JP2600569B2 - Treatment method for fluorine-containing water - Google Patents
Treatment method for fluorine-containing waterInfo
- Publication number
- JP2600569B2 JP2600569B2 JP5048018A JP4801893A JP2600569B2 JP 2600569 B2 JP2600569 B2 JP 2600569B2 JP 5048018 A JP5048018 A JP 5048018A JP 4801893 A JP4801893 A JP 4801893A JP 2600569 B2 JP2600569 B2 JP 2600569B2
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- Prior art keywords
- calcium carbonate
- water
- fluorine
- packed tower
- column
- 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.)
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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、フッ素含有水を炭酸カルシウム充填塔に
通水してフッ素をフッ化カルシウムとして除去・回収す
る方法において、フッ素除去率を高めて処理水水質の向
上を図ると共に、高純度フッ化カルシウムの回収を可能
とするフッ素含有水の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating fluorine-containing water, and more particularly to a method for removing and recovering fluorine as calcium fluoride by passing fluorine-containing water through a column packed with calcium carbonate. The present invention relates to a method for treating fluorine-containing water, which improves the quality of treated water by improving the quality of treated water and enables high-purity calcium fluoride to be recovered.
【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、フッ化水素（ＨＦ）やフッ化アンモニウム（ＮＨ4
Ｆ）を主成分とするエッチング剤が多量使用されること
から、フッ素を含む廃水が排出される。2. Description of the Related Art In the field of semiconductor manufacturing and related fields, and in the field of surface treatment of various metallic materials, single crystal materials, optical materials, etc., hydrogen fluoride (HF) and ammonium fluoride (NH 4 ) are used.
Waste water containing fluorine is discharged because a large amount of the etching agent containing F) is used.
【０００３】このようなフッ素含有廃水は、一般に分別
処理にて、或いは、他の廃水と共に総合廃水として処理
されており、その処理方法としては、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 ）の不溶物を生成させ、固液分離
する方法が一般に用いられている。しかし、この方法で
は、フッ素を含む汚泥が多量に発生するため、この汚泥
発生量の低減が課題となっていた。[0003] Such a fluorine-containing wastewater is generally treated as a separate wastewater or as a general wastewater together with other wastewater. The method of treating the wastewater includes calcium hydroxide such as calcium hydroxide (Ca (OH) 2 ). A method of adding a salt to generate an insoluble calcium fluoride (CaF 2 ) and performing solid-liquid separation is generally used. However, in this method, since a large amount of sludge containing fluorine is generated, reduction of the amount of generated sludge has been a problem.
【０００４】従来、フッ素含有汚泥の低減策として、フ
ッ素含有廃液を複数の炭酸カルシウム充填塔に通液し
て、フッ素を結晶性の良いフッ化カルシウムに転換して
除去、回収する方法が提案されている。また、このよう
な方法において、原水がフッ素含有酸性廃水である場合
には濾材（炭酸カルシウム）崩壊防止の目的で原水にア
ルカリ剤（アンモニアやフッ化アンモニウム等）を添加
するが、この場合、最終充填塔の処理水の一部を原水槽
へ循環することにより、アルカリ剤添加量を低減する方
法も提案されている。Conventionally, as a measure for reducing fluorine-containing sludge, a method has been proposed in which a fluorine-containing waste liquid is passed through a plurality of calcium carbonate packed towers, and fluorine is converted to calcium fluoride having good crystallinity and removed and recovered. ing. In addition, in such a method, when the raw water is a fluorine-containing acidic wastewater, an alkali agent (ammonia, ammonium fluoride, or the like) is added to the raw water for the purpose of preventing filter medium (calcium carbonate) from disintegrating. There has also been proposed a method of circulating a part of treated water of a packed tower to a raw water tank to reduce the amount of an alkali agent added.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、最終充
填塔の処理水の一部を原水槽に循環する方法では、循環
水により、原水中のイオン形態がＨＦ型からＮＨ4 Ｆ及
びＮＨ4 ＨＣＯ3 型へと変化し、それに伴って濾材であ
る炭酸カルシウムとの反応速度が低下する。このため、
フッ素除去率が低下して最終処理水の水質が悪化する
（即ち、フッ素濃度が高いものとなる。）か、或いは、
回収されるフッ化カルシウムの純度が低下するなどの問
題が生起する。この対応策としては、炭酸カルシウム充
填塔の数をさらに増すことが考えられるが、炭酸カルシ
ウム充填塔のさらなる増設は、設備の大型化及び設備費
の増大を招き、工業的に不利である。However, in the method of circulating a part of the treated water of the final packed tower to the raw water tank, the circulating water changes the ion form in the raw water from HF type to NH 4 F and NH 4 HCO 3. It changes into a mold, and the reaction rate with calcium carbonate, which is a filter medium, decreases accordingly. For this reason,
Either the fluorine removal rate decreases and the quality of the final treated water deteriorates (that is, the fluorine concentration becomes high), or
Problems such as a decrease in the purity of the recovered calcium fluoride occur. As a countermeasure for this, it is conceivable to further increase the number of packed columns of calcium carbonate. However, further addition of packed columns of calcium carbonate causes an increase in equipment size and an increase in equipment cost, which is industrially disadvantageous.
【０００６】本発明は上記従来の問題点を解決し、フッ
素含有水を複数の炭酸カルシウム充填塔に通水してフッ
素をフッ化カルシウムとして除去・回収する方法におい
て、炭酸カルシウム充填塔のさらなる増設を要すること
なく、フッ素除去率を高めて高水質処理水を得ると共
に、高純度なフッ化カルシウムを回収するフッ素含有水
の処理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 provides a method of removing and recovering fluorine as calcium fluoride by passing fluorine-containing water through a plurality of calcium carbonate packed towers. It is an object of the present invention to provide a method for treating fluorine-containing water, in which high-quality treated water is obtained by increasing the fluorine removal rate without requiring a high-purity calcium fluoride, and recovering high-purity calcium fluoride.
【０００７】[0007]
【課題を解決するための手段】本発明のフッ素含有水の
処理方法は、フッ素含有水を直列に配置した複数の炭酸
カルシウム充填塔に順次通水し、最終段の炭酸カルシウ
ム充填塔の流出水を処理水として取り出す方法におい
て、各炭酸カルシウム充填塔の流出水の一部を他の炭酸
カルシウム充填塔を通すことなくそのまま当該炭酸カル
シウム充填塔に通水することを特徴とする。According to the method for treating fluorine-containing water of the present invention, the fluorine-containing water is sequentially passed through a plurality of calcium carbonate packed towers arranged in series, and the final stage of calcium carbonate is provided.
A method of retrieving a runoff unfilled column as treated water, some other carbonate effluent of each calcium carbonate packed column
It is characterized by passing water through the calcium carbonate packed tower without passing through the calcium packed tower.
【０００８】[0008]
【作用】フッ素含有水を直列に配置した複数の炭酸カル
シウム充填塔に順次通水し、最終段の炭酸カルシウム充
填塔の流出水を処理水として取り出し、フッ素をフッ化
カルシウムとして回収処理するにあたり、各充填塔の流
出水の一部を他の炭酸カルシウム充填塔を通すことなく
そのまま当該充填塔に循環して処理することにより、装
置の小型化、フッ素除去率の向上、回収フッ化カルシウ
ムの純度向上が図れる。[Function] Fluorine-containing water is sequentially passed through a plurality of calcium carbonate packed columns arranged in series, and the calcium carbonate packed in the final stage is filled.
In taking out the effluent of the packed tower as treated water and recovering fluorine as calcium fluoride, a part of the effluent of each packed tower does not pass through another calcium carbonate packed tower.
By treatment with circulation to the packed column as is, miniaturization of the apparatus, improvement of fluorine removal rate, the increased purity of the recovered calcium fluoride attained.
【０００９】即ち、炭酸カルシウム充填塔の流出水を当
該炭酸カルシウム充填塔の流入水側に循環して炭酸カル
シウム充填塔の流入水を希釈することにより、流入水の
フッ素濃度が低減され、炭酸カルシウム充填塔内でのフ
ッ素除去効率は高くなる。That is, by diluting the inflow water of the calcium carbonate packed tower by circulating the effluent of the calcium carbonate packed tower to the inflow water side of the calcium carbonate packed tower, the fluorine concentration of the inflow water is reduced, Fluorine removal efficiency in the packed tower increases.
【００１０】特に、原水であるフッ素含有水中に硝酸
（ＨＮＯ3 ）や硫酸（Ｈ2 ＳＯ4 ）が含有されている場
合、これらの酸により炭酸カルシウム充填塔内の炭酸カ
ルシウム濾材の崩壊を招く。このため、濾材崩壊防止の
ために、アルカリ剤としてアンモニア（ＮＨ4 ＯＨ）や
フッ化アンモニウム（ＮＨ4 Ｆ）等を添加するが、炭酸
カルシウム充填塔の流出水を循環することにより、この
アルカリ剤添加量を少なくすることができ、薬剤費の低
減が図れる。In particular, when nitric acid (HNO 3 ) or sulfuric acid (H 2 SO 4 ) is contained in the raw water containing fluorine, these acids cause the collapse of the calcium carbonate filter in the calcium carbonate packed tower. Therefore, ammonia (NH 4 OH), ammonium fluoride (NH 4 F) or the like is added as an alkali agent in order to prevent the filter material from collapsing. The amount of addition can be reduced, and the cost of medicine can be reduced.
【００１１】ところで、炭酸カルシウム充填塔内でフッ
素と炭酸カルシウムとの反応で発生する炭酸ガスによ
り、濾材の一部塔外流出が起こるが、この濾材流出も、
流出水の循環による流入水のフッ素濃度の低下及びフッ
素濃度の低下による発生ガス量の低減により防止され
る。更に、流出水の循環に当り、循環水槽を設けた場合
には、この循環水槽でのガス放散によって、発生ガスが
除去され、濾材の流出はより一層防止される。また、下
流側の炭酸カルシウム充填塔では、流入水のフッ素濃度
がより低いために、発生ガス量は極めて少なく、上流側
の炭酸カルシウム充填塔において濾材の流出が起きた場
合においても、下流側の炭酸カルシウム充填塔の捕捉作
用で濾材の流出が防止される。このため、最終処理水中
には全く濾材の流出が起きない。[0011] By the way, carbon dioxide gas generated by the reaction between fluorine and calcium carbonate in the calcium carbonate packed tower causes a part of the filter medium to flow out of the tower.
This is prevented by a decrease in the fluorine concentration of the inflow water due to the circulation of the effluent and a reduction in the amount of generated gas due to the decrease in the fluorine concentration. Furthermore, in the case of providing a circulation water tank for circulation of the effluent, generated gas is removed by gas diffusion in the circulation water tank, and the outflow of the filter medium is further prevented. Further, in the downstream calcium carbonate packed tower, since the fluorine concentration of the inflow water is lower, the amount of generated gas is extremely small. The trapping action of the calcium carbonate packed tower prevents the outflow of the filter medium. Therefore, no outflow of the filter medium occurs in the final treated water.
【００１２】[0012]
【実施例】以下、図面を参照して本発明の実施例につい
て詳細に説明する。Embodiments of the present invention will be described below in detail with reference to the drawings.
【００１３】図１，２は各々本発明のフッ素含有水の処
理方法の一実施例方法を示す系統図である。FIGS. 1 and 2 are system diagrams showing one embodiment of a method for treating fluorine-containing water according to the present invention.
【００１４】本実施例の方法は、炭酸カルシウム充填塔
を３塔直列に設置して上向流にて処理するものであり、
図中、１，２，３は炭酸カルシウム充填塔、４は原水
槽、５は原水ポンプ、６，７，８は循環水槽、９，１
０，１１は循環ポンプを示す。２１〜３１の各符号は配
管を示す。In the method of this embodiment, three calcium carbonate packed towers are installed in series and treated in an upward flow.
In the figure, 1, 2 and 3 are calcium carbonate packed towers, 4 is a raw water tank, 5 is a raw water pump, 6, 7, and 8 are circulating water tanks, and 9.1 and 1
Reference numerals 0 and 11 indicate circulation pumps. 21 to 31 indicate pipes.
【００１５】本実施例において、原水、例えば、フッ
酸、フッ化アンモニウム等を含む高濃度フッ素含有水
は、まず、配管２１、原水槽４、ポンプ５を備える配管
２２を経て循環水槽６に導入され、配管２４からの炭酸
カルシウム充填塔１の流出水と共に、ポンプ９を備える
配管２３より炭酸カルシウム充填塔１内に導入される。
この炭酸カルシウム充填塔１の流出水は配管２４より循
環水槽６に返送され、循環水槽６のオーバーフロー水は
配管２５より循環水槽７に導入される。そして、配管２
７からの炭酸カルシウム充填塔２の流出水と共に、ポン
プ１０を備える配管２６より炭酸カルシウム充填塔２内
に導入される。この炭酸カルシウム充填塔２の流出水は
配管２７より循環水槽７に返送される。循環水槽７のオ
ーバーフロー水は配管２８より循環水槽８に導入され、
配管３０からの炭酸カルシウム充填塔３の流出水と共
に、ポンプ１１を備える配管２９より炭酸カルシウム充
填塔３内に導入される。この炭酸カルシウム充填塔３の
流出水は配管３０より循環水槽８に返送され、循環水槽
８のオーバーフロー水は配管３１より処理水として系外
へ排出される。In this embodiment, raw water, for example, high-concentration fluorine-containing water containing hydrofluoric acid, ammonium fluoride, etc., is first introduced into the circulating water tank 6 through a pipe 21, a raw water tank 4, and a pipe 22 provided with a pump 5. Then, together with the effluent of the calcium carbonate packed tower 1 from the pipe 24, the water is introduced into the calcium carbonate packed tower 1 from the pipe 23 provided with the pump 9.
The effluent of the calcium carbonate packed tower 1 is returned to the circulating water tank 6 from the pipe 24, and the overflow water in the circulating water tank 6 is introduced to the circulating water tank 7 from the pipe 25. And piping 2
Along with the effluent of the calcium carbonate packed tower 2 from 7, the water is introduced into the calcium carbonate packed tower 2 from a pipe 26 provided with the pump 10. The effluent of the calcium carbonate packed tower 2 is returned to the circulating water tank 7 through a pipe 27. The overflow water in the circulating water tank 7 is introduced into the circulating water tank 8 through a pipe 28,
Along with the effluent of the calcium carbonate packed tower 3 from the pipe 30, the water is introduced into the calcium carbonate packed tower 3 from the pipe 29 provided with the pump 11. The effluent of the calcium carbonate packed tower 3 is returned to the circulating water tank 8 from the pipe 30, and the overflow water in the circulating water tank 8 is discharged from the pipe 31 as treated water to the outside of the system.
【００１６】このようなフッ素含有水の処理方法におい
て、原水としては、各種のフッ素含有水を各々別々に処
理しても、これらを混合して処理しても良いが、原水中
にリンが含有される場合には炭酸カルシウム充填塔内の
濾材炭酸カルシウムと反応してゲル状化を起こすため、
リンは予め除去するのが好ましい。In such a method of treating fluorine-containing water, the raw water may be various kinds of fluorine-containing water, each of which may be treated separately or a mixture of these. If it is done, it will react with the filter medium calcium carbonate in the calcium carbonate packed tower and cause gelation,
Preferably, the phosphorus is removed in advance.
【００１７】また、前述の如く、原水にＨＮＯ3 やＨ2
ＳＯ4 が含有されている場合には、濾材崩壊を防止する
ために、アルカリ剤としてＮＨ4 ＯＨやＮＨ4 Ｆを添加
するのが好ましい。As described above, HNO 3 and H 2 are added to the raw water.
When SO 4 is contained, it is preferable to add NH 4 OH or NH 4 F as an alkaline agent in order to prevent the filter medium from collapsing.
【００１８】この場合、アルカリ剤の添加量は、炭酸カ
ルシウム充填塔内への流入水（本実施例では循環水槽６
内の水）中のフッ素濃度の０．３〜０．７当量倍程度と
するのが望ましい。In this case, the amount of the alkali agent to be added is determined by the amount of inflow water into the calcium carbonate packed tower (in this embodiment, the circulating water tank 6).
It is desirable that the concentration of fluorine is about 0.3 to 0.7 equivalent times of the fluorine concentration in (water).
【００１９】各炭酸カルシウム充填塔への流入水の流速
は充填されている炭酸カルシウム濾材の粒径等によって
異なり、濾材が流動状態となりかつ濾材の塔外流出が起
こらない範囲で適宜決定される。通常の場合、濾材粒径
が０．３ｍｍ程度であれば約１０ｍ／ｈｒ以上、特に２
０〜３０ｍ／ｈｒ程度とされる。The flow rate of the inflow water into each of the calcium carbonate packed columns differs depending on the particle size of the calcium carbonate filter medium filled therein, and is appropriately determined within a range where the filter medium is in a fluid state and the filter medium does not flow out of the tower. In a normal case, if the filter medium particle size is about 0.3 mm, it is about 10 m / hr or more, especially 2 m / hr.
It is about 0 to 30 m / hr.
【００２０】また、原水ポンプによる原水の供給量は、
原水のフッ素濃度やフッ素の形態によっても異なるが、
通常の場合、炭酸カルシウム充填塔１の濾材量に対して
実質的に１〜５ｍ3 −原水／ｍ3 −濾材・ｈｒ程度とな
るようにするのが好ましい。The raw water supply by the raw water pump is as follows:
Depending on the fluorine concentration and the form of fluorine in the raw water,
For normal, substantially 1 to 5 m 3 relative to the filter medium of calcium carbonate packed column 1 - preferably made to be about filter media · hr - raw / m 3.
【００２１】なお、炭酸カルシウム充填塔の流入水のフ
ッ素濃度と流出水のフッ素濃度とに差がなくなった場合
には、塔内の濾材はフッ化カルシウムに転換が終了し、
飽和に達したことになる。この場合には、濾材を抜き出
して新しい炭酸カルシウム濾材と交換する。When the difference between the fluorine concentration of the influent water and the fluorine concentration of the effluent water of the column packed with calcium carbonate disappears, the conversion of the filter medium in the column to calcium fluoride is completed.
It has reached saturation. In this case, the filter medium is withdrawn and replaced with a new calcium carbonate filter medium.
【００２２】本発明に従って、複数の炭酸カルシウム充
填塔に原水を直列で通水処理する場合には、最も上流側
の炭酸カルシウム充填塔の流入水のフッ素濃度が最も高
く、この炭酸カルシウム充填塔のフッ化カルシウム転換
率が最も高いことから、最も上流側の炭酸カルシウム充
填塔の濾材の交換を行ない、この交換を行なった炭酸カ
ルシウム充填塔を最も下流側に移動させ、順次下段側の
炭酸カルシウム充填塔を上段側へ繰り上げる。これによ
り、最も上流側の炭酸カルシウム充填塔から高純度のフ
ッ化カルシウムを効率的に回収することが可能とされ、
また、最も下流側の炭酸カルシウム充填塔は濾材のフッ
化カルシウム転換率が常に低いことから、最終処理水と
して高水質処理水を得ることが可能とされる。According to the present invention, when raw water is passed through a plurality of calcium carbonate packed towers in series, the fluorine concentration of the inflow water of the most upstream calcium carbonate packed tower is the highest, and this calcium carbonate packed tower has Since the conversion rate of calcium fluoride is the highest, the filter material of the calcium carbonate packed tower on the most upstream side is replaced, and the calcium carbonate packed tower on which this replacement has been performed is moved to the most downstream side, and the calcium carbonate packed on the lower side is sequentially filled. Raise the tower to the upper side. This makes it possible to efficiently recover high-purity calcium fluoride from the most upstream calcium carbonate packed tower,
Moreover, since the calcium carbonate conversion ratio of the filter medium in the most downstream calcium carbonate packed tower is always low, it is possible to obtain high quality treated water as the final treated water.
【００２３】なお、図示の実施例では、炭酸カルシウム
充填塔を３段に設置した例を示したが、本発明において
は、炭酸カルシウム充填塔は２段に設けても良く、ま
た、４段以上の複数段設けても良い。In the illustrated embodiment, an example is shown in which the calcium carbonate packed tower is provided in three stages. However, in the present invention, the calcium carbonate packed tower may be provided in two stages, or more than four stages. May be provided in a plurality of stages.
【００２４】また、図に示す如く、炭酸カルシウム充填
塔の流出水を循環水槽に戻し、その一部を当該炭酸カル
シウム充填塔の流入水として循環させると共に、残部を
後段の炭酸カルシウム充填塔に送給する循環形態に限ら
ず、図２に示す如く、炭酸カルシウム充填塔の流出水の
一部を当該炭酸カルシウム充填塔の流入水として塔下部
に返送すると共に、残部を後段の炭酸カルシウム充填塔
の流入水として送給しても良い。なお、図２において、
図１と同一機能を奏する部材には同一符号を付してあ
る。As shown in the figure, the effluent of the calcium carbonate packed tower is returned to the circulating water tank, a part of which is circulated as the inflow water of the calcium carbonate packed tower, and the remainder is sent to the subsequent calcium carbonate packed tower. As shown in FIG. 2, a part of the effluent of the calcium carbonate packed tower is returned to the lower part of the calcium carbonate packed tower as the inflow water of the calcium carbonate packed tower, and the remaining part of the calcium carbonate packed tower is provided in the subsequent stage. It may be supplied as influent water. In FIG. 2,
Members having the same functions as in FIG. 1 are denoted by the same reference numerals.
【００２５】いずれの場合においても、本実施例の如
く、循環水槽を設けることにより、炭酸カルシウム充填
塔内で発生したガスの放散効果が得られて極めて有利で
ある。In any case, by providing a circulating water tank as in the present embodiment, the effect of dissipating the gas generated in the calcium carbonate packed tower is obtained, which is extremely advantageous.
【００２６】以下に具体的な実施例を挙げて本発明をよ
り詳細に説明する。Hereinafter, the present invention will be described in more detail with reference to specific examples.
【００２７】実施例１ 直径０．３ｍｍの炭酸カルシウム粒子１リットルを内径
５０ｍｍのカラムに充填し、このカラムを３個（カラム
，，）用いて図１に示す如く、３塔直列方式にて
フッ酸含有水を通水して処理を行なった。原水は試薬フ
ッ化水素を水で２０００ｍｇ−Ｆ／ｌに希釈し、ＮＨ4
ＯＨをフッ化水素に対して０．３当量比添加したものを
２リットル／ｈｒの一定流量で供給した。Example 1 One liter of calcium carbonate particles having a diameter of 0.3 mm was packed in a column having an inner diameter of 50 mm, and three such columns (columns,...) Were used in a three-column series system as shown in FIG. The treatment was carried out by passing water containing acid. Raw water is obtained by diluting the reagent hydrogen fluoride to 2000 mg-F / l with water, and adding NH 4
OH was added at a ratio of 0.3 equivalent to hydrogen fluoride and supplied at a constant flow rate of 2 liter / hr.
【００２８】処理に当り、カラム（炭酸カルシウム充
填塔１）では流出水を４０リットル／ｈｒ（ＬＶ＝２０
ｍ／ｈｒ）の流量で同一カラムに循環させ、循環水の
一部をカラムに移送してカラムと同一条件で通水及
び循環処理した。更に、カラムの循環水の一部をカラ
ムに移送してカラムと同一条件で通水及び循環処理
し、その一部を処理水として排出した。In the treatment, the effluent was supplied to the column (calcium carbonate packed column 1) at a rate of 40 l / hr (LV = 20).
(m / hr), and circulated through the same column. A part of the circulating water was transferred to the column and subjected to water flow and circulation under the same conditions as the column. Further, a part of the circulating water of the column was transferred to the column, subjected to water passing and circulation treatment under the same conditions as the column, and a part thereof was discharged as treated water.
【００２９】各カラム流出水のフッ素濃度を分析し、そ
の経時変化を表１に示す。[0029] The fluorine concentration of each column effluent was analyzed, and the change over time is shown in Table 1.
【００３０】また、通水３２０ｈｒ後にカラム内の濾
材を抜き出して分析した結果を表２に示す。Table 2 shows the results obtained by extracting and analyzing the filter medium in the column after passing water for 320 hours.
【００３１】比較例１ 実施例１において、カラム、カラムにおいては流出
水の循環を行なわず、カラムの流出水はその全量をカ
ラムへ、また、カラムの流出水はその全量をカラム
へ通水し、カラムの流出水のみ、その一部をカラム
の原水槽に戻して循環処理したこと以外は同様にし
て、原水供給量２リットル／ｈｒ、各カラム，，
の流量４０リットル／ｈｒで処理を行なった。COMPARATIVE EXAMPLE 1 In Example 1, the effluent was not circulated in the column and the column, and the entire amount of the effluent of the column passed through the column, and the entire effluent of the column passed through the column. , Only the effluent of the column, a part of which was returned to the raw water tank of the column and circulated, was processed in the same manner as above, and the raw water supply amount was 2 liters / hr.
At a flow rate of 40 L / hr.
【００３２】各カラム流出水のフッ素濃度を分析し、そ
の経時変化を表１に示す。The effluent concentration of each column effluent was analyzed, and the change over time is shown in Table 1.
【００３３】また、通水３２０ｈｒ後にカラム内の濾
材を抜き出して分析した結果を表２に示す。Table 2 shows the results obtained by extracting and analyzing the filter medium in the column after passing water for 320 hours.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】表１，２より明らかなように、本発明の方
法によれば、従来法に比べて、処理水のフッ素濃度は著
しく低減されると共に、回収フッ化カルシウムの純度が
大幅に高められる。As is apparent from Tables 1 and 2, according to the method of the present invention, the fluorine concentration of the treated water is significantly reduced and the purity of the recovered calcium fluoride is greatly increased as compared with the conventional method. .
【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、炭酸カルシウム充填塔の設置数
を増やすことなく、フッ素除去率を高め、高水質処理を
得ると共に高純度フッ化カルシウムを回収することが可
能とされる。As described in detail above, according to the method for treating fluorine-containing water of the present invention, it is possible to increase the fluorine removal rate without increasing the number of calcium carbonate packed towers, to obtain high water quality treatment, and to achieve high purity. It is possible to recover calcium fluoride.
【図１】本発明のフッ素含有水の処理方法の一実施例方
法を示す系統図である。FIG. 1 is a system diagram showing a method for treating fluorine-containing water according to an embodiment of the present invention.
【図２】本発明のフッ素含有水の処理方法の他の実施例
方法を示す系統図である。FIG. 2 is a system diagram showing another embodiment of the method for treating fluorine-containing water according to the present invention.
１，２，３ 炭酸カルシウム充填塔 ４ 原水槽 ５ 原水ポンプ ６，７，８ 循環水槽 ９．１０，１１ 循環ポンプ 1,2,3 Calcium carbonate packed tower 4 Raw water tank 5 Raw water pump 6,7,8 Circulating water tank 9.10,11 Circulating pump
Claims (1)
酸カルシウム充填塔に順次通水し、最終段の炭酸カルシ
ウム充填塔の流出水を処理水として取り出す方法におい
て、 各炭酸カルシウム充填塔の流出水の一部を他の炭酸カル
シウム充填塔を通すことなくそのまま当該炭酸カルシウ
ム充填塔に通水することを特徴とするフッ素含有水の処
理方法。1. A fluorine-containing water sequentially passed through a plurality of calcium carbonate packed column arranged in series, the final stage carbonate calcium
In the method of taking out the effluent of the column packed with calcium carbonate as treated water, a part of the effluent of each column packed with calcium carbonate is
A method for treating fluorine-containing water, wherein the water is passed through the column packed with calcium carbonate without passing through the column packed with calcium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5048018A JP2600569B2 (en) | 1993-03-09 | 1993-03-09 | Treatment method for fluorine-containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5048018A JP2600569B2 (en) | 1993-03-09 | 1993-03-09 | Treatment method for fluorine-containing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06254571A JPH06254571A (en) | 1994-09-13 |
| JP2600569B2 true JP2600569B2 (en) | 1997-04-16 |
Family
ID=12791575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5048018A Expired - Lifetime JP2600569B2 (en) | 1993-03-09 | 1993-03-09 | Treatment method for fluorine-containing water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2600569B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3375154B2 (en) * | 1992-08-24 | 2003-02-10 | 栗田工業株式会社 | Fluorine-containing water treatment equipment |
-
1993
- 1993-03-09 JP JP5048018A patent/JP2600569B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06254571A (en) | 1994-09-13 |
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