WO2018235366A1 - Procédé de commande et procédé de conception de dispositif de désionisation électrique - Google Patents

Procédé de commande et procédé de conception de dispositif de désionisation électrique Download PDF

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Publication number
WO2018235366A1
WO2018235366A1 PCT/JP2018/011102 JP2018011102W WO2018235366A1 WO 2018235366 A1 WO2018235366 A1 WO 2018235366A1 JP 2018011102 W JP2018011102 W JP 2018011102W WO 2018235366 A1 WO2018235366 A1 WO 2018235366A1
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Prior art keywords
chamber
concentration
boron
water
deionization
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PCT/JP2018/011102
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English (en)
Japanese (ja)
Inventor
佐藤　伸
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栗田工業株式会社
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Priority to JP2019525096A priority Critical patent/JPWO2018235366A1/ja
Priority to KR1020197031638A priority patent/KR102521139B1/ko
Priority to CN201880028388.2A priority patent/CN110612154A/zh
Publication of WO2018235366A1 publication Critical patent/WO2018235366A1/fr

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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
    • 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
    • B01D61/54—Controlling or regulating
    • 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
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • 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
    • 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 a control method and a design method of an electrodeionization apparatus, and more particularly to a control method and a design method of an electrodeionization apparatus for obtaining treated water having a low concentration of weak ion components such as boron.
  • FIG. 3 is a schematic view of an electrodeionization apparatus.
  • a plurality of anion exchange membranes 13 and cation exchange membranes 14 are alternately arranged between electrodes (anode 11 and cathode 12) to alternately form a concentration chamber 15 and a deionization chamber 16;
  • An anion exchanger and a cation exchanger composed of ion exchange resin, ion exchange fiber, graft exchanger or the like are filled in the deionization chamber 16 in a mixed or multi-layered manner.
  • 17 is an anode chamber and 18 is a cathode chamber.
  • the required boron concentration in the ultrapure water of a semiconductor factory has been lowered to a level of 1 ppt or less.
  • electrodeionization devices that do not require chemical regeneration have come to be used for the production of ultrapure water.
  • the boron concentration in the treated water of the electrodeionization apparatus is affected by various factors such as current, water flow rate, water recovery rate, raw water concentration and the like.
  • the amount of water used tends to change at regular intervals, and there is also a case where part of the ultrapure water is circulated to the primary pure water tank at that time, but in such a situation It is also possible to carry out energy saving operation by lowering the current value etc. Also, generally, the higher the current value, the shorter the life of the electrodeionization device. For example, the life of 5 years is usually 3 years by doubling the current. Therefore, it is important to optimize the operating conditions to obtain the required and targeted water quality.
  • the electrodeionization apparatus comprises an anode and a cathode, and a concentration chamber and a desalting chamber formed in disposing a cation exchange membrane and an anion exchange membrane between the anode and the cathode.
  • Raw water is passed through to be taken out as produced water (treated water).
  • water may be flowed in parallel with the demineralization chamber, or water may be flowed in the opposite direction (opposite direction) to the flow in the desalting chamber.
  • a part of treated water is made to flow countercurrent to the demineralization chamber in the concentration chamber (patent document 1, 2).
  • Patent Document 3 calculates the movement rate of silica by the potential and the movement rate of silica by the concentration gradient. A method of calculating and controlling the optimum current value based on the demineralization chamber flow rate, the concentration chamber flow rate, the amount of circulating concentrated water, the raw water silica concentration, and the target silica concentration is described. However, Patent Document 3 does not describe what control is to be performed in a water flow type electrodeionization apparatus in which a part of treated water is passed through a concentration chamber and a desalting chamber in a counterflow.
  • the average particle diameter of the ion exchange resin filled in the deionization chamber of the electrodeionization apparatus is boron removed by setting the average particle diameter of about 500 to 600 ⁇ m to 100 to 300 ⁇ m. It is stated that the rate will improve.
  • the thickness of the cell in the deionization compartment of the electrodeionization apparatus is usually about 2 to 10 mm.
  • the smaller the cell thickness the easier it is for ions to be transported to the concentration chamber.
  • the cell thickness is larger (for example, in the case of passing water with the same SV), the ion exchange membrane of the electrodeionization device can be reduced, and the device cost can be reduced.
  • the movement velocity of boron by potential and the boron movement velocity by concentration gradient are calculated. It is an object of the present invention to provide a control method of an electrodeionization apparatus which calculates and controls an optimum current value based on a demineralization chamber flow rate, a concentration chamber flow rate, a raw water boron concentration, and a target boron concentration.
  • a control method of an electrodeionization device is a method of controlling an electrodeionization device for deionizing water, the electrodeionization device comprising: an anode and a cathode; Between the concentration chamber and the desalting chamber formed by disposing a cation exchange membrane and an anion exchange membrane between the raw water is supplied to the deionization chamber from the inlet on one end side, and the other end side Water is taken out as product water from the outlet of the tank, part of the product water is passed through the concentration chamber in a countercurrent flow with the deionization chamber, and a direct current is supplied from the power supply between the anode and the cathode.
  • the controller controls the boron concentration and flow rate of the raw water introduced into the deionization chamber and the boron concentration of the target product water To achieve the target boron concentration of the production water
  • the flow rate Q in the demineralization chamber and the flow rate s ⁇ Q in the concentration chamber are set respectively, these set values are input in advance to the control device, and the boron concentration of the raw water and the target product water boron concentration
  • the current value is calculated according to
  • the transfer amount of boron ions transferred from the concentration chamber to the deionization chamber in proportion to the concentration difference with the boron ion concentration in the salt chamber is set as an amount obtained by subtraction.
  • control is performed on the assumption that boron ions do not move from the desalting chamber to the concentration chamber in a predetermined range on one end side of the desalting chamber.
  • the predetermined range is set in proportion to the current efficiency of the electrodeionization device.
  • the electrodeionization apparatus can be controlled to ensure production of production water having a target boron concentration.
  • the second and third inventions show the degree of influence on the removal of boron by the thickness of the deionization chamber cell, and the degree of influence on the removal of boron by the use of small particle size resin by the ion transfer coefficient by current, etc. It is an object of the present invention to provide a method of designing an electrodeionization device which enables calculation in velocity equation.
  • a method of designing an electrodeionization device is a method of designing an electrodeionization device for deionizing water, the electrodeionization device comprising: an anode and a cathode; Between the concentration chamber and the desalting chamber formed by disposing a cation exchange membrane and an anion exchange membrane between the raw water is supplied to the deionization chamber from the inlet on one end side, and the other end side Water is taken out as product water from the outlet of the tank, part of the product water is passed through the concentration chamber in a countercurrent flow with the deionization chamber, and a direct current is supplied from the power supply between the anode and the cathode. And the amount of current is controlled by the controller.
  • the transfer coefficient of ions transferred from the deionization chamber to the concentration chamber is related to the cell thickness. Calculated by equation, inlet conductivity, inlet concentration, demineralization chamber flow rate, concentration chamber flow rate, current Seeking treated water quality by mass balance equation and mobile from each condition, is characterized in that to set the conditions so that the quality of treated water for the purpose.
  • a method of designing an electrodeionization device is a method of designing an electrodeionization device for deionizing water, the electrodeionization device comprising: an anode and a cathode; Between the concentration chamber and the desalting chamber formed by disposing a cation exchange membrane and an anion exchange membrane between the raw water is supplied to the deionization chamber from the inlet on one end side, and the other end side Water is taken out as product water from the outlet of the tank, part of the product water is passed through the concentration chamber in a countercurrent flow with the deionization chamber, and a direct current is supplied from the power supply between the anode and the cathode.
  • the current amount is controlled by a controller, and when a part of the ion exchange resin filled in the deionization chamber is changed to one having a different average particle diameter, the overall height of the ion exchange resin Measuring the filling height of ion exchange resin with different average particle size in Transfer coefficients of ions transferred from the deionization chamber to the concentration chamber from the relational equation for the mass balance equation and transfer from the conditions of the inlet conductivity, inlet concentration, flow rate of the deionization chamber, flow rate of the concentration chamber, and current value It is characterized in that the treated water quality is determined by a formula, and each condition is set so as to achieve the target treated water quality.
  • the boron concentration and flow rate of raw water introduced into the desalination chamber and the boron concentration of target production water are input to the control device to target
  • a method of designing an electrodeionization apparatus for calculating a current value necessary to achieve a boron concentration wherein the flow rate Q in the deionization chamber and the flow rate s ⁇ Q in the concentration chamber are set, respectively, and these settings are made.
  • a value is previously input to the control device, and the current value is calculated according to the boron concentration of the raw water and the target production water boron concentration.
  • the transfer amount of boron ions transferred from the concentration chamber to the deionization chamber in proportion to the concentration difference between the concentration and the boron ion concentration in the desalting chamber is set as an amount obtained by subtracting.
  • the performance of the electrodeionization apparatus when the thickness of the deionization chamber is changed, or when the height at which the layer in which the diameter of the ion exchange resin is changed is incorporated into the cell height is changed. Can be calculated.
  • FIG. 1 is a schematic model diagram of an electrodeionization apparatus to which an example of the first to third inventions is applied
  • FIG. 2 is a model diagram in the case of performing operation analysis by difference equation.
  • the deionization chamber 3 and the concentration chamber 5 are separated by an ion exchange membrane 9 (in this case, an anion exchange membrane).
  • the raw water inlet of the demineralization chamber 3 and the concentrated water outlet of the concentration chamber 5 are provided on one end side (left end side in FIG. 1) of the electrodeionization device 1.
  • the product water outlet of the demineralization chamber 3 and the inlet of the concentration chamber 5 are provided on the other end side (right end side in FIG. 1) of the electrodeionization device 1.
  • Raw water is introduced from the piping 1 into the deionization chamber 2 at a flow rate Q, and flows out from the deionization chamber 2 as production water through the piping 3.
  • a part of the production water is introduced into the concentration chamber 5 through the piping 4 branched from the piping 3 and is passed through the concentration chamber 5 in a countercurrent flow with the demineralization chamber 2.
  • the concentration chamber outflow water is discharged from the pipe 6 to the outside of the electrodeionization apparatus.
  • the flow rate of the concentration chamber is the flow rate s ⁇ Q obtained by multiplying the deionization chamber flow rate Q by the ratio s. Also, after part of the production water is branched to the pipe 4, the amount of production water taken out from the pipe 3 is (1-s) ⁇ Q.
  • the boron concentration in the raw water is c 0 ( ⁇ g / L), and the boron concentration in the product water flowing out of the demineralization chamber is c N.
  • the boron concentration in the water is c at a point at a distance x from the inlet in the deionization chamber 2.
  • the boron concentration at the outlet is c 0 ', and the boron concentration of the inflowing concentrated water is c N '.
  • the boron concentration in the water is c '.
  • the amount of boron transferred per unit time moving from the deionization chamber 2 to the concentration chamber 5 based on the potential difference between the electrodes of the electrodeionization apparatus is K ( ⁇ g / Hr), and the concentration of boron from the concentration chamber 5 to the deionization chamber 2
  • the current flowing from the anode to the cathode of the electrodeionization apparatus is i (A).
  • the length (hereinafter referred to as “minute section length”) of the minute section in the flow direction of water (the direction connecting the inlet and the outlet; in the left and right direction in FIG. 1) ) Dx.
  • the membrane area of the ion exchange membrane 8 belonging to the minute section length dx is m.
  • This membrane area m is an area obtained by multiplying dx by the width of the demineralization chamber.
  • the width of the demineralization chamber is the width in the direction perpendicular to the flow direction of water (perpendicular to the sheet of FIG. 1).
  • Equation (3) is derived from the material balance at the point of the distance x in the deionization chamber 2.
  • Q ⁇ dc / dx dK / dx-dK '/ dx (3)
  • the dc / dx on the left side is the concentration gradient in the flow direction of water at a point of distance x from the inlet, and Q ⁇ dc / dx is reduced by passing through the cross section of the desalting chamber at this point of distance x It is the amount of boron.
  • the total boron balance of this electrodeionization device that is, the amount of boron in the total amount of raw water to the electrodeionization device per unit time and carried out by produced water (flow rate Q) and discharge concentrated water (flow rate s ⁇ Q)
  • the following equation (5) is derived from the fact that the amount of boron is equal.
  • Q ⁇ c 0 (1 ⁇ s) ⁇ Q ⁇ c N + s ⁇ Q ⁇ c 0 '(5)
  • FIG. 1 is regarded as a difference type in which the concentration distribution in the demineralization chamber changes stepwise as shown in FIG. 2, and the equations (1) to (4) are treated as a difference equation to obtain difference equations (3) and (4).
  • the following equations (12) and (13) are derived by substituting the equations (1) and (2) as the difference equation into the equation).
  • c n + 1 c n + (k ⁇ c n ⁇ i n ⁇ k ′ ⁇ (c n ′ ⁇ c n ) ⁇ m n ) / Q ⁇ ⁇ x (12)
  • c n + 1 ′ c n ′ ⁇ (k ⁇ c n ⁇ i n ⁇ k ′ ⁇ (c n ′ ⁇ c n ) ⁇ m n ) / (S ⁇ Q) ⁇ ⁇ x (13)
  • the current value i may be changed variously to calculate the concentration of produced water boron, and the current value i at which the boron concentration of the produced water becomes a target concentration may be selected to energize the electrodeionization apparatus. In practice, it is preferable to conduct electricity by multiplying i by a safety factor (for example, 1.2).
  • a safety factor for example, 1.2
  • the boron concentration in the demineralization chamber is c 0 at the inlet side, and is stepped in steps of c 1 , c 2 , c 3 ..., C n , c n + 1. changes, product water boron concentration is in the c N.
  • the boron concentration changes in a stepwise manner from the outlet to the inlet as c 0 ′, c 1 ′, c 2 ′..., C n ′, c n + 1 ′... C N ′.
  • the boron concentration in the raw water is preferably measured continuously by a continuous measuring device.
  • a stabilized power supply is preferred as the power supply for the electrodeionization device.
  • the electrodeionization apparatus may be operated in a single stage, or two or more stages may be connected in series.
  • the tap water was treated with activated carbon-RO-deaerated membrane as raw water, and passed through the electrodeionization apparatus of FIG.
  • the electrodeionization apparatus has three deionization chambers, and has an effective height of 60 cm ⁇ width 22.4 cm ⁇ thickness 5.0 mm.
  • As the ion exchange resin a mixed resin of 60% of anion exchange resin and 40% of cation exchange resin was filled only in the deionization chamber. A spacer was placed in the concentration chamber.
  • the computer automatically calculated and controlled the production water boron concentration to be 1 ppt according to the above formulas (9) and (10).
  • the result of continuously monitoring the boron concentration of the treated water was 1 ppt at any time, and it was recognized that production water of low boron concentration can be produced by the automatic control operation.
  • the proportionality constant k increases in proportion to the ratio (d 1 / d 0 ) of the desalting chamber cell thickness.
  • a is a coefficient related to the device and the mobile ion, and the value experimentally obtained by the inventor was 0.813.
  • the transfer coefficient can be calculated even when the cell thickness of the deionization chamber is changed, or when a layer in which the average particle diameter of the ion exchange resin is changed is partially incorporated, using that From the mass transfer type and mass balance type, the concentration of the treated water concentration can be calculated by substituting various conditions such as inflow concentration, inflow conductivity, demineralization chamber flow rate, concentration chamber flow rate, and operating current.
  • the performance reduction due to doubling the cell thickness is filled with a small average particle diameter ion exchange resin having a half average particle diameter in a range of 13.8 cm of the ion exchange resin filling height 60 cm.
  • the performance can be made equal.
  • the position where the ion exchange resin having a small average particle diameter is inserted between the ion exchange resins having a large average particle diameter may be at the inlet side of the deionization chamber, or may be at the middle portion, or at the outlet side. It is preferable to put in the middle part.
  • the small average particle diameter ion exchange resin is filled in the middle part, there is no risk of the small average particle diameter ion exchange resin flowing out, and the ion exchange resin layer can be stabilized.
  • concentration chamber 9 ion exchange membrane 10 ion exchanger 11 anode 12 cathode 13 anion exchange membrane 14 cation exchange membrane 15 concentration chamber 16 deionization chamber 17 anode chamber 18 cathode chamber

Abstract

Dans la présente invention, la concentration en bore et l'écoulement d'eau brute, qui sont introduits dans une chambre de dessalement 2, et la concentration cible en bore de l'eau produite sont entrés dans un dispositif de commande; un débit Q à l'intérieur de la chambre de dessalement 2 et un débit s∙Q à l'intérieur d'une chambre de concentration 5 sont prédéfinis et les valeurs prédéfinies sont entrées dans le dispositif de commande; et une valeur de courant électrique est calculée en fonction de la concentration en bore de l'eau brute et de la concentration cible en bore de l'eau produite. De l'électricité est appliquée à travers une anode et une cathode avec cette valeur de courant électrique.
PCT/JP2018/011102 2017-06-23 2018-03-20 Procédé de commande et procédé de conception de dispositif de désionisation électrique WO2018235366A1 (fr)

Priority Applications (3)

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JP2019525096A JPWO2018235366A1 (ja) 2017-06-23 2018-03-20 電気脱イオン装置の制御方法及び設計方法
KR1020197031638A KR102521139B1 (ko) 2017-06-23 2018-03-20 전기 탈이온 장치의 제어 방법 및 설계 방법
CN201880028388.2A CN110612154A (zh) 2017-06-23 2018-03-20 电去离子装置的控制方法及设计方法

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JP2017-123321 2017-06-23
JP2017123321 2017-06-23
JP2018-030949 2018-02-23
JP2018030949 2018-02-23

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Cited By (3)

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WO2021131130A1 (fr) * 2019-12-25 2021-07-01 栗田工業株式会社 Procédé de commande pour un appareil de production d'eau ultrapure
CN113960116A (zh) * 2021-10-21 2022-01-21 常州博瑞电力自动化设备有限公司 换流阀冷却系统离子交换树脂动力学性能测试装置及方法
WO2022202305A1 (fr) * 2021-03-22 2022-09-29 栗田工業株式会社 Procédé de commande d'un dispositif d'électrodésionisation

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JP2016123914A (ja) * 2014-12-26 2016-07-11 栗田工業株式会社 電気脱イオン装置及び電気脱イオン処理方法

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WO2021131130A1 (fr) * 2019-12-25 2021-07-01 栗田工業株式会社 Procédé de commande pour un appareil de production d'eau ultrapure
JP2021102206A (ja) * 2019-12-25 2021-07-15 栗田工業株式会社 超純水製造装置の制御方法
WO2022202305A1 (fr) * 2021-03-22 2022-09-29 栗田工業株式会社 Procédé de commande d'un dispositif d'électrodésionisation
JP2022146818A (ja) * 2021-03-22 2022-10-05 栗田工業株式会社 電気脱イオン装置の制御方法
JP7176586B2 (ja) 2021-03-22 2022-11-22 栗田工業株式会社 電気脱イオン装置の制御方法
CN113960116A (zh) * 2021-10-21 2022-01-21 常州博瑞电力自动化设备有限公司 换流阀冷却系统离子交换树脂动力学性能测试装置及方法
CN113960116B (zh) * 2021-10-21 2023-06-20 常州博瑞电力自动化设备有限公司 换流阀冷却系统离子交换树脂动力学性能测试装置及方法

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