collect carbon dioxide in the mixed gas. Accordingly, the method of separating carbon dioxide has the advantage that it is not necessary to provide a separate collecting device such as a scrubber to collect the carbon dioxide in the mixed gas.
  • the mixed gas is applied to the first and second electrodes before the voltage is applied to the first and second electrodes, and black is the first and second compartments after the voltage is applied to the first and second electrodes. It can be supplied to either compartment.
  • the mixed gas may be supplied after a layer of hydroxide ions is generated in one of the first and second compartments by applying a voltage to the first and second electrodes.
  • the pH of any one of the first and second sections is about 10 to 14, about 11 to 14, about 12 to 14, about 13 to 14, about 10 to 13, about 11 to 13, about 12 to 13, about 10 to 12, about 11 to 12 black is about 10 to 11, Can be supplied.
  • the mixed gas may be continuously supplied to one of the first and second compartments, or black may be periodically supplied.
  • the mixed gas may be periodically supplied when the pH of one of the first and second compartments reaches the above-mentioned range.
  • the carbon dioxide separation method is capable of separating pure carbon dioxide from various mixed gases containing carbon dioxide.
  • a mixed gas include a mixed gas requiring separation of carbon dioxide, industrial waste gas discharged from a natural gas power generation facility, a cement refining plant, and exhaust gas discharged from a combustion process of fuel.
  • the ratio of carbon dioxide in the mixed gas is not particularly limited.
  • At least 2 volume%, at least 5 volume%, at least 10 volume%, at least 15 volume%, at least 20 volume%, at least 30 volume%, at least 40 volume% black may be at least 50 volume%. In this range, more pure and concentrated carbon dioxide can be obtained.
  • the upper limit of the ratio of carbon dioxide contained in the mixed gas is not particularly limited, 100% by volume or less, 90% by volume or less, 80% by volume or less, 70% by volume or less may be 60% by volume or less.
  • the second compartment is a region where hydroxide ions are generated when a voltage is applied to the first and second electrodes. Therefore, in the first step, carbon dioxide in the mixed gas supplied to the second compartment can be selectively collected into the hydroxide ions present in the second compartment according to Equation 4 below.
  • carbon dioxide in the mixed gas may be collected under normal pressure. Atmospheric pressure means natural pressure that is not pressurized or depressurized. Specifically, the carbon dioxide in the mixed gas may be collected in a pressure range of about 0.1 to 100 MPa. In addition, in the method for producing carbon dioxide according to the embodiment, the carbon dioxide in the mixed gas may be collected at a temperature of about 15 to 80 ° C. or about 15 to 60 ° C. Can be. Accordingly, carbon dioxide can be collected from the mixed gas by supplying the mixed gas such as industrial waste gas or exhaust gas directly to the first or second compartment without cooling the mixed gas.
  • the pH of any one of the first and second compartments in which the carbon dioxide in the mixed gas is collected is about 4 or more, about 5 or more, about 6 or more, about 7 or more, about 8 or more, about 9 or more, about 10 or more, or about 11 or more blacks may be about 12 or more, about 14 or less, about 13 or less blacks may be about 12 or less.
  • the pH of any one of the first and second compartments in which the carbon dioxide in the mixed gas is collected is about 10 to 14, about 11 to 14, about 12 to 14, about 13 to 14, About 10 to 13, about 11 to 13, about 12 to 13, about 10 to 12, about 11 to 12 black may be adjusted to about 10 to 11.
  • carbon dioxide in the mixed gas is selectively collected by hydroxide ions to generate hydrogen carbonate ions (HC0 3 —), and these hydrogen carbonates (HC _) change to dicarbonate (C0 3 2 —) at higher pH. Therefore, the carbon dioxide in the mixed gas supplied to any one of the first and second compartments may be collected by hydroxide ions to generate hydrogen carbonate ions and / or carbonate ions.
  • the term 'carbonate-based ion' is used to collectively refer to a mixture of hydrogen carbonate ions, carbonate ions, black hydrogen carbonate ions and carbonate ions.
  • any one section in which hydroxide ions are generated in the first and second compartments may include a carbonate hydroxide black thereof in the above-described electrolyte. That is, in the first step, the second compartment may contain carbonate, hydroxide black as a electrolyte, and a mixture thereof. In the second step, the first compartment may be carbonate, hydroxide black as its electrolyte. May include a mixture. Therefore, in the first step, carbonate and hydroxide black may be supplied to the second compartment, and in the second step, carbonate and hydroxide black may be supplied to the first compartment.
  • carbonate, hydroxide black and these mixtures include sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, calcium carbonate, magnesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, calcium hydroxide, and magnesium hydroxide black. These can be mentioned a combination.
  • Carbonate supplied as an electrolyte to any of the compartments in which hydroxide ions are generated in the first and second compartments is dissociated into cations and carbonates (C0 3 2 —), and the carbonate ions are carbon dioxide in the mixed gas as shown in Equation 5 below. It can be collected to produce hydrogen bicarbonate.
  • hydroxide supplied as an electrolyte to any of the compartments in which the hydroxide ions are generated in the first and second compartments is also dissociated into cations and hydroxide ions, and the hydroxide ions trap carbon dioxide in the mixed gas as described in Equation 4 to form carbon dioxide. Hydrogen ions can be produced.
  • the carbon dioxide in the initial mixed gas can be stably collected due to the carbonate and hydroxide black supplied as an electrolyte to one of the compartments in which the first and second compartments are added.
  • carbon dioxide in the mixed gas may be continuously collected by hydroxide ions generated by applying voltage to the first and second electrodes.
  • Carbonate ions dissociated from the carbonate supplied to the electrolyte and hydroxide ions dissociated from the hydroxide supplied to the electrolyte or generated by applying a voltage to the first and second electrodes which are black have the advantage of selectively trapping carbon dioxide in the mixed gas, Thereafter, in the second step of reconverting to carbon dioxide, there is an advantage that carbon dioxide can be regenerated without a separate energy supply.
  • the concentrations of carbonates, hydroxides, blacks and the like supplied to the electrolyte may be appropriately adjusted in consideration of carbon dioxide capture efficiency and economic efficiency.
  • the electrolyte may be supplied at a concentration below the saturation concentration of the electrolyte, and more specifically, the electrolyte may be supplied at 50%, 1% to 30% black, and 22% to 28% of the saturation concentration.
  • the saturation concentration of sodium carbonate at 15 ° C is 1.55 M.
  • the concentration of sodium carbonate is 0.0155 to 0.775 M, 0.0155 to 0.465 M, or 0.341 to 0.434 M at 15 ° C. in either compartment where the first and second compartment thick hydroxide ions are generated.
  • Sodium carbonate can be fed. Within this range, carbon dioxide can be captured economically and efficiently.
  • a voltage may be applied such that the first electrode becomes a cathode and the second electrode becomes an anode.
  • the time when the carbon dioxide is collected and the carbonate-based salts or salts thereof are generated in detail is the pH of the first or second compartment, the concentration of the carbonate-based ions in the electrolyte solution of the first or second compartment, or the black or the first or second compartment. This can be checked through electrical conductivity.
  • hydroxide ions are generated in the first and second compartments, so that the second compartment has a high pH, or black in the first stage.
  • Carbonate, hydroxide black can be fed to these mixtures as an electrolyte so that the second compartment can exhibit high pH.
  • the hydroxide ions and the carbonate ions are used to capture carbon dioxide as in Equation 4 and Equation 5, as the carbon dioxide is collected, the pH of the second compartment of the first stage becomes lower gradually.
  • the concentration of carbonic acid ions in the second compartment is measured directly or indirectly, if enough carbonic acid ions are generated, for example, when the concentration of the carbonic acid is higher than or equal to the saturation concentration, the first electrode becomes a cathode and the second electrode. Voltage can be applied to this anode.
  • the concentration of the carbonic acid ions increases to increase the electrical conductivity of the second compartment. Therefore, by measuring the electrical conductivity of the second section of the first step, the increase in electrical conductivity is 0 raS / cm to 50 mS / cm, 10 mS / cm to 50 mS / cra, 20 raS / cm to 50 mS / cm, When 30 mS / cm to 50 mS / cm, black is 40 mS / cm to 50 mS / cm, a voltage may be applied such that the first electrode becomes a cathode and the second electrode becomes an anode.
  • the method of applying a voltage to the first and second electrodes is not particularly limited so that the first electrode serving as the anode becomes the cathode in the first step, and the second electrode serving as the cathode serves as the anode.
  • it may be performed by applying a voltage to the first and second electrodes by setting which of the first and second electrodes will function as the anode black or the cathode.
  • it is very easy to set which of the two electrodes to function as the anode in the power supply.
  • the first and second steps may be performed by setting the anode and the cathode to be interchanged when a signal indicating that the carbonate-based ions or salts thereof are generated through the sensors installed in the first and second compartments.
  • the signal that the carbonate ions or salts thereof are sufficiently produced means that the pH of the first or second compartment, the concentration of the carbonate ions, and the black or black electrical conductivity have reached a certain value.
  • a voltage is applied to the first and second electrodes such that the first electrode serving as the anode becomes the cathode and the second electrode serving as the cathode becomes the anode.
  • the carbonate-based ions or salts thereof produced in the second compartment are reconverted to carbon dioxide.
  • the first compartment becomes a region where hydroxide ions are generated and the second compartment generates hydrogen ions. It becomes an area. Therefore, the carbonate-based ions or salts thereof present in the second compartment may be converted into carbon dioxide according to the pH equilibrium principle as shown in Equations 6 and 7. Specifically, carbonate ions dissolved in the electrolyte black carbonate dissociated from the carbonate is converted to hydrogen carbonate ions as shown in Equation 6, hydrogen carbonate ions may be converted to carbon dioxide as shown in Equation 7.
  • the collected carbon dioxide may be reconverted into carbon dioxide without adding an additive or supplying energy.
  • carbonic acid-based ions or salts thereof may be converted into carbon dioxide under normal pressure.
  • the carbonate-based ions or salts thereof may be reconverted to carbon dioxide at a pressure in the range of about 0.1 to 100 MPa.
  • the carbonate-based ions or salts thereof may be reconverted to carbon dioxide at a temperature of about 15 to 80 ° C. black or about 15 to 60 ° C. Accordingly, even if the industrial waste gas black or the mixed gas such as the exhaust gas is used without cooling, carbon dioxide can be separated from the mixed gas with excellent efficiency.
  • the pH of the second compartment in which the carbonate-based salt or salt thereof is reconverted to carbon dioxide may be about 7 or less, about 6 or less, about 5 or less, about 4. or less and about 3 or less, and black may be about 2 or less, About 0 or more, about 1 or more Black is about 2 It may be abnormal. Among them, for the efficient reconversion to carbon dioxide,
  • the pH of the second stage of the second stage is about 0-6, about 0-5 Pa about 0-4, about 0-3, about 0-2, about 0-1, about 1-6, about 1-5, about 1 to 4, about 1 to 3, about 2 to 6, about 2 to 5, about 2 to 4 or about 2 to 3.
  • the carbonic acid-based ions or salts thereof are converted into carbon dioxide by hydrogen ions generated through oxidation reaction of hydrogen gas in the second step, 0.83 V to 2 V at the first and second electrodes.
  • the voltage of can be applied. Applying a voltage in this range can significantly reduce the energy required to separate carbon dioxide.
  • the theoretical voltage for oxidizing water to generate hydrogen ions and oxygen gas is 2.06V. Therefore, by adjusting the voltage range as described above, the purity of carbon dioxide is improved by consuming hydrogen gas generated in the second section of the first stage and suppressing generation of oxygen gas in the second section of the second stage. You can.
  • the method of separating carbon dioxide according to the embodiment may pretreat the mixed gas before the first step.
  • the mixed gas may be contacted with a solvent to remove other gases other than carbon dioxide from the mixed gas.
  • the mixed gas is a gas such as S0 X , HF, HC1, NH 3) Cl 2 j SiF 4 , 0 2 , N 2 , CO, N0 X , SH 2 in addition to carbon dioxide. It may include. C0 2 may be a pH of 3.5 to 5.5 which is not very soluble in water, S0 X, HF, HC1, NH 3, Cl 2, SiF 4 and so on is smoothly dissolved. Therefore, the mixed gas has a pH of about 3. 5 to ⁇ , about 3.5 to 6 ⁇ about 3. 5 to 5. 5, about 3.
  • the mixed gas is passed through a container, a black tube, or the like, containing the water in the pH range, or black, by injecting water in the pH range in a flow through which the mixed gas passes, to advance other gases other than C0 2 in the mixed gas in advance. Can be removed
  • the pretreatment of the mixed gas may be performed using a scrubber.
  • the pretreated mixed gas may be obtained by filling the scrubber with water in the pH range and dispersing the mixed gas under high pressure through a porous spray plate into a scrubber.
  • water of the pH range may be injected into the flow of the mixed gas to obtain the mixed gas pretreated from the outlet of the scrubber.
  • gases other than C0 2 not removed in this pretreatment step may be naturally dissolved because they do not dissolve in the high pH electrolyte in any one compartment where hydroxide ions are generated in the first and second compartments.
  • the gas such as 0 2 , N 2 , CO, N0 X , SH 2 in the mixed gas does not dissolve in the high pH electrolyte solution, so even if the mixed gas containing such gas is supplied to the first or second compartment, the mixed gas You can selectively capture C3 ⁇ 4 from.
  • the carbon dioxide in the mixed gas is converted by the hydroxide ions as shown in Equation 4 above. Is collected.
  • sulfur dioxide in the mixed gas may be collected by hydroxide ions as shown in Equation 8.
  • the mixed gas may not be pretreated so that the mixed gas may contain NO x .
  • ⁇ 0 ⁇ is not dissolved in an electrolytic solution of high ⁇ . Therefore, ⁇ can be removed by not melting in the electrolyte when supplying the mixed gas to the second compartment of the first stage.
  • the concentration of sulfite ions (sul fi te, S0 3 2 —) in the second compartment of the first step is increased, similarly to the carbonic acid-based silver.
  • some sulfite ions may be combined with cations derived from an electrolyte or the like to precipitate as a salt. Therefore, when the mixed gas is supplied to the second section of the first stage, carbon dioxide in the mixed gas is collected to form carbonate-based ions, black carbonate-based ions and salts thereof, and salts of black carbonate-based ions, and sulfur dioxide in the mixed gas. This trapping can produce sulfite ions, sulfite ions and salts thereof, and salts of black or sulfite ions.
  • the first electrode serving as the anode in the first step becomes the cathode, and the voltage is applied to the first and second electrodes so that the second electrode serving as the cathode becomes the anode.
  • the ions or their salts can be reconverted to carbon dioxide and sulfate ions or salts thereof can be produced from the sulfite ions or salts thereof.
  • the first and second steps may be performed as described above, unless otherwise described.
  • the sulfite ions dissociated from the sulfite ions or salts thereof present in the second compartment of the second step may react with water to generate hydrogen ions as shown in Equation 9 below.
  • the carbonic acid-based ions or salts thereof are reconverted into hydrogen dioxide by hydrogen ions, and thus the reaction for generating sulfate ions from sulfite ions generating hydrogen ions results in reconversion of carbon dioxide. Can be promoted.
  • sulfate ions generated from sulfite ions can improve the electrical conductivity by increasing the total amount of ions in the second compartment.
  • hydrogen ions are required to reconvert carbon dioxide from carbonate ions or salts thereof in the second compartment of the second step, and the hydrogen ions are not sulfur dioxide or silver sulfite according to Equation 9, but the electrolysis of water according to Equation 1 above.
  • the hydrogen ions are not sulfur dioxide or silver sulfite according to Equation 9, but the electrolysis of water according to Equation 1 above.
  • a voltage of 1.03 V to 2 V may be applied to the first and second electrodes in order to minimize the oxygen gas generated in the second section of the second step. Since the theoretical voltage for oxidizing water to generate hydrogen ions and oxygen gas is 2.06 V, oxygen gas generation can be suppressed by adjusting the voltage range as described above.
  • the carbon dioxide separation method according to the embodiment may repeat the first step after the second step. Thereby, high purity and high concentration of carbon dioxide can be separated continuously from the mixed gas.
  • hydroxide ions are generated in the first compartment 1st CP of the second stage similarly to the second compartment 2nd CP of the first stage (see 10 and 20 of FIG. 10). Accordingly, the second step may collect carbon dioxide in the mixed gas including carbon dioxide in the first compartment to generate carbonic acid ions or salts thereof (see 20 in FIG. 10). Since the method of capturing carbon dioxide in the second compartment of the first stage has been described in detail above, a detailed description of the method of capturing carbon dioxide in the first compartment of the second stage will be omitted.
  • carbonate and hydroxide as an electrolyte are supplied to the second compartment to improve the collection efficiency of carbon dioxide, and in the second step, carbonate and hydroxide are used as the electrolyte in the first compartment. Black can feed these mixtures.
  • the sulfur dioxide is captured together with the carbon dioxide
  • the first compartment of the second stage can also collect sulfur dioxide together with the carbon dioxide.
  • carbon dioxide in the mixed gas is collected in the first compartment (1st CP) of the second stage to generate carbonic acid-based ions or salts thereof, hydrogen ions are generated in the first compartment when the first stage is repeated.
  • the carbonate-based ions or salts thereof may be reconverted to carbon dioxide (see 10 ′ in FIG. 10). This allows the use of both pairs of first and second compartments to separate more carbon dioxide from more mixed gases.
  • the first and second steps described above may be performed using the electrolysis device described above.
  • the electrolysis device used in the carbon dioxide separation method according to the embodiment will be described in detail.
  • the electrolysis device includes a first electrode (1st EL); Second electrode (2nd EL); A cat ion exchange membrane (CEM) positioned between the first electrode and the second electrode, and a pair of first and second compartments separated by the cation exchange membrane, the second electrode positioned on the first electrode side; F irst compartment (1st CP) and second electrode A second compartment located on the side (2nd CP).
  • the carbon dioxide in the mixed gas in the second compartment of the first stage is captured by the hydroxide ions, and in the second compartment of the second stage, the carbonic acid-based ions or salts thereof may be converted into carbon dioxide by hydrogen ions.
  • hydroxide ions can pass through the anion exchange membrane by electrical attraction to other compartments, thereby degrading the capture efficiency of carbon dioxide.
  • hydrogen ions may pass through the cation exchange membrane by electrical attraction to other compartments, thereby reducing carbon dioxide reconversion efficiency.
  • the degree of reduction of the carbon dioxide collection efficiency due to the migration of hydroxide ions by the anion exchange membrane is greater than the degree of reduction of the reconstruction efficiency of the carbon dioxide by the transfer of hydrogen ions by the different exchange membrane.
  • hydrogen ions are provided in more routes than hydroxide ions.
  • hydrogen ions can be obtained from hydrogen gas generated at the time of capture of carbon dioxide.
  • the method for separating carbon dioxide according to the embodiment may further include regenerating the electrolyte after the second step. Then, after the electrolyte regeneration, the first step may be repeated.
  • Regenerating the electrolyte may be performed by mixing the electrolyte solution of the first and second compartments, and supplying the electrolyte solution mixed uniformly to the first and second compartments.
  • regenerating the electrolyte may be performed by applying a voltage to the first and second electrodes to adjust the pH of one compartment to 3-5. After adjusting the pH of the compartments to 11 to 12, the electrolyte of the first and second compartments may be mixed to produce an electrolyte of pH 8 to 10. The resulting electrolyte of pH 8 to 10 may be supplied to the first and second compartments again.
  • the electrolysis device may comprise two or more pairs of first and second compartments using a bipolar membrane. When voltage is applied to the first and second electrodes, water is separated into hydrogen ions and hydroxide ions by the bipolar membrane, and the hydrogen ions and hydroxide ions can move by electrical attraction.
  • the bipolar membrane may be replaced with a water migration passage whose sidewall is composed of the bipolar membrane.
  • water is poured into the water passage and voltage is applied to the first and second electrodes, water is separated into hydrogen ions and hydroxide ions in the bipolar membrane where the water is a sidewall.
  • Hydrogen ions are supplied by an electrical attraction to the compartment located on the anode side of the pair of first and second compartments based on the cation exchange membrane located between the first and second compartments, and the compartment located on the cathode side is electrically Hydroxide ions can be supplied by attraction.
  • the electrolysis device includes a first electrode 1st EL; Second electrode 2nd EL; A bipol ar membrane (BM) positioned between the first and second electrodes; between the first electrode (1st EL) and the bipolar membrane (BM) and between the bipolar membrane (BM) and the second electrode (2nd EL) Two cation exchange membranes (CEM) located between the; Two pairs of first and second partitions separated by the respective cation exchange membranes (CEMs), two first compartments (1st CP) and a second electrode (2nd EL) positioned on the first electrode (1st EL) side. It may include two second compartment (2nd CP) located on the side).
  • CEM cation exchange membranes
  • the electrolysis device includes a first electrode 1st EL; A second electrode (2nd EL); two or more bipol ar membranes (BMs) positioned between the first and second electrodes; Three or more cation exchange membranes (CEM) positioned between the first electrode 1st EL and the bipolar membrane BM, between the bipolar membrane and the bipolar membrane, and between the bipolar membrane BM and the second electrode 2nd EL; At least three pairs of first and second compartments separated by the respective cation exchange membranes (CEM), wherein at least three first compartments (1st CP) and a second electrode (2nd) positioned on the first electrode (1st EL) side. It may include three or more second compartments (2nd CP) located on the EL side.
  • CEM cation exchange membranes
  • a mixed gas may be supplied to each of two or more second sections in the first step.
  • a mixed gas may be supplied to each of two or more first sections in the second step.
  • the carbonate-based ions or salts thereof generated in the compartment may be reconverted to carbon dioxide in the compartment while changing the roles of the first and second electrodes as the anode and the cathode.
  • the electrolysis device may be configured as known in the art.
  • the component which comprises the said electrolysis apparatus is demonstrated in detail.
  • cation exchange membrane various kinds of divalent silver exchange membranes applied to an electrolysis device or a fuel cell may be used.
  • the cation exchange membrane for example, commercially available Nafion from Dupont, CMX from Tokuyama, Japan, and the like can be used.
  • the first and second electrodes may be installed at appropriate positions so as to exert an electrical attraction to the ionic species included in the first and second compartments.
  • the shape of the first and second electrodes is not particularly limited, and may be variously modified as known in the art.
  • first and second electrodes all kinds of electrodes applied to an electrolysis device or a fuel cell may be used.
  • various types of conductors may be used as the first and second electrodes, or an electrode including a black electrode substrate and a catalyst applied to the electrode substrate may be used.
  • the above conductors include titanium (Ti), stainless steel, nickel (Ni), nickel / chromium (Ni / Cr) alloys, platinum (Pt), gold (Au), palladium (Pd), iridium (Ir), and rhodium ( Rh), ruthenium (Ru) or those selected from the group consisting of these oxides can be used.
  • an electrode including a catalyst coated on the electrode substrate carbon cloth or the like may be used as the electrode substrate, and platinum (Pt), ruthenium (Ru), osmium (0s), or baffle may be used as the catalyst.
  • Platinum (Pt), ruthenium (Ru), osmium (0s), or baffle may be used as the catalyst.
  • Radium (Pd), iridium (Ir), carbon (0, other transition metals and mixtures thereof) may be used.
  • the first and second electrodes may be connected to a power supply device. remind As the power supply device, voltages in the above-described ranges may be applied to the first and second electrodes, and if it is possible to change the roles of the first and second electrodes as the anode and the cathode, those known in the art. Both can be used.
  • the electrolysis device may be connected to one or more reservoirs so as to continuously supply a mixed gas and an electrolyte to the electrolysis device, and collect carbon dioxide and the like obtained from the electrolysis device.
  • the electrolysis device includes a fluid flow rate adjusting device capable of adjusting the flow rate of the fluid flow; Sensors for monitoring the status of the first and second compartments; And a recording device capable of recording an electrical signal related to the electrolysis device and a change in solution properties of each compartment.
  • the electrolysis device may further include a configuration commonly employed in the electrolysis device known in the art to which the present invention pertains, or may be employed as a part of a large-scale facility in connection with other device parts.
  • the carbon dioxide separation system in a mixed gas containing carbon dioxide, the first electrode; Second electrode; A cation exchange membrane positioned between the first and second electrodes; A pair of first and second compartments separated by the cation exchange membrane, the first compartment located on the first electrode side and the second compartment located on the second electrode side; And a power supply for applying a voltage such that the first electrode becomes an anode and the second electrode becomes a cathode, and then applies a voltage such that the first electrode becomes a cathode and the second electrode becomes an anode.
  • a system is provided.
  • the carbon dioxide separation system is a system capable of performing the above-described method of separating carbon dioxide, which has been described in detail above, and thus a detailed description thereof will be omitted.
  • the method for separating carbon dioxide according to one embodiment of the present invention is capable of purely separating carbon dioxide from a mixed gas discharged during combustion, it is expected to be applicable to various technical fields for separating, using, or treating carbon dioxide.
  • the carbon dioxide separation method is ecus technology It is expected to be able to provide carbon dioxide useful for cost reduction and useful in fields requiring ultra high purity carbon dioxide, for example, chemical reaction processes.
  • the operation and effects of the invention will be described in more detail with reference to specific examples. However, this is presented as an example of the invention, whereby the scope of the invention is not limited in any sense.
  • Carbon dioxide was separated from the mixed gas using an electrolysis device as shown in FIG. 2. Specifically, the supply of 15 ° C based on an aqueous solution of sodium carbonate of about 0.4 M in the electrolyte in the anode compartment, and supplying the 15 ° C based on aluminum oxide aqueous solution of about 1.0 M in the electrolyte in the cathode compartment and the intermediate compartment to the electrolytic solution 15 ° C A standard about 1.0 M aqueous sodium chloride solution was supplied. A voltage of 4 V was applied to the positive electrode and the negative electrode, and a mixed gas containing 10 vol% of carbon dioxide was supplied to the negative electrode compartment at a rate of 80 cc / min.
  • the initial pH of the cathode compartment at room temperature was measured to be about 11.75.
  • the pH is gradually lowered, and it is confirmed that the pH is maintained at about 7.9.
  • Anode compartment exhibits a very low p H as described above and the carbon black-based ion moved to the cathode compartment has been released is again a salt thereof is converted to carbon dioxide.
  • the concentration at room temperature 25 ° C
  • the concentration at room temperature was about 1.0 M
  • the concentration at room temperature was about 1.0 M when the concentration of hydrogen ions in the anode compartment was measured.
  • H 2 of about 0.5 M to approximately 1.0 M was added to H 2 S0 4 solution of about 0.5 M in the NaHC0 3 solution was about 1.0 M
  • the content was measured to define the amount of carbon dioxide expected to be theoretically recovered in the anode compartment. Since 1 mol of H 2 S0 4 dissociated to generate 2 mol of hydrogen ions, the concentration of the H 2 S0 4 solution was adjusted to 0.5 M.
  • Carbon dioxide generation amount according to the addition of the H 2 S0 4 solution of about 0.5 M is
  • Example 2 In the same manner as in Example 1, the electrolyte was supplied to the cathode compartment, the anode compartment, and the intermediate compartment, and carbon dioxide was separated from the mixed gas in the same manner as in Example 1 except that the temperature of the electrolysis device was increased to 50 ° C.
  • the initial pH of the cathode compartment at 50 ° C. was measured at about 11. And, as the carbon dioxide continues to be collected, the pH is gradually lowered, and it is confirmed that the pH is maintained at about 8.2.
  • the initial pH of the anode compartment at 50 ° C is about
  • the first and second steps were carried out at 50 ° C., and the purity of the carbon dioxide released from the anode compartment was about 100% by volume.
  • the exhaust gas is normally discharged.
  • a temperature about 50 ° C
  • no physical defects of the electrolysis device were found, and there was no difference in tendency and separation efficiency from Example 1 implemented at room temperature.
  • the present invention can be directly applied to the carbon dioxide separation system of the present invention without cooling the exhaust gas.
  • Carbon dioxide was separated from the mixed gas using an electrolysis device as shown in FIG. 10. Specifically, an aqueous solution of about 0.4 M sodium carbonate based on 15 ° C. was supplied to Crab 1 and the second compartment. A voltage of 4 V is applied to the first and second electrodes so that the first electrode becomes the anode and the second electrode becomes the cathode, and the mixed gas containing 10 vol% of carbon dioxide is added to the second compartment at 80 cc / min. Feed at rate (see 10 of FIG. 10).
  • the initial pH of the second compartment at room temperature was measured to be about 11.75. And, as the carbon dioxide continues to be collected, the pH was gradually lowered and reached about 7.9 to be maintained.
  • the concentration change of the inorganic carbon in the second compartment with time was measured and shown in FIG. 16.
  • a voltage of 3 V is applied to the first and second electrodes, it is confirmed that a larger amount of carbon dioxide is released faster than when a voltage of 2.5 V is applied. However, it is about 3 hours whether the voltage of 3 V or the voltage of 2.5 V is applied to the first and second electrodes. As time passes, it is confirmed that all carbon dioxide trapped in the second compartment is released.
  • a voltage of 2.5 V and a voltage of 3 V were applied to the first and second electrodes, carbon dioxide having a purity of about 90% by volume was emitted from the second compartment.
  • the second electrode functions as an anode and the first electrode functions as a cathode
  • hydroxide ions were generated in the first compartment. Accordingly, when a mixed gas was supplied to the first compartment, carbon dioxide was collected. Thereafter, when the pH of the first compartment decreases gradually and reaches a constant value, a voltage of 4 V is applied to the first and second electrodes so that the first electrode becomes the anode and the second electrode becomes the cathode. The carbon dioxide-based ions or salts thereof were converted into carbon dioxide while carbon dioxide was collected in the second compartment (see 10 'in FIG. 10). By repeating this process, it was confirmed that carbon dioxide can be continuously separated from the mixed gas.
  • I EM ion exchange membrane
  • CEM catorr exchange membrane
  • AEM an ion exchange membrane
  • BM bipolar membrane
  • MX salt consisting of cation (M + ) and negative 0 ⁇ )

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Abstract

La présente invention concerne un procédé et un système permettant de séparer sélectivement du dioxyde de carbone d'un gaz résiduaire industriel ou analogue sur la base d'un système électrochimique. L'utilisation du procédé et du système pour séparer le dioxyde de carbone peut efficacement séparer, avec un minimum d'énergie, du dioxyde de carbone concentré de haute pureté dans un mélange gazeux.
PCT/KR2017/005904 2016-06-07 2017-06-07 Procédé de séparation de dioxyde de carbone et système de séparation de dioxyde de carbone Ceased WO2017213413A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617192A (zh) * 2020-05-08 2021-11-09 王昱飞 一种利用pcet反应电化学循环捕集so2的方法
CN114703493A (zh) * 2022-03-30 2022-07-05 西安热工研究院有限公司 一种新能源制氢与二氧化碳捕集耦合应用的系统及方法
WO2025064523A1 (fr) * 2023-09-19 2025-03-27 Wiiliam Marsh Rice University Régénération électrochimique de co2 de haute pureté et de sorbant basique à partir de carbonates et/ou de bicarbonates pour une capture efficace de carbone

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112899708B (zh) * 2021-01-15 2022-05-20 大连理工大学 一种双膜分离与电化学氢泵加氢耦合的石化尾气高效资源化方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11169661A (ja) * 1997-12-12 1999-06-29 Ishikawajima Harima Heavy Ind Co Ltd 二酸化炭素回収装置
KR100697681B1 (ko) * 2001-02-07 2007-03-22 황성길 이산화탄소 제거용 전기투석장치 및 이를 이용한이산화탄소 제거시스템
JP2008100211A (ja) * 2006-09-21 2008-05-01 Yukio Yanagisawa 混合ガス分離方法およびシステム
KR20110038691A (ko) * 2008-07-16 2011-04-14 칼레라 코포레이션 전기화학 시스템에서 ｃｏ２를 사용하는 방법
KR20110043178A (ko) * 2009-10-21 2011-04-27 한국에너지기술연구원 이산화탄소 분리 장치 및 방법
WO2015116964A1 (fr) * 2014-01-31 2015-08-06 Fuelcell Energy, Inc. Ensemble reformeur-électrolyseur-purificateur (rep) pour production d'hydrogène, systèmes le comprenant et procédé de production d'hydrogène

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11169661A (ja) * 1997-12-12 1999-06-29 Ishikawajima Harima Heavy Ind Co Ltd 二酸化炭素回収装置
KR100697681B1 (ko) * 2001-02-07 2007-03-22 황성길 이산화탄소 제거용 전기투석장치 및 이를 이용한이산화탄소 제거시스템
JP2008100211A (ja) * 2006-09-21 2008-05-01 Yukio Yanagisawa 混合ガス分離方法およびシステム
KR20110038691A (ko) * 2008-07-16 2011-04-14 칼레라 코포레이션 전기화학 시스템에서 ｃｏ２를 사용하는 방법
KR20110043178A (ko) * 2009-10-21 2011-04-27 한국에너지기술연구원 이산화탄소 분리 장치 및 방법
WO2015116964A1 (fr) * 2014-01-31 2015-08-06 Fuelcell Energy, Inc. Ensemble reformeur-électrolyseur-purificateur (rep) pour production d'hydrogène, systèmes le comprenant et procédé de production d'hydrogène

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617192A (zh) * 2020-05-08 2021-11-09 王昱飞 一种利用pcet反应电化学循环捕集so2的方法
CN113617192B (zh) * 2020-05-08 2024-03-26 王昱飞 一种利用pcet反应电化学循环捕集so2的方法
CN114703493A (zh) * 2022-03-30 2022-07-05 西安热工研究院有限公司 一种新能源制氢与二氧化碳捕集耦合应用的系统及方法
WO2025064523A1 (fr) * 2023-09-19 2025-03-27 Wiiliam Marsh Rice University Régénération électrochimique de co2 de haute pureté et de sorbant basique à partir de carbonates et/ou de bicarbonates pour une capture efficace de carbone

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