WO2022118522A1 - 電気脱イオン装置及び脱イオン水の製造方法 - Google Patents

電気脱イオン装置及び脱イオン水の製造方法 Download PDF

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Publication number
WO2022118522A1
WO2022118522A1 PCT/JP2021/034792 JP2021034792W WO2022118522A1 WO 2022118522 A1 WO2022118522 A1 WO 2022118522A1 JP 2021034792 W JP2021034792 W JP 2021034792W WO 2022118522 A1 WO2022118522 A1 WO 2022118522A1
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WO
WIPO (PCT)
Prior art keywords
chamber
water
deionized water
concentration
desalting
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PCT/JP2021/034792
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English (en)
French (fr)
Japanese (ja)
Inventor
晃久 加藤
幸也 阿部
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栗田工業株式会社
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Publication of WO2022118522A1 publication Critical patent/WO2022118522A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
    • 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
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination

Definitions

  • the present invention relates to an electrodeionizer capable of preventing deterioration of the ion exchange resin even if it is installed after the UV oxidizer, and a method for producing deionized water using this electrodeionizer.
  • a cation exchange membrane and an anion exchange membrane are alternately arranged between a cathode and an anode to form a desalting chamber and a concentration chamber, and the desalting chamber is filled with an ion exchange resin.
  • ion exchange membranes such as cation exchange membranes and anion exchange membranes, heterogeneous membranes formed by adding a binder such as polystyrene to powdered ion exchange resins, and homogeneous membranes formed by polymerization of styrene-divinylbenzene and the like. Further, those obtained by forming a film of various anion exchange functions or monomers having a cation exchange function by graft polymerization are used.
  • the electrodeionization device when raw water is passed through the desalination chamber and concentrated water is passed through the concentration chamber and an electric current is passed between the cathode and the anode, the enrichment chamber is passed from the desalination chamber through the anion exchange membrane and the cation exchange membrane.
  • Deionized water (pure water) is obtained from the desalting chamber by the movement of ions to. Concentrated water with concentrated ions flowing through the concentration chamber is either discarded or partially recycled.
  • Such an electric deionization device is used as an ultrapure water production device used in various industries, for example, semiconductor manufacturing.
  • Patent Document 1 as a method of improving the water quality of the deionized water produced by the electrodeionization device, a part of the deionized water (outflow water from the desalting chamber) is separated and placed in a concentration chamber and a desalting chamber. The method of passing water in a countercurrent manner is described. According to this method, the concentration of concentrated water near the deionized water outlet of the desalting chamber and the vicinity of the adjacent concentrating chamber inlet is the same as that of deionized water, so that weak electrolytes such as carbon dioxide, silica, and boron are released from the concentrating chamber.
  • weak electrolytes such as carbon dioxide, silica, and boron are released from the concentrating chamber.
  • High-purity deionized water can be obtained by preventing it from diffusing (back-diffusing) into the desalting chamber due to the concentration gradient.
  • diffusing back-diffusing
  • Carbonic acid is one of the weak electrolytes that easily reverse diffuses.
  • the presence of carbonic acid in the concentrated water in the concentrating chamber causes free carbon dioxide to back-diffuse from the concentrating chamber to the desalting chamber, reducing the resistivity of the treated water. The reason is as follows.
  • Carbon dioxide exists in the form of carbonate ions and bicarbonate ions in water when the pH is high, and exists as uncharged free carbon dioxide when the pH is low.
  • the charged forms such as bicarbonate ion and carbonate ion first move from the desalination chamber to the concentration chamber by the electrodialysis action, and these in the desalination chamber. Concentration decreases.
  • the free carbon dioxide in the desalination chamber also dissociates into bicarbonate and carbonate ions, and finally moves to the concentration chamber by electrodialysis. And be removed.
  • the pH of the concentrated water in the concentrated water is a weak acid of about 5 to 7 in most cases, free carbon dioxide having a certain concentration is present in the concentrated water.
  • This free carbon dioxide is not subjected to the electrodialysis action, and a part of the free carbon dioxide passes through the ion exchange membrane and back-diffuses into the desalting chamber, resulting in deterioration of the water quality of the deionized water.
  • the resistivity of deionized water of 17 to 18 M ⁇ ⁇ cm is reduced to 15 to 16 M ⁇ ⁇ cm due to the backdiffusion of free carbon dioxide.
  • the life of the cartridge polisher which is usually installed after the electric deionized water production device, is shortened faster.
  • carbonate ions have a slow moving speed after being adsorbed on the ion exchange resin and tend to accumulate inside the ion exchange resin.
  • the energization resistance increases and the applied voltage between the anode and the cathode rises.
  • the accumulated ions leak into the treated water, and the quality of the treated water deteriorates.
  • An object of the present invention is to provide an electrodeionizer capable of suppressing the accumulation of carbon dioxide in an ion exchange resin in an electrodeionizer, and a method for producing deionized water using the electrodeionizer. And.
  • a concentration chamber and a desalting chamber are partitioned between an anode and a cathode by an ion exchange membrane, concentrated water is circulated to the concentration chamber, and raw water is used as treated water in the desalting chamber.
  • a carbonate ion purge substance is supplied to at least one of the desalting chamber and the concentrating chamber in an electrodeionizer in which the desalting chamber and the concentrating chamber are filled with an ion exchange resin. It is characterized by having a means to do so.
  • the carbonate ion purging material is at least one of NaCl, NaOH, HCl and H 2 SO 4 .
  • the carbonate ion purging substance is NaCl.
  • a part of the deionized water from the desalting chamber is distributed to the concentrating chamber in a countercurrent manner with the desalting chamber.
  • One aspect of the method for producing deionized water of the present invention is a method for producing deionized water using the electric deionizing device of the present invention, in which raw water is passed through a desalting chamber to produce deionized water. It is characterized by having a production step and a carbonate ion purging step in which water containing a carbonate ion purging substance is passed through at least one of a desalting chamber and a concentration chamber.
  • Another aspect of the method for producing deionized water of the present invention is the method for producing deionized water using the electric deionization device of the present invention, in which raw water is passed through a desalting chamber to produce deionized water.
  • the method for producing deionized water to be produced is characterized in that a carbonate ion purging substance is supplied to the raw water flowing into the desalting chamber.
  • the electrodeionization apparatus and the method for producing deionized water of the present invention by supplying the carbonate ion purging substance to at least one of the desalting chamber and the concentrating chamber, the accumulation of carbonate ions in the ion exchange resin is prevented. The quality of deionized water is improved.
  • FIG. 1 is a schematic cross-sectional view of an electrodeionizer 10 showing an embodiment of the present invention.
  • this electrodeionization device 10 a plurality of anion exchange films 13 and cation exchange films 14 are alternately arranged between the electrodes (anode 11 and cathode 12) to alternately form a concentration chamber 15 and a desalting chamber 16.
  • An anode chamber 17 and a cathode chamber 18 are formed along each electrode.
  • concentration chamber 15, the desalting chamber 16, the anode chamber 17, and the cathode chamber 18 are filled with an ion exchange resin.
  • the water to be treated (raw water) is introduced from the inlet side of the desalting chamber 16 by the pipes 20 and 21, and the deionized water (produced water) is taken out from the outlet side of the desalting chamber 16 by the pipes 30 and 31.
  • a part of this deionized water is passed through the concentration chamber 15 by pipes 40 and 41 in a direction opposite to the water flow direction of the desalination chamber 16 in a transient direction.
  • the outflow water of the concentration chamber 15 is discharged to the outside of the system by the pipes 50 and 51.
  • the concentrating chamber 15 and the desalting chamber 16 are alternately arranged side by side, and the inlet of the concentrating chamber 15 is provided on the deionized water take-out side of the desalting chamber 16 for desalting.
  • the outlet of the concentration chamber 15 is provided on the raw water inflow side of the chamber 16.
  • a part of the deionized water is supplied to the inlet side of the anode chamber 17 by the pipe 60, and the outflow water of the anode chamber 17 is supplied to the inlet side of the cathode chamber 18 by the pipe 61, and the outflow of the cathode chamber 18 is performed. Water is discharged to the outside of the system as drainage.
  • the ion exchange resin filling height of the desalting chamber 16 is preferably 400 to 800 mm, and the width is preferably 30 to 60 mm.
  • the ion exchange resin to be filled in the concentration chamber 15, the desalting chamber 16, the anode chamber 17, and the cathode chamber 18 is preferably a mixed resin of an anion exchange resin and a cation exchange resin.
  • an anion exchange resin: a cation exchange resin 40 to 70:60 to 30, preferably a mixed resin of 50 to 70:50 to 30 (dry weight ratio) is preferable.
  • the particle size of the ion exchange resin is preferably in the range of 0.1 to 0.7 mm.
  • the average diameter (average particle size) and the resin ratio of the ion exchange resin are the values in the wet state of the regenerated type (OH type, H type), and the average diameter is the weight average.
  • the small particle size ion exchange resin has the effect of lowering the operating voltage as well as the purpose of improving the ion removal performance of difficult-to-remove carbonic acid, boron, silica, etc. If an ion exchange resin having a small average particle size is used, the surface area of the ions becomes large, so that the electric resistance becomes small, the upper limit of the voltage that determines the operation life is given a margin, and the operation with a longer life becomes possible. ..
  • the thickness of the desalting chamber 16 may be increased to 2.5 to 20 mm for the purpose of cost reduction.
  • the number of desalting chambers is preferably 1 to 300, particularly 40 to 200.
  • the water to be treated is passed through the desalination chamber of the electrodeionizer, and a part of the deionized water (outflow water of the desalination chamber), for example, about 3 to 10% is put into the concentration chamber and the desalination chamber. It is preferable to pass water in the direction opposite to the water flow direction in order to obtain excellent treated water quality.
  • the water flow rate at that time is preferably about 60 to 100 m / h for the water flow LV of the desalination chamber and about 5 to 20 m / h for the water flow LV of the concentration chamber.
  • the current density is preferably about 50 to 150 A / m 2 , especially about 60 to 120 A / m 2 .
  • NaCl is supplied to the concentration chamber 15 as a carbonate ion purging substance in the form of an aqueous solution.
  • the means 70 is provided.
  • the supply means 70 has a tank 71 for an aqueous NaCl solution, a water supply pump 72, and a pipe 73, and the pipe 73 is connected to the pipe 40.
  • a valve 74 is provided in the pipe 73.
  • the pipe 40 is provided with a valve 40V on the upstream side of the connection point of the pipe 73. During normal operation, the valve 40V is open and the valve 74 is closed.
  • the electrodeionization device 10 When the resistivity of deionized water drops below a predetermined value due to the accumulation of carbonate ions, the electrodeionization device 10 is stopped (energization is stopped and water supply to be treated is stopped), and then a carbonate ion purge operation is performed. That is, the valve 40V is closed, the valve 74 is opened, the pump 72 is operated, and the NaCl aqueous solution in the tank 71 is passed from the pipe 73 to each concentration chamber 15 via the pipes 40 and 41.
  • the carbonate ions accumulated in the ion exchange resin in the concentration chamber 15 are replaced with sodium ions, and the carbonate ions are discharged through the pipes 50 and 51 together with the outflow water from the concentration chamber 15.
  • the pump 72 is stopped, the valve 74 is closed, the valve 40V is opened, and normal operation is resumed.
  • the NaCl concentration (wt%) in the NaCl-added water flowing from the pipe 41 into the concentration chamber 15 during the purge operation is preferably about 3 to 10%, particularly about 5%.
  • the amount of water to which NaCl is added to the concentration chamber 15 is preferably about 4 to 10 times (4 to 10 BV), particularly 6 times (6 BV) with respect to the amount of resin, and the water flow LV is 1.2 to 3.6 m / h. In particular, about 2.4 to 3.6 m / h is preferable.
  • water may be passed through the desalting chamber 16 or both.
  • FIG. 2 shows an electrodeionizer 10A according to another embodiment.
  • the electric deionization device 10A is configured to add NaCl to the water to be treated (raw water) flowing into the desalting chamber 16 by the NaCl supply means 70.
  • the NaCl supply means 70 has a tank 71 for an aqueous NaCl solution, a water supply pump 72, and a pipe 73, and the pipe 73 is connected to the water supply pipe 20 to be treated.
  • the valve 40V is not installed.
  • Other configurations are the same as those in FIG. 1, and the same reference numerals indicate the same parts.
  • the pump 72 is constantly operated, the valve 74 is constantly opened, and the NaCl aqueous solution is constantly added to the water supply to the desalting chamber 16. This prevents the accumulation of carbonate ions in the ion exchange resin in the desalting chamber 16. Further, the action of sodium ions that have passed through the ion exchange membrane and moved from the desalting chamber 16 to the concentration chamber 15 prevents the accumulation of carbonate ions in the ion exchange resin in the concentration chamber 15.
  • the amount of NaCl added to the water to be treated is preferably about 0.1 to 1.0 mg / L, particularly about 0.5 mg / L, and in particular, the conductivity of the water to be treated flowing into the desalting chamber 16 is 0.1.
  • NaCl is used as the carbonate ion purging substance, but NaOH, HCl, H 2 SO 4 and the like may be used.
  • the desalting chamber 16, the concentration chamber 15, the anode chamber 17, and the cathode chamber 18 were filled with a mixed resin of an anion exchange resin and a cation exchange resin (anion exchange resin: cation exchange resin ratio 50:50).
  • MONOSPHERE 550A (average particle size 600 ⁇ m) manufactured by DuPont was used
  • MONOSPHERE 650C (average particle size 650 ⁇ m) manufactured by DuPont was used.
  • the ion exchange resin to be filled in the concentration chamber and the desalting chamber is a water flow rate of 5% sodium hydrogen carbonate (NaHCO 3 ) aqueous solution 4 times (4 BV) with respect to the resin amount and a water flow rate of 2.4 m / h. It was replaced with a carbonic acid type by passing the liquid through.
  • a current is passed through the electrodeionizer 10 at a current density of 10 A / m 2 , and the reverse osmosis membrane device treated water (conductivity 0.1 mS / m, CO 2 concentration 500 ⁇ g / L) of industrial water is used as raw water in the desalting chamber.
  • Figure 3 shows the change over time in the specific resistance value of the obtained deionized water.
  • Example 2 In Comparative Example 1, as shown in FIG. 2, raw water having a conductivity of 0.5 mS / m was supplied to the desalting chamber by adding an aqueous NaCl solution (NaCl concentration 0.3 mg / L) to the raw water. Other conditions were the same as in Comparative Example 1. The change with time of the specific resistance value of this deionized water is shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Urology & Nephrology (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
PCT/JP2021/034792 2020-12-04 2021-09-22 電気脱イオン装置及び脱イオン水の製造方法 WO2022118522A1 (ja)

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JP2020202034A JP2022089558A (ja) 2020-12-04 2020-12-04 電気脱イオン装置及び脱イオン水の製造方法
JP2020-202034 2020-12-04

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113281A (ja) * 1999-08-11 2001-04-24 Kurita Water Ind Ltd 電気脱イオン装置及び純水製造装置
JP2002205069A (ja) * 2001-01-05 2002-07-23 Kurita Water Ind Ltd 電気脱イオン装置及びその運転方法
JP2003170169A (ja) * 2001-12-07 2003-06-17 Japan Organo Co Ltd 電気式脱イオン水製造装置及び製造方法
JP2004267907A (ja) * 2003-03-07 2004-09-30 Kurita Water Ind Ltd 電気脱イオン装置及びその運転方法
JP2006051423A (ja) * 2004-08-10 2006-02-23 Kurita Water Ind Ltd 電気脱イオンシステム、電気脱イオン方法及び純水製造装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113281A (ja) * 1999-08-11 2001-04-24 Kurita Water Ind Ltd 電気脱イオン装置及び純水製造装置
JP2002205069A (ja) * 2001-01-05 2002-07-23 Kurita Water Ind Ltd 電気脱イオン装置及びその運転方法
JP2003170169A (ja) * 2001-12-07 2003-06-17 Japan Organo Co Ltd 電気式脱イオン水製造装置及び製造方法
JP2004267907A (ja) * 2003-03-07 2004-09-30 Kurita Water Ind Ltd 電気脱イオン装置及びその運転方法
JP2006051423A (ja) * 2004-08-10 2006-02-23 Kurita Water Ind Ltd 電気脱イオンシステム、電気脱イオン方法及び純水製造装置

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