JPH0592187A - Treatment of fluorine-containing water - Google Patents
Treatment of fluorine-containing waterInfo
- Publication number
- JPH0592187A JPH0592187A JP3253500A JP25350091A JPH0592187A JP H0592187 A JPH0592187 A JP H0592187A JP 3253500 A JP3253500 A JP 3253500A JP 25350091 A JP25350091 A JP 25350091A JP H0592187 A JPH0592187 A JP H0592187A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing water
- water
- treatment
- concn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフッ素含有水の処理方法
に係り、特に、低濃度フッ素含有水及び高濃度フッ素含
有水が排出される系において、各々のフッ素含有水を効
率的に処理する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating fluorine-containing water, and particularly to efficiently treat each fluorine-containing water in a system in which low-concentration fluorine-containing water and high-concentration fluorine-containing water are discharged. Regarding the method.
【０００２】[0002]
【従来の技術】半導体製造分野やその関連分野、各種金
属材料、単結晶材料、光学系材料等の表面処理分野で
は、多量のエッチング剤が使われる。このエッチング剤
としては、主として、フッ化水素或いはフッ化水素及び
フッ化アンモニウムを主成分とするエッチング剤が使用
されている。2. Description of the Related Art A large amount of etching agents are used in the field of semiconductor manufacturing and related fields, and in the field of surface treatment of various metal materials, single crystal materials, optical materials and the like. As the etching agent, hydrogen fluoride or an etching agent containing hydrogen fluoride and ammonium fluoride as main components is mainly used.
【０００３】フッ化水素を主成分とするエッチング剤
は、フッ素をＨＦとして０．９％程度含むエッチング剤
であって、大量に使用される。一方、フッ化水素及びフ
ッ化アンモニウムを含むエッチング剤（バッファードフ
ッ酸）は、その使用量は少ないものの、フッ素をＨＦと
して７％程度含有するものであり、廃水系統へ移行した
際問題となる。即ち、廃水系統へは、これらのエッチン
グ剤がそのまま流出し、高濃度フッ素含有廃液となる。An etching agent containing hydrogen fluoride as a main component is an etching agent containing about 0.9% of fluorine as HF, and is used in a large amount. On the other hand, although the etching agent containing hydrogen fluoride and ammonium fluoride (buffered hydrofluoric acid) is used in a small amount, it contains about 7% of fluorine as HF, which becomes a problem when it is transferred to a wastewater system. .. That is, these etching agents flow out to the wastewater system as they are, and become a high concentration fluorine-containing waste liquid.
【０００４】一方、エッチング途中や終了時にはこれら
のエッチング剤で処理された材料を大量の洗浄水で洗浄
するため、その洗浄工程からは、大量の低濃度フッ素含
有廃液が排出される。On the other hand, during or after the etching, since the materials treated with these etching agents are washed with a large amount of washing water, a large amount of low concentration fluorine-containing waste liquid is discharged from the washing step.
【０００５】従来、これらの高濃度フッ素含有廃液及び
低濃度フッ素含有廃液は、混合されて一括処理されてい
た。このフッ素含有廃水の処理には、水酸化カルシウム
（Ｃａ（ＯＨ）2 ）等のカルシウム塩を添加してフッ化
カルシウム（ＣａＦ2 ）として沈殿除去する方法が一般
に用いられている。Conventionally, these high-concentration fluorine-containing waste liquids and low-concentration fluorine-containing waste liquids have been mixed and collectively processed. For the treatment of this fluorine-containing wastewater, a method of adding a calcium salt such as calcium hydroxide (Ca (OH) 2 ) and precipitating and removing it as calcium fluoride (CaF 2 ) is generally used.
【０００６】[0006]
【発明が解決しようとする課題】上記従来の方法によ
り、フッ素を排水基準値以下に処理するためには、大過
剰のカルシウム塩の添加が必要である。しかも、このカ
ルシウム塩を添加するだけでは、短時間で効率良く処理
することは極めて困難であった。According to the above-mentioned conventional method, it is necessary to add a large excess of calcium salt in order to treat fluorine at a level not higher than the standard value of waste water. Moreover, it has been extremely difficult to treat efficiently in a short time only by adding this calcium salt.
【０００７】本発明は上記従来の問題点を解決し、低濃
度フッ素含有廃水及び高濃度フッ素含有廃水が排出され
る系において、これらフッ素含有廃水を短時間で効率的
に処理し、高純度処理水を得る方法を提供することを目
的とする。The present invention solves the above-mentioned conventional problems, and in a system in which low-concentration fluorine-containing wastewater and high-concentration fluorine-containing wastewater are discharged, these fluorine-containing wastewater are efficiently treated in a short time and highly purified The purpose is to provide a method of obtaining water.
【０００８】[0008]
【課題を解決するための手段】請求項１のフッ素含有水
の処理方法は、フッ素含有水をカルシウム化合物とフッ
素吸着樹脂とを用いて処理するフッ素含有水の処理方法
において、フッ素含有水を低濃度フッ素含有水と高濃度
フッ素含有水に分別する工程、低濃度フッ素含有水をフ
ッ素吸着樹脂と接触させる工程、フッ素吸着樹脂を再生
処理する工程、及び高濃度フッ素含有水に前記フッ素吸
着樹脂の再生廃液を添加した後、カルシウム化合物を加
えて凝集処理し、次いで固液分離する工程、を備えるこ
とを特徴とする。The method for treating fluorine-containing water according to claim 1 is a method for treating fluorine-containing water, which comprises treating a fluorine-containing water with a calcium compound and a fluorine-adsorbing resin. The step of separating the high concentration fluorine containing water and the high concentration fluorine containing water, the step of contacting the low concentration fluorine containing water with the fluorine adsorption resin, the step of regenerating the fluorine adsorption resin, and the high concentration fluorine containing water of the fluorine adsorption resin After the addition of the regenerated waste liquid, a step of adding a calcium compound for coagulation treatment, and then performing solid-liquid separation is provided.
【０００９】請求項２のフッ素含有水の処理方法は、請
求項１の方法において、固液分離して得られた分離水を
フッ素吸着樹脂と接触させることを特徴とする。The method for treating fluorine-containing water according to a second aspect is characterized in that, in the method according to the first aspect, the separated water obtained by solid-liquid separation is brought into contact with a fluorine-adsorbing resin.
【００１０】以下に図面を参照して本発明を詳細に説明
する。The present invention will be described in detail below with reference to the drawings.
【００１１】図１は本発明のフッ素含有水の処理方法の
一実施方法を示す系統図である。FIG. 1 is a system diagram showing a method for carrying out the method for treating fluorine-containing water according to the present invention.
【００１２】図中、１は吸着塔、２は第１の反応槽、３
は第１の沈殿槽、４は第２の反応槽、５は第２の沈殿槽
である。１１は低濃度フッ素含有水を吸着塔１に導入す
る配管、１２は高濃度フッ素含有水を第１の反応槽２に
導入する配管、１３は第１の反応槽２内の反応液を第１
の沈殿槽３に送給する配管、１４は第１の沈殿槽３の分
離水を第２の反応槽４に送給する配管、１５は第２の反
応槽４内の反応液を第２の沈殿槽５に送給する配管、１
６は第２の沈殿槽５の分離水を吸着塔１に送給する配管
である。１７は吸着塔１に再生剤を送給する配管であ
り、１８は再生廃液を第１の反応槽２に送給する配管で
ある。１９は第１の沈殿槽３の汚泥の抜き出し配管であ
り、汚泥処理系へ排出する配管１９Ａと、第１の反応槽
２に汚泥を返送する配管１９Ｂとに分岐している。２０
は第２の沈殿槽５の汚泥の抜き出し配管であり、汚泥処
理系へ排出する配管２０Ａと、第２の反応槽４に汚泥を
返送する配管２０Ｂとに分岐している。２１、２２はそ
れぞれ第１の反応槽２及び第２の反応槽４にカルシウム
化合物を添加する配管である。また、２３は処理水の排
出管である。In the figure, 1 is an adsorption tower, 2 is a first reaction tank, 3
Is a first precipitation tank, 4 is a second reaction tank, and 5 is a second precipitation tank. Reference numeral 11 is a pipe for introducing low-concentration fluorine-containing water into the adsorption tower 1, 12 is a pipe for introducing high-concentration fluorine-containing water into the first reaction tank 2, and 13 is a first reaction liquid in the first reaction tank 2.
Of the first precipitation tank 3 to the second reaction tank 4, and 15 to the second reaction tank 4 of the reaction liquid in the second reaction tank 4. Piping for feeding to the settling tank 5, 1
Reference numeral 6 is a pipe for feeding the separated water of the second settling tank 5 to the adsorption tower 1. Reference numeral 17 is a pipe for feeding the regenerant to the adsorption tower 1, and 18 is a pipe for feeding the regeneration waste liquid to the first reaction tank 2. Reference numeral 19 denotes a pipe for extracting sludge from the first settling tank 3, which is branched into a pipe 19A for discharging the sludge to the sludge treatment system and a pipe 19B for returning the sludge to the first reaction tank 2. 20
Is a pipe for extracting sludge from the second settling tank 5, and is branched into a pipe 20A for discharging the sludge to the sludge treatment system and a pipe 20B for returning the sludge to the second reaction tank 4. Reference numerals 21 and 22 are pipes for adding a calcium compound to the first reaction tank 2 and the second reaction tank 4, respectively. Reference numeral 23 is a discharge pipe for treated water.
【００１３】本発明においては、高濃度フッ素含有水と
低濃度フッ素含有水とを混合することなく、分別処理す
る。In the present invention, the separation treatment is carried out without mixing the high concentration fluorine-containing water and the low concentration fluorine-containing water.
【００１４】ここで、高濃度フッ素含有水及び低濃度フ
ッ素含有水としては、例えば、前述したエッチング剤を
用いる処理工程廃水とその洗浄廃水が挙げられる。な
お、高濃度フッ素含有水の目安は、５０ｍｇ−ＨＦ／li
t.以上の廃水、低濃度フッ素含有水の目安は、５０ｍｇ
−ＨＦ／lit.以下の廃水である。Here, examples of the high-concentration fluorine-containing water and the low-concentration fluorine-containing water include treatment process wastewater using the above-mentioned etching agent and cleaning wastewater thereof. In addition, the standard of high concentration fluorine-containing water is 50mg-HF / li.
50 mg or more of waste water over t. and water containing low concentration fluorine
-Wastewater below HF / lit.
【００１５】図示の実施例においては、低濃度フッ素含
有廃水は、配管１１を経て吸着塔１に送給し、フッ素吸
着樹脂と接触させて吸着処理する。これにより、低濃度
フッ素含有廃水は、もとよりそのフッ素含有量が少ない
ことから、容易に放流水基準値（１５ｍｇ／lit.）以下
に処理され、処理水は排出管２３より排出される。In the illustrated embodiment, the low-concentration fluorine-containing wastewater is sent to the adsorption tower 1 through the pipe 11 and brought into contact with the fluorine-adsorption resin for adsorption treatment. As a result, since the low-concentration fluorine-containing wastewater has a low fluorine content as a matter of course, it is easily treated to the discharge water standard value (15 mg / lit.) Or less, and the treated water is discharged from the discharge pipe 23.
【００１６】ここで、フッ素吸着樹脂としては、例え
ば、セリウム、ハフニウム、チタン、ジルコニウム、
鉄、アルミニウム、ランタニド等のフッ素イオンと錯化
合物を形成する金属イオンを吸着した樹脂、活性炭、活
性アルミナ、含水酸化チタン、ゼオライト、マグネシア
系吸着剤などが挙げられる。また、吸着処理条件は特に
限定されないが、例えば、ＳＶ０．５〜３０ｈｒ-1程度
で処理される。Here, as the fluorine-adsorbing resin, for example, cerium, hafnium, titanium, zirconium,
Examples thereof include resins adsorbing metal ions forming complex compounds with fluorine ions such as iron, aluminum and lanthanide, activated carbon, activated alumina, hydrous titanium oxide, zeolite, and magnesia adsorbents. Further, the adsorption treatment condition is not particularly limited, but for example, the treatment is carried out at SV of about 0.5 to 30 hr −1 .
【００１７】吸着塔１は、必要に応じて、吸着処理を停
止すると共に配管１７より再生剤を供給して再生処理す
る。再生剤としては、水酸化カリウム、塩酸、炭酸ナト
リウム等の水溶液が用いられる。この再生処理により得
られる、フッ素成分を多量に含有する濃厚再生廃液は、
配管１８を経て後述の第１の反応槽２に送給され高濃度
フッ素含有水と共に処理される。In the adsorption tower 1, if necessary, the adsorption process is stopped and a regenerant is supplied from the pipe 17 to perform the regeneration process. An aqueous solution of potassium hydroxide, hydrochloric acid, sodium carbonate or the like is used as the regenerant. The concentrated recycling waste liquid containing a large amount of fluorine component obtained by this recycling treatment is
It is fed to a first reaction tank 2 to be described later through a pipe 18 and treated together with high-concentration fluorine-containing water.
【００１８】一方、高濃度フッ素含有水は、配管１２よ
り第１の反応槽２に送給され、配管１８からの再生廃液
と共に処理される。この第１の反応槽では、ｐＨをアル
カリ側に調整し、配管２１より被処理液中のフッ素
（Ｆ）量に対して１〜２倍当量程度のカルシウム化合物
を添加すると共に、配管１９Ｂより次工程の第１の沈殿
槽３で得られた汚泥の一部を添加して、被処理液中のＦ
をＣａＦ2 として凝集させる。On the other hand, the high-concentration fluorine-containing water is fed to the first reaction tank 2 through the pipe 12 and treated together with the regenerated waste liquid from the pipe 18. In this first reaction tank, the pH is adjusted to the alkaline side, and a calcium compound is added from the pipe 21 in an amount of 1 to 2 times the equivalent of the amount of fluorine (F) in the liquid to be treated. A part of the sludge obtained in the first settling tank 3 of the process is added, and F in the liquid to be treated is added.
Are aggregated as CaF 2 .
【００１９】ここで、第１の沈殿槽３からの汚泥の循環
は必ずしも必要とされないが、汚泥の循環により、凝集
性が向上し、固液分離時間が大幅に短縮されるため、極
めて有利である。Here, the circulation of the sludge from the first settling tank 3 is not always required, but the circulation of the sludge improves the cohesiveness and significantly reduces the solid-liquid separation time, which is extremely advantageous. is there.
【００２０】カルシウム化合物としては、酸化カルシウ
ム（ＣａＯ）、水酸化カルシウム（Ｃａ（ＯＨ）2 ）等
の塩基性カルシウム化合物の他、塩化カルシウム（Ｃａ
Ｃｌ2 ）を用いることができる。ＣａＣｌ2を用いる場
合には、必要に応じて、適当なアルカリ剤を併用してｐ
Ｈ調整を行なう。Examples of the calcium compound include basic calcium compounds such as calcium oxide (CaO) and calcium hydroxide (Ca (OH) 2 ) as well as calcium chloride (Ca).
Cl 2 ) can be used. When CaCl 2 is used, a suitable alkaline agent may be used in combination if necessary.
Adjust H.
【００２１】第１の反応槽２における反応条件には特に
制限はないが、通常の場合、滞留時間１０分〜２時間程
度で、急速撹拌下処理される。The reaction conditions in the first reaction vessel 2 are not particularly limited, but in the usual case, the treatment is carried out under rapid stirring with a residence time of about 10 minutes to 2 hours.
【００２２】第１の反応槽２の反応液（懸濁液）は、次
いで配管１３より第１の沈殿槽３に送給されて固液分離
され、分離された上澄水は配管１４を経て第２の反応槽
４に送給される。一方、汚泥は配管１９より抜き出さ
れ、一部は配管１９Ｂより第１の反応槽２に返送され、
残部は配管１９Ａより排出されて、常法に従ってＣａＦ
2 の回収処理等の処理に付される。ここで得られる汚泥
は、高濃度フッ素含有水の凝集処理により得られたもの
であるため、ＣａＦ2 含有率が高く、容易にＣａＦ2 を
回収してフッ化水素酸製造用原料等として再使用するこ
とができる。The reaction liquid (suspension) in the first reaction tank 2 is then fed from the pipe 13 to the first settling tank 3 for solid-liquid separation, and the separated supernatant water is passed through the pipe 14 to the first 2 is fed to the reaction tank 4. On the other hand, the sludge is extracted from the pipe 19 and part of it is returned to the first reaction tank 2 via the pipe 19B.
The rest is discharged from the pipe 19A, and CaF
It is attached to the processing such as the collection processing of 2 . Since the sludge obtained here is obtained by coagulation treatment of water containing high-concentration fluorine, the content of CaF 2 is high, and CaF 2 can be easily recovered and reused as a raw material for hydrofluoric acid production. can do.
【００２３】配管１４を経て第２の反応槽４に導入され
た液は、配管２２よりカルシウム化合物が添加されると
共に、配管２０Ｂより次工程の第２の沈殿槽５で得られ
た汚泥の一部が添加されて、液中のＦがＣａＦ2 として
凝集される。The liquid introduced into the second reaction tank 4 through the pipe 14 is added with a calcium compound through the pipe 22, and at the same time, one of the sludge obtained in the second precipitation tank 5 in the next step through the pipe 20B. Part is added, and F in the liquid is aggregated as CaF 2 .
【００２４】この第２の反応槽４で使用されるカルシウ
ム化合物、反応条件等は、第１の反応槽２におけるもの
と同様である。The calcium compound used in the second reaction tank 4 and the reaction conditions are the same as those in the first reaction tank 2.
【００２５】第２の反応槽４の反応液（懸濁液）は、次
いで配管１５より第２の沈殿槽５に送給されて固液分離
される。そして、分離された上澄水は配管１６を経て吸
着塔１に送給されて吸着処理され、処理水は排出管２３
より排出される。一方、汚泥は配管２０より抜き出さ
れ、一部は配管２０Ｂより第２の反応槽４に返送され、
残部は配管２０Ａより排出されて、配管１９Ａからの汚
泥と同様に常法に従って処理される。The reaction liquid (suspension) in the second reaction tank 4 is then fed to the second precipitation tank 5 through the pipe 15 and solid-liquid separated. Then, the separated supernatant water is sent to the adsorption tower 1 through the pipe 16 for adsorption treatment, and the treated water is discharged into the discharge pipe 23.
More discharged. On the other hand, the sludge is extracted from the pipe 20 and part of it is returned to the second reaction tank 4 via the pipe 20B.
The rest is discharged from the pipe 20A and treated in the same manner as the sludge from the pipe 19A.
【００２６】排出管２３より排出される、低濃度フッ素
含有水及び／又は第２の沈殿槽５の上澄水を吸着塔１で
処理して得られる処理水は、放流水基準値以下であるの
で、このまま放流しても良く、また、超純水製造用原
水、その他工業用水として回収再使用することも可能で
ある。The treated water obtained by treating the low-concentration fluorine-containing water and / or the supernatant water of the second settling tank 5 discharged from the discharge pipe 23 in the adsorption tower 1 is lower than the discharge water standard value. The water may be discharged as it is, or it may be recovered and reused as raw water for producing ultrapure water or other industrial water.
【００２７】なお、図１に示す例は、本発明のフッ素含
有水の処理方法の一実施例であって、本発明は何ら図示
の方法に限定されるものではない。The example shown in FIG. 1 is an embodiment of the method for treating fluorine-containing water of the present invention, and the present invention is not limited to the method shown.
【００２８】例えば、図示の方法では、反応槽及び沈殿
槽をそれぞれ２槽設けて凝集沈殿、固液分離処理を２段
階で行なっているが、この凝集沈殿、固液分離処理は１
段処理でも十分な効果を得ることができる場合には、１
段処理でも良い。或いは、必要に応じて３段以上処理を
繰り返しても良い。また、沈殿槽の上澄水が放流水基準
値以下まで処理されていれば、更に吸着塔１に送給する
必要はなく、そのまま放流しても良い。さらに、固液分
離手段も沈殿槽５を用いて行なっているが、それに限ら
れず、例えば逆浸透膜や限外濾過膜又は精密濾過膜を用
いた膜分離装置を用いても良い。For example, in the method shown in the figure, two reaction tanks and two precipitation tanks are provided to carry out the coagulation sedimentation and solid-liquid separation treatment in two stages.
If sufficient effects can be obtained even by stage treatment, 1
Stage treatment is also acceptable. Alternatively, the processing may be repeated in three or more steps as needed. Further, if the supernatant water of the settling tank is treated to the discharge water standard value or less, it is not necessary to further feed it to the adsorption tower 1, and it may be discharged as it is. Further, the solid-liquid separation means is also performed by using the settling tank 5, but the solid-liquid separation means is not limited to this. For example, a membrane separation device using a reverse osmosis membrane, an ultrafiltration membrane, or a microfiltration membrane may be used.
【００２９】[0029]
【作用】本発明のフッ素含有水の処理方法においては、
低濃度フッ素含有水と高濃度フッ素含有水とを混合する
ことなく分別処理し、各々のフッ素濃度に応じて、最適
な処理を行なえる。即ち、低濃度フッ素含有水は吸着処
理により、容易に放流水基準値以下の高純度水とするこ
とができる。一方、高濃度フッ素含有水は、高濃度フッ
素含有再生廃液と混合してカルシウム化合物を添加する
ことにより、効率的に凝集沈殿処理することができる。
この場合、カルシウム化合物は高濃度フッ素含有水及び
再生廃液の処理のみに用いるため、その使用量を低減で
きる。しかも、同時に再生廃液の処理も行なえる。しか
して、得られる汚泥は、高濃度フッ素含有水を適量のカ
ルシウム化合物で凝集処理してなるものであるため、Ｃ
ａＦ2 含有量が多く、不純物含有量が少ないため、容易
にＣａＦ2 を回収してフッ化水素酸製造用原料等として
有効に再使用することができる。また、吸着処理により
得られる処理水も、極めて高純度であることから、超純
水製造用原水等として有効に再使用することができる。In the method for treating fluorine-containing water of the present invention,
The low concentration fluorine-containing water and the high concentration fluorine-containing water can be separately treated without mixing, and optimal treatment can be performed according to each fluorine concentration. That is, the low-concentration fluorine-containing water can be easily made into high-purity water having a discharge water reference value or less by adsorption treatment. On the other hand, high-concentration fluorine-containing water can be efficiently coagulated and precipitated by mixing it with a high-concentration fluorine-containing regenerated waste liquid and adding a calcium compound.
In this case, since the calcium compound is used only for treating the high-concentration fluorine-containing water and the reclaimed waste liquid, the amount used can be reduced. Moreover, at the same time, it is possible to process the recycled waste liquid. The sludge thus obtained is obtained by coagulating high-concentration fluorine-containing water with an appropriate amount of calcium compound.
Since the content of aF 2 is large and the content of impurities is small, CaF 2 can be easily recovered and effectively reused as a raw material for hydrofluoric acid production or the like. Further, since the treated water obtained by the adsorption treatment has an extremely high purity, it can be effectively reused as raw water for producing ultrapure water or the like.
【００３０】特に、高濃度フッ素含有水の凝集、固液分
離処理により得られた分離水（上澄水）を更に吸着処理
することにより、より一層高純度な処理水を確保するこ
とが可能とされる。Particularly, by further adsorbing the separated water (supernatant water) obtained by the coagulation of the high-concentration fluorine-containing water and the solid-liquid separation treatment, it is possible to secure the treated water of higher purity. It
【００３１】[0031]
【実施例】以下に実施例を挙げて、本発明をより具体的
に説明する。なお、以下において、フッ素濃度はＨＦ換
算値で示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. In the following, the fluorine concentration is shown in HF conversion value.
【００３２】実施例１ フッ化水素酸とバッファードフッ酸を含むエッチング剤
を使用する工程から排出された、０．８％のフッ素を含
む高濃度フッ素含有廃液１０ｋｇ／ｈｒと、エッチング
後の洗浄工程で発生した、フッ素を３５ｍｇ／lit.含む
ｐＨ３．５の低濃度フッ素廃液１５００ｋｇ／ｈｒとを
本発明の方法により処理した。Example 1 10 kg / hr of highly concentrated fluorine-containing waste liquid containing 0.8% fluorine discharged from the step of using an etching agent containing hydrofluoric acid and buffered hydrofluoric acid, and cleaning after etching A low-concentration fluorine waste liquid of pH 3.5 containing 35 mg / lit. Of fluorine generated in the step and 1500 kg / hr was treated by the method of the present invention.
【００３３】まず、低濃度フッ素含有水はセリウム系フ
ッ素吸着剤（旭硝子（株）製のＲＥＡＤ−Ｆ）を５０ｍ
lit.充填した吸着塔にＳＶ１５ｈｒ-1で通水したとこ
ろ、フッ素濃度１０ｍｇ／lit.以下の処理水が得られ
た。通水２５時間後に通水を止め、１．６％のＮａＯＨ
水溶液１lit.を用いてＳＶ５ｈｒ-1で再生したところ、
フッ素を６５０ｍｇ／lit.含む再生廃液が得られた。First, the water containing low concentration of fluorine was treated with 50m of cerium-based fluorine adsorbent (READ-F manufactured by Asahi Glass Co., Ltd.).
When water was passed through the adsorption tower filled with lit. with SV15 hr -1 , treated water having a fluorine concentration of 10 mg / lit. or less was obtained. Stop water flow after 25 hours, 1.6% NaOH
When regenerated with SV5hr −1 using 1 liter of aqueous solution,
A recycled waste liquid containing 650 mg / lit. Of fluorine was obtained.
【００３４】一方、高濃度フッ素廃液に上記再生廃液を
添加し、廃液の分離汚泥５０ｇを混合したものにＣａ
（ＯＨ）2 を液中のフッ素と当量添加し（ｐＨ７．
２）、急速撹拌下３０分間凝集処理した後、沈殿槽に送
って固液分離した。On the other hand, the above-mentioned regenerated waste liquid was added to the high-concentration fluorine waste liquid, and 50 g of waste liquid separation sludge was mixed with Ca.
(OH) 2 was added in an amount equivalent to that of fluorine in the liquid (pH 7.
2) After aggregating treatment for 30 minutes under rapid stirring, it was sent to a sedimentation tank for solid-liquid separation.
【００３５】上澄水のフッ素濃度は５０ｍｇ／lit.であ
ったのでもう一度Ｃａ（ＯＨ）2 を添加して固液分離す
る工程（再生廃液を添加しないこと以外、条件は上記工
程と同様）を繰り返したところ、フッ素濃度１０ｍｇ／
lit.の上澄液が得られた。Since the fluorine concentration of the supernatant water was 50 mg / lit., The step of adding Ca (OH) 2 again to perform solid-liquid separation (the conditions are the same as those of the above step except that the recycled waste liquid is not added) is repeated. Freshly, fluorine concentration 10mg /
A lit. supernatant was obtained.
【００３６】実施例２ 実施例１において、高濃度フッ素含有水に再生廃液を添
加した後凝集沈殿、固液分離処理して得られたフッ素濃
度５０ｍｇ／lit.の上澄水を吸着塔に送給して処理した
こと以外は同様にして処置を行なった。その結果、フッ
素濃度１．１ｍｇ／lit.の処理水が得られた。Example 2 In Example 1, the regenerated waste liquid was added to the high-concentration fluorine-containing water, and after coagulation sedimentation and solid-liquid separation treatment, the supernatant water with a fluorine concentration of 50 mg / lit. Was sent to the adsorption tower. The same treatment was carried out except that the above treatment was performed. As a result, treated water having a fluorine concentration of 1.1 mg / lit. Was obtained.
【００３７】[0037]
【発明の効果】以上詳述した通り、本発明のフッ素含有
水の処理方法によれば、高濃度フッ素含有水及び低濃度
フッ素含有水が排出される系において、各フッ素含有水
をそれぞれ最適な方法により短時間で効率的かつ低コス
トに処理し、高純度処理水及び高濃度フッ素含有汚泥を
回収することが可能とされる。しかも、吸着塔の再生廃
液も同時に処理することができ、工業的に極めて有利で
ある。As described in detail above, according to the method for treating fluorine-containing water of the present invention, each fluorine-containing water is optimized in a system in which high-concentration fluorine-containing water and low-concentration fluorine-containing water are discharged. The method enables efficient and low-cost treatment in a short time to recover highly purified treated water and sludge containing high concentration of fluorine. Moreover, the regeneration waste liquid in the adsorption tower can be treated at the same time, which is extremely advantageous industrially.
【図１】本発明のフッ素含有水の処理方法の一実施方法
を示す系統図である。FIG. 1 is a system diagram showing an implementation method of a method for treating fluorine-containing water according to the present invention.
１ 吸着塔 ２ 第１の反応槽 ３ 第１の沈殿槽 ４ 第２の反応槽 ５ 第２の沈殿槽 1 Adsorption Tower 2 First Reaction Tank 3 First Precipitation Tank 4 Second Reaction Tank 5 Second Precipitation Tank
フロントページの続き (72)発明者 三木 正博 大阪府大阪市西区西本町２丁目３番６号 橋本化成株式会社内 (72)発明者 前野 又五郎 大阪府大阪市西区西本町２丁目３番６号 橋本化成株式会社内 (72)発明者 後藤 忠一 東京都新宿区西新宿３丁目４番７号 栗田 工業株式会社内 (72)発明者 恵藤 良弘 東京都新宿区西新宿３丁目４番７号 栗田 工業株式会社内 (72)発明者 阪田 正博 東京都新宿区西新宿３丁目４番７号 栗田 工業株式会社内Front page continuation (72) Inventor Masahiro Miki 2-3-6 Nishihonmachi, Nishi-ku, Osaka City, Osaka Prefecture Hashimoto Kasei Co., Ltd. (72) Inventor Magoro Maeno 2-3-6 Nishihonmachi, Nishi-ku, Osaka City, Osaka Prefecture Hashimoto Kasei Co., Ltd. (72) Inventor Chuichi Goto 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd. (72) Yoshihiro Eto 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industrial Co., Ltd. (72) Inventor Masahiro Sakata 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd.
Claims (2)
素吸着樹脂とを用いて処理するフッ素含有水の処理方法
において、 フッ素含有水を低濃度フッ素含有水と高濃度フッ素含有
水に分別する工程、 低濃度フッ素含有水をフッ素吸着樹脂と接触させる工
程、 フッ素吸着樹脂を再生処理する工程、及び高濃度フッ素
含有水に前記フッ素吸着樹脂の再生廃液を添加した後、
カルシウム化合物を加えて凝集処理し、次いで固液分離
する工程、を備えることを特徴とするフッ素含有水の処
理方法。1. A method for treating fluorine-containing water, which comprises treating a fluorine-containing water with a calcium compound and a fluorine-adsorbing resin, the method comprising: separating the fluorine-containing water into low-concentration fluorine-containing water and high-concentration fluorine-containing water; A step of contacting the fluorine-containing water with a fluorine-adsorbing resin, a step of regenerating the fluorine-adsorbing resin, and adding a regeneration waste liquid of the fluorine-adsorbing resin to the high-concentration fluorine-containing water,
A method of treating fluorine-containing water, comprising the steps of adding a calcium compound, performing a coagulation treatment, and then performing solid-liquid separation.
得られた分離水をフッ素吸着樹脂と接触させることを特
徴とするフッ素含有水の処理方法。2. The method for treating fluorine-containing water according to claim 1, wherein separated water obtained by solid-liquid separation is brought into contact with a fluorine-adsorbing resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25350091A JP3334142B2 (en) | 1991-10-01 | 1991-10-01 | Treatment method for fluorine-containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25350091A JP3334142B2 (en) | 1991-10-01 | 1991-10-01 | Treatment method for fluorine-containing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0592187A true JPH0592187A (en) | 1993-04-16 |
| JP3334142B2 JP3334142B2 (en) | 2002-10-15 |
Family
ID=17252247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25350091A Expired - Fee Related JP3334142B2 (en) | 1991-10-01 | 1991-10-01 | Treatment method for fluorine-containing water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3334142B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004174416A (en) * | 2002-11-28 | 2004-06-24 | Kurita Water Ind Ltd | Recovery method for hydrofluoric acid |
| WO2005066080A1 (en) * | 2004-01-08 | 2005-07-21 | Sophia Co., Ltd. | Method of cleaning wastewater and cleaning method |
| JP2006255499A (en) * | 2005-03-15 | 2006-09-28 | Kurita Water Ind Ltd | Fluorine-containing wastewater treatment method and apparatus |
| JP2007000768A (en) * | 2005-06-23 | 2007-01-11 | Kurita Water Ind Ltd | Fluorine-containing water treatment method and apparatus |
| JP2008086840A (en) * | 2006-09-04 | 2008-04-17 | Japan Organo Co Ltd | Crystallization method of fluorine-containing wastewater |
| CN107698092A (en) * | 2017-11-25 | 2018-02-16 | 昆明有色冶金设计研究院股份公司 | A kind of packaged type fluorine-containing wastewater treatment method and device |
| US10259646B2 (en) | 2017-03-20 | 2019-04-16 | Chan Kyung Park | Insert-structured container bag having inner bag to be inserted in outer bag |
| CN109637687A (en) * | 2018-12-27 | 2019-04-16 | 中核四0四有限公司 | A kind of processing unit for uranium conversion fluoride waste |
| US10266338B2 (en) | 2017-03-20 | 2019-04-23 | Chan Kyung Park | Manufacturing method for overlap-structured container bag |
| CN113582430A (en) * | 2021-08-10 | 2021-11-02 | 福建省清流县东莹化工有限公司 | Fluorine-containing industrial wastewater treatment process and final-stage treatment device and process thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016035101A1 (en) * | 2014-09-02 | 2016-03-10 | Council Of Scientific And Industrial Research | A process for the defluoridation of drinking water |
-
1991
- 1991-10-01 JP JP25350091A patent/JP3334142B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004174416A (en) * | 2002-11-28 | 2004-06-24 | Kurita Water Ind Ltd | Recovery method for hydrofluoric acid |
| JP4507271B2 (en) * | 2002-11-28 | 2010-07-21 | 栗田工業株式会社 | Method for recovering hydrofluoric acid |
| WO2005066080A1 (en) * | 2004-01-08 | 2005-07-21 | Sophia Co., Ltd. | Method of cleaning wastewater and cleaning method |
| JP2006255499A (en) * | 2005-03-15 | 2006-09-28 | Kurita Water Ind Ltd | Fluorine-containing wastewater treatment method and apparatus |
| JP2007000768A (en) * | 2005-06-23 | 2007-01-11 | Kurita Water Ind Ltd | Fluorine-containing water treatment method and apparatus |
| JP2008086840A (en) * | 2006-09-04 | 2008-04-17 | Japan Organo Co Ltd | Crystallization method of fluorine-containing wastewater |
| US10259646B2 (en) | 2017-03-20 | 2019-04-16 | Chan Kyung Park | Insert-structured container bag having inner bag to be inserted in outer bag |
| US10266338B2 (en) | 2017-03-20 | 2019-04-23 | Chan Kyung Park | Manufacturing method for overlap-structured container bag |
| CN107698092A (en) * | 2017-11-25 | 2018-02-16 | 昆明有色冶金设计研究院股份公司 | A kind of packaged type fluorine-containing wastewater treatment method and device |
| CN109637687A (en) * | 2018-12-27 | 2019-04-16 | 中核四0四有限公司 | A kind of processing unit for uranium conversion fluoride waste |
| CN113582430A (en) * | 2021-08-10 | 2021-11-02 | 福建省清流县东莹化工有限公司 | Fluorine-containing industrial wastewater treatment process and final-stage treatment device and process thereof |
| CN113582430B (en) * | 2021-08-10 | 2023-06-20 | 福建省清流县东莹化工有限公司 | Fluorine-containing industrial wastewater treatment process, final treatment device and final treatment process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3334142B2 (en) | 2002-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4880656B2 (en) | Water treatment apparatus and water treatment method | |
| JP3334142B2 (en) | Treatment method for fluorine-containing water | |
| JP2004141799A (en) | Silica-containing waste water treatment method | |
| JP3203745B2 (en) | Fluorine-containing water treatment method | |
| JP3227760B2 (en) | Fluorine-containing water treatment method | |
| JP3908585B2 (en) | Treatment method for fluorine-containing wastewater | |
| US6936177B2 (en) | Method for removing metal from wastewater | |
| JP4543481B2 (en) | Method for treating water containing boron and fluorine | |
| JP3319053B2 (en) | Treatment method for fluoride-containing water | |
| JP3942235B2 (en) | Method for treating boron-containing water | |
| JP3252521B2 (en) | Rinse wastewater treatment method | |
| JP2004000846A (en) | Treatment method for fluorine-containing water | |
| JP3697800B2 (en) | Wastewater treatment method | |
| JPH0137997B2 (en) | ||
| JP3622407B2 (en) | Water treatment method | |
| JP2001232372A (en) | Treatment process for water containing boron | |
| JP4021688B2 (en) | Method and apparatus for treatment of wastewater containing fluorine and silicon | |
| JP6318193B2 (en) | Water treatment method and equipment | |
| JPH10263532A (en) | Treatment of fluorine-containing waste water | |
| JPS59222292A (en) | Treatment of waste liquid of chemical cleaning containing ethylenediamine tetraacetate | |
| JPH11165179A (en) | Method for treating fluorine-containing water | |
| JP3364308B2 (en) | Wastewater treatment method and apparatus | |
| JPH0716564A (en) | Treatment of exhaust gas-desulfurization wastewater | |
| JPH10314797A (en) | Method for treating water containing fluoride ion and cod component | |
| JP2001192867A (en) | Surface treating method for aluminum material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020702 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080802 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090802 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090802 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100802 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110802 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |