WO2020195894A1 - 水処理装置及び水処理方法 - Google Patents
水処理装置及び水処理方法 Download PDFInfo
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- WO2020195894A1 WO2020195894A1 PCT/JP2020/010815 JP2020010815W WO2020195894A1 WO 2020195894 A1 WO2020195894 A1 WO 2020195894A1 JP 2020010815 W JP2020010815 W JP 2020010815W WO 2020195894 A1 WO2020195894 A1 WO 2020195894A1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
- B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
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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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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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
- B01D61/58—Multistep processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
Definitions
- the present invention relates to a water treatment apparatus and a water treatment method.
- the present application claims priority based on Japanese Patent Application No. 2019-626620 filed in Japan on March 28, 2019, the contents of which are incorporated herein by reference.
- these wastewaters are collected in one place and purified by a water treatment device.
- the purified purified water is supplied to the pure water production apparatus, supplied to the scrubber as water for the scrubber, or discharged to the outside.
- the purified water supplied to the pure water production equipment and scrubber becomes pure water or water for scrubber and is reused in the semiconductor factory.
- Fluorine, ammonia, etc. are contained in the wastewater discharged from the semiconductor manufacturing process. Further, in the scrubber, a part of the scrubber water evaporates, so that the impurity component in the scrubber water is concentrated. Examples of such impurity components include calcium. Therefore, the water treatment equipment of the semiconductor manufacturing factory is required to have the ability to remove these substances.
- Patent Document 1 contains fluoride as a method for treating fluorine-containing wastewater, which is adjusted to pH 8 or higher by adding an alkali metal hydroxide when the wastewater is separated into permeated water and concentrated water by a reverse osmosis membrane. A treatment method for separating a reverse osmosis membrane by passing wastewater through a reverse osmosis membrane is described. Further, Patent Document 1 describes that a denitrification step of removing ammoniacal nitrogen remaining in the permeated water is performed after the reverse osmosis membrane is separated.
- the method for treating fluorine-containing wastewater described in Patent Document 1 does not assume the treatment of wastewater from equipment in which the water used is concentrated by evaporation.
- the wastewater from the scrubber Ca is concentrated by evaporating a part of the water used, but in the wastewater containing Ca and fluorine, CaF 2 is precipitated, and this CaF 2 clogs the reverse osmosis membrane. It may end up.
- the pH of the wastewater is adjusted to 8 or more at the time of reverse osmosis membrane separation, but at this time, ammonia in the wastewater is gasified and released. May be done.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water treatment apparatus and a water treatment method for obtaining treated water that can be used as raw water for pure water production, water for equipment, and the like. ..
- a first pretreatment means for adjusting the pH in the range of 9 to 11 and adding a scale dispersant
- a first reverse osmosis membrane which is installed after the first pretreatment means and separates the wastewater into primary permeated water and primary concentrated water.
- a second pretreatment means for adjusting the pH of the primary permeated water that has permeated the first reverse osmosis membrane in the range of 5 to 9 and adding a slime inhibitor, and
- a water treatment apparatus provided after the second pretreatment means and provided with a second reverse osmosis membrane that separates the primary permeated water into secondary permeated water and secondary concentrated water.
- the water treatment apparatus further comprising a fluorine removing means for removing fluorine in the primary concentrated water.
- a first pretreatment step of adjusting the pH to the range of 9 to 11 and adding a scale dispersant by the first pretreatment means
- a first reverse osmosis membrane separation step of separating the wastewater after the first pretreatment step into primary permeated water and primary concentrated water by a first reverse osmosis membrane.
- a second pretreatment step of adjusting the pH to the range of 5 to 9 and adding a slime inhibitor to the primary permeated water after the first reverse osmosis separation step by a second pretreatment means.
- a second reverse osmosis membrane separation step of separating the primary permeated water after the second pretreatment step into secondary permeated water and secondary concentrated water by a second reverse osmosis membrane is provided.
- a water treatment method characterized by sequentially performing the first pretreatment step, the first reverse osmosis membrane separation step, the second pretreatment step, and the second reverse osmosis membrane separation step. .. [5] The water treatment method according to [4], wherein the fluorine removing step of removing fluorine in the primary concentrated water is further performed by a fluorine removing means.
- the water treatment apparatus of the present invention it is not necessary to install a large-scale water softener because it is not necessary to add Ca when removing fluorine from wastewater. Further, in the water treatment apparatus of the present invention, since ammonium is removed by the second reverse osmosis membrane after adjusting the pH, ammonium can be removed without vaporizing ammonium into ammonia. Further, according to the water treatment apparatus of the present invention, even wastewater containing organic substances can be treated without performing biological treatment such as the activated sludge method.
- the fluorine removing means may remove fluorine in the primary concentrated water having a smaller amount of water than wastewater.
- the treatment capacity required for the fluorine removing means is relatively small, and the water treatment device can be made smaller.
- the water treatment apparatus of the present invention provides a control unit that supplies Ca-free water produced by the calcium removing means to the secondary permeated water tank when the amount of secondary permeated water is less than the demand for use points.
- Ca-free water can be replenished in the water treatment apparatus when the secondary permeated water is insufficient for the demand amount.
- the reverse osmosis membrane is clogged by flowing the wastewater to which the pH adjustment and the scale dispersant have been added to the first reverse osmosis membrane by the first pretreatment means. Fluorine can be removed without producing it. In addition, ammonium can be removed by flowing the primary permeated water to which the pH adjustment and the slime inhibitor have been added by the second pretreatment means through the second reverse osmosis membrane. As a result, it is possible to obtain secondary permeated water that can be used as raw water for pure water production equipment and water for equipment.
- water treatment method of the present invention it is not necessary to install a large-scale water softener because it is not necessary to add Ca when removing fluorine from wastewater. Further, in the water treatment method of the present invention, since ammonium is removed by a second reverse osmosis membrane after adjusting the pH, ammonium can be removed without vaporizing ammonium into ammonia. Further, according to the water treatment method of the present invention, even wastewater containing organic substances can be treated without performing biological treatment such as the activated sludge method.
- the fluorine removing step of removing fluorine in the primary concentrated water when the fluorine removing step of removing fluorine in the primary concentrated water is further performed, the fluorine removing step may remove fluorine in the primary concentrated water having a smaller amount of water than wastewater.
- the processing capacity required for fluorine removal is relatively small, and the energy required for water treatment can be reduced.
- the water treatment method of the present invention when the amount of secondary permeated water is less than the demand amount of the use point, Ca-free water produced by the calcium removing means is supplied to the use point. Ca-free water can be replenished when the next permeated water is insufficient for the demand. As a result, the Ca concentration of the water circulating in the water circulation system composed of the water treatment device and the point of use is suppressed to a low level, and the generation of scale is prevented. Then, it is possible to prevent clogging of the reverse osmosis membrane of the water treatment apparatus and scale generation at the point of use.
- the Ca concentration of the water flowing in the water circulation system composed of the water treatment device and the use point is low. It is suppressed and scale generation is prevented. Then, it is possible to prevent clogging of the reverse osmosis membrane of the water treatment apparatus and scale generation at the point of use.
- the wastewater w1 to be treated by the water treatment apparatus and the water treatment method of the present embodiment is wastewater containing fluorine and ammonium.
- the waste water w1 contains, for example, pure water used for processing such as etching and film formation in the semiconductor manufacturing process. Further, the wastewater w1 also includes wastewater discharged from an exhaust gas cleaning facility such as a scrubber, and may include wastewater from the use point 31 to which the secondary permeated water w21 is supplied, as will be described later in this embodiment.
- the wastewater w1 may contain phosphate, hydrogen peroxide, calcium, organic substances and the like.
- the wastewater w1 contains, for example, fluorine is about 1 ppm to 100 ppm, ammonium is about 10 ppm to 500 ppm, hydrogen peroxide is about 0 ppm to 300 ppm, calcium is about 1 ppm, and organic matter is about 1 ppm to 100 ppm as the total organic carbon content.
- ammonium in the present specification means ammonium ion. However, if present in the wastewater in the form of ammonia, ammonia is also contained in ammonium.
- the water treatment apparatus 1 of the present embodiment includes a first pretreatment means 2, a first reverse osmosis membrane 3, a second pretreatment means 4, and a second reverse osmosis membrane. 5 and. Further, the water treatment device 1 of the present embodiment includes the fluorine removing means 11. Further, the water treatment device 1 of the present embodiment supplies raw water w3 to the first water tank 6 and the second water tank 7 (water tank) for storing the secondary permeated water, the calcium removing means 21, and the calcium removing means 21. A unit 20 and a control unit 22 are provided. The first water tank 6 is connected to another use point 32, and the second water tank 7 is connected to the use point 31. Further, the water treatment device 1 of the present embodiment includes a neutralization treatment means 41.
- the water treatment device 1 of the present embodiment includes hydrogen peroxide removing means 51 for removing hydrogen peroxide in the waste water w1.
- hydrogen peroxide removing means 51 may be omitted.
- the water treatment device 1 of the present embodiment includes a water channel for flowing water between the devices. That is, as shown in FIG. 1, the hydrogen peroxide removing means 51 and the first reverse osmosis membrane 3 are connected by the water channel L1. Further, the first reverse osmosis membrane 3 and the second reverse osmosis membrane 5 are connected by the water channel L2. Further, the second reverse osmosis membrane 5 and the first water tank 6 are connected by the water channel L3.
- first reverse osmosis membrane 3 and the fluorine removing means 11 are connected by the water channel L4. Further, the fluorine removing means 11 and the neutralizing treatment means 41 are connected by the water channel L5. Further, the second reverse osmosis membrane 5 and the neutralization treatment means 41 are connected by the water channel L6.
- first water tank 6 and the second water tank 7 are connected by the water channel L7. Further, the raw water supply unit 20 and the calcium removing means 21 are connected by the water channel L8. Further, the calcium removing means 21 and the second water tank 7 are connected by the water channel L9. Further, the second water tank 7 and the use point 31 are connected by the water channel L10. Further, the first water tank 6 and another use point 32 are connected by the water channel L11.
- the hydrogen peroxide removing means 51 is used when treating the waste water w1 containing hydrogen peroxide.
- Hydrogen peroxide is bactericidal and itself is a COD source, so it cannot be discharged directly into public water bodies. Therefore, a decomposition treatment of hydrogen peroxide is required.
- Examples of the hydrogen peroxide removing means 51 include means for adding a reducing agent such as sodium bisulfite and an activated carbon tower capable of continuous water flow. When the waste water w1 contains hydrogen peroxide, it is preferable to first remove the hydrogen peroxide by the hydrogen peroxide removing means 51.
- the first pretreatment means 2 adjusts the pH of the wastewater w1 flowing through the water channel L1 to the range of 9 to 11, and adds the scale dispersant Sc.
- the first pretreatment means 2 for example, one provided with a primary pH adjusting unit 2a and a primary drug injection unit 2b can be exemplified.
- the primary pH adjusting unit 2a adjusts the pH of the waste water w1 to the range of 9 to 11 with potassium hydroxide or the like.
- the primary agent injection unit 2b adds the scale dispersant Sc to the wastewater w1 after adjusting the pH.
- the first reverse osmosis membrane 3 separates the wastewater w1 to which the pH adjustment and the scale dispersant Sc has been added into the primary permeated water w11 and the primary concentrated water w12. Fluorine is removed from the wastewater w1 by passing water through the first reverse osmosis membrane 3, and phosphate, calcium and organic substances are also removed to obtain primary permeated water w11. The removed fluorine and the like are contained in the primary concentrated water w12.
- the first reverse osmosis membrane 3 may be operated, for example, in a state where the recovery rate is adjusted so that the total amount of organic carbon in the primary concentrated water w12 is less than 100 mg / L.
- the first reverse osmosis membrane 3 is not particularly limited, but for example, a spiral type module in which osmosis membranes (membranes) are stacked in multiple layers and wrapped in a seaweed roll can be preferably used. Further, the first reverse osmosis membrane 3 is connected to a water channel L2 that sends the primary permeated water w11 to the second reverse osmosis film and a water channel L4 that sends the primary concentrated water w12 to the fluorine removing means 11.
- the fluorine in the wastewater w1 is concentrated in the primary concentrated water w12 by the first reverse osmosis membrane 3, the volume of the target water to be treated by the fluorine removing means 11 is reduced. As a result, the scale of the fluorine removing means 11 can be reduced, and the processing capacity required for the fluorine removing means 11 is reduced.
- the second pretreatment means 4 adjusts the pH of the primary permeated water w11 flowing through the water channel L2 to the range of 5 to 9, and adds a slime inhibitor Slm.
- Examples of the second pretreatment means 4 include those provided with a secondary pH adjusting unit 4a and a secondary drug injection unit 4b.
- the secondary pH adjusting unit 4a adjusts the pH of the primary permeated water w11 in the range of 5 to 9 with sulfuric acid or the like. Further, the secondary agent injection unit 4b adds the slime inhibitor Slm to the primary permeated water w11 after adjusting the pH.
- the second reverse osmosis membrane 5 separates the primary permeated water w11 to which the pH adjustment and slime inhibitor Slm is added into the secondary permeated water w21 and the secondary concentrated water w22.
- Ammonium is mainly removed from the primary permeated water w11 by passing through the second reverse osmosis membrane 5, to obtain the secondary permeated water w21.
- the removed ammonium and the like are contained in the secondary concentrated water w22.
- the second reverse osmosis membrane 5 may be operated, for example, in a state where the recovery rate is adjusted so that the total amount of nitrogen in the secondary concentrated water w22 is equal to or less than the emission standard.
- the second reverse osmosis membrane 5 is not particularly limited, but for example, a spiral type module in which osmosis membranes (membranes) are stacked in multiple layers and wrapped in a seaweed roll can be preferably used. Further, the second reverse osmosis membrane 5 is connected to a water channel L3 that sends the secondary permeated water w21 to the first water tank 6 and a water channel L6 that sends the secondary concentrated water w22 to the neutralization treatment means 41.
- the amount of Ca in the secondary permeated water w21 is preferably less than 1 mg / L.
- the first water tank 6 stores the secondary permeated water w21 sent from the second reverse osmosis membrane 5 via the water channel L3.
- a water channel L7 for supplying the secondary permeated water w21 to the second water tank 7 is connected to the first water tank 6.
- a water channel L11 for supplying the secondary permeated water w21 to another use point 32 is connected.
- the second water tank 7 stores the secondary permeated water w21 sent from the first water tank 6 via the water channel L7. Further, the second water tank 7 is connected to the water channel L9, and Ca-free water w4 sent from the calcium removing means 21 via the water channel L9 can also be stored. Further, a water channel L10 for supplying the secondary permeated water w21 and Ca-free water w4 to the use point 31 is connected to the second water tank 7.
- the fluorine removing means 11 is for removing fluorine contained in the primary concentrated water w12.
- the fluorine removing means 11 for example, an equipment in which the pH of the primary concentrated water w12 is adjusted to 8 or more and calcium is added to convert fluorine into CaF 2 and the CaF 2 is coagulated and separated can be exemplified.
- the fluorine removing means 11 is connected to a water channel L5 that sends the treated water w40 treated by the fluorine removing means 11 to the neutralizing treatment means 41.
- the raw water supply unit 20 is a source of raw water w3 composed of clean water or industrial water.
- the raw water supply unit 20 supplies the raw water w3 to the calcium removing means 21 via the water channel L8.
- the calcium removing means 21 removes calcium contained in the raw water w3 to obtain Ca-free water w4.
- a reverse osmosis membrane or a deionizing device can be used as the calcium removing means 21.
- the calcium removing means 21 is connected to a water channel L9 for sending the Ca-free water w4 to the second water tank 7.
- the calcium removing means 21 is a reverse osmosis membrane
- the permeated water is sent to the second water tank 7 as Ca-free water w4
- the concentrated water w5 is sent to the neutralization treatment means 41 via the water channel L12.
- the calcium removing means 21 is a deionizing device, the water channel L12 becomes unnecessary, and the Ca-free water w4 after the deionizing treatment is sent to the second water tank 7.
- the calcium removing means 21 is preferably one that can reduce the amount of Ca in Ca-free water w4 to less than 1 mg / L. That is, Ca-free water w4 refers to water in which the amount of Ca is reduced to less than 1 mg / L.
- the control unit 22 supplies the Ca-free water w4 generated by the calcium removing means 21 to the second water tank 7.
- the control unit 22 monitors the amount of water stored in the second water tank 7 and the amount of water used in the use point 31. Then, based on these monitoring results, a command is issued to the calcium removing means 21 and the raw water supply unit 20 to generate Ca-free water w4, which is supplied to the second water tank 7. Further, the control unit 22 controls the supply amounts of the Ca-free water w4 and the secondary permeated water w21 supplied from the second water tank 7 to the use point 31.
- control unit 22 for example, a data input unit that receives the amount of water stored in the second water tank 7 and the amount of water used in the use point 31, a central processing unit, a memory device, and a monitoring result of the raw water supply unit 20 and A computer provided with a data output unit for outputting to the calcium removing means 21 and a display unit can be used.
- the memory device holds a computer program for operating the control unit 22. This computer program may be executed by a central processing unit.
- the second water tank 7, the use point 31, and the control unit 22 may be connected by a wired line or may be connected by a wireless line.
- the raw water supply unit 20, the calcium removing means 21, and the control unit 22 may be connected by a wired line or a wireless line.
- the neutralization treatment means 41 stores the treated water w40 treated by the fluorine removing means 11, the secondary concentrated water w22 sent from the second reverse osmosis membrane 5, and the like, and adjusts the pH of the stored water to 6 to 8. It is a facility that adjusts to neutrality.
- the treated water w41 neutralized by the neutralizing means 41 can be discharged into a sewer or a public water area.
- the use point 31 is a facility or facility in which the secondary permeated water w21 or Ca-free water w4 can be used as facility water.
- an exhaust gas cleaning equipment from a semiconductor manufacturing process hereinafter, simply referred to as “exhaust gas cleaning equipment”
- exhaust gas cleaning equipment a cooling tower, or the like
- the secondary permeated water w21 used at the use point 31 is treated again by the water treatment device 1 as a part of the wastewater w1. Therefore, a water channel for sending the wastewater from the use point 31 may be provided in front of the hydrogen peroxide removing means 51 or before the first pretreatment means 2 from the use point 31.
- Another use point 32 is a facility or facility that uses the secondary permeated water w21.
- a pure water production apparatus in which the secondary permeated water w21 can be used as raw water for pure water production can be exemplified.
- the water treatment device 1 of the present embodiment mainly supplies the secondary permeated water w21 to the use point 31. If there is a surplus in the secondary permeated water w21, the secondary permeated water w21 may be supplied to another use point 32. Therefore, the water treatment device 1 may be provided with a supply control unit that adjusts the supply destination of the secondary permeated water w21 or the Ca-free water w4. For example, the supply control unit monitors the amount of water stored in the first water tank 6 and the second water tank 7, and also monitors the amount of water used in the use points 31 and 32, and based on these monitoring results, the water channel L10 and Those that control the amount of water flowing through the water channel L11 are preferable.
- the control unit 22 may have the function of the supply control unit.
- the water treatment method of the present embodiment includes a first pretreatment step, a first reverse osmosis membrane separation step, a second pretreatment step, and a second reverse osmosis membrane separation step.
- a first pretreatment step is performed on the wastewater w1
- a second pretreatment step on the primary permeated water w11
- a fluorine removing step may be performed on the primary concentrated water w12.
- the water treatment method of the present embodiment includes a step of supplying Ca-free water w4 to the use point 31 when the amount of the secondary permeated water w21 is less than the demand amount at the use point 31 of the secondary permeated water w21. You may go. Hereinafter, each step will be described.
- the hydrogen peroxide removing means 51 removes the hydrogen peroxide from the waste water w1.
- the treatment in the hydrogen peroxide removing means 51 may be omitted.
- the pH of the wastewater w1 flowing through the water channel L1 is adjusted to the range of 9 to 11 by the primary pH adjusting unit 2a, and the pH-adjusted wastewater w1 is adjusted by the primary agent injection unit 2b.
- the scale dispersant Sc is added to the water.
- the pH of the wastewater w1 is raised to promote the growth of microorganisms. Suppress. If the pH of the wastewater w1 is low, it becomes difficult to suppress the growth of microorganisms. Further, if the pH of the wastewater w1 is too high, metal hydroxides or metal oxides may precipitate in the wastewater w1 and block the first reverse osmosis film 3, so that the wastewater is discharged in the first pretreatment step. Adjust the pH of w1 to the range of 9-11.
- the scale dispersant Sc is added to the wastewater w1 after pH adjustment.
- a chelating agent such as ethylenediaminetetraacetic acid salt, a polymer dispersant such as polymaleic acid, or a mixture thereof can be preferably used.
- the wastewater w1 is separated into the primary permeated water w11 and the primary concentrated water w12 by the first reverse osmosis membrane 3.
- Fluorine is removed from the wastewater w1 by the first reverse osmosis membrane 3, and phosphate, calcium and organic substances are also removed to obtain primary permeated water w11.
- the removed fluorine and the like are contained in the primary concentrated water w12.
- the primary permeated water w11 is sent to the second reverse osmosis membrane 5 via the water channel L2.
- the primary concentration w12 is sent to the fluorine removing means 11 via the water channel L4.
- the fluorine in the wastewater w1 is concentrated in the primary concentrated water w12, and the volume of the target water to be treated in the fluorine removal step is reduced. This makes it possible to suppress the energy to be input when performing the fluorine removing step.
- the pH of the primary permeated water w11 flowing through the water channel L2 is adjusted to the range of 5 to 9 by the secondary pH adjusting unit 4a, and after the pH is adjusted by the secondary drug injection unit 4b.
- the slime inhibitor Slm is added to the primary permeated water w11.
- the pH of the wastewater w1 since the pH of the wastewater w1 was raised in the first pretreatment step, ammonium in the wastewater w1 may change to ammonia and scatter as ammonia gas, so that the primary permeation after the first reverse osmosis membrane separation step Ammonia is changed to ammonium by lowering the pH of water w11. If the pH of the primary permeated water w11 is low, slime may be generated and block the second reverse osmosis membrane 5. Further, if the pH of the primary permeated water w11 is too high, ammonia may remain. Therefore, in the second pretreatment step, the pH of the primary permeated water w11 is adjusted to the range of 5 to 9.
- the slime inhibitor Slm is added to the pH-adjusted primary permeated water w11.
- the slime inhibitor Slm include stabilized halogens such as chlorosulfamate and other halogens such as chlorine and bromine, 5-chloro-2-methyl-4-isothiazolin-3-one, and 2-methyl-.
- Isothiazolone compounds such as 4-isothiazolin-3-one and halocyanoacetamide compounds such as 2,2-dibromo-3-nitrilopropionamide can be preferably used.
- the primary permeated water w11 is separated into the secondary permeated water w21 and the secondary concentrated water w22 by the second reverse osmosis membrane 5.
- Ammonium is removed from the primary permeated water w11 by the second reverse osmosis membrane 5, and phosphate, calcium and organic substances are also removed to obtain the secondary permeated water w21.
- the removed ammonium and the like are contained in the secondary concentrated water w22.
- the secondary permeated water w21 is sent to the first water tank 6 by the water channel L3, and the secondary concentrated water w22 is sent to the neutralization treatment means 41 by the water channel L6.
- the amount of Ca in the secondary permeated water w21 is preferably less than 1 mg / L.
- the secondary permeated water w21 sent to the first water tank 6 is stored in the first water tank 6 and then sent to the second water tank 7. Then, it is sent from the second water tank 7 to the use point 31 and used as equipment water.
- the use point 31 is an exhaust gas cleaning facility
- the secondary permeated water w21 is discharged as drainage after being used as scrubber water in the exhaust gas cleaning facility.
- the wastewater discharged from the exhaust gas cleaning facility is sent to the water treatment device 1 together with other wastewater discharged from the semiconductor manufacturing process, and is again used in the water treatment method of the present embodiment.
- the amount of secondary permeated water w21 produced exceeds the amount of water demand at use point 31, the amount of secondary permeated water w21 becomes surplus.
- the surplus secondary permeated water w21 may be supplied from the first water tank 6 to another use point 32. This control may be controlled by the supply control unit described above.
- the use point 31 is a pure water production apparatus
- the secondary permeated water w21 is made pure water by the pure water production apparatus. Pure water is discharged as wastewater after being used in, for example, a semiconductor manufacturing process. The wastewater discharged from the semiconductor manufacturing process is sent to the water treatment apparatus 1 and again used for the water treatment method of the present embodiment.
- the primary concentrated water w12 produced in the first reverse osmosis membrane separation step is sent to the fluorine removing means 11 via the water channel L4 and is used in the fluorine removing step.
- fluorine is removed from the primary concentrated water w12.
- a step of adjusting the pH of the primary concentrated water w12 to 8 or more and then adding calcium to convert fluorine into CaF 2 and coagulating and separating the CaF 2 can be exemplified.
- the treated water w40 after the fluorine removing step is sent to the neutralization treatment means 41 by the water channel L5, and the neutralization step is performed.
- the treated water w40, the secondary concentrated water w22 sent from the second reverse osmosis membrane 5, and the like are collected, the pH is adjusted to 6 to 8 neutral, and then the water is treated outside the water treatment device 1. Release. It may be discharged into sewers or public water bodies.
- the raw water supply unit 20 supplies the raw water w3 composed of clean water or industrial water to the calcium removing means 21.
- the calcium removing means 21 removes calcium contained in the raw water w3 to obtain Ca-free water w4, and then supplies the calcium to the second water tank 7. Then, the secondary permeated water w21 and Ca-free water w4 stored in the second water tank 7 are sent to the use point 31.
- the secondary permeated water w21 of the second water tank 7 is small, only Ca-free water w4 may be sent to the use point 31.
- the amount of Ca in the Ca-free water w4 is preferably less than 1 mg / L.
- the wastewater w1 to which the pH adjustment and the scale dispersant is added is flowed through the first reverse osmosis membrane 3 by the first pretreatment means 2. Fluorine can be removed without causing clogging in the reverse osmosis membrane 3 of 1. In addition, ammonium can be removed by flowing the primary permeated water w11 to which the pH adjustment and the slime inhibitor have been added by the second pretreatment means 4 through the second reverse osmosis membrane 5. As a result, it is possible to obtain secondary permeated water that can be used as raw water for pure water production equipment and water for equipment.
- the water treatment device 1 of the present embodiment it is not necessary to install a large-scale water softener because it is not necessary to add Ca when removing fluorine from the waste water w1. Further, in the water treatment apparatus 1 of the present embodiment, since ammonium is removed by the second reverse osmosis membrane 5 after adjusting the pH, ammonium can be removed without vaporizing ammonium into ammonia. Further, according to the water treatment apparatus 1 of the present embodiment, even wastewater containing organic substances can be treated without performing biological treatment such as the activated sludge method.
- the fluorine removing means 11 for removing fluorine in the primary concentrated water w12
- the fluorine removing means 11 is in the primary concentrated water w12 in which the amount of water is smaller than that of the wastewater w1.
- the treatment capacity required for the fluorine removing means 11 is relatively small, and the water treatment apparatus 1 can be made smaller.
- the water treatment device 1 of the present embodiment when the amount of water in the secondary permeated water w21 is less than the demand amount of the use point 31, Ca-free water w4 produced by the calcium removing means 21 is introduced into the second water tank 7.
- Ca-free water w4 can be replenished in the water treatment device 1 when the secondary permeated water w21 is insufficient with respect to the demand amount.
- the Ca concentration of the water flowing in the water circulation system can be suppressed to a low level, for example, less than 1 mg / L, and scale generation can occur. It is possible to prevent clogging of the first reverse osmosis membrane 3 and the second reverse osmosis membrane 5 of the water treatment apparatus 1 and generation of scale at the use point 31.
- the wastewater to which the pH adjustment and the scale dispersant has been added is flowed through the first reverse osmosis membrane 3 by the first pretreatment means 2, thereby causing the first reverse.
- Fluorine can be removed without causing clogging in the osmosis membrane 3.
- ammonium can be removed by flowing the primary permeated water w11 to which the pH adjustment and the slime inhibitor have been added by the first pretreatment means 2 through the second reverse osmosis membrane 5.
- the secondary permeated water w21 that can be used as raw water for the pure water production apparatus or water for equipment.
- the water treatment method of the present embodiment it is not necessary to install a large-scale water softener because it is not necessary to add Ca when removing fluorine from the waste water w1. Further, in the water treatment method of the present embodiment, since ammonium is removed by the second reverse osmosis membrane 5 after adjusting the pH, ammonium can be removed without vaporizing ammonium into ammonia. Further, according to the water treatment method of the present embodiment, even wastewater containing organic substances can be treated without performing biological treatment such as the activated sludge method.
- the fluorine removing step of removing the fluorine in the primary concentrated water w22 when the fluorine removing step of removing the fluorine in the primary concentrated water w22 is further performed, the fluorine removing step is performed with the fluorine in the primary concentrated water w12 having a smaller amount of water than the waste water w1.
- the treatment capacity required for fluorine removal is relatively small, and the energy required for water treatment can be reduced.
- the Ca-free water w4 produced by the calcium removing means 21 is used as the use point 31.
- Ca-free water w4 can be replenished when the secondary permeated water w21 is insufficient with respect to the demand amount.
- the Ca concentration of the water circulating in the water circulation system composed of the water treatment device 1 and the use point 31 can be suppressed to a low level, for example, less than 1 mg / L, and scale generation is prevented. Then, it is possible to prevent clogging of the first reverse osmosis membrane 3 and the second reverse osmosis membrane 5 of the water treatment apparatus 1 and generation of scale at the use point 31.
- the wastewater w1 contains the water used at the use point 31, the water circulated in the water circulation system composed of the water treatment device 1 and the use point 31.
- Ca concentration can be kept low, for example, less than 1 mg / L, and scale generation is prevented. Then, it is possible to prevent clogging of the first reverse osmosis membrane 3 and the second reverse osmosis membrane 5 of the water treatment apparatus 1 and generation of scale at the use point 31.
- Water treatment device 2 First pretreatment means 2a Primary pH adjustment unit 2b Primary drug injection unit 3 First reverse osmosis membrane 4 Second pretreatment means 4a Secondary pH adjustment unit 4b Secondary drug injection unit 5 2nd reverse osmosis membrane 6 1st water tank 7 2nd water tank (water tank) 11 Fluorine removing means 20 Raw water supply unit 21 Calcium removing means 22 Control unit 31 Use point 32 Another use point 41 Neutralization treatment means Sc Scale dispersant Slm Slime inhibitor w1 Wastewater w3 Raw water w4 Ca free water w5 Ca concentrated water w11 Primary Permeated water w12 Primary concentrated water w21 Secondary permeated water w22 Secondary concentrated water w40, w41 Treated water
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- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Removal Of Specific Substances (AREA)
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- Treatment Of Water By Ion Exchange (AREA)
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CN105384316A (zh) * | 2015-12-18 | 2016-03-09 | 无锡德宝水务投资有限公司 | 一种电子工业含氟含氨氮废水的处理方法 |
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CN103011441B (zh) * | 2011-09-23 | 2013-12-25 | 宝山钢铁股份有限公司 | 一种含氰、氟、氨氮废水的深度处理方法 |
JP6534524B2 (ja) * | 2014-12-25 | 2019-06-26 | オルガノ株式会社 | ろ過処理システムおよびろ過処理方法 |
JP6807219B2 (ja) * | 2016-11-18 | 2021-01-06 | オルガノ株式会社 | 逆浸透膜処理システムおよび逆浸透膜処理方法 |
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JP2002143850A (ja) * | 2000-11-15 | 2002-05-21 | Hitachi Zosen Corp | 排水処理装置 |
JP2003103260A (ja) * | 2001-09-28 | 2003-04-08 | Nomura Micro Sci Co Ltd | フッ化物含有排水の処理方法 |
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TW202039373A (zh) | 2020-11-01 |
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