WO2023026554A1 - Method and device for treating fluorine-containing water - Google Patents
Method and device for treating fluorine-containing water Download PDFInfo
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- WO2023026554A1 WO2023026554A1 PCT/JP2022/013093 JP2022013093W WO2023026554A1 WO 2023026554 A1 WO2023026554 A1 WO 2023026554A1 JP 2022013093 W JP2022013093 W JP 2022013093W WO 2023026554 A1 WO2023026554 A1 WO 2023026554A1
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- fluorine
- water
- containing water
- osmosis membrane
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 46
- 239000011737 fluorine Substances 0.000 title claims abstract description 46
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 229940043430 calcium compound Drugs 0.000 claims abstract description 12
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000010979 pH adjustment Methods 0.000 claims abstract description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 11
- 229910004261 CaF 2 Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 2
- 108010053835 Catalase Proteins 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
-
- 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
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a fluorine-containing water treatment method and apparatus, and more particularly to a reverse osmosis (RO) membrane apparatus after adding a calcium (Ca) compound to fluorine-containing water to precipitate and separate fluorine as calcium fluoride (CaF 2 ). It relates to a method and apparatus for treating fluorine-containing water treated with.
- RO reverse osmosis
- Patent Document 1 As a method for treating fluorine-containing water such as semiconductor manufacturing process wastewater, a method of adding a Ca compound to fluorine-containing water to generate CaF 2 and precipitating and separating it is widely used (Patent Document 1). As for semiconductor manufacturing wastewater containing hydrogen peroxide, hydrogen peroxide is decomposed by adding a hydrogen peroxide decomposing agent such as catalase or sulfite to raw water (Patent Document 2).
- Patent Document 1 in order to reuse the treated water of fluorine-containing water as recovered water, as shown in FIG.
- Filtration treated water obtained by generating and separating CaF 2 through a flocculation tank 3 to be treated, a sedimentation tank 4 for generating precipitates, and a filter 5 for separating the generated precipitates is further added to a softening tower (cation exchange resin tower ) 6 and a reverse osmosis (RO) membrane separator 7 for treatment.
- the backwash wastewater from the filter 5, the regeneration waste liquid from the softening tower 6, and the concentrated water from the RO membrane separator 7 are fed to the raw water tank 1 and treated together with the raw water.
- the present invention provides a method and apparatus for treating fluorine-containing water in which fluorine is removed by a calcium compound and then subjected to RO treatment, in which the clogging of the RO apparatus can be suppressed even if the number of processes is reduced.
- An object is to provide an apparatus.
- the fluorine-containing water treatment method of the present invention is a method for treating fluorine-containing water in which the fluorine-containing water is filtered by a filtration means and then passed through a reverse osmosis membrane device, in which the permeated water of the reverse osmosis membrane device is reused. Water is sent to a process, and a calcium compound is added to the concentrated water of the reverse osmosis membrane device to remove fluorine.
- the fluorine-containing water contains hydrogen peroxide, and after adding a hydrogen peroxide decomposing agent to the fluorine-containing water and adjusting the pH to 6 to 12, it is filtered by the filtering means. process.
- the filtration process includes filtration by a filter, activated carbon filtration, and filtration by an MF device.
- the fluorine-containing water treatment apparatus of the present invention comprises a pH-adjusting tank for adding a hydrogen peroxide decomposing agent and a pH-adjusting agent to the fluorine-containing water, a filter for filtering outflow water from the pH-adjusting tank, and the filter.
- an activated carbon tower through which the filtered water of the vessel is passed; an MF device through which the effluent water of the activated carbon tower is passed; a reverse osmosis membrane device through which the permeated water of the MF device is passed; and the reverse osmosis membrane device and fluorine removing means for adding a calcium compound to the concentrated water of (1) to remove fluorine.
- fluorine is removed from the concentrated water of the RO device by adding a calcium compound, and no calcium compound is added to the RO feed water.
- the RO water supply is not treated for Ca removal, the number of processes is small and the number of chemicals to be treated is also small.
- FIG. 1 is a configuration diagram of a fluorine-containing water treatment apparatus according to an embodiment
- FIG. FIG. 11 is a configuration diagram of a conventional example
- Fluorine-containing water containing fluorine and hydrogen peroxide such as semiconductor manufacturing process wastewater is introduced from the raw water pipe 10 into the pH adjustment tank 11, and a hydrogen peroxide decomposing agent such as catalase and sodium sulfite and a pH adjusting agent such as sodium hydroxide are added. is added to decompose the hydrogen peroxide, and the pH is adjusted to pH 6 to 12, especially about pH 10.
- the outflow water from the pH adjustment tank 11 is passed through the pipe 12 to the filter 13 to remove SS (suspended solids). Supporting gravel, sand, anthracite, or the like is used as the filter medium of the filter 13 .
- the filtered water is passed through a pipe 14 to an activated carbon tower 15 to decompose residual hydrogen peroxide.
- a slime inhibitor such as NaClO is added in the pipe 10, the pH adjustment tank 11, the pipe 12, or the pipe 14. Also, a heavy metal masking agent such as a chelating agent is added in line 16 or line 18 .
- Effluent water from the activated carbon tower 15 is passed through a pipe 16 to an MF (ultrafiltration) device 17 to remove fine particles.
- the MF membrane filtered water is passed through the RO device 19 through the pipe 18, and the RO membrane permeated water is taken out through the pipe 20 as treated water.
- An anti-slime agent such as NaClO is added to this treated water, and the water is sent to a process for reuse as water for a semiconductor cleaning process or the like.
- Condensed water from the RO device 19 is introduced into the reaction tank 22 through the pipe 21, and a calcium compound is added to generate CaF2 .
- the CaF 2 -containing reaction solution from the reaction tank 22 is added with a polymer flocculant in the flocculation tank 23 and subjected to flocculation treatment, and then introduced into the sedimentation tank 24 to sediment and separate the sludge. Supernatant water is sent to the discharge process.
- a calcium compound is added to the RO concentrated water for fluorine removal treatment, and no calcium compound is added to the RO water supply.
- the calcium concentration is low, and clogging of the RO membrane is suppressed without performing Ca removal treatment by adding sodium carbonate or treatment with a softener.
- the permeated water of the RO device 19 has a low calcium concentration, it is suitable for reuse as water for the semiconductor cleaning process.
- the RO water supply is pH 6-12.
- the pH of the RO concentrated water is controlled to about 10. This is because if the pH of the RO concentrated water is alkaline, slime damage can be prevented and stable RO treatment can be performed.
- the pH control may be either pH control with RO water supply or pH control with RO concentrated water.
- this fluorine-containing water treatment method and apparatus only one stage of coagulating sedimentation equipment is required to separate the coagulated sludge, so the equipment is simple, low cost, and easy to maintain.
- this fluorine-containing water treatment method and apparatus uses a small number of chemicals, and the cost of the chemicals is also low.
- the hydrogen peroxide decomposing agent is added because the raw water contains hydrogen peroxide.
- the raw water does not contain hydrogen peroxide, the addition of the hydrogen peroxide decomposing agent is unnecessary. be.
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- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Provided are a method and a device for treating fluorine-containing water, the method and device making it possible to suppress blockages in a RO device even if the number of processes is reduced. According to the present invention, fluorine-containing water is treated by using a device for treating fluorine-containing water, the device having: a pH adjustment tank 11 for adding a hydrogen peroxide decomposition agent and a pH adjustment agent to the fluorine-containing water; a filter 14 for filtering the water flowing out from the pH adjustment tank 11; an activated carbon tower 15 into which the filtered water from the filter 14 flows; an MF device 17 into which the water flowing out from the activated carbon tower 15 flows; a reverse-osmosis membrane device 19 into which the water that has passed through the MF device flows; and a reaction tank 22, a flocculation tank 23, and a sludge tank 24 for adding a calcium compound to the water concentrated in the reverse-osmosis membrane device 19 to carry out a fluorine removal treatment.
Description
本発明はフッ素含有水の処理方法及び装置に係り、特にフッ素含有水にカルシウム（Ｃａ）化合物を添加してフッ素をフッ化カルシウム（ＣａＦ２）として沈殿分離した後、逆浸透（ＲＯ）膜装置で処理するフッ素含有水の処理方法及び装置に関する。
The present invention relates to a fluorine-containing water treatment method and apparatus, and more particularly to a reverse osmosis (RO) membrane apparatus after adding a calcium (Ca) compound to fluorine-containing water to precipitate and separate fluorine as calcium fluoride (CaF 2 ). It relates to a method and apparatus for treating fluorine-containing water treated with.
半導体製造工程排水等のフッ素含有水の処理方法として、フッ素含有水にＣａ化合物を添加してＣａＦ２を生成させ、これを沈殿分離する方法が広く行われている（特許文献１）。また、過酸化水素を含有する半導体製造排水については、原水にカタラーゼ、亜硫酸塩などの過酸化水素分解剤を添加して過酸化水素を分解することが行われている（特許文献２）。
As a method for treating fluorine-containing water such as semiconductor manufacturing process wastewater, a method of adding a Ca compound to fluorine-containing water to generate CaF 2 and precipitating and separating it is widely used (Patent Document 1). As for semiconductor manufacturing wastewater containing hydrogen peroxide, hydrogen peroxide is decomposed by adding a hydrogen peroxide decomposing agent such as catalase or sulfite to raw water (Patent Document 2).
特許文献１には、フッ素含有水の処理水を回収水として再利用するために、図２に示す通り、原水槽１、原水にＣａ化合物を添加する中和槽２、中和処理液を凝集処理する凝集槽３、沈殿を生成させる沈殿槽４及び生成した沈殿を分離する濾過器５を経てＣａＦ２の生成、分離を行って得られた濾過処理水を、更に軟化塔（カチオン交換樹脂塔）６及び逆浸透（ＲＯ）膜分離装置７に通水して処理することが記載されている。濾過器５の逆洗排水、軟化塔６の再生廃液、ＲＯ膜分離装置７の濃縮水は原水槽１に送給され、原水と共に処理される。
In Patent Document 1, in order to reuse the treated water of fluorine-containing water as recovered water, as shown in FIG. Filtration treated water obtained by generating and separating CaF 2 through a flocculation tank 3 to be treated, a sedimentation tank 4 for generating precipitates, and a filter 5 for separating the generated precipitates, is further added to a softening tower (cation exchange resin tower ) 6 and a reverse osmosis (RO) membrane separator 7 for treatment. The backwash wastewater from the filter 5, the regeneration waste liquid from the softening tower 6, and the concentrated water from the RO membrane separator 7 are fed to the raw water tank 1 and treated together with the raw water.
なお、半導体製造排水からＣａＦ２の生成、分離を行って得られた上記濾過処理水中には、Ｃａ２＋やＳＯ２－等スケール原因物質が残留するため、これをそのままＲＯ膜分離装置７に通水して脱塩処理すると、これらのスケール原因物質がＲＯ膜分離装置７内で濃縮されてスケールが析出し、ＲＯ膜を閉塞させる。そこで、ＲＯ膜分離装置７の前段に軟化塔６を設け、カチオン交換樹脂でＣａ２＋を除去する。
また、図示は省略するが、ＣａＦ２を沈殿分離した後、炭酸ナトリウムを添加し、Ｃａ２＋をＣａＣＯ３として沈殿分離した後、濾過処理することがある。また、この濾過処理水に次亜塩素酸ナトリウムを添加してＲＯ膜のスライム障害を防止することも行われている。 In addition, since scale-causing substances such as Ca 2+ and SO 2− remain in the filtered water obtained by generating and separating CaF 2 from semiconductor manufacturing waste water, it is passed through the RO membrane separation device 7 as it is. When water is used for desalination, these scale-causing substances are concentrated in the RO membrane separation device 7, depositing scale, and clogging the RO membrane. Therefore, asoftening tower 6 is provided upstream of the RO membrane separation device 7, and Ca 2+ is removed with a cation exchange resin.
Also, although illustration is omitted, after precipitating and separating CaF 2 , sodium carbonate may be added to precipitate and separate Ca 2+ as CaCO 3 , followed by filtration. In addition, sodium hypochlorite is added to this filtered water to prevent slime damage to the RO membrane.
また、図示は省略するが、ＣａＦ２を沈殿分離した後、炭酸ナトリウムを添加し、Ｃａ２＋をＣａＣＯ３として沈殿分離した後、濾過処理することがある。また、この濾過処理水に次亜塩素酸ナトリウムを添加してＲＯ膜のスライム障害を防止することも行われている。 In addition, since scale-causing substances such as Ca 2+ and SO 2− remain in the filtered water obtained by generating and separating CaF 2 from semiconductor manufacturing waste water, it is passed through the RO membrane separation device 7 as it is. When water is used for desalination, these scale-causing substances are concentrated in the RO membrane separation device 7, depositing scale, and clogging the RO membrane. Therefore, a
Also, although illustration is omitted, after precipitating and separating CaF 2 , sodium carbonate may be added to precipitate and separate Ca 2+ as CaCO 3 , followed by filtration. In addition, sodium hypochlorite is added to this filtered water to prevent slime damage to the RO membrane.
特許文献１のように、フッ素含有水にカルシウム化合物を添加してＣａＦ２を分離した後、ＲＯ処理する方法では、ＲＯ処理前にＣａ２＋の除去処理を行うようにしており、プロセス数が多いと共に、使用する薬品の種類も多い。
As in Patent Document 1, in the method in which a calcium compound is added to fluorine-containing water to separate CaF 2 and then RO treatment is performed, Ca 2+ removal treatment is performed before RO treatment, and the number of processes is large. At the same time, there are many types of chemicals used.
本発明は、カルシウム化合物によりフッ素を除去した後、ＲＯ処理するフッ素含有水の処理方法及び装置において、プロセス数を少なくしてもＲＯ装置の閉塞を抑制することができるフッ素含有水の処理方法及び装置を提供することを課題とする。
The present invention provides a method and apparatus for treating fluorine-containing water in which fluorine is removed by a calcium compound and then subjected to RO treatment, in which the clogging of the RO apparatus can be suppressed even if the number of processes is reduced. An object is to provide an apparatus.
本発明のフッ素含有水の処理方法は、フッ素含有水を濾過手段で濾過処理した後、逆浸透膜装置に通水するフッ素含有水の処理方法において、該逆浸透膜装置の透過水を再利用工程に送水し、該逆浸透膜装置の濃縮水にカルシウム化合物を添加してフッ素除去処理することを特徴とする。
The fluorine-containing water treatment method of the present invention is a method for treating fluorine-containing water in which the fluorine-containing water is filtered by a filtration means and then passed through a reverse osmosis membrane device, in which the permeated water of the reverse osmosis membrane device is reused. Water is sent to a process, and a calcium compound is added to the concentrated water of the reverse osmosis membrane device to remove fluorine.
本発明の一態様では、前記フッ素含有水は過酸化水素を含有しており、該フッ素含有水に過酸化水素分解剤を添加すると共にｐＨを６～１２に調整した後、前記濾過手段で濾過処理する。
In one aspect of the present invention, the fluorine-containing water contains hydrogen peroxide, and after adding a hydrogen peroxide decomposing agent to the fluorine-containing water and adjusting the pH to 6 to 12, it is filtered by the filtering means. process.
本発明の一態様では、前記濾過処理は、濾過器による濾過と、活性炭濾過と、ＭＦ装置による濾過とである。
In one aspect of the present invention, the filtration process includes filtration by a filter, activated carbon filtration, and filtration by an MF device.
本発明のフッ素含有水の処理装置は、フッ素含有水に対し過酸化水素分解剤及びｐＨ調整剤を添加するｐＨ調整槽と、該ｐＨ調整槽からの流出水を濾過する濾過器と、該濾過器の濾過水が通水される活性炭塔と、該活性炭塔の流出水が通水されるＭＦ装置と、該ＭＦ装置の透過水が通水される逆浸透膜装置と、該逆浸透膜装置の濃縮水にカルシウム化合物を添加してフッ素除去処理するフッ素除去手段とを有する。
The fluorine-containing water treatment apparatus of the present invention comprises a pH-adjusting tank for adding a hydrogen peroxide decomposing agent and a pH-adjusting agent to the fluorine-containing water, a filter for filtering outflow water from the pH-adjusting tank, and the filter. an activated carbon tower through which the filtered water of the vessel is passed; an MF device through which the effluent water of the activated carbon tower is passed; a reverse osmosis membrane device through which the permeated water of the MF device is passed; and the reverse osmosis membrane device and fluorine removing means for adding a calcium compound to the concentrated water of (1) to remove fluorine.
本発明では、カルシウム化合物添加によるフッ素除去をＲＯ装置の濃縮水に対して行い、ＲＯ給水にはカルシウム化合物を添加しないので、ＲＯ給水中のＣａ濃度が低く、ＲＯ膜の閉塞が抑制される。また、ＲＯ給水をＣａ除去処理しないので、プロセス数が少ないと共に、処理薬品数も少ない。
In the present invention, fluorine is removed from the concentrated water of the RO device by adding a calcium compound, and no calcium compound is added to the RO feed water. In addition, since the RO water supply is not treated for Ca removal, the number of processes is small and the number of chemicals to be treated is also small.
以下、図１を参照して実施の形態について説明する。
An embodiment will be described below with reference to FIG.
半導体製造工程排水等のフッ素及び過酸化水素を含んだフッ素含有水が原水配管１０からｐＨ調整槽１１に導入され、カタラーゼ、亜硫酸ナトリウム等の過酸化水素分解剤と水酸化ナトリウム等のｐＨ調整剤とが添加され、過酸化水素が分解されると共、ｐＨ６～１２特にｐＨ１０程度にｐＨ調整される。
Fluorine-containing water containing fluorine and hydrogen peroxide such as semiconductor manufacturing process wastewater is introduced from the raw water pipe 10 into the pH adjustment tank 11, and a hydrogen peroxide decomposing agent such as catalase and sodium sulfite and a pH adjusting agent such as sodium hydroxide are added. is added to decompose the hydrogen peroxide, and the pH is adjusted to pH 6 to 12, especially about pH 10.
ｐＨ調整槽１１の流出水は、配管１２から濾過器１３に通水され、ＳＳ（懸濁固形物）が除去される。濾過器１３の濾材としては、支持砂利、砂、アンスラサイトなどが用いられる。濾過処理水は、配管１４を介して活性炭塔１５に通水され、残留する過酸化水素が分解される。
The outflow water from the pH adjustment tank 11 is passed through the pipe 12 to the filter 13 to remove SS (suspended solids). Supporting gravel, sand, anthracite, or the like is used as the filter medium of the filter 13 . The filtered water is passed through a pipe 14 to an activated carbon tower 15 to decompose residual hydrogen peroxide.
なお、配管１０、ｐＨ調整槽１１、配管１２、又は配管１４でＮａＣｌＯなどのスライム防止剤が添加される。また、配管１６又は配管１８でキレート剤などの重金属マスキング剤が添加される。
A slime inhibitor such as NaClO is added in the pipe 10, the pH adjustment tank 11, the pipe 12, or the pipe 14. Also, a heavy metal masking agent such as a chelating agent is added in line 16 or line 18 .
活性炭塔１５の流出水は、配管１６を介してＭＦ（限外濾過）装置１７に通水され、微細粒子が除去される。ＭＦ膜濾過水は、配管１８を介してＲＯ装置１９に通水され、ＲＯ膜透過水が配管２０を介して処理水として取り出される。この処理水にＮａＣｌＯなどのスライム防止剤が添加され、半導体洗浄工程用水等として再利用する工程に送水される。
Effluent water from the activated carbon tower 15 is passed through a pipe 16 to an MF (ultrafiltration) device 17 to remove fine particles. The MF membrane filtered water is passed through the RO device 19 through the pipe 18, and the RO membrane permeated water is taken out through the pipe 20 as treated water. An anti-slime agent such as NaClO is added to this treated water, and the water is sent to a process for reuse as water for a semiconductor cleaning process or the like.
ＲＯ装置１９の濃縮水は、配管２１を介して反応槽２２に導入され、カルシウム化合物が添加され、ＣａＦ２が生成する。反応槽２２からのＣａＦ２含有反応液は、凝集槽２３にて高分子凝集剤が添加され、凝集処理された後、沈殿槽２４に導入され、汚泥が沈殿分離される。上澄水は放流工程に送水される。
Condensed water from the RO device 19 is introduced into the reaction tank 22 through the pipe 21, and a calcium compound is added to generate CaF2 . The CaF 2 -containing reaction solution from the reaction tank 22 is added with a polymer flocculant in the flocculation tank 23 and subjected to flocculation treatment, and then introduced into the sedimentation tank 24 to sediment and separate the sludge. Supernatant water is sent to the discharge process.
このフッ素含有水の処理方法及び装置によると、ＲＯ濃縮水にカルシウム化合物を添加してフッ素除去処理するようにしており、ＲＯ給水にはカルシウム化合物を添加しないので、ＲＯ装置１９への給水中のカルシウム濃度が低く、炭酸ナトリウム添加によるＣａ除去処理や、軟化器による処理を行うことなく、ＲＯ膜の閉塞が抑制される。また、ＲＯ装置１９の透過水は、カルシウム濃度が低いので、半導体洗浄工程用水等に再利用するのに好適である。
According to this fluorine-containing water treatment method and apparatus, a calcium compound is added to the RO concentrated water for fluorine removal treatment, and no calcium compound is added to the RO water supply. The calcium concentration is low, and clogging of the RO membrane is suppressed without performing Ca removal treatment by adding sodium carbonate or treatment with a softener. In addition, since the permeated water of the RO device 19 has a low calcium concentration, it is suitable for reuse as water for the semiconductor cleaning process.
この実施の形態では、ＲＯ給水はｐＨ６～１２とする。特にＲＯ給水が高バイオポテンシャルの場合には、ＲＯ濃縮水ｐＨを１０程度となるように制御する。これは、ＲＯ濃縮水のｐＨがアルカリ性であれば、スライム障害を防止し安定したＲＯ処理を行うことができるためである。なお、ｐＨ制御はＲＯ給水でのｐＨ制御でも、ＲＯ濃縮水でのｐＨ制御でも、どちらでも良い。
In this embodiment, the RO water supply is pH 6-12. Especially when the RO feed water has a high biopotential, the pH of the RO concentrated water is controlled to about 10. This is because if the pH of the RO concentrated water is alkaline, slime damage can be prevented and stable RO treatment can be performed. It should be noted that the pH control may be either pH control with RO water supply or pH control with RO concentrated water.
このフッ素含有水の処理方法及び装置では、凝集汚泥を分離するための凝集沈殿設備が１段で足りるため、設備が簡素となり、低コストであると共に、保守管理が容易となる。また、このフッ素含有水の処理方法及び装置では、使用する薬剤の種類が少なく、薬剤コストも低い。
In this fluorine-containing water treatment method and apparatus, only one stage of coagulating sedimentation equipment is required to separate the coagulated sludge, so the equipment is simple, low cost, and easy to maintain. In addition, this fluorine-containing water treatment method and apparatus uses a small number of chemicals, and the cost of the chemicals is also low.
上記実施の形態では、原水が過酸化水素を含んでいるため過酸化水素分解剤を添加しているが、原水が過酸化水素を含んでいない場合には過酸化水素分解剤の添加は不要である。
本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
本出願は、２０２１年８月２３日付で出願された日本特許出願２０２１－１３５６９６に基づいており、その全体が引用により援用される。 In the above embodiment, the hydrogen peroxide decomposing agent is added because the raw water contains hydrogen peroxide. However, if the raw water does not contain hydrogen peroxide, the addition of the hydrogen peroxide decomposing agent is unnecessary. be.
Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2021-135696 filed on August 23, 2021, which is incorporated by reference in its entirety.
本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
本出願は、２０２１年８月２３日付で出願された日本特許出願２０２１－１３５６９６に基づいており、その全体が引用により援用される。 In the above embodiment, the hydrogen peroxide decomposing agent is added because the raw water contains hydrogen peroxide. However, if the raw water does not contain hydrogen peroxide, the addition of the hydrogen peroxide decomposing agent is unnecessary. be.
Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2021-135696 filed on August 23, 2021, which is incorporated by reference in its entirety.
１１ ｐＨ調整槽
１３ 濾過器
１４ 活性炭塔
１７ ＭＦ装置
１９ ＲＯ装置
11pH adjustment tank 13 filter 14 activated carbon tower 17 MF device 19 RO device
１３ 濾過器
１４ 活性炭塔
１７ ＭＦ装置
１９ ＲＯ装置
11
Claims (4)
- フッ素含有水を濾過手段で濾過処理した後、逆浸透膜装置に通水するフッ素含有水の処理方法において、
該逆浸透膜装置の透過水を再利用工程に送水し、
該逆浸透膜装置の濃縮水にカルシウム化合物を添加してフッ素除去処理する
ことを特徴とするフッ素含有水の処理方法。 In the method for treating fluorine-containing water in which the fluorine-containing water is filtered by a filtering means and then passed through a reverse osmosis membrane device,
sending the permeated water of the reverse osmosis membrane device to a recycling step;
A method for treating fluorine-containing water, which comprises adding a calcium compound to the concentrated water of the reverse osmosis membrane apparatus to remove fluorine. - 前記フッ素含有水は過酸化水素を含有しており、
該フッ素含有水に過酸化水素分解剤を添加すると共にｐＨを６～１２に調整した後、前記濾過手段で濾過処理することを特徴とする請求項１のフッ素含有水の処理方法。 The fluorine-containing water contains hydrogen peroxide,
2. The method for treating fluorine-containing water according to claim 1, wherein a hydrogen peroxide decomposing agent is added to the fluorine-containing water and the pH thereof is adjusted to 6 to 12, and then filtered by the filtering means. - 前記濾過処理は、濾過器による濾過と、活性炭濾過と、ＭＦ装置による濾過とである請求項１又は２のフッ素含有水の処理方法。 The method for treating fluorine-containing water according to claim 1 or 2, wherein the filtration treatment is filtration with a filter, filtration with activated carbon, and filtration with an MF device.
- フッ素含有水に対し過酸化水素分解剤及びｐＨ調整剤を添加するｐＨ調整槽と、
該ｐＨ調整槽からの流出水を濾過する濾過器と、
該濾過器の濾過水が通水される活性炭塔と、
該活性炭塔の流出水が通水されるＭＦ装置と、
該ＭＦ装置の透過水が通水される逆浸透膜装置と、
該逆浸透膜装置の濃縮水にカルシウム化合物を添加してフッ素除去処理するフッ素除去手段と
を有するフッ素含有水の処理装置。
a pH adjusting tank for adding a hydrogen peroxide decomposing agent and a pH adjusting agent to fluorine-containing water;
a filter for filtering effluent from the pH adjustment tank;
an activated carbon tower through which filtered water from the filter is passed;
an MF device through which the effluent of the activated carbon tower is passed;
a reverse osmosis membrane device through which the permeated water of the MF device is passed;
An apparatus for treating fluorine-containing water, comprising fluorine removing means for adding a calcium compound to the concentrated water of the reverse osmosis membrane apparatus to remove fluorine.
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| JP2020157273A (en) * | 2019-03-28 | 2020-10-01 | 栗田工業株式会社 | Water treatment apparatus and water treatment method |
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2022
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| JPH11165179A (en) * | 1997-12-03 | 1999-06-22 | Kurita Water Ind Ltd | Method for treating fluorine-containing water |
| JP2003103260A (en) * | 2001-09-28 | 2003-04-08 | Nomura Micro Sci Co Ltd | Method for processing wastewater containing fluoride |
| JP2005230731A (en) * | 2004-02-20 | 2005-09-02 | Kurita Water Ind Ltd | Method and apparatus for water treatment |
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