WO2015076438A1 - Électrode de désionisation capacitive utilisant des fibres de carbone activé hybrides perméables - Google Patents

Électrode de désionisation capacitive utilisant des fibres de carbone activé hybrides perméables Download PDF

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Publication number
WO2015076438A1
WO2015076438A1 PCT/KR2013/010684 KR2013010684W WO2015076438A1 WO 2015076438 A1 WO2015076438 A1 WO 2015076438A1 KR 2013010684 W KR2013010684 W KR 2013010684W WO 2015076438 A1 WO2015076438 A1 WO 2015076438A1
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WIPO (PCT)
Prior art keywords
electrode
carbon fiber
activated carbon
unit
hybrid
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PCT/KR2013/010684
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English (en)
Korean (ko)
Inventor
김창수
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(주)청연
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Publication of WO2015076438A1 publication Critical patent/WO2015076438A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices

Definitions

  • the present invention relates to a CDI electrode using a coated permeable hybrid activated carbon fiber according to the electrode polarity, to uniformly compress the electrode during the adsorption of water ions to narrow the distance between the electrodes to increase the capacitance of the electrode and remove Graphite with high elastic fiber woven cover that promotes deionization by widening electrode spacing and permeable pores to prevent short circuit between electrodes and reduce volume resistance of electrodes Foil, coated activated carbon fiber electrode and spacers for insulation between electrodes are stacked in parallel and adsorbed on the surface of activated carbon fiber by electrostatic force generated by supplying external DC power to this electrode, After removing the adsorption force by static electricity by short circuit, supply backwash water to discharge the high concentration of ions released to the outside It relates to electrodes for CDI using the pitcher castle-coated permeability hybrid (Hybrid) activated carbon fibers for group.
  • Hybrid permeability hybrid
  • all water including seawater, contains water-insoluble suspensions and water-soluble ions. Due to the asymmetric molecular structure of the water molecules, the material does not have free polarity in the presence of water, but in the presence of ions in the water. According to the polarity of ions, the water molecules are arranged in a radial arrangement around the ions and have a polarity, which is called a hydration ion.
  • the electrodes also have polarity, so they are surrounded by water molecules to form a polarized, hydratable interface whereby cations adsorb to the cathode of the external electrode and anions to the anode of the external electrode.
  • the water-insoluble fine suspension material also has a negative electrode and is adsorbed to the positive electrode of the external electrode.
  • the removal method is mainly used, but it is a method of filtration with fixed filter pores smaller than the size of ions. Therefore, the permeability is low and it is operated at high pressure, which consumes a large amount of power and consumes pores due to micropores under high pressure. And there is a drawback of the long life of the foreign matter (Plugging) occurs because of this.
  • CDI was developed with nanoporous (Micro-Pore) foamed carbon (Carbon Aerogel) as the electrode material, but the effective adsorption part of ions is limited to the surface area of the electrode, so the mm unit electrode The effective adsorption area is much lower than the total pore area, and the closed pores inside the electrode are very large compared to the thickness of the electrode, so that the volume resistance is increased, so that the potential supplied to the electrode is lowered, and the amount of adsorption of ions decreases accordingly. .
  • the specific surface area due to the closed pores inside the electrode is 1/3 lower than that of the activated carbon fiber, resulting in an increase in the specific surface area (BET) per electrode weight but decreasing the BET per unit volume of the electrode.
  • the opening porosity of the electrode surface is small, so that the adsorbed ions are difficult to escape from the electrode during the deionization process, and since the electrode itself is an impermeable electrode, the raw water to be treated should be diffused and flowed between the small electrode intervals.
  • the depletion layer is generated to generate a site that depends on ion diffusion, the regeneration time for adsorption and deionization is prolonged, and the overall ion removal efficiency is reduced. Therefore, CDI using the carbon aerogel as an electrode is only at the pilot plant level.
  • the present invention is applied to the laminated electrode portion of the electrode module by narrowing the interval of the electrode when adsorbed to increase the electrostatic force and relaxes during deionization (regeneration) to reduce the residual electrostatic force and high flow rate (High Flow Rate)
  • the electrode compression part, and the activated carbon fiber electrode Permeable permeable doped with SiO2 on the anode and Al2O3 on the cathode to increase Zeta-Potential of the electrode for stable adsorption of ions and to remove polyions such as calcium and magnesium.
  • activated carbon fiber yarns are concentrated on the surface of the fiber yarns, so the distribution of large meso-pore is large. Due to the extremely small distribution of closed pores in the quasi-inner, activated carbon fiber electrode having a low specific volume resistance and a low potential drop of the electrode, and a fast ion adsorption / desorption cycle, and an insulator composed of woven fibers for insulating each electrode. By alternately stacking them in parallel, the electrolysis voltage of water (power of 3.5V or less is supplied to each electrode to adsorb underwater ions due to electrostatic force generated between the electrodes, and then the power supply is cut off or short-circuited to reverse the water supply. It is to provide an electrode for CDI using a permeable hybrid activated carbon fiber to increase the total amount of water ions removed by the quick discharge / desorption cycle by discharging.
  • Electrode for CDI using the water-permeable hybrid activated carbon fiber of the present invention for achieving the above object 290 ⁇ 310 °C by phosphate impregnated Rayon-based fabric woven with insulation for insulating between the anode and cathode After carbonization at a relatively low temperature, the + 'electrode is impregnated with SiO2 solution, and the'-'electrode with Al2O 3 solution, depending on the polarity of the electrode to be used.
  • a hybrid (Hybrid) activated carbon fiber By injecting steam into the kiln at a temperature of can be produced a hybrid (Hybrid) activated carbon fiber.
  • Both sides of the hybrid activated carbon fiber are covered by two sheets of flexible graphite foil having a plurality of pores to constitute a unit electrode part, and are arranged in a lengthwise direction on one side of the insulator part, but the types of negative and positive electrodes Arranged to be inclined in the opposite direction according to the alternately stacked according to the cathode and anode.
  • Coupling of the unit electrode part and the insulating part is fixed to the insulating part by the electrode coupling pin penetrating the electrode on one side and by epoxy bonding on the other.
  • the unit electrode part of the stacked top electrode layer is exposed to the flexible graphite foil, and thus, it is covered with an insulating part and then covered with a high permeability and a highly elastic fiber fabric cover thereon to form an electrode module in which a plurality of unit electrodes are stacked. Will be constructed.
  • Electrodes of the same polarity among the stacked electrode modules are electrically connected in parallel by electrode coupling pins in a state in which they are stacked in parallel in the same direction and are connected to an external DC power source.
  • Mechanical coupling of the electrode module is coupled by the electrode module fixing portion by a fixing pin penetrating the insulation and the fiber fabric cover, the electrode is excluded.
  • the electrode module fixing part is fixed to the wall surface of the CDI body and the electrode module is in contact with one surface of the filtration unit having a plurality of bends on the surface, and pressing the electrode portion of the electrode module according to the curved surface of the filtration unit and the filtration unit;
  • the electrode compression unit may be in close contact with the electrode module while mechanically compressing the electrodes of the electrode module to reduce the distance between the electrodes.
  • the present invention improves the stable ion adsorption power of the electrode by increasing the Zeta Potential by doping the electrode, and can remove polyvalent ions such as Ca / Mg, which are difficult to remove ions, which is applicable to the removal of ions from groundwater.
  • the unit electrode part which consists of activated carbon and flexible flexible graphite foil, has a total effective surface area of the ion adsorption pores less than carbon aerogels, so the amount of ions adsorbed per unit electrode weight (u-mol / g) is 1/3 or higher. This is three times larger than this, so it cancels out based on the volume of the electrode,
  • Membrane As a precision filter for sewage wastewater treatment of 1,000ppm unit from the desalination of seawater with a high concentration of 30,000ppm or more, and it will be positioned as the best technology according to the optimal technology or future research or material development.
  • FIG. 1 is a view showing a unit electrode using a hybrid activated carbon fiber according to an embodiment of the present invention.
  • FIG. 2 is a view showing a CDI electrode using a water-permeable hybrid activated carbon fiber according to an embodiment of the present invention in the shape.
  • Figure 3 is a Zeta Potential diagram according to the Doping material of the activated carbon electrode according to the present invention.
  • Figure 4 is a functional diagram of the adsorption pores of activated carbon according to the present invention.
  • each of two sheets of porous stretchable carbon film around the hybrid activated carbon fiber electrode 2 cover the both sides of the electrode with foil (1) to form the unit electrode part, and arrange it in the longitudinal direction on one side of the insulating part 3, but arrange it so that the bias direction depends on the type of negative and positive electrode Laminate alternately.
  • Coupling of the unit electrode portion and the insulating portion is fixed to the insulating portion by the electrode coupling pins penetrating the electrode on one side and by the epoxy on the other side.
  • FIG. 2 is a view showing a CDI electrode using a water-permeable hybrid activated carbon fiber according to an embodiment of the present invention in the shape.
  • the unit electrode part of the top layer of the stacked electrode bundles is exposed to the flexible graphite foil 2 so that it is covered with the insulating part 3 again and then covered with the high permeability and high elastic fiber fabric cover 11 thereon.
  • the unit electrodes of are stacked.
  • Electrodes of the same polarity among the stacked electrode modules are electrically connected in parallel by electrode coupling pins 15 in a state in which they are stacked in parallel in the same direction and are connected to an external DC power source.
  • the mechanical coupling of the electrode module is coupled by the electrode module fixing part 13 by the fixing pin 18 penetrating through the insulation and the fiber fabric cover, the electrode is excluded. That is, the stacked electrodes are stacked in the insulator 3, the positive electrode, the insulator 3, and the negative electrode in the order of being stacked, and the unit electrodes are oriented in one of the longitudinal directions on the insulator, so that both ends of the stacked electrodes are stacked. Since the silver is biased along one side of the electrode, penetrating both ends of the electrode through the metallic electrode coupling pin 15 causes the same electrodes to be electrically coupled in parallel.
  • the electrode module fixing part 13 is fixed to the wall surface of the CDI body and the electrode module is in contact with one surface of the filtering part 16 having a plurality of bends formed on the surface thereof, and according to the curved surface of the filtering part of the electrode module. Pressing an electrode portion to be in close contact with the filtration unit 16 and the electrode module 14, and the electrode compression unit 10 that can reduce the distance of the electrode by mechanically pressing the electrodes of the electrode module.
  • Figure 3 is a diagram showing the Zeta Potential according to the Doping material of the activated carbon electrode according to an embodiment of the present invention.
  • Table 1 summarizes the functions of the pores by size based on FIG. 4, and it is advantageous that the specific surface area (BET) distribution of Meso-Pore is large for removing water ions.
  • BET specific surface area
  • Table 1 Type of pore size () function Remarks Micro-pore 2-4 Manure Provide high capacitance for ion adsorption but increase specific volume resistance 6 Start gas adsorption 10 Liquid ion adsorption 20 Charge depletion layer Overlap of electric double layer Meso-pore 20-500 Adsorption of Hydration Ions Hydration Ion 7-8 Macro-pore 500 Rise in specific volume resistance
  • FIG. 5 is a diagram illustrating a process of manufacturing a hybrid activated carbon fiber electrode, and the hybrid activated carbon fiber electrode 1 is 290-310 ° C. after impregnating a rayon-based fabric fabric with phosphate. Carbonize the hybrid activated carbon fiber electrode at a temperature of, and impregnate the carbonized fabric fabric with SiO 3 solution and '-' electrode with AlO 3 solution according to the polarity of the electrode. It is produced by active firing by injecting steam into the kiln at a temperature of 850 ⁇ 950 °C.
  • the electrode module 14 of the present invention configured as described above is fixed in plural according to the capacity to be treated on the wall of the CID main body, and the electrode module is compressed through the electrode compression unit 10 to narrow the gap between the electrodes to increase the capacitance of the electrode.
  • the ions are adsorbed by the electrostatic force on the electrode surface and the electric conductivity in the water starts to fall. If the decrease in the electrical conductivity after this time is stagnant, the power supply is cut off or the electrode is shorted and then the compression unit 10 is relaxed to reduce the residual capacity of the electrode while adsorbing backwash water through the filter unit 16. It is fed in the opposite direction of the flow so that the released ions are discharged to the outside. Once the initial conductivity of the adsorption is equal to the electrical conductivity of the raw water back to the adsorption process is repeated.
  • the present invention configured as described above allows the adsorption / desorption of ions like the non-water permeable electrode to reduce residual static electricity by widening the electrode intervals without depending on ion diffusion, while simultaneously flowing the raw water and the backwash water directly to the electrode.
  • the material can be finely filtered, and when backwashing, there is an advantage that the filtered foreign matter can be easily released without being attached to the filter cloth.
  • this permeable hybrid activated carbon electrode is used to determine the current consumption in proportion to the electrical conductivity of raw water and is supplied at a low pressure of 3.5V or less. Therefore, it is possible to precisely filter wastewater including seawater desalination with lower power consumption than Membrane. It has the advantage of wide application range, and the adsorption pores of Meso-pore with large openings are concentrated on the surface of the electrode, so the amount of ions accumulated and remaining in the pores of the electrode is very small, so the adsorption / desorption reaction is fast and due to the doped catalyst material In addition to chemical treatment, since it can easily remove multivalent Ca / Mg ions that are not easy to remove, there is an advantage that it can be applied to groundwater and mine wastewater.
  • the electrode for CDI using such a permeable hybrid activated carbon fiber is not limited to the configuration and operation of the embodiments described above.
  • the above embodiments may be configured such that various modifications may be made by selectively combining all or part of the embodiments.
  • unit electrode part Hybrid activated carbon fiber electrode + flexible graphite foil

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Metallurgy (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

La présente invention permet d'augmenter la zone d'adsorption efficace grâce à l'activation de fibres de carbone afin d'améliorer l'efficacité d'adsorption/désorption ionique. Elle se présente sous la forme d'une électrode hybride dont la surface est dopée afin d'améliorer la capacité d'adsorption et d'éliminer facilement les ions polyvalents, et elle permet d'éviter une dégradation de la capacité d'adsorption associée à une chute de tension au niveau de l'électrode grâce à une réduction de la résistivité volumique dans chaque partie de l'électrode. La présente invention concerne, donc, la fabrication d'un module électrode en fibres de carbone activé hybrides de désionisation capacitive conçu de façon à ce que l'électricité statique résiduelle soit minimisée du fait de l'augmentation de la force électrostatique de l'électrode par compression mécanique de l'espacement entre les électrodes afin de réduire la durée de la réaction d'adsorption/désorption ionique, puis par élargissement de l'espacement entre les électrodes par relâchement durant la désorption ionique, tous les composants du module électrode étant perméables si bien qu'un grand nombre des ions présents dans l'eau entrent en contact avec l'électrode en l'espace d'un bref laps de temps.
PCT/KR2013/010684 2013-11-21 2013-11-22 Électrode de désionisation capacitive utilisant des fibres de carbone activé hybrides perméables WO2015076438A1 (fr)

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KR1020130142077A KR20150059202A (ko) 2013-11-21 2013-11-21 투수성 하이브리드 활성탄소섬유를 이용한 cdi용 전극
KR10-2013-0142077 2013-11-21

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Cited By (4)

* Cited by examiner, † Cited by third party
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US11351478B2 (en) 2018-09-06 2022-06-07 Uchicago Argonne, Llc Oil skimmer with oleophilic coating
US11548798B2 (en) * 2019-04-23 2023-01-10 Uchicago Argonne, Llc Compressible foam electrode
US11590456B2 (en) 2018-05-31 2023-02-28 Uchicago Argonne, Llc Systems and methods for oleophobic composite membranes
US11896935B2 (en) 2017-08-17 2024-02-13 Uchicago Argonne, Llc Filtration membranes

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WO2017051963A1 (fr) * 2015-09-25 2017-03-30 금오공과대학교 산학협력단 Électrode en fibre de carbone utilisant une fibre de carbone et son procédé de fabrication
KR20180066665A (ko) * 2016-12-09 2018-06-19 엘지전자 주식회사 수처리 장치용 필터모듈 및 이를 포함하는 수처리 장치
KR102203637B1 (ko) * 2019-05-14 2021-01-18 세방전지(주) 저 전도성 직물시트를 이용한 전극용 활성탄 시트의 제조 방법
KR102349311B1 (ko) 2021-08-20 2022-01-10 덕산네오룩스 주식회사 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치

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Publication number Priority date Publication date Assignee Title
WO2001009907A1 (fr) * 1999-07-30 2001-02-08 Andelman Marc D Condensateur a ecoulement continu et procede
JP2004097915A (ja) * 2002-09-06 2004-04-02 Nomura Micro Sci Co Ltd 電気脱塩方法及び電気脱塩装置
KR100934161B1 (ko) * 2009-01-30 2009-12-29 (주) 시온텍 Ｃｄｉ 전극 모듈
US20100306979A1 (en) * 2007-11-30 2010-12-09 Roy Joseph Bourcier Electrode stack for capacitive device
KR101015728B1 (ko) * 2007-05-14 2011-02-22 산요덴키가부시키가이샤 수처리 장치
JP2012086189A (ja) * 2010-10-21 2012-05-10 Kitz Corp 電気二重層キャパシタとこれを用いた脱イオン装置並びにその装置の運転方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001009907A1 (fr) * 1999-07-30 2001-02-08 Andelman Marc D Condensateur a ecoulement continu et procede
JP2004097915A (ja) * 2002-09-06 2004-04-02 Nomura Micro Sci Co Ltd 電気脱塩方法及び電気脱塩装置
KR101015728B1 (ko) * 2007-05-14 2011-02-22 산요덴키가부시키가이샤 수처리 장치
US20100306979A1 (en) * 2007-11-30 2010-12-09 Roy Joseph Bourcier Electrode stack for capacitive device
KR100934161B1 (ko) * 2009-01-30 2009-12-29 (주) 시온텍 Ｃｄｉ 전극 모듈
JP2012086189A (ja) * 2010-10-21 2012-05-10 Kitz Corp 電気二重層キャパシタとこれを用いた脱イオン装置並びにその装置の運転方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11896935B2 (en) 2017-08-17 2024-02-13 Uchicago Argonne, Llc Filtration membranes
US11590456B2 (en) 2018-05-31 2023-02-28 Uchicago Argonne, Llc Systems and methods for oleophobic composite membranes
US11351478B2 (en) 2018-09-06 2022-06-07 Uchicago Argonne, Llc Oil skimmer with oleophilic coating
US11548798B2 (en) * 2019-04-23 2023-01-10 Uchicago Argonne, Llc Compressible foam electrode

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