WO2009107332A1 - Appareil de traitement des eaux usées et procédé de traitement des eaux usées - Google Patents

Appareil de traitement des eaux usées et procédé de traitement des eaux usées Download PDF

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Publication number
WO2009107332A1
WO2009107332A1 PCT/JP2009/000560 JP2009000560W WO2009107332A1 WO 2009107332 A1 WO2009107332 A1 WO 2009107332A1 JP 2009000560 W JP2009000560 W JP 2009000560W WO 2009107332 A1 WO2009107332 A1 WO 2009107332A1
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Prior art keywords
water
treated
separation means
filtration
calcium
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Ceased
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PCT/JP2009/000560
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English (en)
Japanese (ja)
Inventor
桑木康之
梅沢浩之
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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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
    • 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
    • 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
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/18—Details relating to membrane separation process operations and control pH control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/06—Submerged-type; Immersion type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/022—Reject series
    • 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
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
    • 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
    • C02F2201/005—Valves
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/11—Turbidity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/043—Treatment of partial or bypass streams

Definitions

  • the present invention relates to a wastewater treatment apparatus and a wastewater treatment method for removing fluorine from wastewater.
  • drainage a substance containing a substance to be removed in a fluid such as water or chemicals will be referred to as drainage.
  • a wafer processing or carbon tetrafluoride in cleaning the apparatus CF 4
  • hexafluoroethane C 2 F 6
  • perfluorocyclobutane Rob Tan C 4
  • a fluorine-based gas such as F 8
  • F 8 a fluorine-based gas
  • hydrofluoric acid in wet etching equipment that uses fluorine-based materials (for example, hydrofluoric acid), concentrated hydrofluoric acid wastewater (waste liquid), which is a waste chemical after wafer processing, and dilute hydrofluoric acid wastewater, which is pure water rinse wastewater (Waste liquid) is discharged.
  • fluorine-based materials for example, hydrofluoric acid
  • waste liquid concentrated hydrofluoric acid wastewater
  • dilute hydrofluoric acid wastewater which is pure water rinse wastewater (Waste liquid) is discharged.
  • hydrofluoric acid will be referred to as hydrofluoric acid.
  • the fluorine removed from the waste water can be reused in semiconductor processing equipment by using hydrofluoric acid or the like.
  • fluorine can be removed from the waste water as calcium fluoride by reacting wastewater containing fluorine (waste liquid) with a calcium compound to produce calcium fluoride.
  • Patent Document 1 a method of treating water containing calcium and fluorine using a cation exchange tower and an RO membrane separation device is disclosed.
  • Ca is removed by the cation exchange tower 2, and then the RO membrane separation device 3 To remove F.
  • the RO membrane separation device 3 By doing in this way, since Ca in water is removed beforehand by the cation exchange tower 2, blockage of the RO membrane by CaF 2 is prevented.
  • Patent Document 2 discloses a method in which calcium carbonate or the like is added to water to be treated to produce hardly soluble fluoroapatite, and the fluoroapatite is subjected to ion filtration after membrane filtration.
  • raw water in which calcium ion-containing water and fluorine ion-containing water are mixed is stored in the raw water tank 1.
  • fluoroapatite is produced
  • Patent Document 1 and Patent Document 2 described above have the following problems.
  • the waste water treatment apparatus of the present invention includes an adding means for adding calcium to water to be treated containing fluorine to generate calcium fluoride, a first separating means for separating the calcium fluoride from the water to be treated, And second separation means for removing fluorine ions from the treated water from which calcium fluoride has been separated, and the treated water in which the calcium component that has not reacted with the fluorine is concentrated by the second separating means. Is returned before the first separation means.
  • the step of generating calcium fluoride by adding calcium to the water to be treated containing fluorine and the step of separating the calcium fluoride from the water to be treated by the first separation means. And removing fluorine ions from the water to be treated from which the calcium fluoride has been separated by the second separation means, and the calcium component that has not reacted with the fluorine is concentrated by the second separation means.
  • the treated water is returned to a stage preceding the first separation means.
  • the fluorine and the unreacted calcium content are concentrated by the second separation means, and returned to the previous stage rather than the first separation means. ing. Therefore, since the calcium content that has not contributed to the generation of calcium fluoride can be reused, the total amount of calcium required to remove the fluorine content is reduced, and the processing cost is reduced accordingly.
  • hydrofluoric acid aqueous solution of hydrogen fluoride (HF)
  • HF hydrogen fluoride
  • the waste water treatment apparatus 10 of the present embodiment includes a first treatment tank 11A (addition means) in which calcium fluoride is generated by adding calcium to treated water 12 containing fluorine, and an immersed filtration membrane A second treatment tank 11B in which calcium fluoride is filtered by 13 (first separation means), and an RO filtration device 14 (second separation means) for further filtering the treated water 12 filtered by the filtration membrane 13;
  • the sixth treatment path P6 mainly returns the treated water 12 concentrated in the RO filtration device 14 to the first treatment tank 11A.
  • the first treatment tank 11A is a tank in which treated water 12 which is wastewater containing fluorine is stored, and calcium fluoride is generated by adding calcium to the treated water 12.
  • the water to be treated 12 is waste water containing fluorine.
  • This waste water is discharged from a semiconductor processing factory, and is discharged by, for example, an etching process of semiconductor, glass, metal, etc., a wafer processing process such as formation of a CVD film, or cleaning of a semiconductor processing apparatus.
  • a fluorine-based gas such as CF 4 , C 2 F 6 , or C 4 F 8 is often used. These gases are also used when cleaning the inside of the chamber after wafer processing. Most of these gases are discharged out of the chamber as CF 4. However, since these are substances having a global warming promoting effect (Perfluorocompounds (PFCs) gas), detoxification treatment is required. Fluorine burned and decomposed in this detoxification treatment is absorbed by water, and dilute hydrofluoric acid wastewater is discharged.
  • PFCs Perfluorocompounds
  • wet etching equipment uses hydrofluoric acid to improve the corrosiveness during etching, so concentrated hydrofluoric acid wastewater that is a waste chemical after wafer processing and dilute hydrogen fluoride that is drainage of pure water rinse Acid wastewater is discharged.
  • hydrogen fluoride (HF) contained in the water to be treated 12 is dissociated by 99.9% or more into hydrogen ions (H + ) and fluorine ions (F ⁇ ) (the following formula A).
  • the to-be-processed water 12 may be stirred with stirring means, such as a propeller, in the inside of the first treatment tank 11A.
  • the first path P1 is a path through which the treated water 12 discharged from the environment described above is supplied to the first treatment tank 11A.
  • the water to be treated 12 containing fluorine ions (F ⁇ ) is introduced into the first treatment tank 11A via the first path P1.
  • water to be treated having a fluorine ion concentration of 100 mg / L is supplied from the first path P1 at 10 t / day.
  • the pH of water to be treated containing hydrogen fluoride is, for example, about PH 3 to 4, and is very strong acidic. Therefore, the pH of the water to be treated 12 may be between 7 and 9 by adding NaOH as an alkaline agent.
  • the chemical tank 15 is a tank in which an aqueous solution of calcium is stored in order to fix the fluorine contained in the water 12 to be treated.
  • calcium chloride CaCl 2
  • Ca (OH) 2 calcium hydroxide
  • the chemical tank 15 stores an aqueous solution containing 35% by weight of calcium chloride.
  • the aqueous solution stored in the chemical tank 15 passes through the second path P2 (addition means) to the first treatment tank 1. Introduced into 1A.
  • the fluorine ions contained in the water to be treated 12 introduced from the first path P1 and the calcium content introduced from the second path P2 combine to generate calcium fluoride.
  • the fluorine content contained in the water to be treated 12 is fixed as calcium fluoride by the reaction shown in the following formula (B).
  • a larger amount of calcium chloride than the theoretically required amount is charged into the water to be treated 12.
  • an amount of calcium chloride more than twice the amount theoretically required to immobilize the total amount of fluorine contained in the water to be treated 12 is passed through the second path P2. It has thrown into 1 process tank 11A.
  • emitted from 11 A of 1st process tanks can be 4 mg / L or less, for example. This fluorine ion concentration satisfies the general discharge standard.
  • the treatment cost may increase. From this, in order to reduce processing cost, the to-be-processed water concentrated by the RO filtration apparatus 14 is returned to the 1st processing tank 11A, and the calcium content is reused. This matter will be described later.
  • the water to be treated 12 in which fluorine ions are fixed as calcium fluoride is introduced into the second treatment tank 11B via the third path P3.
  • the second treatment tank 11B calcium fluoride is separated from the treated water 12 by filtering the treated water 12 through the filtration membrane 13 (first separation means).
  • the filtration membrane 13 a filtration mechanism capable of performing filtration in a fluid can be generally employed.
  • solid-liquid separation between calcium fluoride and the water to be treated 12 is performed by performing filtration using a self-forming film formed on the surface of the filtration film 13. Details of the self-forming film will be described later.
  • the treated water 12 filtered by the filter membrane 13 immersed in the second treatment tank 11B is in a state in which calcium fluoride is almost separated and removed, and calcium content and unreacted fluorine ions (F ⁇ ) are removed.
  • F ⁇ calcium content and unreacted fluorine ions
  • it contains about 4 mg / L.
  • the fluorine content and unreacted calcium ions (Ca 2+ ) are also contained in the filtered water 12 to be treated. Fluorine ions and calcium ions remaining in the water to be treated 12 are removed by the RO filtration device 14 in the next stage.
  • the self-forming film described above may be a self-forming film made of an object to be removed containing calcium fluoride generated in the water 12 to be treated. That is, the water to be treated 12 is filtered by the removal object adsorbed on the filtration surface of the filtration membrane 13. Further, when the calcium fluoride is recovered, the self-forming film is also peeled off from the filtration film 13 and recovered.
  • the air diffuser 18 has a function of supplying bubbles to the filtration membrane 13 from below in the treated water 12. Specifically, gas is supplied to the air diffuser 18 from a pump (not shown) provided outside to generate bubbles. Bubbles generated from the air diffuser 18 move upward along the filtration surface of the filtration membrane 13. As described above, by generating bubbles from the air diffuser 18, the thickness of the self-forming film formed on the surface of the filtration film 13 can be made constant or less. From this, it becomes possible to filter the water 12 to be treated while suppressing the blockage of the self-forming film and securing a certain amount of flux.
  • an inert gas such as helium, neon, argon or nitrogen can be employed.
  • carbon dioxide gas contained in the air reacts with fluoride ions contained in the water 12 to be treated, which may reduce the concentration of calcium fluoride. is there.
  • an inert gas as the gas supplied from the air diffuser 18, the fear can be eliminated.
  • the fourth path P4 is a path through which filtered water filtered by the filter membrane 13 passes.
  • a storage tank 15C is provided in the branched path in the middle of the fourth path P4.
  • the storage tank 15C In the storage tank 15C, a part of filtrate water filtered by the filtration membrane 13 is stored.
  • the position of the storage tank 15C is set above the liquid level of the water 12 to be treated stored in the separation tank 11C.
  • the filtered water or tap water stored in the storage tank 15C is used by causing the fourth path P4 to flow backward when the self-forming film formed on the surface of the filtration film 13 is peeled off.
  • route P7 is a path
  • the treated water 12 to be transported contains calcium fluoride with high purity.
  • the neutralization salt is also contained in the to-be-processed water 12 transferred.
  • the to-be-removed object containing calcium fluoride is supplied to the filter press 17 by the 7th path
  • the water content of the object to be removed that has been dehydrated by the filter press 17 is, for example, about 50% by weight. Further, when the object to be removed is dried, a block (solid matter) having a calcium fluoride purity of about 85% by weight is obtained. Calcium fluoride contained in the object to be removed with high purity is reused as a fluorine source.
  • route P8 is a path
  • FIG. For example, about 15% by weight of neutralized salt (NaCl) is contained in the object to be removed in the water to be treated whose pH has been adjusted.
  • neutralized salt NaCl
  • the water injected into the filter press 17 is temporarily stored in the receiving tank 19.
  • the treated water stored in the receiving tank 19 is returned to the second processing tank 11B through the ninth path P9 and filtered.
  • first processing tank 11A and the second processing tank 11B described above may be the same processing tank. This makes it possible to fix fluoride ions and separate the solid and liquid in the same tank, simplify the configuration of the entire facility and reduce the size. Furthermore, since the number of tanks is reduced, initial cost and running cost are also reduced.
  • the pump 20 has been refurbished in the middle of the fourth path P4, and filtration by the filtration membrane 13 is performed by the suction pressure generated by the pump 20, and the RO filtration device 14 (the first filter is generated by the applied pressure generated by the pump 20).
  • the treated water 12 is filtered by the two separation means. In this way, by using the pump 20 together for the filtration of the filtration membrane 13 and the RO filtration device 14, the number of pumps required is reduced, so that the cost required for the facility is reduced.
  • the RO filtration device 14 is a device that filters a fluid with an RO (Reverse Osmosis Membrane) membrane, and has an action of further filtering and purifying the water to be treated 12 filtered by the filtration membrane 13 in this embodiment.
  • the RO filtration device 14 is composed of a filtration membrane having pores with a diameter of several nanometers, and can separate impurities such as fluorine ions and calcium ions from the water to be treated 12.
  • the concentration of the treated water 12 can be reduced to 1 mg / L.
  • calcium ions and chloride ions are removed from the water to be treated 12 in addition to fluorine ions.
  • a filtration device having an NF (Nanofiltration Membrane) membrane may be employed.
  • the treated water 12 filtered by the RO filtration device 14 is discharged out of the wastewater treatment device 10 via the fifth path P5.
  • the treated water 12 released through the fifth path P5 is in a state in which impurities such as fluorine ions are highly removed, and can be used as cleaning water in the semiconductor manufacturing process. Furthermore, since the concentration of the fluorine ions contained is extremely low, it can be directly discharged into the natural world such as a river.
  • the treated water 12 remaining in the RO filtration device 14 is in a state where impurities such as fluorine ions, calcium ions and chloride ions are concentrated.
  • the concentrated water 12 to be treated is returned to the first treatment tank 11A via the sixth path P6. This makes it possible to reuse fluorine ions and unreacted calcium ions as calcium components for producing calcium fluoride. As a result, it is possible to increase the concentration of calcium ions in the first treatment tank 11A while reducing the amount of consumed calcium chloride.
  • the concentration of chloride ions is measured by measuring the conductivity of the treated water.
  • a conductivity meter 32 is interposed.
  • a chloride ion concentration meter can be adopted in addition to the conductivity meter 32, but the conductivity meter 32 that can be used in-line is more suitable. Preferred as a means.
  • the means for measuring the concentration of chloride ions can be interposed in a place other than the sixth path P6 as long as it is a path through which the water to be treated is circulated. It can also be prepared on the way. However, for example, if the conductivity meter 32 is interposed in the middle of the third path P3, the water to be treated passing through the third path P3 contains a large amount of suspended solids (SS). 32 makes it difficult to obtain the chloride ion concentration with high accuracy. On the other hand, in the sixth path P6, the water to be treated 12 from which SS or the like has been removed by the RO filtration device 14 passes, so that the concentration of chloride ions can be obtained with high accuracy.
  • SS suspended solids
  • the concentration of chloride ions can be obtained with high accuracy.
  • the eleventh route P11 has one end communicating in the middle of the fourth route P4 and the other end communicating in the middle of the sixth route P6.
  • the water to be treated passes through the eleventh path P11, the water to be treated filtered by the filtration membrane 13 is not supplied to the RO filtration device 14 but returned to the first treatment tank 11A and circulated.
  • the eleventh path P11 is provided with a turbidimeter 30 for measuring the turbidity of the water to be treated that has passed through the filtration membrane 13.
  • the to-be-processed water detected by the turbidimeter 30 is above a certain level (if the amount of to-be-removed substance contained in the to-be-processed water is large), the to-be-processed water will be supplied to the RO filtration apparatus 14. Instead, it is returned to the first processing tank 11A via the eleventh path P11. On the other hand, if the turbidity of the water to be treated detected by the turbidimeter 30 is below a certain level, the water to be treated is supplied to the RO filtration device 14.
  • the turbidimeter 30 is suitable as a means for detecting the turbidity of the water to be treated.
  • the twelfth path P12 has one end connected to the middle of the fifth path P5 and the other end connected to the storage tank 15C.
  • a portion of the water to be treated filtered by the RO filtration device 14 is transferred to the storage tank 15C through the twelfth path P12 and stored as filtered water 16.
  • the filtered water 16 is flowed back to the filtration membrane 13 and used to peel the self-forming membrane constituting the filtration membrane 13. Therefore, it is necessary to prepare pure water with low turbidity as the filtered water 16, and the tap water is stored in the storage tank 15C during the first period in which the waste water treatment apparatus 10 is operated. And after the steady driving
  • the head of the filtered water 16 stored in the storage tank 15C is higher than the head of the treated water 12 stored in the second processing tank 11B. Therefore, when the self-forming film formed on the surface of the filtration membrane 13 is peeled off, it is stored in the storage tank 15C using the hydraulic head difference of the fluid stored in both tanks without using a driving force such as a pump.
  • the filtered water 16 can be made to flow backward to the filtration membrane 13. Therefore, power such as a pump is not required for peeling the self-forming film, and the running cost of the processing apparatus is reduced.
  • the tenth path P10 has one end connected to the fourth path P4 upstream of the pump 20 and the other end connected to the fourth path P4 downstream of the pump 20. That is, the tenth route P10 is a bypass route of the fourth route P4.
  • An adjustment valve 36 is provided in the tenth path P10, and the adjustment valve 36 is adjusted according to the output of the pressure gauge 34 that detects the pressure inside the fourth path P4. As a result, the suction pressure applied to the filtration membrane 13 by the pump 20 and the applied pressure applied to the RO filtration device 14 are adjusted to predetermined values.
  • the first treatment tank 11A when the calcium component charged from the chemical tank 15 is combined with fluorine ions to be calcium fluoride, the first treatment tank 11A ⁇ the second treatment tank 11B ⁇ the RO filtration device 14 ⁇ It is circulated in the order of the first treatment tank 11A. Therefore, almost the entire amount of calcium added can be used for the production of calcium fluoride.
  • the treated water 12 from which calcium fluoride has been removed by the filtration membrane 13 is further filtered by the RO filtration device 14. Therefore, since there is no possibility that the pores of the fine filtration membrane of the RO filtration device 14 are clogged with calcium fluoride, the RO filtration device 14 can be used continuously for a long period of time.
  • a plurality of the RO filtration devices 14 are arranged in series with respect to the path through which the water to be treated 12 is treated. Specifically, from the first RO filtration device 14A, the second RO filtration device 14B, and the third RO filtration device 14C.
  • the RO filtration device 14 is configured.
  • Each RO filtration device is configured to include an RO filtration membrane 28 inside. Further, here, filtration by the first RO filtration device 14A, the second RO filtration device 14B, and the third RO filtration device 14C is performed by applying a pressurizing force by the pump 20.
  • the first RO filtration device 14A is provided in the foremost stage, and the treated water 12 from which calcium fluoride has been removed by being filtered by the filtration membrane 13 (see FIG. 1) is introduced into the first RO filtration device 14A.
  • the The first RO filtration device 14A is filtered by the pressure applied by the pump 20, and the treated water that has passed through the RO filtration membrane 28 is free from impurities such as fluorine ions and calcium ions in the fifth path. Released to the outside via P5.
  • the treated water that does not pass through the RO filtration membrane 28 of the first RO filtration device 14A is transported to the second RO filtration device 14B in a state where impurities such as fluorine ions and calcium ions are concentrated.
  • 55% of the introduced water to be treated is filtered by the RO filtration membrane 28, and the remaining 45% of the water to be treated is transported to the second RO filtration device 14B.
  • the water to be treated is filtered by the RO filtration membrane. Again, the treated water that has passed through the RO filtration membrane is taken out from the fifth path P5.
  • the water to be treated that has been concentrated without passing through the RO filtration membrane is transported to the third RO filtration device 14C in a state where fluorine ions and calcium ions are further concentrated.
  • the amount of treated water that passes through the RO filtration membrane of the second RO filtration device 14B and is discharged to the outside is about 25% of the treated water that flows into the RO filtration device 14. Then, about 20% of the water to be treated is introduced into the third RO filtration device 14C in a state of being further concentrated without being filtered by the second RO filtration device 14B.
  • the water to be treated is further filtered in the same manner as the first RO filtration device 14A and the like. Accordingly, the treated water that has passed through the RO filtration membrane of the third RO filtration device 14C is discharged to the outside, and the treated water that has not passed through the RO filtration membrane is further concentrated and then the first treatment via the sixth path P6. It is returned to the tank 11A (see FIG. 1).
  • the amount of water to be treated that passes through the RO filtration membrane of the third RO filtration device 14 ⁇ / b> C is about 11% with respect to the total amount of water to be treated introduced into the RO filtration device 14.
  • a plurality of RO filtration devices 14 are arranged in series with respect to the path of the water to be treated, thereby preventing clogging of individual RO filtration devices and performing advanced filtration treatment.
  • the RO filtration devices are arranged in three stages in series.
  • the permeated water ratio of each RO filtration device is 55%
  • filtered water is taken out from each RO filtration device, so that the water recovery rate of the entire device can be increased to about 90%.
  • the water recovery rate becomes high the water to be treated having a very high concentration of calcium ions contained therein can be obtained from the third RO filtration device 14C. Accordingly, since the amount of water to be treated returned for reuse is reduced, the efficiency of the first separation means (filtration membrane 13) is increased, and the cost can be reduced accordingly.
  • the proportion of fluorine ions captured is about 80%.
  • the proportion of fluorine ions supplemented is a theoretical value. It can be raised to about 99%.
  • the first RO filtration device 14A and the like are provided in three stages in series with respect to the treatment water path, but the number of the RO filtration devices provided may be two or four or more.
  • the above is the configuration of the wastewater treatment apparatus 10 according to the present embodiment.
  • the wastewater treatment method of the present embodiment includes step S1 for generating calcium fluoride, step S2 for performing solid-liquid separation of calcium fluoride by filtration, and further filtration.
  • This step mainly includes step S3 for removing fluorine ions, step S4 for returning the calcium content concentrated in step S3, and step S5 for recovering calcium fluoride.
  • Step S1 Step of generating calcium fluoride
  • the treated water 12 containing the fluorine content discharged from the semiconductor manufacturing process or the like is supplied to the first treatment tank 11A via the first path P1.
  • This treated water 12 contains fluorine ions at a concentration of about 100 mg / L, for example. Since the water to be treated 12 containing hydrofluoric acid exhibits extremely strong acidity, the neutralization treatment is performed in the first treatment tank 11A or before the first treatment tank 11A, and the pH of the water to be treated 12 is set to 7-9, for example. It may be controlled to the value of.
  • a calcium content is added from the chemical tank 15 to the first treatment tank 11A via the second path P2.
  • an aqueous solution of calcium chloride is added from the chemical tank 15 to the first treatment tank 11A.
  • the amount of added calcium is required to be 1/2 the number of moles of fluorine ions contained in the water 12 to be treated.
  • a larger amount of chloride for example, 2 times or more, more preferably 5 times or more than the amount theoretically required. Calcium is added.
  • Step S2 Step of separating calcium fluoride from the water to be treated by membrane filtration
  • the calcium fluoride generated in the previous step is separated from the water to be treated 12.
  • a filter capable of filtration can be employed as a device for separating calcium fluoride from the water 12 to be treated.
  • a flat membrane filter having a pore diameter of 0.2 ⁇ m is employed as the filtration membrane 13.
  • a self-forming film made of a deposited object to be removed (calcium fluoride) is employed as the filtered water filtered by the filtration membrane 13 is transported to the RO filtration device 14 via the fourth path P4.
  • the filtration membrane 13 used in this step is a filtration membrane that blocks the passage of calcium fluoride, but allows the passage of fluorine ions at the atomic level. Accordingly, fluorine ions remain at a concentration of about 4 mg / L in the water to be treated 12 filtered by the filter membrane 13. This fluorine ion is not bonded to the calcium component in the previous step S1.
  • a part of the to-be-processed water 12 filtered by the filtration membrane 13 is stored in the storage tank 15C.
  • the filtered water 16 stored in the storage tank 15C is used to peel off the self-forming film attached to the surface of the filtration film 13. Specifically, by continuously performing filtration through the filtration membrane 13, the self-forming membrane attached to the surface of the filtration membrane 13 is blocked and the flux gradually decreases. And when the quantity of this flux becomes below fixed, filtration by the filter membrane 13 is stopped. Further, the filtered water 16 stored in the storage tank 15 ⁇ / b> C is caused to flow back to the filtration membrane 13 to peel off the self-forming membrane attached to the surface of the filtration membrane 13. Furthermore, after that, the self-forming film is formed again on the surface of the filtration membrane 13 by restarting the filtration by the filtration membrane 13 and circulating the water to be treated.
  • tap water is stored in the storage tank 15C.
  • the water to be treated filtered by the RO filtration device 14 may be stored in the storage tank 15C via the twelfth path P12.
  • the filtration in this step is performed by the suction force of the pump 20 interposed in the fourth path P4.
  • This pump 20 is also used in the next step as a pressurizing means.
  • the rotation of the pump 20 may be controlled so that the suction pressure is constant, or the flow rate of the water to be treated filtered by the filtration membrane 13 is constant.
  • a tenth path P10 that bypasses the fourth path P4 before and after the place where the pump 20 is provided is provided, and an adjustment valve 36 is interposed in the tenth path P10.
  • the adjustment valve 36 by adjusting the adjustment valve 36 according to the pressure value measured by the pressure gauge 34, the suction pressure acting on the filtration membrane 13 and the applied pressure acting on the RO filtration device 14 are set to appropriate values. Is controlling.
  • the water to be treated filtered by the filtration membrane 13 is not introduced into the RO filtration device 14, It returns to 11A of 1st process tanks via the 11th path
  • the turbidity of the water to be treated filtered by the filtration membrane 13 is not sufficient.
  • the water to be treated filtered by the filtration membrane 13 is returned to the first treatment tank 11A via the eleventh path P11.
  • the water to be treated filtered by the filtration membrane 13 is subjected to RO filtration. Introduced into the device 14.
  • Step S3 Step of further filtering the treated water from which calcium fluoride has been removed
  • further filtration by the RO filtration device 14 is performed using the pressure applied by the pump 20, and fluorine ions contained in the treated water Remove.
  • the filtration membrane 13 that has been filtered in the previous step supplements calcium fluoride having a relatively large particle diameter, but does not supplement ions of atomic size. Therefore, fluorine ions remain at about 4 mg / L in the water to be treated that has passed through the filtration membrane 13. If the concentration of the remaining fluorine ions is about this level, it can be released into the natural environment such as a river as it is, but it is not suitable for use as washing water or the like in a semiconductor manufacturing process.
  • the filtered water that has passed through the filtration membrane 13 is further purified using the RO filtration device 14.
  • the treated water filtered by the RO filtration device 14 is discharged to the outside via the fifth path P5.
  • the water to be treated in which calcium ions and the like are concentrated without passing through the RO filtration membrane inside the RO filtration device 14 is returned to the first treatment tank 11A via the sixth path P6 and used as a calcium source. Reused.
  • the RO filtration device 14 filters the water to be treated by the applied pressure given by the pump 20. As described above, the pump 20 is shared by the filtration membrane 13 and the RO filtration device 14.
  • the RO filtration device 14 includes a plurality of RO filtration devices 14 arranged in series with respect to the treatment path of the water to be treated. Specifically, the first RO filtration device 14A, the second RO filtration device 14B, and the third RO filtration device 14C are arranged from the upstream side of the path where the treated water 12 is treated. And the to-be-processed water is first introduce
  • the second RO filtration device 14B filtration by the RO membrane is performed similarly to the first RO filtration device 14A, and the treated water that has been filtered is discharged to the outside via the fifth path P5 and has not been filtered.
  • the treated water is transferred to the third RO filtration device 14C after further concentration. Further, the same filtration by the RO filtration membrane was performed in the third RO filtration device 14C, and the water to be treated that passed through the RO filtration membrane was discharged to the outside via the fifth path P5 and did not pass through the RO filtration membrane.
  • the treated water is reused via the sixth path P6. That is, it is returned to the first processing tank 11A shown in FIG.
  • the water to be treated which is concentrated by the RO filtration device arranged in three stages and passes through the sixth path P6, calcium ions and fluorine ions are concentrated about 10 times, for example.
  • Step S4 Returning the concentrated calcium content
  • the treated water 12 that has not been filtered by the RO filtration device 14 is returned to the first treatment tank 11A via the sixth path P6, and the Reuse to produce calcium fluoride.
  • the amount of calcium content (calcium chloride) added to reduce the amount of fluorine ions remaining in the water to be treated 12 is twice the theoretically required amount. 10 times the range. From this, the to-be-treated water 12 that has passed through the first treatment tank 11A, the second treatment tank 11B, and the RO filtration device 14 contains a large amount of calcium ions that have not been combined with the fluorine content.
  • the treated water 12 is concentrated about 10 times by the filtration device 14.
  • Calcium ions contained in the water to be treated returned to the first treatment tank 11A are used to fix the fluorine content contained in the water to be treated introduced from the first path P1 as calcium fluoride.
  • the water to be treated containing calcium in a high concentration passes through the sixth path P6. 2 Returned to treatment tank 11B.
  • the calcium added from the chemical tank 15 to the first treatment tank 11A is circulated through the treatment path of the waste water treatment apparatus 10 except for the part that combines with the fluorine ions to generate calcium fluoride. Will be. Accordingly, most of the calcium supplied from the chemical tank 15 contributes to the fixation of fluorine ions, and there is almost no calcium released to the outside from the fifth path P5. For this reason, the calcium content required for immobilization of fluorine ions is reduced, and the processing cost is reduced.
  • the concentration of ions (for example, chloride ions) contained in the water to be treated that passes through the sixth path P6 is measured by the conductivity meter 32. And if the quantity of the measured ion is more than predetermined amount, the to-be-processed water to circulate will be replaced.
  • step S5 is performed in order to collect the precipitated calcium fluoride.
  • Step S5 Step of recovering calcium fluoride precipitated in the second processing tank 11B
  • the object to be removed containing calcium fluoride precipitated at the bottom of the second processing tank 11B is passed through the seventh path P7. Then, it is transferred to the filter press 17.
  • the neutralized salt (NaCl) contained in the water 12 to be treated is washed and removed. Since the pH-adjusted water to be treated 12 contains neutralized salt, the object to be removed separated from the water to be treated 12 is also neutralized with calcium fluoride and other calcium salts (for example, Calcium carbonate). Further, for example, in the case of drainage from a wet etching apparatus, silicon may be included.
  • the neutralized salt is dissolved in water and released to the outside. Since calcium fluoride has a large diameter, it is not released from the filter press 17 to the outside even if washed with water. By doing in this way, the density
  • the object to be removed is dehydrated by the filter press 17, the object to be removed in a semi-solid state is taken out. In this state, the water content of the object to be removed is about 50% by weight.
  • the object to be removed is dried to form a solid block of the object to be removed. In this embodiment, an object to be removed containing 85% by weight of calcium fluoride is obtained.
  • immobilized calcium fluoride can be obtained with high purity from wastewater containing fluoride ions.
  • the obtained calcium fluoride can be reused in the semiconductor manufacturing process as hydrofluoric acid by reacting with a strong acid (for example, sulfuric acid).
  • calcium chloride can be obtained by adding hydrochloric acid to the obtained calcium fluoride.
  • sulfuric acid, hydrochloric acid, etc. added to recycle calcium fluoride are chemicals that are always used in semiconductor factories, it is possible to reuse calcium fluoride without adding new equipment in the factory. It can be performed.
  • filtration mechanism filter apparatus 23
  • filter apparatus 23 a filtration mechanism using a self-forming film
  • other forms of filtration devices can be applied to the present invention.
  • filtration membrane 1 3 it is also possible to use a normal filtration membrane made of a polymer compound.
  • the filter device 23 removes the water to be treated mixed with the object to be removed, which is calcium fluoride, with a filter made of a self-forming film formed from the object to be removed.
  • a second filter 22 self-forming film formed from an object to be removed containing calcium fluoride is formed on the surface of the organic polymer first filter 21. It is a thing. Using the second filter 22 which is this self-forming film, the water to be treated mixed with the material to be removed is filtered.
  • the first filter 21 can be either organic polymer type or inorganic type (ceramic type) in principle, as long as a self-forming film can be attached.
  • a polyolefin polymer film having an average pore diameter of 0.25 ⁇ m and a thickness of 0.1 mm was employed.
  • a photograph of the surface of the polyolefin filter membrane is shown in FIG.
  • the first filter 21 has a flat membrane structure provided on both sides of the frame 24, and is immersed so as to be perpendicular to the liquid level of the fluid. By sucking with a pump 26 from the hollow portion 25 of the frame 24, the filtrate 27 (water to be treated) can be taken out.
  • the second filter 22 is a self-forming film that is attached to the entire surface of the first filter 21 and solidified by sucking the aggregated particles of the object to be removed.
  • This self-forming film may be agglomerated in a gel or cake form.
  • the filtration for forming the second filter 22 that is the self-forming film of the object to be removed and removing the object to be removed will be described.
  • the first filter 21 has a number of filter holes 21A, and the self of the object to be removed that is formed in layers in the opening of the filter hole 21A and the surface of the first filter 21.
  • the formed film is the second filter 22.
  • the surface of the first filter 21 has agglomerated particles of the object to be removed made of calcium fluoride. The agglomerated particles are sucked through the first filter 21 by the suction pressure from the pump, and the fluid moisture is sucked out.
  • the second filter 22 is formed on the surface of the first filter 21 by solidifying immediately after drying (dehydration).
  • the second filter 22 is formed from aggregated particles of the object to be removed, the film immediately has a predetermined film thickness, and filtration of the aggregated particles of the object to be removed is started using the second filter 22. Therefore, if the filtration is continued while sucking with the pump 26 (see FIG. 4), a self-forming film of agglomerated particles is laminated on the surface of the second filter 22 to become thick, and the second filter 22 is eventually clogged and filtered. I can't continue. During this time, the calcium fluoride as the object to be removed is solidified, adheres to the surface of the second filter 22, and the treated water passes through the first filter 21 and is taken out as filtered water.
  • one side of the first filter 21 has treated water mixed with an object to be removed such as calcium fluoride, and the other side of the first filter 21 passes through the first filter 21. Filtered water is produced.
  • the treated water is sucked and flows in the direction of the arrow, and the agglomerated particles in the treated water 12 are solidified as they approach the first filter 21 by this suction.
  • the self-forming film to which some aggregated particles are bonded is adsorbed on the surface of the first filter 21 to form the second filter 22.
  • the object to be removed in the solution is solidified by the action of the second filter 22 and the water to be treated is filtered.
  • the water in the water to be treated can be taken out as filtered water, and the object to be removed is dried and solidified and laminated on the surface of the second filter 22.
  • the aggregated particles of the removal object are captured as a self-forming film.
  • the first filter 21 is immersed vertically in the water to be treated, and the material to be removed is dispersed in the water to be treated.
  • the water to be treated is sucked by the pump 26 through the first filter 21 with a weak suction pressure
  • the aggregated particles of the objects to be removed are combined with each other on the surface of the first filter 21 and adsorbed on the surface of the first filter 21. Is done.
  • the agglomerated particles S1 having a diameter smaller than the filter hole 21A pass through the first filter 21, but there is no problem in the process of forming the second filter 22 because the filtered water is circulated again to the water to be treated.
  • the water to be treated is filtered by the first filter 21 to form a second filter on the surface of the first filter.
  • the agglomerated particles S1 are stacked while forming gaps of various shapes, and the first self-forming film having a very high degree of swelling is formed.
  • Two filters 22 are obtained. Water in the water to be treated permeates through this highly swelled self-forming film and is sucked, passes through the first filter 21 and is taken out as filtered water, and finally the water to be treated is filtered.
  • the parallel flow is formed in the to-be-processed water along the surface of the 1st filter 21 by sending the bubble A from the bottom face of the to-be-treated water (aeration device 18 shown in FIG. 1).
  • the second filter 22 adheres uniformly to the entire surface of the first filter 21 and forms a gap in the second filter 22 and adheres softly.
  • the air flow rate is set to 1.8 liters / minute, but it is selected depending on the film quality of the second filter 22.
  • the process proceeds to the filtration process.
  • the aggregated particles S1 made of calcium fluoride are gradually stacked on the surface of the second filter 22 while being adsorbed by a weak suction pressure.
  • the purified water permeates the second filter 22 and the further aggregated particles S1 and is taken out from the first filter 21 as filtered water.
  • the hollow portion 25 of the first filter 21 has a negative pressure compared to the outside due to a weak suction pressure, and therefore the first filter 21 has a shape recessed inward. Yes. Therefore, the second filter 22 adsorbed on the surface is similarly recessed inward.
  • the weak suction pressure is stopped and returned to almost atmospheric pressure, so that the first filter 21 returns to the original state.
  • the second filter 22 and the self-forming film adsorbed on the surface of the second filter 22 are similarly returned to the original state.
  • the self-forming film loses the adsorbing force to the first filter 21 and receives a force that expands outward.
  • the adsorbed self-forming film starts to be detached by its own weight.
  • the first filter 21 is helped to return to the original state, and a hydrostatic pressure of the filtered water is applied and a force that further expands outward is applied.
  • the first The filtered water oozes out from the inside of the filter 21 through the filter hole 21 ⁇ / b> A (see FIG. 5A) to the boundary between the first filter 21 and the second filter 22, and the self-forming film of the second filter 22 from the surface of the first filter 21. Promotes withdrawal.
  • the reverse flow can be performed by causing the filtered water 16 temporarily stored in the storage tank 15C shown in FIG. 1 to flow into the filtration membrane.
  • the concentration of the object to be removed from the water to be treated 12 increases, and the viscosity of the water to be treated 12 eventually increases. Therefore, when the concentration of the object to be removed in the water to be treated 12 exceeds a predetermined concentration, the filtering operation is stopped and left to settle. Then, the concentrated slurry is stored at the bottom of the second treatment tank 11B (FIG. 1), and this cake-like concentrated slurry is recovered. The recovered concentrated slurry is dehydrated using a filter press 17 (see FIG. 1), and further compressed or heat dried to remove the water contained therein and reduce the amount.
  • This slurry can be reused as a hydrofluoric acid source. That is, the concentration efficiency of the concentrated slurry that is a raw material of hydrofluoric acid can be improved by causing the filtered water 16 stored in the storage tank 15C to flow backward and repeating the peeling of the self-forming film.
  • FIG. 6 is a graph showing the change with time of the flux during the filtration process.
  • the horizontal axis indicates the time for which the processing is continuously performed, and the vertical axis indicates the magnitude of the flux.
  • the average flux was 0.4 m / day, and it was proved that the filtration membrane 13 of this embodiment can sufficiently withstand practical use. Furthermore, the concentration of fluoride ions contained in the filtered water obtained by the filtration membrane is 3.5 mg / L, and this value satisfies the general discharge standard.
  • a self-forming film is formed on the surface of the filtration membrane by circulating an object to be removed such as calcium fluoride, and filtered water having a certain level of transparency can be obtained. At this point, filtration begins.
  • the flux at the start of filtration is about 0.7 m / day, and the flux gradually decreases as filtration continues. This is because the self-forming film is blocked as the filtration progresses.
  • the flux at the time when 130 minutes have passed since the start of filtration is about 0.2 m / day. At this point, the self-forming membrane is peeled off from the filtration membrane, and the removal target concentrated in the water to be treated is recovered.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Filtration Of Liquid (AREA)

Abstract

L'invention porte sur un appareil de traitement des eaux usées (10) qui comprend un réservoir de produit chimique (15) dans lequel est stocké un ingrédient de calcium qui génère du fluorure de calcium après addition d'eau brute contenant du fluor à traiter (12) ; une membrane filtrante (13) grâce à laquelle le fluorure de calcium est séparé de l'eau brute (12) ; et un filtre à osmose inverse (14) par lequel des ions fluor sont retirés de l'eau brute (12) dont a été séparé le fluorure de calcium. L'appareil (10) a une structure dans laquelle l'eau brute (12) dans laquelle l'ingrédient de calcium qui n'a pas réagi avec le fluor a été concentré par le filtre à osmose inverse (14) est renvoyée à un étage précédant la membrane filtrante (13).
PCT/JP2009/000560 2008-02-29 2009-02-12 Appareil de traitement des eaux usées et procédé de traitement des eaux usées Ceased WO2009107332A1 (fr)

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JP2018143919A (ja) * 2017-03-01 2018-09-20 オルガノ株式会社 フッ素含有水の処理装置、フッ素含有水の処理方法及び膜ろ過システム
CN110510777A (zh) * 2019-09-05 2019-11-29 煤科集团杭州环保研究院有限公司 一种矿井水深度除氟系统及方法

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JP5502924B2 (ja) * 2012-03-30 2014-05-28 株式会社東芝 水処理方法
JP5649749B2 (ja) * 2014-01-31 2015-01-07 株式会社東芝 水処理方法

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TWI477466B (zh) * 2011-07-08 2015-03-21 Ｍ Ｍ Ｔｅｃｈ股份有限公司 玻璃薄形化系統
JP2018143919A (ja) * 2017-03-01 2018-09-20 オルガノ株式会社 フッ素含有水の処理装置、フッ素含有水の処理方法及び膜ろ過システム
CN110510777A (zh) * 2019-09-05 2019-11-29 煤科集团杭州环保研究院有限公司 一种矿井水深度除氟系统及方法

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