JP2001212574A - Method for treating fluorine-containing water - Google Patents
Method for treating fluorine-containing waterInfo
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- JP2001212574A JP2001212574A JP2000025513A JP2000025513A JP2001212574A JP 2001212574 A JP2001212574 A JP 2001212574A JP 2000025513 A JP2000025513 A JP 2000025513A JP 2000025513 A JP2000025513 A JP 2000025513A JP 2001212574 A JP2001212574 A JP 2001212574A
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- fluorine
- amount
- salt
- ions
- containing water
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はフッ素含有水にカル
シウム（Ｃａ）塩を添加してフッ素をフッ化カルシウム
（ＣａＦ２）として沈殿分離する方法に係り、特に、こ
の方法において、Ｃａ塩の必要添加量を容易かつ的確に
求め、この添加量により効率的な処理を行って、高水質
な処理水を得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 adding calcium (Ca) salt to fluorine-containing water to precipitate and separate fluorine as calcium fluoride (CaF 2 ). The present invention relates to a method for treating fluorine-containing water in which the amount of addition is easily and accurately determined, and the amount of addition is used to carry out efficient treatment to obtain high-quality treated water.
【０００２】[0002]
【従来の技術】半導体部品製造におけるシリコンウェハ
製造工程から排出されるフッ素含有廃水、ステンレス鋼
板製造工程から排出される酸洗廃水、フッ酸製造廃水、
ゴミ焼却廃水等のフッ素含有水の処理方法としては、フ
ッ素含有水にＣａ塩を添加してＣａＦ２を生成させ、こ
れを沈殿分離する方法が、薬剤コストが安価であること
から広く普及している。この方法において、フッ素含有
水中のフッ素はＣａ塩と下記反応式に従って反応するこ
とから、フッ素含有水中のフッ素を十分に反応させてフ
ッ素濃度の低い処理水を得るためには、フッ素含有水中
のフッ素と当量以上のＣａ塩を添加して反応を進行させ
るのが最も一般的な方法である。2. Description of the Related Art Fluorine-containing wastewater discharged from a silicon wafer manufacturing process in semiconductor component manufacturing, pickling wastewater discharged from a stainless steel plate manufacturing process, hydrofluoric acid manufacturing wastewater,
As a method of treating fluorine-containing water such as garbage incineration wastewater, a method of adding Ca salt to fluorine-containing water to generate CaF 2 and separating the precipitate by sedimentation is widely used because of its low chemical cost. I have. In this method, since fluorine in the fluorine-containing water reacts with the Ca salt according to the following reaction formula, in order to sufficiently react the fluorine in the fluorine-containing water to obtain treated water having a low fluorine concentration, the fluorine in the fluorine-containing water is required. The most common method is to add a Ca salt in an amount equal to or more than the above to advance the reaction.
【０００３】Ｃａ２＋＋２Ｆ−→ＣａＦ２↓ 従って、従来、この処理法において、Ｃａ塩の添加量は
フッ素含有水中のフッ素濃度に基いて、フッ素含有水中
のフッ素に対して当量以上のＣａ塩添加量となるように
添加制御されている。Ca 2 ++ + 2F − → CaF 2 ↓ Therefore, conventionally, in this treatment method, the amount of Ca salt added is based on the concentration of fluorine in the fluorine-containing water, and at least an equivalent of Ca salt is added to the fluorine in the fluorine-containing water. The addition is controlled so as to obtain the amount.
【０００４】[0004]
【発明が解決しようとする課題】しかし、フッ素含有水
中のフッ素に対して当量以上のＣａ塩を添加しても、処
理水のフッ素濃度を十分に低くすることができない場合
があり、従来においては、このような問題を解決するた
めに、Ｃａ塩を過剰添加したり、煩雑な予備実験を行っ
てＣａ塩添加量を求めたりしているのが実情である。However, even if the Ca salt is added in an amount equal to or more than the fluorine in the fluorine-containing water, the fluorine concentration of the treated water may not be sufficiently reduced. In order to solve such a problem, the fact is that Ca salt is excessively added or the amount of Ca salt added is determined by performing complicated preliminary experiments.
【０００５】本発明は上記従来の問題点を解決し、フッ
素含有水にＣａ塩を添加してフッ素をＣａＦ２として沈
殿分離する方法において、Ｃａ塩の必要添加量を容易か
つ的確に求め、適正な薬注を行って、フッ素濃度が著し
く低減された高水質な処理水を得ることができるフッ素
含有水の処理方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and in a method of adding Ca salt to fluorine-containing water to precipitate and separate fluorine as CaF 2 , the required amount of Ca salt can be easily and accurately determined. It is an object of the present invention to provide a method for treating fluorine-containing water that can obtain high-quality treated water in which the fluorine concentration is significantly reduced by performing a proper chemical injection.
【０００６】[0006]
【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、フッ素含有水にカルシウム塩を添加してフ
ッ素をフッ化カルシウムとして沈殿分離する方法におい
て、該フッ素含有水中のフッ素イオン量及びカルシウム
と難溶性塩を生成するフッ素イオン以外のイオンの量に
基いて、前記カルシウム塩の添加量を設定することを特
徴とする。The method for treating fluorine-containing water according to the present invention comprises the steps of: adding a calcium salt to fluorine-containing water to precipitate and separate fluorine as calcium fluoride; The addition amount of the calcium salt is set based on the amount of ions other than fluorine ions that form a sparingly soluble salt with calcium.
【０００７】従来、Ｃａ塩の添加量は、原水中のフッ素
濃度のみに基いて決定されており、その他のイオンが考
慮されることはなかったが、本発明者らは、各種のフッ
素含有水の処理特性について鋭意検討を行った結果、得
られる処理水のフッ素濃度は、原水中の、フッ素以外
の、Ｃａと難溶性塩を生成する共存イオン（以下、この
イオンを「難溶性塩生成イオン」と称す。）の影響を受
けること、Ｃａ塩は原水中のフッ素イオンに対してのみ
ならず、原水中の難溶性塩生成イオンに対しても当量以
上必要であることを見出した。Heretofore, the amount of Ca salt added has been determined only based on the concentration of fluorine in the raw water, and other ions have not been taken into account. As a result of diligent study on the treatment characteristics of the treated water, the fluorine concentration of the treated water obtained was determined to be the coexisting ion that forms a sparingly soluble salt with Ca other than fluorine in the raw water (hereinafter, this ion is referred to as a “sparing salt-forming ion ), And that Ca salts are necessary not only for the fluoride ions in the raw water but also for the hardly soluble salt-forming ions in the raw water in an equivalent amount or more.
【０００８】この難溶性塩生成イオンとしては、リン酸
イオン（ＰＯ４ ３−）、硫酸イオン（ＳＯ４ ２−）、炭
酸イオン（ＣＯ３ ２−）等が挙げられるが、このような
難溶性塩生成イオンが処理水のフッ素濃度に影響を及ぼ
す機構は次の様に推定される。[0008] As the sparingly soluble salt-forming ion, phosphate ion (PO 4 3-), sulfate ion (2-SO 4), carbonate ions (CO 3 2-) and the like, but although such sparingly soluble The mechanism by which the salt-forming ions affect the fluorine concentration of the treated water is presumed as follows.
【０００９】即ち、例えば硫酸イオンの場合、ＣａＳＯ
４の溶解度は２０００ｍｇ／Ｌ，ＣａＦ２の溶解度は１
５ｍｇ／Ｌで、ＣａＦ２の溶解度はＣａＳＯ４の溶解度
に比べて格段に小さいことから、フッ素と当量のＣａ塩
が存在すれば、一般的にはＣａＦ２の生成反応がＣａＳ
Ｏ４の生成反応に優先して起こるはずである。しかし、
実際にはＣａＦ２の沈殿生成と同時に、沈殿を生じない
ＣａＳＯ４（ａｑ．）、いわゆる分子状のＣａＳＯ４が
生成し、Ｃａ塩がＳＯ４ ２−に固定されるため、Ｃａ
２＋＋２Ｆ−→ＣａＦ２の反応が阻害される。従って、
このような難溶性塩生成イオンと反応するＣａ塩も添加
する必要がある。That is, for example, in the case of sulfate ions, CaSO
The solubility of 4 was 2000 mg / L, and the solubility of CaF 2 was 1
At 5 mg / L, the solubility of CaF 2 is much lower than the solubility of CaSO 4. Therefore, if Ca salts equivalent to fluorine are present, the reaction of CaF 2 formation is generally CaS 2.
It should occur in preference to the O 4 formation reaction. But,
Actually, simultaneously with the precipitation of CaF 2 , CaSO 4 (aq.) Which does not cause precipitation, that is, so-called molecular CaSO 4 is generated, and the Ca salt is fixed to SO 4 2- ,
2+ + 2F - → reaction of CaF 2 is inhibited. Therefore,
It is also necessary to add a Ca salt that reacts with such poorly soluble salt-forming ions.
【００１０】なお、本出願人は、先にフッ素含有水にＣ
ａ塩を添加して処理するに当たり、処理水の水質の向
上、ＣａＦ２の結晶化促進の目的で、フッ素含有水に硫
酸及び／又は硫酸塩を添加する方法を提案した（特願平
１１−１４６８２２号、特願平１１−２１８９９０
号）。[0010] The applicant of the present invention has previously reported that fluorine-containing water contains C
In the treatment with the addition of salt a, a method of adding sulfuric acid and / or sulfate to fluorine-containing water for the purpose of improving the quality of the treated water and accelerating the crystallization of CaF 2 was proposed (Japanese Patent Application No. Hei 11-1999). No. 146822, Japanese Patent Application No. 11-218990
issue).
【００１１】このように原水に硫酸及び／又は硫酸塩を
添加する場合には、添加される硫酸及び／又は硫酸塩の
硫酸イオン量も考慮する必要があり、従って、この場合
にはＣａ塩添加量は原水中のフッ素イオン量、難溶性塩
生成イオン量及び添加により増加する硫酸イオン量に基
いて決定する。When sulfuric acid and / or sulfate is added to raw water in this way, it is necessary to consider the amount of sulfuric acid and / or sulfate ion to be added. The amount is determined on the basis of the amount of fluorine ions in the raw water, the amount of sparingly soluble salt-forming ions, and the amount of sulfate ions that increase with the addition.
【００１２】また、原水中に難溶性塩生成イオンが複数
種類ある場合、すべての難溶性塩生成イオン量を測定す
る必要はなく、主要な難溶性塩生成イオン、即ち原水中
の濃度が高い難溶性塩生成イオンの１種又は２種以上を
選択し、この難溶性塩生成イオン量を測定してＣａ塩添
加量を設定しても良い。When there are a plurality of types of hardly soluble salt-forming ions in the raw water, it is not necessary to measure all the amounts of the hardly soluble salt-forming ions. One or more of the soluble salt-forming ions may be selected, and the amount of the sparingly soluble salt-forming ions may be measured to set the Ca salt addition amount.
【００１３】[0013]
【発明の実施の形態】以下に本発明のフッ素含有水の処
理方法の実施の形態を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the method for treating fluorine-containing water of the present invention will be described below in detail.
【００１４】本発明においては、半導体部品製造におけ
るシリコンウェハ製造工程から排出されるフッ素含有廃
水、ステンレス鋼板製造工程から排出される酸洗廃水、
フッ酸製造廃水、ゴミ焼却廃水等のフッ素含有水にＣａ
塩を添加してＣａＦ２を生成させ、このＣａＦ２を沈殿
分離する。In the present invention, fluorine-containing wastewater discharged from a silicon wafer manufacturing process in manufacturing semiconductor parts, pickling wastewater discharged from a stainless steel plate manufacturing process,
Ca is added to fluorine-containing water such as hydrofluoric acid production wastewater and waste
Salts to generate CaF 2 was added and the precipitate separated the CaF 2.
【００１５】添加するＣａ塩としては、一般に、安価な
水酸化カルシウム（消石灰：Ｃａ（ＯＨ）２）が用いら
れているが、これに限らず、炭酸カルシウム、生石灰等
を用いても良い。As the Ca salt to be added, inexpensive calcium hydroxide (slaked lime: Ca (OH) 2 ) is generally used, but not limited thereto, calcium carbonate, quick lime and the like may be used.
【００１６】このようなＣａ塩の添加でＣａＦ２が析出
するｐＨ条件は、５〜１０、好ましくは５．５〜７．５
であるため、Ｃａ塩として特にＣａ（ＯＨ）２を添加し
た場合、ｐＨが高くなり過ぎ、このようなｐＨ条件に調
整することができない場合には、硫酸、塩酸等の酸を添
加して適宜ｐＨ調整する必要がある。The pH condition at which CaF 2 is precipitated by the addition of such a Ca salt is 5 to 10, preferably 5.5 to 7.5.
Therefore, particularly when Ca (OH) 2 is added as a Ca salt, the pH becomes too high, and when it is not possible to adjust to such a pH condition, an acid such as sulfuric acid, hydrochloric acid or the like is added and appropriately added. It is necessary to adjust the pH.
【００１７】また、前述の如く、処理水の水質の向上、
ＣａＦ２の結晶化促進の目的で、フッ素含有水に硫酸及
び／又は硫酸塩を添加する場合、添加する硫酸や硫酸塩
としては、工業硫酸、硫酸ナトリウム等を用いることが
でき、また、この硫酸源としては硫酸イオンを含有する
他の廃水、例えば、鋼板酸洗廃水、排煙脱硫廃水を用い
ることもできる。Further, as described above, the quality of treated water can be improved,
When sulfuric acid and / or sulfate is added to the fluorine-containing water for the purpose of promoting crystallization of CaF 2 , industrial sulfuric acid, sodium sulfate, or the like can be used as the sulfuric acid or sulfate to be added. As a source, other wastewater containing sulfate ions, for example, steel plate pickling wastewater and flue gas desulfurization wastewater can also be used.
【００１８】本発明においては、フッ素含有水にＣａ塩
或いはＣａ塩と硫酸及び／又は硫酸塩、その他ｐＨ調整
のための酸等を添加してＣａＦ２を生成させるに当た
り、原水中のフッ素イオン量と難溶性塩生成イオン量に
基いて、或いは、硫酸及び／又は硫酸塩を添加する場合
には、更に添加により増加する硫酸イオン量に基いてＣ
ａ塩添加量を決定する。In the present invention, when CaF 2 is produced by adding Ca salt or Ca salt and sulfuric acid and / or sulfate, and other acids for adjusting pH to fluorine-containing water, the amount of fluorine ions in raw water is reduced. And when sulfuric acid and / or a sulfate are added, the amount of C is determined based on the amount of sulfate ions that increase with the addition of sulfuric acid and / or sulfate.
a Determine the amount of salt added.
【００１９】この難溶性塩生成イオンとは、一般的に
は、Ｃａとの反応で、溶解度が５００ｍｇ／Ｌ以下であ
るような難溶性塩を生成するものである。The poorly soluble salt forming ions generally form a poorly soluble salt having a solubility of 500 mg / L or less by reaction with Ca.
【００２０】このような原水中の難溶性塩生成イオンと
しては、前述の如く、ＰＯ４ ３−、ＳＯ４ ２−、ＣＯ３
２−等が挙げられることから、本発明では、原水中のＦ
−濃度、ＰＯ４ ３−濃度、ＳＯ４ ２−濃度、ＣＯ３ ２−
濃度に基いて、Ｃａ塩添加量は下記式により算出するこ
とができる。 Ｃａ(mg/L)＝（Ｆ−濃度×Ｃａ／２Ｆ）＋（ＰＯ４ ３−
濃度×３Ｃａ／２ＰＯ４）＋（ＳＯ４ ２−濃度×Ｃａ／
ＳＯ４）＋（ＣＯ３ ２−濃度×Ｃａ／ＣＯ３） ＝（Ｆ−濃度×４０／３８）＋（ＰＯ４ ３−濃度×１２
０／１９０）＋（ＳＯ４ ２−濃度×４０／９６）＋（Ｃ
Ｏ３ ２−濃度×４０／６０）As described above, the poorly soluble salt-forming ions in the raw water include PO 4 3− , SO 4 2− and CO 3 , as described above.
2-, etc., in the present invention, F in the raw water
- concentration, PO 4 3- concentration, SO 4 2-concentration, CO 3 2-
Based on the concentration, the amount of Ca salt added can be calculated by the following equation. Ca (mg / L) = (F − concentration × Ca / 2F) + (PO 4 3−
Concentration × 3Ca / 2PO 4 ) + (SO 4 2- concentration × Ca /
SO 4 ) + (CO 3 2- concentration × Ca / CO 3 ) = (F − concentration × 40/38) + (PO 4 3- concentration × 12
0/190) + (SO 4 2- concentration × 40/96) + (C
O 3 2- concentration × 40/60)
【００２１】また、前述の如く、硫酸及び／又は硫酸塩
を添加する場合のように、難溶性塩生成イオンを原水に
添加する場合には、上述の反応式に更に、添加された難
溶性塩生成イオンに対する当量を加える。As described above, when a sparingly soluble salt-forming ion is added to raw water as in the case of adding sulfuric acid and / or a sulfate, the added sparingly soluble salt is further added to the above reaction formula. Add an equivalent to the product ion.
【００２２】なお、原水中に難溶性塩生成イオンが複数
種類ある場合、すべての難溶性塩生成イオン量を測定し
てＣａ塩添加量の算出に用いる必要はなく、主要な難溶
性塩生成イオン、即ち原水中の濃度が高い、例えば１０
０ｐｐｍ以上の難溶性塩生成イオンの１種又は２種以上
を選択し、こ難溶性塩生成イオン量を測定してＣａ塩添
加量を設定しても良い。When there are a plurality of types of sparingly soluble salt-forming ions in the raw water, it is not necessary to measure the amounts of all the sparingly soluble salt-forming ions to calculate the amount of Ca salt added. That is, the concentration in raw water is high, for example, 10
One or two or more types of the sparingly soluble salt forming ions of 0 ppm or more may be selected, and the amount of the sparingly soluble salt forming ions may be measured to set the Ca salt addition amount.
【００２３】例えば、ＨＦ５０００ｍｇ／Ｌ，Ｎａ２Ｓ
Ｏ４１２００ｍｇ／Ｌ（Ｈ２ＳＯ４換算）を含む原水の
場合、Ｃａ塩の必要添加量（Ｃａ量）は、５４９０ｍｇ
／Ｌ（＝（５００×４０／４０）＋（１２００×４０／
９８）である。この添加量はＣａ（ＯＨ）２の場合、１
０１６０ｍｇ／Ｌ（＝５４９０×７４／４０）である。
この添加量は、２ＨＦ＋Ｃａ（ＯＨ）２→ＣａＦ２↓＋
２Ｈ２Ｏの反応でＣａＦ２のみを生成させるために必要
なＣａ（ＯＨ）２量９２５０ｍｇ／Ｌ（＝５０００×７
４／４０）よりも９１０ｍｇ／Ｌ（＝１０１６０−９２
５０）多い。For example, HF 5000 mg / L, Na 2 S
In the case of raw water containing 1200 mg / L of O 4 (in terms of H 2 SO 4 ), the required amount of Ca salt (Ca amount) is 5490 mg.
/ L (= (500 × 40/40) + (1200 × 40 /
98). In the case of Ca (OH) 2 , the added amount is 1
It is 0160 mg / L (= 5490 × 74/40).
This addition amount is 2HF + Ca (OH) 2 → CaF 2 ↓ +
9250 mg / L of Ca (OH) 2 necessary to generate only CaF 2 in the reaction of 2H 2 O (= 5000 × 7
910 mg / L (= 10160-92)
50) Many.
【００２４】この過剰分のＣａ（ＯＨ）２はＣａＳＯ４
を生成させる反応と同時にｐＨを上昇させる要因とな
り、前述のＣａＦ２析出のための好適ｐＨ条件に調整で
きない場合がある。This excess Ca (OH) 2 is converted to CaSO 4
Is a factor that raises the pH at the same time as the reaction for generating, and it may not be possible to adjust the pH to the above-mentioned suitable conditions for CaF 2 precipitation.
【００２５】この場合には、この９１０ｍｇ／ＬのＣａ
（ＯＨ）２に相当する塩酸（９１０×２ＨＣｌ／Ｃａ
（ＯＨ）２＝９００ｍｇ／Ｌ）を添加してＣａ（ＯＨ）
２＋２ＨＣｌ→ＣａＣｌ２＋２Ｈ２Ｏで中和させるのが
好ましい。In this case, 910 mg / L of Ca
Hydrochloric acid equivalent to (OH) 2 (910 × 2 HCl / Ca
(OH) 2 = 900 mg / L) to add Ca (OH)
It is preferable to neutralize with 2 + 2HCl → CaCl 2 + 2H 2 O.
【００２６】なお、Ｃａ塩の添加量の最低必要量は原水
中のフッ素イオン量及び難溶性塩生成イオン量と添加さ
れた難溶性塩生成イオン量の合計に当たる当量であり、
これよりも過剰に添加しても処理水のフッ素濃度の低下
は殆どなく、むしろ薬注コストの高騰、残留Ｃａイオン
によるＣａＣＯ３スケール発生の問題等が生じ好ましく
ない。従って、Ｃａ塩は上記当量以上であって、処理水
中に残留するＣａ濃度が４００ｍｇ／Ｌ以下、特に２０
０ｍｇ／Ｌ以下となるように添加するのが好ましい。The minimum required amount of the Ca salt to be added is equivalent to the sum of the amount of the fluoride ion and the amount of the hardly soluble salt forming ion in the raw water and the amount of the added hardly soluble salt forming ion.
Even if it is added in excess, the fluorine concentration of the treated water hardly decreases, but rather the chemical injection cost rises and CaCO 3 scale is generated due to residual Ca ions, which is not preferable. Therefore, the Ca salt is equal to or more than the above equivalent, and the Ca concentration remaining in the treated water is 400 mg / L or less, particularly 20 mg / L.
It is preferable to add so as to be 0 mg / L or less.
【００２７】[0027]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明する。The present invention will be described more specifically below with reference to examples and comparative examples.
【００２８】実施例１、比較例１，２ ＨＦ５０００ｍｇ／Ｌ，Ｈ２ＳＯ４１０００ｍｇ／Ｌの
合成廃水を原水として用い、Ｃａ（ＯＨ）２を添加して
ｐＨ６．５〜７．０に調整し、３０分反応させた。この
とき、Ｃａ（ＯＨ）２は、原水中のＦ−及びＳＯ４ ２−
の両方に対して当量添加された。反応後、反応液をＮ
ｏ．５Ａ濾紙で濾過して濾液（処理水）のフッ素濃度を
測定した（実施例１）。Example 1, Comparative Examples 1 and 2 Synthetic wastewater of 5000 mg / L HF and 1000 mg / L H 2 SO 4 was used as raw water, and Ca (OH) 2 was added to adjust the pH to 6.5 to 7.0. For 30 minutes. At this time, Ca (OH) 2 is converted into F − and SO 4 2− in the raw water.
Were added in equivalent amounts. After the reaction, the reaction solution is
o. The solution was filtered through a 5A filter paper and the fluorine concentration of the filtrate (treated water) was measured (Example 1).
【００２９】比較例１，２においては、Ｃａ（ＯＨ）２
を不足させるために、表１に示す如く、Ｈ２ＳＯ４の一
部をＮａ２ＳＯ４に置換した合成廃水を原水とし、Ｃａ
（ＯＨ）２を添加してｐＨ６．５〜７．０に調整し、同
様に３０分反応させた後濾過して処理水を得、そのフッ
素濃度を測定した。In Comparative Examples 1 and 2, Ca (OH) 2
To shortage, as shown in Table 1, a portion of H 2 SO 4 and raw synthetic wastewater was replaced by Na 2 SO 4, Ca
(OH) 2 was added to adjust the pH to 6.5 to 7.0, and after similarly reacting for 30 minutes, filtration was performed to obtain treated water, and the fluorine concentration was measured.
【００３０】即ち、ＮａＳＯ４は中性であるため、酸性
のＨ２ＳＯ４の一部をＮａＳＯ４で置換することにより
少ないＣａ（ＯＨ）２量で中和するため、Ｃａ塩が不足
する場合の処理が行える。[0030] That is, since NaSO 4 is a neutral, to neutralize with less Ca (OH) 2 amounts by substituting a part of acidic H 2 SO 4 in NaSO 4, if the Ca salt is insufficient Can be performed.
【００３１】実施例１及び比較例１，２で得られた処理
水のフッ素濃度は表１に示す通りであり、Ｆ−量のみな
らずＳＯ４ ２−量にも対応するＣａ（ＯＨ）２が添加さ
れない場合は、処理水の水質が著しく低下することがわ
かる。The fluorine concentration of the treated water obtained in Example 1 and Comparative Examples 1 and 2 is as shown in Table 1, and Ca (OH) 2 corresponding to not only F - content but also SO 4 2- content. It can be seen that when no is added, the quality of the treated water is significantly reduced.
【００３２】[0032]
【表１】 [Table 1]
【００３３】比較例３〜５ 実施例１の合成廃水にＮａ２ＳＯ４を表２に示す量添加
した後、Ｃａ（ＯＨ） ２を添加してｐＨ６．５〜７．０
に調整し、実施例１と同様に反応させた後、処理水を
得、そのフッ素濃度を測定して結果を表２に示した。Comparative Examples 3 to 5 Na was added to the synthetic wastewater of Example 1.2SO4In the amounts shown in Table 2
And then Ca (OH) 2To pH 6.5 to 7.0.
And reacted in the same manner as in Example 1.
The fluorine concentration was measured and the results are shown in Table 2.
【００３４】なお、表２には、対比のために実施例１の
結果も併記した。Table 2 also shows the results of Example 1 for comparison.
【００３５】比較例３〜５では、原水中のＨ２ＳＯ４に
対応するＣａ（ＯＨ）２量は確保されているが、添加し
たＮａ２ＳＯ４に対応するＣａ（ＯＨ）２量が不足する
ため、処理水の水質が悪化した。[0035] In Comparative Example 3-5, although the Ca (OH) 2 quantity corresponding to H 2 SO 4 in the raw water is ensured, insufficient to Ca (OH) 2 amounts corresponding to Na 2 SO 4 was added Therefore, the quality of the treated water deteriorated.
【００３６】[0036]
【表２】 [Table 2]
【００３７】実施例２〜５、比較例６ ＨＦ２５００ｍｇ／Ｌ，Ｈ２ＳＯ４１０００ｍｇ／Ｌの
合成廃水を原水として用い、Ｃａ（ＯＨ）２を添加して
ｐＨ６．５〜７．０に調整し、３０分反応させた。この
とき、Ｃａ（ＯＨ）２は原水中のＦ−及びＳＯ４ ２−の
両方に対して当量添加された。反応後、反応液をＮｏ．
５Ａ濾紙で濾過して濾液（処理水）のフッ素濃度を測定
した（実施例２）。Examples 2 to 5 and Comparative Example 6 Using synthetic wastewater of 2500 mg / L of HF and 1000 mg / L of H 2 SO 4 as raw water, Ca (OH) 2 was added to adjust the pH to 6.5 to 7.0. For 30 minutes. At this time, Ca (OH) 2 is in the raw water F - is equivalent added to both, and SO 4 2-of. After the reaction, the reaction mixture was
The solution was filtered through a 5A filter paper and the fluorine concentration of the filtrate (treated water) was measured (Example 2).
【００３８】実施例３〜５及び比較例６おいては、Ｃａ
（ＯＨ）２を過剰とするために、Ｃａ（ＯＨ）２と共
に、ＣａＣｌ２を添加してｐＨ６．５〜７．０に調整
し、同様に３０分反応させた後、濾過して処理水を得、
そのフッ素濃度を測定した。In Examples 3 to 5 and Comparative Example 6, Ca
In order to make (OH) 2 excessive, CaCl 2 is added together with Ca (OH) 2 to adjust the pH to 6.5 to 7.0, and the reaction is similarly performed for 30 minutes. Get
The fluorine concentration was measured.
【００３９】即ち、ＣａＣｌ２は中性でＣａ（ＯＨ）２
の添加量は実施例２の場合と同量でＣａＣｌ２を増加さ
せて中和することができ、Ｃａ塩が過剰の場合の処理が
行える。That is, CaCl 2 is neutral and Ca (OH) 2
Can be neutralized by increasing the amount of CaCl 2 in the same amount as in the case of Example 2, and can perform the treatment when the Ca salt is excessive.
【００４０】実施例２〜５及び比較例６で得られた処理
水のフッ素濃度は表３に示す通りであり、Ｃａ塩添加量
はＦ−及びＳＯ４ ２−の合計当量に対して若干過剰とす
ることにより処理水のフッ素濃度は低下するが、過度な
過剰添加は、処理水のＣａ濃度が増加し、薬剤コストも
高騰する上にスケール発生の問題が生じる恐れもあるこ
とがわかる。The fluorine concentration in the treated water obtained in Examples 2-5 and Comparative Example 6 are as shown in Table 3, Ca salt amount is F - and SO 4 slight excess relative to the total equivalents of 2 It can be seen that the fluorine concentration of the treated water is reduced by the above, but the excessive addition of the treated water increases the Ca concentration of the treated water, increases the chemical cost, and may cause a problem of scale generation.
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【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、フッ素含有水にＣａ塩を添加し
てフッ素をＣａＦ２として沈殿分離する方法において、
Ｃａ塩の必要添加量を容易かつ的確に求め、適正な薬注
を行って、フッ素濃度が著しく低減された高水質な処理
水を得ることができる。本発明の方法では、単にフッ素
含有水中のフッ素イオン量と特定の共存イオン量を測定
するのみで、この測定値に基いて適正なＣａ塩添加量を
求めることができ、Ｃａ塩の過剰添加による薬剤コスト
の高騰やスケール発生等の問題が防止されると共に、煩
雑な予備実験も不要となり、効率的な処理が行える。As described above in detail, according to the method for treating fluorine-containing water of the present invention, a method of adding a Ca salt to fluorine-containing water to precipitate and separate fluorine as CaF 2 comprises:
The required amount of Ca salt to be added can be easily and accurately obtained, and appropriate chemical injection can be performed to obtain high-quality treated water having a significantly reduced fluorine concentration. In the method of the present invention, an appropriate amount of Ca salt can be obtained based on the measured value only by simply measuring the amount of fluorine ions and the amount of specific coexisting ions in the fluorine-containing water. Problems such as soaring drug costs and generation of scale are prevented, and complicated preliminary experiments are not required, and efficient processing can be performed.
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Claims (3)
フッ素をフッ化カルシウムとして沈殿分離する方法にお
いて、該フッ素含有水中のフッ素イオン量及びカルシウ
ムと難溶性塩を生成するフッ素イオン以外のイオンの量
に基いて、前記カルシウム塩の添加量を設定することを
特徴とするフッ素含有水の処理方法。1. A method of adding a calcium salt to fluorine-containing water to precipitate and separate fluorine as calcium fluoride, wherein the amount of fluorine ions in the fluorine-containing water and the amount of ions other than fluorine ions forming a sparingly soluble salt with calcium are determined. A method for treating fluorine-containing water, comprising setting the amount of the calcium salt to be added based on the amount.
含有水に更に硫酸及び／又は硫酸塩を添加する方法であ
って、該フッ素含有水中のフッ素イオン量、カルシウム
と難溶性塩を生成するフッ素イオン以外のイオン量並び
に該硫酸及び／又は硫酸塩の添加により増加する硫酸イ
オン量に基いて、前記カルシウム塩の添加量を設定する
ことを特徴とするフッ素含有水の処理方法。2. The method according to claim 1, further comprising adding sulfuric acid and / or a sulfate to the fluorine-containing water, wherein the amount of fluorine ions in the fluorine-containing water, calcium and a sparingly soluble salt are produced. A method for treating fluorine-containing water, comprising setting the amount of the calcium salt to be added based on the amount of ions other than fluorine ions and the amount of sulfate ions increased by the addition of the sulfuric acid and / or sulfate.
カルシウムと難溶性塩を生成するフッ素イオン以外のイ
オンのうちの１種又は２種以上を選択し、該イオンの量
に基いて前記カルシウム塩の添加量を設定することを特
徴とするフッ素含有水の処理方法。3. The method according to claim 1, wherein one or more ions other than a fluorine ion which forms the sparingly soluble salt with the calcium are selected, and based on the amount of the ions, A method for treating fluorine-containing water, comprising setting the amount of calcium salt to be added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000025513A JP2001212574A (en) | 2000-02-02 | 2000-02-02 | Method for treating fluorine-containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000025513A JP2001212574A (en) | 2000-02-02 | 2000-02-02 | Method for treating fluorine-containing water |
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| Publication Number | Publication Date |
|---|---|
| JP2001212574A true JP2001212574A (en) | 2001-08-07 |
Family
ID=18551366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000025513A Pending JP2001212574A (en) | 2000-02-02 | 2000-02-02 | Method for treating fluorine-containing water |
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| Country | Link |
|---|---|
| JP (1) | JP2001212574A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001246385A (en) * | 2000-03-06 | 2001-09-11 | Kurita Water Ind Ltd | Treatment process of water containing fluorine |
| JP2002035766A (en) * | 2000-07-21 | 2002-02-05 | Japan Organo Co Ltd | Method for removing fluorine and phosphorus in wastewater |
| JP2009233568A (en) * | 2008-03-27 | 2009-10-15 | Kurita Water Ind Ltd | Method and apparatus for treating fluorine-containing water |
| JP2010158633A (en) * | 2009-01-09 | 2010-07-22 | Sumitomo Metal Mining Co Ltd | Method for separating fluorine from fluorine-containing waste water |
| CN102815774A (en) * | 2011-06-07 | 2012-12-12 | 富士电机株式会社 | Processing method and processing device for industrial wastewater |
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| JP2010158633A (en) * | 2009-01-09 | 2010-07-22 | Sumitomo Metal Mining Co Ltd | Method for separating fluorine from fluorine-containing waste water |
| CN102815774A (en) * | 2011-06-07 | 2012-12-12 | 富士电机株式会社 | Processing method and processing device for industrial wastewater |
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