JP2002292205A - Crystallization reaction apparatus provided with means for measuring turbidity and crystallization method to use the same - Google Patents
Crystallization reaction apparatus provided with means for measuring turbidity and crystallization method to use the sameInfo
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、原水中のフッ素、
リンおよび重金属をはじめとする晶析対象成分を晶析除
去する晶析反応装置、並びに該晶析反応装置を用いた晶
析処理方法に関する。TECHNICAL FIELD The present invention relates to fluorine in raw water,
The present invention relates to a crystallization reactor for crystallizing and removing components to be crystallized, such as phosphorus and heavy metals, and a crystallization treatment method using the crystallization reactor.
【０００２】[0002]
【従来の技術】工場などからの排水の水質については厳
しい制限がなされているが、その規制は年々厳しくなる
傾向にある。電子産業（特に半導体関連）、発電所、ア
ルミニウム工業などから排出される原水中には、フッ
素、リンまたは重金属類という、近年厳しい排水基準が
設けられている元素が含まれている場合が多い。このた
め、これらを排水から効率良く除去することが求められ
ており、フッ素、リン、重金属等を除去する従来の技術
としては、凝集沈殿法、晶析法等が知られている。2. Description of the Related Art Strict restrictions are imposed on the quality of wastewater from factories and the like, but the regulations tend to be stricter year by year. Raw water discharged from the electronics industry (especially semiconductor-related), power plants, aluminum industry, and the like often contains elements such as fluorine, phosphorus, and heavy metals, which have been set to stricter drainage standards in recent years. For this reason, it is required to efficiently remove these from wastewater, and a coagulation sedimentation method, a crystallization method, and the like are known as conventional techniques for removing fluorine, phosphorus, heavy metals, and the like.
【０００３】フッ素の除去技術としては、フッ素を含む
原水に、水酸化カルシウム（Ｃａ（ＯＨ）２）、塩化カ
ルシウム（ＣａＣｌ２）、炭酸カルシウム（ＣａＣ
Ｏ３）をはじめとするカルシウム化合物を添加し、式
（Ｉ）に示されるように、難溶性のフッ化カルシウムを
生じさせることを基本とする。 Ｃａ２＋＋２Ｆ−→ ＣａＦ２↓ （Ｉ） 最も多く用いられているフッ化カルシウム沈殿法では、
硫酸バン土、ポリ塩化アルミニウム、高分子凝集剤等を
添加することにより、式（Ｉ）の反応により生成された
フッ化カルシウムをフロック化し、沈殿槽で固液分離を
することにより、原水からのフッ素除去を行っている。
この沈殿法は、沈殿槽の設置面積が大きいこと、生成さ
れた沈殿汚泥の量が多いこと、汚泥の脱水性が良くない
こと等が問題となっている。[0003] As a technique for removing fluorine, calcium hydroxide (Ca (OH) 2 ), calcium chloride (CaCl 2 ), and calcium carbonate (CaC) are added to raw water containing fluorine.
Basically, a calcium compound such as O 3 ) is added to generate hardly soluble calcium fluoride as shown in the formula (I). Ca 2+ + 2F − → CaF 2 ↓ (I) In the calcium fluoride precipitation method most frequently used,
Calcium fluoride produced by the reaction of the formula (I) is flocculated by adding bansulfate, polyaluminum chloride, a polymer flocculant, etc. Removes fluorine.
This sedimentation method has problems such as a large installation area of a sedimentation tank, a large amount of sedimentation sludge generated, and poor sludge dewatering property.
【０００４】フッ化カルシウムの生成を利用した他のフ
ッ素除去技術としては、特願昭５９−６３８８４号（特
開昭６０−２０６４８５号）に示されるように、フッ素
とカルシウムを含有する種晶を充填した反応糟にフッ素
含有原水をカルシウム剤と共に導入して、種晶上にフッ
化カルシウムを析出させる、いわゆるフッ化カルシウム
晶析法がある。この晶析法においては、一般的に、反応
糟の底部から原水を導入し、種晶を流動化させながら上
向流で通水して処理を行い、必要に応じて反応糟からの
流出水を循環している。この方法の長所としては装置設
置面積を低減できること、汚泥発生量が少ないこと等が
挙げられる。なお、反応糟内に充填される種晶として
は、フッ素とカルシウムを含有する粒子が一般的である
が、必ずしもこれに限定されるものではなく、砂や活性
炭などの微細粒子が用いられる場合もある。As another fluorine removal technique utilizing the formation of calcium fluoride, as disclosed in Japanese Patent Application No. 59-63884 (JP-A-60-206485), a seed crystal containing fluorine and calcium is used. There is a so-called calcium fluoride crystallization method in which fluorine-containing raw water is introduced into a filled reaction vessel together with a calcium agent to precipitate calcium fluoride on seed crystals. In this crystallization method, in general, raw water is introduced from the bottom of the reaction vessel, the seed crystal is fluidized in an upward flow while fluidizing, and the effluent from the reaction vessel is treated as necessary. Is circulating. Advantages of this method include that the installation area of the apparatus can be reduced and the amount of generated sludge is small. In addition, as a seed crystal to be filled in the reaction vessel, particles containing fluorine and calcium are generally used, but the present invention is not necessarily limited thereto, and fine particles such as sand and activated carbon may be used. is there.
【０００５】また、原水からのリンの除去方法として
は、物理化学的な方法や生物学的な方法があるが、生物
学的なリン除去法は下水処理での利用が主であり、上述
のような産業排水の処理においては、カルシウム化合物
やアルミニウム化合物を用いた物理化学的なリン除去法
が採用されることが多い。カルシウム化合物によるリン
除去技術としては、リンを含む原水に、水酸化カルシウ
ム（Ｃａ（ＯＨ）２）、塩化カルシウム（ＣａＣｌ２）
をはじめとするカルシウム化合物を添加し、式（ＩＩ）
および（ＩＩＩ）に示されるように、難溶性のリン酸カ
ルシウムおよびリン酸ヒドロキシアパタイト（以下、リ
ン酸カルシウム等という）を生じさせることを基本とす
る。 ３Ｃａ２＋＋２ＰＯ４ ３−→Ｃａ３（ＰＯ４）２↓ （ＩＩ） ５Ｃａ２＋＋ＯＨ−＋３ＰＯ４ ３−→Ｃａ５ＯＨ（ＰＯ４）３↓ （ＩＩＩ） 最も多く用いられている凝集沈殿法では、硫酸バン土、
ポリ塩化アルミニウム、高分子凝集剤等を添加すること
により、式（ＩＩ）、（ＩＩＩ）の反応により生成され
たリン酸カルシウム等をフロック化し、これを沈殿槽で
固液分離することによって、原水からリンが除去され
る。この方法は沈殿槽の設置面積が大きいこと、生成さ
れた沈殿汚泥の量が多いこと、汚泥の脱水性が良くない
こと等が問題となっている。[0005] As a method for removing phosphorus from raw water, there are physicochemical methods and biological methods. The biological phosphorus removing method is mainly used for sewage treatment. In such treatment of industrial wastewater, a physicochemical phosphorus removal method using a calcium compound or an aluminum compound is often employed. As a phosphorus removal technique using a calcium compound, calcium hydroxide (Ca (OH) 2 ) and calcium chloride (CaCl 2 ) are added to raw water containing phosphorus.
And a calcium compound such as
As shown in (III) and (III), it is based on generating poorly soluble calcium phosphate and hydroxyapatite (hereinafter referred to as calcium phosphate and the like). 3Ca 2+ + 2PO 4 3- → Ca 3 (PO 4 ) 2 ↓ (II) 5Ca 2+ + OH − + 3PO 4 3- → Ca 5 OH (PO 4 ) 3 ↓ (III) In the most frequently used coagulation precipitation method, Bansulfate,
By adding polyaluminum chloride, a polymer flocculant, and the like, calcium phosphate and the like generated by the reaction of the formulas (II) and (III) are flocculated and solid-liquid separated in a sedimentation tank to obtain phosphorus from raw water. Is removed. This method has problems in that the installation area of the sedimentation tank is large, the amount of generated sedimentary sludge is large, and the dewatering property of the sludge is not good.
【０００６】リン酸カルシウムの生成を利用した他のリ
ン除去技術としては、リンとカルシウムを含有する種
晶、または砂や活性炭などの微細粒子を充填した反応糟
に、リン含有原水をカルシウム剤と共に導入して、種晶
上にリン酸カルシウムを析出させる、いわゆるリン酸カ
ルシウム晶析法が提案されている。この方法の長所とし
ては、装置設置面積を低減できること、汚泥発生量が少
ないこと等が挙げられる。しかし、いわゆる下水処理の
場合には、原水中のリンの濃度がそれほど高くない場合
が多いことや、きわめて多量の原水の処理が要求される
場合が多いことから、現時点ではあまり実用化されてい
ない。Another phosphorus removal technique utilizing the formation of calcium phosphate is as follows. A phosphorus-containing raw water is introduced together with a calcium agent into a reaction vessel filled with seed crystals containing phosphorus and calcium, or fine particles such as sand or activated carbon. Thus, a so-called calcium phosphate crystallization method in which calcium phosphate is precipitated on a seed crystal has been proposed. Advantages of this method include that the installation area of the apparatus can be reduced and the amount of generated sludge is small. However, in the case of so-called sewage treatment, the concentration of phosphorus in raw water is often not so high, and the processing of very large amounts of raw water is often required. .
【０００７】さらに、銅、鉄、鉛などの重金属を原水か
ら除去する技術としては、水酸化ナトリウムなどの添加
によりｐＨを上昇させ、金属水酸化物の不溶体を生じさ
せることにより、凝集沈殿あるいは晶析除去する技術が
代表的なものとして知られている。Further, as a technique for removing heavy metals such as copper, iron, and lead from raw water, the pH is increased by adding sodium hydroxide or the like, and an insoluble metal hydroxide is formed to cause coagulation or precipitation. The crystallization removal technique is known as a typical technique.
【０００８】上述の様に、フッ素、リンおよび／または
重金属を含む原水からこれらを除去するために晶析処理
を利用することができ、該晶析処理に使用される従来の
晶析反応装置の概略図を図２に示す。図２の態様におい
ては、晶析反応装置は、内部に種晶２が充填され、原水
中の晶析対象成分を晶析反応により除去する晶析反応糟
１と、原水を該晶析反応糟１に供給する原水供給手段
と、晶析用薬液を該晶析反応糟１に供給する晶析用薬液
供給手段と、該晶析反応糟１から排出される処理水の少
なくとも一部を該晶析反応糟１に返送する処理水循環手
段とを具備している。また、原水供給手段は、原水を貯
留する原水タンク３、該原水タンク３と晶析反応糟１と
を連結する原水供給ライン４を具備し、該原水供給ライ
ン４には原水移送のためのポンプ、および原水中の晶析
対象成分の濃度を測定する濃度測定手段５が介装されて
いる。晶析用薬液供給手段は、晶析用薬液を貯留する晶
析用薬液タンク６、該晶析用薬液タンク６と晶析反応糟
１とを連結する晶析用薬液供給ライン７を具備し、該晶
析用薬液供給ライン７には薬液移送のためのポンプが介
装されている。晶析反応糟１で得られる処理水は該晶析
反応糟１の上部から処理水排出ライン８を通って排出さ
れ、該処理水排出ライン８には砂ろ過装置９および処理
水貯留タンク１０が介装されている。図２の態様におい
ては、処理水循環手段として、処理水貯留タンク１０と
晶析反応糟１を連結する処理水循環ライン１１が設けら
れており、該処理水循環ライン１１には処理水移送のた
めのポンプが介装されている。As described above, a crystallization process can be used to remove fluorine, phosphorus and / or heavy metals from raw water, and the conventional crystallization reaction apparatus used for the crystallization process can be used. A schematic diagram is shown in FIG. In the embodiment of FIG. 2, the crystallization reaction apparatus includes a crystallization reaction tank 1 filled with seed crystals 2 and removing a component to be crystallized in raw water by a crystallization reaction, and a raw crystal water in the crystallization reaction tank. A raw water supply means for supplying the crystallization liquid to the crystallization reaction tank 1; and a crystallization liquid supply means for supplying at least a part of the treated water discharged from the crystallization reaction tank 1 to the crystallization reaction tank 1. A circulating means for returning treated water to the reaction vessel 1. The raw water supply means includes a raw water tank 3 for storing raw water, and a raw water supply line 4 connecting the raw water tank 3 and the crystallization reaction tank 1. The raw water supply line 4 has a pump for transferring raw water. , And a concentration measuring means 5 for measuring the concentration of the component to be crystallized in the raw water. The crystallization solution supply means includes a crystallization solution tank 6 for storing the crystallization solution, and a crystallization solution supply line 7 connecting the crystallization solution tank 6 and the crystallization reactor 1. The crystallization solution supply line 7 is provided with a pump for transferring the solution. The treated water obtained in the crystallization reaction tank 1 is discharged from the upper part of the crystallization reaction tank 1 through a treated water discharge line 8, and the treated water discharge line 8 is provided with a sand filtration device 9 and a treated water storage tank 10. It is interposed. In the embodiment of FIG. 2, a treated water circulation line 11 that connects the treated water storage tank 10 and the crystallization reactor 1 is provided as a treated water circulation means, and the treated water circulation line 11 has a pump for transferring treated water. Is interposed.
【０００９】図２の従来の晶析反応装置では、原水供給
ラインに介装された濃度測定手段５で測定される原水中
の晶析対象成分の濃度に応じて、晶析用薬液供給制御手
段１３によって、晶析用薬液供給ライン７に介装された
ポンプを制御し、晶析用薬液の供給量を制御することが
行われる。すなわち、晶析反応糟１に供給される原水中
の晶析対象成分の濃度が上昇した場合には、それに応じ
て晶析用薬液の供給量を増加することにより晶析反応を
促進し、晶析反応糟１から排出される処理水中の晶析対
象成分の濃度を低減させることができる。In the conventional crystallization reaction apparatus shown in FIG. 2, a crystallization chemical liquid supply control means is provided in accordance with the concentration of the component to be crystallized in the raw water measured by the concentration measuring means 5 interposed in the raw water supply line. By 13, the pump interposed in the crystallization solution supply line 7 is controlled to control the supply amount of the crystallization solution. That is, when the concentration of the component to be crystallized in the raw water supplied to the crystallization reaction tank 1 increases, the crystallization reaction is promoted by increasing the supply amount of the crystallization solution in accordance with the increase. The concentration of the component to be crystallized in the treated water discharged from the crystallization reaction tank 1 can be reduced.
【００１０】[0010]
【発明が解決しようとする課題】晶析処理により除去が
望まれるフッ素を含む排水として、半導体工場において
排出されるフッ酸排水があり、該フッ酸排水はシリコン
基板の洗浄工程で用いられるフッ酸やエッチング工程で
用いられるバッファードフッ酸を排水中に含むものであ
る。シリコン基板のフッ酸洗浄においては、一般的に数
％のフッ酸が１〜数回使用された後に廃棄されるので、
高濃度のフッ酸排水が１時間〜数時間に１度排出される
こととなる。また、エッチング工程で使用されるバッフ
ァードフッ酸は、数〜十数％の濃厚なフッ酸とフッ化ア
ンモニウムの混合液であり、エッチング処理は基板を数
分〜数十分の間、前記混合液に浸漬するバッチ式で行わ
れ、バッファードフッ酸排水は基板洗浄排水と同様に１
時間〜数時間に一度排出される。これらのフッ酸排水は
半導体工場における他の排水と混合して排出されるの
で、該半導体工場から排出される最終的な排水中のフッ
素濃度は０〜５０００ｍｇ／Ｌ程度の範囲で変動する。
排水中の晶析対象成分の濃度変動が大きい例として、上
記半導体工場でのフッ素含有排水を挙げたが、フッ素以
外の晶析対象成分であっても、上述のような大きな濃度
変動が生じるようなものは存在している。As a waste water containing fluorine which is desired to be removed by a crystallization treatment, there is a hydrofluoric acid waste water discharged in a semiconductor factory, and the hydrofluoric acid waste water is used in a cleaning process of a silicon substrate. And buffered hydrofluoric acid used in the etching process. In hydrofluoric acid cleaning of a silicon substrate, since a few percent of hydrofluoric acid is generally discarded after being used once or several times,
High-concentration hydrofluoric acid wastewater is discharged once every one to several hours. The buffered hydrofluoric acid used in the etching process is a mixed solution of concentrated hydrofluoric acid and ammonium fluoride having a concentration of several to several tens of percent, and the etching process is performed on the substrate for several minutes to several tens minutes. It is carried out in a batch mode by immersion in a liquid.
Discharged every hour to several hours. Since these hydrofluoric acid wastewaters are mixed with other wastewater in the semiconductor factory and discharged, the final fluorine concentration in the wastewater discharged from the semiconductor factory varies in the range of about 0 to 5000 mg / L.
As an example in which the concentration fluctuation of the crystallization target component in the wastewater is large, the fluorine-containing wastewater in the semiconductor factory is mentioned. However, even in the case of the crystallization target component other than fluorine, such a large concentration fluctuation as described above occurs. Things exist.
【００１１】このような晶析対象成分の濃度の上昇に対
応するために、原水中および／または処理水中の晶析対
象成分の濃度をモニターし、晶析用薬液の供給量を増加
する方法が行われている。しかし、晶析反応において
は、晶析反応糟内で、晶析用薬液中の晶析反応成分（例
えば、フッ化カルシウムの生成における「Ｃａ」等）
と、晶析対象成分との存在割合が、晶析対象成分の溶解
度に対する過飽和条件の、液中に核が存在しなければ晶
析反応を生じない準安定域に制御されることが要求され
る。よって、単に晶析用薬液の供給量を増加したので
は、存在割合が、より過飽和度が大きい不安定域に達
し、晶析対象成分が種晶上に晶析するのではなく、微細
な結晶を形成し、該微細結晶が処理水中に排出され、処
理水の水質が悪化するという問題があった。In order to cope with such an increase in the concentration of the component to be crystallized, a method of monitoring the concentration of the component to be crystallized in the raw water and / or the treated water and increasing the supply amount of the chemical for crystallization has been proposed. Is being done. However, in the crystallization reaction, a crystallization reaction component (for example, “Ca” in the formation of calcium fluoride) in the crystallization solution in the crystallization reaction tank.
It is required that the abundance ratio of the component to be crystallized and the component to be crystallized be controlled in a metastable region under supersaturation conditions with respect to the solubility of the component to be crystallized, in which no crystallization reaction occurs unless nuclei are present in the liquid. . Therefore, simply increasing the supply amount of the crystallization solution would result in the presence ratio reaching an unstable region where the degree of supersaturation was greater, and the component to be crystallized would not be crystallized on the seed crystal, but rather a fine crystal. And the fine crystals are discharged into the treated water, and the quality of the treated water deteriorates.
【００１２】処理水中での微細結晶の存在は、処理水排
出ライン８に介装される場合が多い砂ろ過装置９の目詰
まりを起こし、差圧を上昇させる。また、数μｍ以下の
粒径の結晶は砂ろ過装置９を通過して処理水にリークす
るので、処理水中に溶存している晶析対象成分だけでな
く、処理水中に含まれるトータルの晶析対象成分を考え
た場合に、系外に排出される処理水の水質が悪化する。
さらに、処理水の濁度が増加するという問題も招く。The presence of fine crystals in the treated water causes clogging of the sand filtration device 9, which is often interposed in the treated water discharge line 8, and raises the differential pressure. In addition, since crystals having a particle size of several μm or less pass through the sand filtration device 9 and leak into the treated water, not only the components to be crystallized dissolved in the treated water but also the total crystallization contained in the treated water. Considering the target component, the quality of the treated water discharged out of the system deteriorates.
Further, there is a problem that the turbidity of the treated water increases.
【００１３】上述の該微細結晶の生成は、晶析対象成分
の増加だけでなく、水温の変動、共存する他のイオンや
界面活性剤の混入などにより溶解度が変化した場合にも
起こるものである。つまり、原水中の晶析対象成分を測
定し、これを基準に制御するだけでは微細結晶の形成を
完全に防ぐことはできず、安定に運転を行うことができ
ない。また、生じた微細結晶は、処理水を循環すること
により晶析反応糟に返送されるので、そのまま原水の供
給を続け、微細結晶が生じやすい状態が続いた場合に
は、さらなる処理水の白濁を引き起こし、上記弊害を助
長することとなる。また、一旦白濁が起こると、微細結
晶が発生しないような状態に晶析反応糟１が戻るまでに
は数時間から数十時間が必要であり、生じた微細結晶を
早急に取り除くには、晶析反応糟の洗浄や、処理水の引
き抜きを行うために装置を停止する必要があるという問
題があった。The above-mentioned formation of the fine crystals occurs not only when the number of components to be crystallized increases, but also when the solubility changes due to fluctuations in water temperature, mixing of other coexisting ions or surfactants, and the like. . In other words, simply measuring the components to be crystallized in the raw water and controlling the components based on the measured components cannot completely prevent the formation of fine crystals, and cannot operate stably. In addition, since the generated fine crystals are returned to the crystallization reaction tank by circulating the treated water, the supply of raw water is continued as it is. And the above adverse effects are promoted. Further, once cloudiness occurs, it takes several hours to several tens of hours for the crystallization reactor 1 to return to a state where fine crystals do not occur. There was a problem that the apparatus had to be stopped in order to wash the reaction vessel and to withdraw the treated water.
【００１４】本発明は、このような事情に鑑みてなされ
たものであって、フッ素、リンおよび／または重金属を
はじめとする晶析対象成分を含む原水を晶析処理する晶
析反応装置において、晶析反応糟から排出される処理水
の濁度を測定する濁度測定手段と、該濁度測定手段によ
って測定された濁度に応じて、該原水供給手段から該晶
析反応糟に供給される該原水の量を制御する原水供給制
御手段、および／または該晶析用薬液供給手段から該晶
析反応糟に供給される該晶析用薬液の量を制御する晶析
用薬液供給制御手段とをさらに具備することにより、微
細結晶の生成に素早く対応して装置の運転を停止するこ
となく、さらなる悪化を防止できる晶析反応装置、並び
に該装置を用いた晶析処理方法を提供することを目的と
する。The present invention has been made in view of such circumstances, and a crystallization reaction apparatus for crystallizing raw water containing a component to be crystallized including fluorine, phosphorus and / or heavy metal, A turbidity measuring means for measuring the turbidity of the treated water discharged from the crystallization reaction vessel; and the raw water supply means supplies the treated water to the crystallization reaction vessel in accordance with the turbidity measured by the turbidity measuring means. Raw water supply control means for controlling an amount of the raw water, and / or a crystallization liquid supply control means for controlling an amount of the crystallization liquid supplied to the crystallization reaction tank from the crystallization liquid supply means The present invention further provides a crystallization reaction apparatus capable of preventing further deterioration without stopping operation of the apparatus in response to the generation of fine crystals quickly, and a crystallization treatment method using the apparatus, by further comprising: With the goal.
【００１５】[0015]
【課題を解決するための手段】本発明は請求項１とし
て、内部に種晶が充填され、原水中の晶析対象成分が低
減された処理水を排出する晶析反応糟と、該原水を該晶
析反応糟に供給する原水供給手段と、晶析用薬液を該晶
析反応糟に供給する晶析用薬液供給手段と、該晶析反応
糟から排出される処理水の少なくとも一部を該晶析反応
糟に返送する処理水循環手段とを具備する晶析反応装置
において、該晶析反応糟から排出される処理水の濁度を
測定する濁度測定手段と、該濁度測定手段によって測定
された濁度に応じて、該原水供給手段から該晶析反応糟
に供給される該原水の量を制御する原水供給制御手段、
および／または該晶析用薬液供給手段から該晶析反応糟
に供給される該晶析用薬液の量を制御する晶析用薬液供
給制御手段とをさらに具備する前記晶析反応装置を提供
する。本発明は請求項２として、晶析対象成分を含む原
水と晶析用薬液とを晶析反応糟に供給し、該晶析反応糟
の内部の種晶上に該晶析対象成分と、該晶析用薬液に含
まれる晶析反応成分との反応物を析出させることによ
り、晶析対象成分が低減された処理水を生じさせ、該晶
析反応糟から排出される該処理水の少なくとも一部を該
晶析反応糟に返送する晶析処理方法において、該晶析反
応糟から排出される該処理水の濁度を測定し、該濁度が
許容値以上となった場合に、該晶析反応糟への原水供給
量を低減させ、および／または該晶析反応糟への晶析用
薬液供給量を低減させる前記晶析処理方法を提供する。
本発明は請求項３として、晶析反応糟への原水供給量の
低減が、原水を該晶析反応糟に間欠的に供給するか、低
減された流量で連続的に供給することにより行われる請
求項２記載の晶析処理方法を提供する。本発明は請求項
４として、晶析反応糟への晶析用薬液供給量の低減が、
晶析用薬液を該晶析反応糟に間欠的に供給するか、低減
された流量で連続的に供給することにより行われる請求
項２記載の晶析処理方法を提供する。According to the present invention, as a first aspect, a crystallization reaction tank for discharging treated water in which seed crystals are filled and the amount of components to be crystallized in raw water is reduced; A raw water supply means for supplying the crystallization reaction tank, a crystallization liquid supply means for supplying a crystallization liquid to the crystallization reaction tank, and at least a part of treated water discharged from the crystallization reaction tank. A crystallization reaction apparatus comprising: a circulating means for returning treated water to the crystallization reaction vessel; a turbidity measuring means for measuring turbidity of treated water discharged from the crystallization reaction vessel; and a turbidity measuring means. Raw water supply control means for controlling an amount of the raw water supplied to the crystallization reaction tank from the raw water supply means according to the measured turbidity,
And / or a crystallization liquid supply control means for controlling an amount of the crystallization liquid supplied to the crystallization reaction tank from the crystallization liquid supply means. . The present invention provides, as claim 2, raw water containing a component to be crystallized and a chemical solution for crystallization to a crystallization reaction vessel, and the component to be crystallized on a seed crystal inside the crystallization reaction vessel; By precipitating a reaction product with the crystallization reaction component contained in the crystallization solution, treated water in which the component to be crystallized is reduced is generated, and at least one of the treated water discharged from the crystallization reaction tank is generated. In the crystallization treatment method of returning the part to the crystallization reaction tank, the turbidity of the treated water discharged from the crystallization reaction tank is measured, and when the turbidity exceeds an allowable value, the crystallization is performed. The present invention provides the above-mentioned crystallization treatment method, which reduces the supply amount of raw water to a crystallization reaction tank and / or reduces the supply amount of a crystallization solution to the crystallization reaction tank.
According to a third aspect of the present invention, the amount of raw water supplied to the crystallization reactor is reduced by intermittently supplying raw water to the crystallization reactor or by continuously supplying raw water at a reduced flow rate. A crystallization treatment method according to claim 2 is provided. The present invention as claim 4 reduces the supply amount of the crystallization solution to the crystallization reactor,
The crystallization treatment method according to claim 2, which is performed by intermittently supplying the crystallization solution to the crystallization reaction vessel or continuously supplying the solution at a reduced flow rate.
【００１６】[0016]
【発明の実施の形態】本発明の晶析反応装置で処理され
る原水は、晶析処理により除去される晶析対象成分を含
むものであれば、如何なる由来の原水であっても良く、
例えば、半導体関連産業をはじめとする電子産業、発電
所、アルミニウム工業などから排出される原水が挙げら
れるが、これらに限定されるものではない。本発明にお
ける原水中の晶析対象成分としては、晶析反応により晶
析し、原水中から除去可能であれば任意の元素が挙げら
れ、特に限定されるものではない。また、晶析対象成分
となる元素の種類は１種類であっても良いし、２種類以
上であっても良い。特に、原水中における存在が問題と
なるという観点から、本発明の晶析対象成分としては、
フッ素、リンおよび重金属元素、並びにこれらの混合物
が挙げられる。また、重金属元素としては、Ｖ、Ｃｒ、
Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｏ、Ａｇ、Ｃ
ｄ、Ｈｇ、Ｓｎ、Ｐｂ、Ｔｅが挙げられるが、これに限
定されるものではない。晶析対象成分となる元素は、晶
析反応により晶析するのであれば、任意の状態で原水中
に存在することが可能である。原水中に溶解していると
いう観点から、晶析対象成分はイオン化した状態である
のが好ましい。晶析対象成分がイオン化した状態として
は、例えば、Ｆ−、Ｃｕ２＋等をはじめとする原子がイ
オン化したもの、メタリン酸、ピロリン酸、オルトリン
酸、三リン酸、四リン酸、亜リン酸等をはじめとする晶
析対象成分を含む化合物がイオン化したもの、また、重
金属等の錯イオンなどが挙げられるがこれらに限定され
るものではない。DETAILED DESCRIPTION OF THE INVENTION Raw water to be treated in the crystallization reactor of the present invention may be raw water of any origin as long as it contains a component to be crystallized to be removed by crystallization.
Examples include, but are not limited to, raw water discharged from the electronics industry, including the semiconductor-related industry, power plants, the aluminum industry, and the like. The component to be crystallized in the raw water in the present invention includes any element as long as it can be crystallized by a crystallization reaction and can be removed from the raw water, and is not particularly limited. The type of the element to be crystallized may be one type or two or more types. In particular, from the viewpoint that the presence in raw water poses a problem, as the crystallization target component of the present invention,
Fluorine, phosphorus and heavy metal elements, and mixtures thereof. Also, as heavy metal elements, V, Cr,
Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag, C
d, Hg, Sn, Pb, and Te, but are not limited thereto. The element to be crystallized can exist in raw water in any state as long as it is crystallized by a crystallization reaction. From the viewpoint of being dissolved in raw water, the crystallization target component is preferably in an ionized state. Examples of the ionized state of the component to be crystallized include those in which atoms such as F − and Cu 2+ are ionized, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, phosphorous acid, and the like. And ionized compounds including the components to be crystallized, and complex ions such as heavy metals, but are not limited thereto.
【００１７】晶析用薬液としては、晶析対象成分と反応
して難溶性化合物を形成することにより、原水から晶析
対象成分を除去できる晶析反応成分を含むものであれ
ば、任意の化合物を含む薬液を使用することができ、除
去されるべき晶析対象成分に応じて適宜設定される。な
お、晶析反応成分とは、上述のように晶析対象成分と反
応して難溶性化合物を形成するものであり、例えば、カ
ルシウム、マグネシウム、ストロンチウム、バリウム等
の元素またはイオンが挙げられるが、これらに限定され
るものではない。また、晶析用薬液に含まれる、晶析反
応成分は１種類であっても良いし、複数種類であっても
良い。また、薬液を構成する液体媒体としては、本発明
の目的に反しない限りは任意の物質が可能であり、好ま
しくは水である。例えば、晶析対象成分がフッ素の場合
には、晶析用薬液としては、水酸化カルシウム、塩化カ
ルシウム、炭酸カルシウムをはじめとするカルシウム化
合物、炭酸マグネシウム、塩化マグネシウムをはじめと
するマグネシウム化合物、水酸化ストロンチウム、塩化
ストロンチウムをはじめとするストロンチウム化合物を
含む薬液、またはこれらの混合物を含む薬液が挙げられ
るがこれらに限定されるものではない。また、フッ素と
反応して形成されるフッ化物の溶解度が低いという観点
から、晶析用薬液としては、マグネシウム化合物および
／またはカルシウム化合物を含む薬液が好ましく、より
好ましくは、カルシウム化合物を含む薬液である。The chemical for crystallization may be any compound as long as it contains a crystallization reaction component capable of removing the crystallization target component from raw water by reacting with the crystallization target component to form a hardly soluble compound. Can be used, and is appropriately set depending on the component to be crystallized to be removed. The crystallization reaction component is a component that reacts with the crystallization target component to form a hardly soluble compound as described above, and includes, for example, elements or ions such as calcium, magnesium, strontium, and barium. It is not limited to these. Further, the crystallization reaction component contained in the crystallization solution may be one type or a plurality of types. As the liquid medium constituting the liquid medicine, any substance can be used as long as the object of the present invention is not adversely affected, and water is preferable. For example, when the component to be crystallized is fluorine, the chemical solution for crystallization includes calcium compounds such as calcium hydroxide, calcium chloride and calcium carbonate, magnesium compounds such as magnesium carbonate and magnesium chloride, and hydroxides. A chemical solution containing a strontium compound such as strontium and strontium chloride, or a chemical solution containing a mixture thereof is exemplified, but not limited thereto. In addition, from the viewpoint that the solubility of fluoride formed by reacting with fluorine is low, the chemical solution for crystallization is preferably a chemical solution containing a magnesium compound and / or a calcium compound, and more preferably a chemical solution containing a calcium compound. is there.
【００１８】晶析対象成分がリン元素であり、原水中に
リン酸等のリン化合物として存在している場合には、晶
析用薬液としては、水酸化カルシウム、塩化カルシウム
をはじめとするカルシウム化合物、塩化バリウムをはじ
めとするバリウム化合物、塩化マグネシウムをはじめと
するマグネシウム化合物が挙げられるがこれらに限定さ
れるものではない。リン酸等の形態のリンと反応して形
成される化合物の溶解度が低いという観点から、晶析用
薬液としては、カルシウム化合物および／またはバリウ
ム化合物を含む薬液が好ましい。晶析対象成分が上述の
重金属である場合には、晶析用薬液としては、水酸化カ
ルシウム、水酸化カリウム、水酸化ナトリウム、炭酸ナ
トリウムをはじめとする、水に溶解された場合にアルカ
リ性を示すアルカリ化合物が好ましいが、これらに限定
されるものではない。When the component to be crystallized is a phosphorus element and is present in the raw water as a phosphorus compound such as phosphoric acid, the chemical for crystallization includes calcium compounds such as calcium hydroxide and calcium chloride. , Barium compounds such as barium chloride, and magnesium compounds such as magnesium chloride, but are not limited thereto. From the viewpoint that the solubility of a compound formed by reacting with phosphorus in the form of phosphoric acid or the like is low, the crystallization solution is preferably a solution containing a calcium compound and / or a barium compound. When the component to be crystallized is the above-mentioned heavy metal, the crystallization chemical solution, including calcium hydroxide, potassium hydroxide, sodium hydroxide, and sodium carbonate, shows alkalinity when dissolved in water. Alkali compounds are preferred, but not limited thereto.
【００１９】晶析対象成分が原水中に複数種類存在し、
この中の全部もしくは２以上の成分の晶析除去が望まれ
る場合には、除去が望まれる晶析対象成分のいずれに対
しても難溶性塩を形成する晶析反応成分を含む晶析用薬
液が適宜選択される。例えば、晶析対象成分としてフッ
素とリン酸を含む場合には、晶析用薬液としては、フッ
素およびリン酸のいずれにも適した晶析反応成分である
カルシウムを含む晶析用薬液が使用されても良いし、ま
た、それぞれに適した複数の晶析反応成分を含む晶析用
薬液でも良い。また、晶析用薬液中の晶析反応成分の濃
度は、晶析反応糟の処理能力、循環される処理水量、晶
析対象成分の種類および濃度等に応じて適宜設定され
る。A plurality of types of crystallization target components exist in raw water,
When crystallization removal of all or two or more of the components is desired, a crystallization solution containing a crystallization reaction component that forms a sparingly soluble salt for any of the components to be crystallized that is desired to be removed Is appropriately selected. For example, in the case where fluorine and phosphoric acid are contained as components to be crystallized, the crystallization solution containing calcium, which is a crystallization reaction component suitable for both fluorine and phosphoric acid, is used as the crystallization solution. Alternatively, a crystallization solution containing a plurality of crystallization reaction components suitable for each may be used. The concentration of the crystallization reaction component in the crystallization solution is appropriately set according to the processing capacity of the crystallization reaction tank, the amount of circulating water to be treated, the type and concentration of the component to be crystallized, and the like.
【００２０】図１に本発明の晶析反応装置の一態様を示
し、以下、詳述する。本発明の晶析反応装置は、内部に
種晶２が充填され、原水中の晶析対象成分が低減された
処理水を排出する晶析反応糟１と、該原水を晶析反応糟
１に供給する原水供給手段と、晶析用薬液を晶析反応糟
１に供給する晶析用薬液供給手段と、該晶析反応糟から
排出される処理水の少なくとも一部を晶析反応糟１に返
送する処理水循環手段とを具備する晶析反応装置におい
て、晶析反応糟１から排出される処理水の濁度を測定す
る濁度測定手段１５と、該濁度測定手段１５によって測
定された濁度に応じて、原水供給手段から該晶析反応糟
に供給される該原水の量を制御する原水供給制御手段１
２、および／または該晶析用薬液供給手段から該晶析反
応糟に供給される該晶析用薬液の量を制御する晶析用薬
液供給制御手段１４とをさらに具備することを特徴とす
る。FIG. 1 shows one embodiment of the crystallization reaction apparatus of the present invention, which will be described in detail below. The crystallization reaction apparatus of the present invention comprises a crystallization reaction vessel 1 in which seed crystals 2 are filled, and discharges treated water in which the components to be crystallized in raw water are reduced, and the raw water is supplied to the crystallization reaction vessel 1. A raw water supply means for supplying, a crystallization chemical liquid supply means for supplying a crystallization chemical liquid to the crystallization reaction tank 1, and at least a part of the treated water discharged from the crystallization reaction tank to the crystallization reaction tank 1 In a crystallization reaction apparatus having a treated water circulation means for returning, a turbidity measuring means 15 for measuring the turbidity of treated water discharged from the crystallization reaction tank 1, and a turbidity measured by the turbidity measuring means 15. Raw water supply control means 1 for controlling the amount of the raw water supplied to the crystallization reactor from the raw water supply means according to the degree
2, and / or a crystallization liquid supply control means 14 for controlling the amount of the crystallization liquid supplied to the crystallization reaction tank from the crystallization liquid supply means. .
【００２１】晶析反応装置を用いて晶析処理を行う場
合、晶析対象成分および／または晶析反応成分の増加、
水温の変動、共存する他のイオンや界面活性剤の混入等
による溶解度の変化によって、晶析対象成分の反応物が
種晶２の上に析出するのではなく、微細結晶を形成する
場合がある。本発明の晶析反応装置においては、上記濁
度測定手段１５と、原水供給制御手段１２および／また
は晶析用薬液供給制御手段１４とを具備することによ
り、系内で微細結晶が生じ、処理水の濁度が許容値以上
となった場合に、原水および／または晶析用薬液の供給
を低減させることにより、系内に供給される晶析対象成
分および／または晶析反応成分の量を低減させ、系内を
該微細結晶が生じないような状態にすることを可能にす
る。微細結晶が生じた場合に原水の供給を低減させる
か、もしくは晶析用薬液の供給量を低減させるか、また
はこれら両方の供給量を低減させるかは系内の状態に応
じて適宜決定される。本発明における濁度の「許容値」
は、系外に排出できる晶析対象成分の濃度、微細結晶に
よる砂ろ過装置９の目詰まりなどの該晶析反応装置に与
える影響を考慮して、系内に存在し得る微細結晶の存在
限界量から決定される。本発明においては、晶析対象成
分および晶析反応成分の両方を制御できるので、図１の
態様のように、原水供給制御手段１２および晶析用薬液
供給制御手段１４の両方を有する態様が好ましい。ま
た、任意に、濁度測定手段１５によって測定された処理
水の濁度に応じて、循環される処理水の量を制御する処
理水循環制御手段（図示しない）を設けることも可能で
ある。When crystallization treatment is performed using a crystallization reaction apparatus, the number of components to be crystallized and / or crystallization reaction components increases,
The reactant of the component to be crystallized may not form on the seed crystal 2 but form a fine crystal due to a change in solubility due to fluctuations in water temperature, mixing of other coexisting ions or surfactants, and the like. . In the crystallization reaction apparatus of the present invention, by providing the turbidity measuring means 15, the raw water supply control means 12 and / or the chemical liquid supply control means 14 for crystallization, fine crystals are generated in the system, and When the turbidity of the water becomes equal to or more than the allowable value, by reducing the supply of the raw water and / or the chemical for crystallization, the amount of the crystallization target component and / or the crystallization reaction component supplied to the system is reduced. This makes it possible to make the inside of the system such that the fine crystals do not occur. Whether the supply of raw water is reduced when fine crystals are generated, or the supply amount of the crystallization solution is reduced, or the supply amount of both is reduced is appropriately determined according to the state of the system. . "Allowable value" of turbidity in the present invention
In consideration of the concentration of the component to be crystallized that can be discharged out of the system and the influence on the crystallization reaction device such as clogging of the sand filtration device 9 by the fine crystals, the existence limit of the fine crystals that can be present in the system is considered. Determined from the quantity. In the present invention, since both the crystallization target component and the crystallization reaction component can be controlled, an embodiment having both the raw water supply control means 12 and the chemical liquid supply control means for crystallization 14 as in the embodiment of FIG. 1 is preferable. . Optionally, a treated water circulation control means (not shown) for controlling the amount of the treated water circulated according to the turbidity of the treated water measured by the turbidity measuring means 15 may be provided.
【００２２】濁度測定手段１５としては、処理水中の濁
度を測定できるものであれば任意の手段を使用でき、例
えば、分光光度計、光電光度計などが挙げられるが、こ
れらに限定されるものではない。原水供給制御手段１
２、晶析用薬液供給制御手段１４としては、濁度測定手
段１５により測定された濁度に応じて、原水または晶析
用薬液の供給量を制御できるものであれば任意の態様が
可能であり、特に限定されるものではない。例えば、図
１の態様のように、原水供給制御手段１２または晶析用
薬液供給制御手段１４は、原水供給ライン４または晶析
用薬液供給ライン７に介装されたポンプの流量を制御す
るような態様であっても良いし、濁度測定手段１５によ
り測定された濁度に応じて開閉される流量制御弁が、原
水供給ライン４または晶析用薬液供給ライン７に介装さ
れるような態様も可能である。As the turbidity measuring means 15, any means can be used as long as it can measure turbidity in the treated water, and examples thereof include a spectrophotometer and a photoelectric photometer, but are not limited thereto. Not something. Raw water supply control means 1
2. As the crystallization liquid supply control means 14, any mode is possible as long as the supply amount of raw water or the crystallization liquid can be controlled in accordance with the turbidity measured by the turbidity measuring means 15. There is no particular limitation. For example, as in the embodiment of FIG. 1, the raw water supply control means 12 or the chemical liquid supply control means 14 for crystallization controls the flow rate of a pump interposed in the raw water supply line 4 or the chemical liquid supply line 7 for crystallization. Or a flow control valve that is opened and closed according to the turbidity measured by the turbidity measuring means 15 is interposed in the raw water supply line 4 or the chemical liquid supply line 7 for crystallization. Embodiments are also possible.
【００２３】本発明の晶析反応装置において原水供給量
および／または晶析用薬液供給量の低減が行われる場合
には、該供給量の低減の態様としては、原水および／ま
たは晶析用薬液を晶析反応糟に間欠的に供給すること、
低減された流量で連続的に供給することにより行われる
もののいずれの態様でも良い。When the supply amount of raw water and / or the supply amount of the chemical solution for crystallization is reduced in the crystallization reaction apparatus of the present invention, the supply amount may be reduced in the form of raw water and / or the chemical solution for crystallization. Intermittently to the crystallization reactor,
Any mode may be adopted, which is performed by continuously supplying at a reduced flow rate.
【００２４】本発明における晶析反応糟１は、内部に種
晶２が充填されており、該種晶２の表面上に、原水に含
まれる晶析対象成分と、該晶析用薬液に含まれる晶析反
応成分との反応物が析出することにより、原水中の晶析
対象成分を低減させ、晶析対象成分の濃度が低下した処
理水を排出するものである。晶析反応糟１は前記機能を
有するものであれば、長さ、内径、形状などについて
は、任意の態様が可能であり、特に限定されるものでは
ない。The crystallization reactor 1 according to the present invention has a seed crystal 2 filled therein, and a component to be crystallized contained in raw water and a chemical solution for crystallization contained on the surface of the seed crystal 2. The reaction product with the crystallization reaction component to be precipitated is precipitated, whereby the crystallization target component in the raw water is reduced, and the treated water having a reduced concentration of the crystallization target component is discharged. As long as the crystallization reaction vessel 1 has the above function, the length, the inner diameter, the shape, and the like can be in any modes, and are not particularly limited.
【００２５】晶析反応糟１に充填される種晶２の充填量
も、晶析対象成分を晶析反応により除去できるのであれ
ば特に限定されるものではなく、晶析対象成分の濃度、
種類、使用される晶析用薬液の種類、濃度、また、晶析
反応装置の運転条件等に応じて適宜設定される。本発明
の晶析反応装置においては、晶析反応糟１内に上向流を
形成し、該上向流によって種晶２が流動するような流動
床の晶析反応糟１が好ましいので、種晶２は流動可能な
量で晶析反応糟１に充填されるのが好ましい。種晶２
は、本発明の目的に反しない限りは、任意の材質が可能
であり、例えば、ろ過砂、活性炭、金属酸化物の１以上
からなる粒子、または、晶析対象成分と晶析反応成分が
反応して生じる化合物からなる粒子等が挙げられるが、
これらに限定されるものではない。種晶２の上で晶析反
応が起こりやすいという観点、また、種晶２の上に晶析
対象成分と晶析反応成分の反応物が析出して成長した粒
子から、より純粋な反応物を回収できるという観点か
ら、晶析反応により生じる化合物と同じ化合物、例え
ば、原水中の晶析対象成分がフッ素であり、晶析用薬液
がカルシウム化合物を含む薬液の場合には、フッ化カル
シウム（蛍石）が種晶２として使用されるのが好まし
い。The amount of the seed crystal 2 to be charged into the crystallization reaction vessel 1 is not particularly limited as long as the component to be crystallized can be removed by the crystallization reaction.
It is appropriately set according to the type, the type and concentration of the crystallization solution to be used, and the operating conditions of the crystallization reactor. In the crystallization reactor of the present invention, a crystallization reactor 1 of a fluidized bed in which an upward flow is formed in the crystallization reactor 1 and the seed crystal 2 flows by the upward flow is preferable. Crystal 2 is preferably charged into crystallization reactor 1 in a flowable amount. Seed 2
Any material can be used as long as it does not violate the object of the present invention. For example, particles composed of one or more of filter sand, activated carbon, and metal oxide, or a reaction between a component to be crystallized and a crystallization reaction component are performed. Particles and the like consisting of a compound resulting from,
It is not limited to these. From the viewpoint that the crystallization reaction is likely to occur on the seed crystal 2, and from the particles obtained by the reaction product of the component to be crystallized and the crystallization reaction component being precipitated and grown on the seed crystal 2, a more pure reactant is obtained. From the viewpoint of recoverability, when the same compound as the compound generated by the crystallization reaction, for example, the component to be crystallized in raw water is fluorine and the chemical for crystallization is a chemical containing a calcium compound, calcium fluoride (fluorine) Stone) is preferably used as seed crystal 2.
【００２６】また、晶析反応糟１内に上向流が形成され
る場合に、この上向流の流速が大きくなると、種晶２が
晶析反応糟１の外に流出してしまうことがある。よっ
て、晶析反応糟１内の上向流の流速を上げることができ
るという観点から、種晶２は比重が大きい粒子が好まし
い。さらに、本発明の晶析反応装置において処理される
原水はフッ酸をはじめとする、腐食性、酸性物質を含む
場合が多いので、種晶２は金属などの様に、酸によって
溶解される材質は好ましくない。腐食性でないとの観点
からは、種晶２はケイ素、チタン、アルミニウム、マグ
ネシウム、鉄、ジルコニウムなどをはじめとする金属元
素の酸化物からなる粒子が好ましい。比重も考慮する
と、ジルコンサンド、ガーネットサンド、サクランダム
（商品名、日本カートリット株式会社製）がより好まし
い。種晶２の形状、粒径は、晶析反応糟１内での流速、
晶析対象成分の濃度等に応じて適宜設定され、本発明の
目的に反しない限りは特に限定されるものではない。Further, when an upward flow is formed in the crystallization reaction vessel 1 and the flow rate of the upward flow is increased, the seed crystal 2 may flow out of the crystallization reaction vessel 1. is there. Therefore, from the viewpoint that the upward flow velocity in the crystallization reaction vessel 1 can be increased, the seed crystal 2 is preferably a particle having a large specific gravity. Further, since the raw water treated in the crystallization reactor of the present invention often contains corrosive and acidic substances such as hydrofluoric acid, the seed crystal 2 is made of a material dissolved by an acid, such as a metal. Is not preferred. From the viewpoint of not being corrosive, the seed crystal 2 is preferably a particle made of an oxide of a metal element such as silicon, titanium, aluminum, magnesium, iron, and zirconium. In consideration of the specific gravity, zircon sand, garnet sand, and sacrifice (trade name, manufactured by Nippon Cartrit Co., Ltd.) are more preferable. The shape and particle size of the seed crystal 2 are determined by the flow rate in the crystallization reactor 1,
It is appropriately set according to the concentration of the component to be crystallized and the like, and is not particularly limited as long as the object of the present invention is not violated.
【００２７】本発明の原水供給手段は、原水を晶析反応
糟１に供給できるものであれば任意の態様が可能であ
る。図１の態様においては、原水供給手段は、原水を貯
留する原水タンク３、該原水タンク３と晶析反応糟１と
を連結する原水供給ライン４を具備し、該原水供給ライ
ン４には原水移送のためのポンプ、および原水中の晶析
対象成分の濃度を測定する濃度測定手段５が介装されて
いる。原水を一旦貯留し、晶析対象成分を一定濃度にで
きるので、原水供給手段は、図１のように原水タンク３
を有する態様が好ましい。晶析用薬液供給手段は、晶析
用薬液を晶析反応糟１に供給できるものであれば任意の
態様が可能である。図１の態様においては、晶析用薬液
供給手段は、晶析用薬液を貯留する晶析用薬液タンク
６、該晶析用薬液タンク６と晶析反応糟１とを連結する
晶析用薬液供給ライン７を具備し、該晶析用薬液供給ラ
イン７には薬液移送のためのポンプが介装されている。The raw water supply means of the present invention may be in any mode as long as it can supply raw water to the crystallization reactor 1. In the embodiment of FIG. 1, the raw water supply means includes a raw water tank 3 for storing raw water, and a raw water supply line 4 connecting the raw water tank 3 and the crystallization reactor 1. A pump for transfer and a concentration measuring means 5 for measuring the concentration of the component to be crystallized in the raw water are provided. Since raw water can be temporarily stored and the concentration of the component to be crystallized can be kept at a constant concentration, the raw water supply means is, as shown in FIG.
Is preferable. The crystallization solution supply means may be in any mode as long as it can supply the crystallization solution to the crystallization reactor 1. In the embodiment of FIG. 1, the crystallization solution supply means comprises a crystallization solution tank 6 for storing the crystallization solution, and a crystallization solution connecting the crystallization solution tank 6 and the crystallization reaction tank 1. A supply line 7 is provided, and a pump for transferring the chemical solution is interposed in the chemical solution supply line 7 for crystallization.
【００２８】原水供給ライン４および晶析用薬液供給ラ
イン７は晶析反応糟１の任意の部分に接続することがで
きる。本発明の晶析反応装置においては、晶析反応糟１
内に上向流を形成して晶析処理を行う場合には、効率的
に反応を行うという観点から、原水供給ライン４および
晶析用薬液供給ライン７は晶析反応糟１の底部に接続さ
れるのが好ましい。また、図１の態様においては、原水
タンク３、原水供給ライン４、晶析用薬液タンク６、お
よび晶析用薬液供給ライン７はそれぞれ１つであるが、
これに限定されるものではなく、本発明の晶析反応装置
においてはこれらが複数設けられても良い。The raw water supply line 4 and the crystallization chemical solution supply line 7 can be connected to any part of the crystallization reactor 1. In the crystallization reactor of the present invention, the crystallization reactor 1
When the crystallization treatment is performed by forming an upward flow in the raw material, the raw water supply line 4 and the chemical liquid supply line 7 for crystallization are connected to the bottom of the crystallization reaction tank 1 from the viewpoint of efficient reaction. Preferably. In the embodiment of FIG. 1, the number of the raw water tank 3, the raw water supply line 4, the crystallization chemical liquid tank 6, and the crystallization chemical liquid supply line 7 is one.
The present invention is not limited to this, and a plurality of these may be provided in the crystallization reactor of the present invention.
【００２９】晶析反応糟１は、晶析反応により生じた晶
析対象成分が低減された処理水を該晶析反応糟１の外部
に排出する。処理水は、晶析反応糟１における液体の流
れに従って任意の部分から排出される。晶析反応糟１内
で上向流が形成される場合には、晶析反応糟１の上部か
ら処理水が排出される。図１の態様では、該晶析反応糟
１の上部から排出される処理水は、処理水排出ライン８
を通って最終的に系外に排出される。図１の態様におい
ては、処理水排出ライン８には砂ろ過装置９および処理
水貯留タンク１０が介装されているがこれらの設置は任
意であり、通常の排水処理で使用されるその他の手段を
設けることも可能である。The crystallization reaction vessel 1 discharges the treated water in which the components to be crystallized generated by the crystallization reaction are reduced, to the outside of the crystallization reaction vessel 1. The treated water is discharged from an arbitrary part according to the flow of the liquid in the crystallization reaction tank 1. When an upward flow is formed in the crystallization reactor 1, the treated water is discharged from the upper portion of the crystallization reactor 1. In the embodiment of FIG. 1, the treated water discharged from the upper part of the crystallization reaction tank 1
And finally discharged out of the system. In the embodiment of FIG. 1, a sand filtration device 9 and a treated water storage tank 10 are interposed in the treated water discharge line 8, but their installation is optional, and other means used in normal wastewater treatment are used. It is also possible to provide.
【００３０】本発明の晶析反応装置は、晶析反応糟１か
ら排出される処理水の少なくとも一部を該晶析反応糟１
に返送する処理水循環手段を有する。処理水循環手段と
しては、処理水の少なくとも一部を晶析反応糟１に返送
できるものであれば任意の態様が可能であり、特に限定
されるものではない。図１の態様においては、処理水循
環手段として、処理水貯留タンク１０と晶析反応糟１を
連結する処理水循環ライン１１が設けられており、該処
理水循環ライン１１には処理水移送のためのポンプが介
装されている。処理水循環手段が循環させる処理水は
「処理水の少なくとも一部」であるから、処理水の一部
だけでなく、全てを循環させることも本発明の範囲内で
ある。The crystallization reaction apparatus of the present invention uses at least a part of the treated water discharged from the crystallization reaction vessel 1
Circulating means for returning the treated water to As the treated water circulation means, any mode is possible as long as at least a part of the treated water can be returned to the crystallization reactor 1, and is not particularly limited. In the embodiment of FIG. 1, a treated water circulation line 11 that connects a treated water storage tank 10 and a crystallization reaction tank 1 is provided as a treated water circulation means, and a pump for transferring treated water is provided in the treated water circulation line 11. Is interposed. Since the treated water circulated by the treated water circulating means is "at least a part of the treated water", it is within the scope of the present invention to circulate not only part of the treated water but also all of the treated water.
【００３１】処理水循環手段は、処理水を晶析反応糟１
に循環させることにより、晶析反応糟１内に供給された
原水を希釈すると共に、晶析用薬液と原水を混合し、さ
らに、晶析反応糟１内で所定の流れ、特に上向流を形成
させるものである。よって、晶析反応糟１内で上向流が
形成される場合には、図１のように、処理水循環ライン
１１は晶析反応糟１の底部に接続されるような態様が好
ましい。また、図１の態様において処理水貯留タンク１
０は、循環される処理水と、系外に排出される処理水と
の分岐のための手段として機能し、処理水循環手段を形
成しているが、処理水循環手段の形成はこの態様に限定
されるものではなく、処理水排出ライン８から処理水循
環ライン１１が直接分岐するような態様など、任意の態
様が可能である。[0031] The treated water circulating means converts the treated water into a crystallization reaction vessel 1
By diluting the raw water supplied into the crystallization reaction vessel 1, the chemical liquid for crystallization and the raw water are mixed, and further, a predetermined flow, particularly an upward flow, is supplied in the crystallization reaction vessel 1. It is formed. Therefore, when an upward flow is formed in the crystallization reaction vessel 1, it is preferable that the treated water circulation line 11 is connected to the bottom of the crystallization reaction vessel 1 as shown in FIG. 1. In the embodiment shown in FIG.
0 functions as a means for branching the circulated treated water and the treated water discharged out of the system to form a treated water circulating means, but the formation of the treated water circulating means is not limited to this mode. Instead, any mode such as a mode in which the treated water circulation line 11 directly branches from the treated water discharge line 8 is possible.
【００３２】本発明の晶析反応装置は、任意に、原水お
よび／または処理水中の晶析対象成分の濃度、または処
理水中の晶析反応成分を測定する濃度測定手段５を備え
ることができる。図１の態様においては、原水供給ライ
ン４に濃度測定手段５が介装されているが、測定すべき
対象に応じて処理水排出ライン８、処理水循環ライン１
１等、本発明の晶析反応装置の任意の部位に介装するこ
とができる。微細結晶が生じた場合に、原水中の晶析対
象成分または晶析反応成分のいずれが増加したかを明ら
かにでき、その後の対処が容易になるという観点から、
原水および／または処理水中の晶析対象成分、処理水中
の晶析反応成分のいずれかを測定するように濃度測定手
段５を具備することが好ましく、晶析対象成分および晶
析反応成分の両方を測定できるように濃度測定手段５を
具備することがより好ましい。The crystallization reaction apparatus of the present invention can optionally include a concentration measuring means 5 for measuring the concentration of the component to be crystallized in the raw water and / or the treated water or the crystallization reaction component in the treated water. In the embodiment of FIG. 1, the raw water supply line 4 is provided with the concentration measuring means 5, but the treated water discharge line 8, the treated water circulation line 1,
1 and the like can be interposed at any part of the crystallization reaction apparatus of the present invention. In the case where fine crystals are generated, it is possible to clarify whether the crystallization target component or the crystallization reaction component in the raw water has increased, and from the viewpoint that the subsequent measures are easily performed.
It is preferable to include a concentration measuring means 5 so as to measure any one of a crystallization target component in raw water and / or treated water and a crystallization reaction component in treated water. More preferably, a concentration measuring means 5 is provided so that measurement can be performed.
【００３３】濃度測定手段５としては、液中の晶析対象
成分および／または晶析反応成分の濃度を測定できるも
のであれば、その種類に応じて適宜、任意の手段が可能
であり、特に限定されるものではない。例えば、晶析対
象成分がフッ素の場合には、ランタン−アリザリンコン
プレキソン吸光光度法やイオン電極法（ＪＩＳ Ｋ０１
０２ ３４）を使用することができ、自動フッ素イオン
測定装置（ＦＬＩＡ−１０１；堀場製作所製）等を使用
して、連続的に測定することも可能である。測定が容易
であるとの観点からイオン電極法が好ましく、自動フッ
素イオン測定装置を使用するのがより好ましい。晶析対
象成分がリンの場合には、リン酸イオンとしてはモリブ
デン青（アスコルビン酸還元）吸光光度法を使用するこ
とができ、全リンとしては、試料にペルオキソ２硫酸カ
リウムを加え、高圧蒸気滅菌器で加熱して有機物を分解
した後にリン酸イオンを測定する方法がある（ＪＩＳ
Ｋ０１０２ ４６）。また、全リン濃度の測定におけ
る、自動全リン測定装置（ＴＯＰＡ−２００；堀場製作
所製）等、自動測定装置を使用することもできる。晶析
対象成分が重金属の場合には、イオン電極を使用するこ
とができ、別法としては原子吸光度計、分光光度計など
により測定することも可能である。例えば、重金属が銅
の場合には、ジエチルジチオカルバミド酸吸光光度法、
フレーム原子吸光法、電気加熱原子吸光法、ＩＣＰ発光
分光分析法、ＩＣＰ質量分析法などが適用できる（ＪＩ
Ｓ Ｋ０１０２ ５２）。As the concentration measuring means 5, any means can be appropriately used depending on the type, as long as it can measure the concentration of the component to be crystallized and / or the crystallization reaction component in the liquid. It is not limited. For example, when the component to be crystallized is fluorine, a lanthanum-alizarin complexone spectrophotometer or an ion electrode method (JIS K01) is used.
No. 0234) can be used, and continuous measurement can be performed using an automatic fluoride ion measuring device (FLIA-101; manufactured by Horiba, Ltd.) or the like. The ion electrode method is preferable from the viewpoint of easy measurement, and it is more preferable to use an automatic fluorine ion measuring device. When the component to be crystallized is phosphorus, molybdenum blue (ascorbic acid reduction) absorption spectrophotometry can be used as the phosphate ion. For total phosphorus, potassium peroxodisulfate is added to the sample, and high-pressure steam sterilization is performed. There is a method of measuring phosphate ions after decomposing organic matter by heating with a vessel (JIS)
K0102 46). In the measurement of the total phosphorus concentration, an automatic measuring device such as an automatic total phosphorus measuring device (TOPA-200; manufactured by HORIBA, Ltd.) can also be used. When the component to be crystallized is a heavy metal, an ion electrode can be used. Alternatively, it can be measured by an atomic absorption spectrometer, a spectrophotometer, or the like. For example, when the heavy metal is copper, diethyldithiocarbamic acid spectrophotometry,
Flame atomic absorption spectrometry, electric heating atomic absorption spectrometry, ICP emission spectroscopy, ICP mass spectrometry, etc. can be applied (JI
S K0102 52).
【００３４】本発明の晶析反応装置は、任意に、濃度測
定手段５により測定された晶析対象成分および／または
晶析反応成分の濃度に応じて、晶析用薬液の供給量を制
御する晶析用薬液供給制御手段１３および／または循環
される処理水の量を制御する処理水循環制御手段（図示
しない）を具備することができる。図１の態様において
は、晶析用薬液供給制御手段１３は晶析用薬液供給ライ
ン７に介装されたポンプを制御しているが、この態様に
限定されるものではない。The crystallization reaction apparatus of the present invention optionally controls the supply amount of the crystallization solution according to the concentration of the crystallization target component and / or the crystallization reaction component measured by the concentration measuring means 5. A crystallization chemical liquid supply control means 13 and / or a treated water circulation control means (not shown) for controlling the amount of circulated treated water can be provided. In the embodiment of FIG. 1, the chemical liquid supply control means 13 for crystallization controls the pump interposed in the chemical liquid supply line 7 for crystallization, but is not limited to this embodiment.
【００３５】[0035]
【発明の効果】以上、説明したように、本発明は、フッ
素、リンおよび／または重金属をはじめとする晶析対象
成分を含む原水を晶析処理する晶析反応装置において、
処理水中の濁度を測定する濁度測定手段と、原水供給制
御手段および／または晶析用薬液供給制御手段とを具備
することにより、晶析反応装置の系内で微細結晶が生
じ、処理水が白濁した場合に、この微細結晶の生成を早
期に検知し、系内に供給される晶析対象成分および／ま
たは晶析反応成分を低減させることにより、速やかな微
細結晶の除去が可能となる。また、このような微細結晶
の除去を晶析反応装置を停止させることなく行うことが
できるという利点もある。As described above, the present invention relates to a crystallization reaction apparatus for crystallizing raw water containing components to be crystallized such as fluorine, phosphorus and / or heavy metals.
By providing a turbidity measuring means for measuring turbidity in the treated water, and a raw water supply control means and / or a chemical liquid supply control means for crystallization, fine crystals are generated in the system of the crystallization reaction apparatus, and the treated water In the case where is clouded, the generation of the fine crystals is detected at an early stage, and by reducing the components to be crystallized and / or the components of the crystallization supplied to the system, the fine crystals can be quickly removed. . There is also an advantage that such fine crystals can be removed without stopping the crystallization reactor.
【図１】 図１は、本発明の晶析反応装置の一態様を示
す概略図である。FIG. 1 is a schematic view showing one embodiment of the crystallization reaction device of the present invention.
【図２】 図２は、従来の晶析反応装置の一態様を示す
概略図である。FIG. 2 is a schematic view showing one embodiment of a conventional crystallization reaction apparatus.
１ 晶析反応糟 ２ 種晶 ３ 原水タンク ４ 原水供給ライン ５ 濃度測定手段 ６ 晶析用薬液タンク ７ 晶析用薬液供給ライン ８ 処理水排出ライン ９ 砂ろ過装置 １０ 処理水貯留タンク １１ 処理水循環ライン １２ 原水供給制御手段 １３ 晶析用薬液供給制御手段 １４ 晶析用薬液供給制御手段 １５ 濁度測定手段 DESCRIPTION OF SYMBOLS 1 Crystallization reaction tank 2 Seed crystal 3 Raw water tank 4 Raw water supply line 5 Concentration measuring means 6 Chemical liquid tank for crystallization 7 Chemical liquid supply line for crystallization 8 Treated water discharge line 9 Sand filtration device 10 Treated water storage tank 11 Treated water circulation line 12 Raw water supply control means 13 Crystallization chemical liquid supply control means 14 Crystallization chemical liquid supply control means 15 Turbidity measuring means
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｄ 9/02 ６０２ Ｂ０１Ｄ 9/02 ６０２Ｅ ６０３ ６０３Ｄ ６０８ ６０８Ａ Ｃ０２Ｆ 1/58 Ｃ０２Ｆ 1/58 Ｍ ＺＡＢ ＺＡＢＳ 1/62 1/62 Ｆターム(参考） 4D038 AA08 AB41 AB45 AB48 AB64 AB65 AB66 AB67 AB68 AB69 AB71 AB72 AB73 AB74 AB76 AB88 BA06 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01D 9/02 602 B01D 9/02 602E 603 603D 608 608A C02F 1/58 C02F 1/58 M ZAB ZABS 1 / 62 1/62 F term (reference) 4D038 AA08 AB41 AB45 AB48 AB64 AB65 AB66 AB67 AB68 AB69 AB71 AB72 AB73 AB74 AB76 AB88 BA06
Claims (4)
象成分が低減された処理水を排出する晶析反応糟と、 該原水を該晶析反応糟に供給する原水供給手段と、 晶析用薬液を該晶析反応糟に供給する晶析用薬液供給手
段と、 該晶析反応糟から排出される処理水の少なくとも一部を
該晶析反応糟に返送する処理水循環手段とを具備する晶
析反応装置において、 該晶析反応糟から排出される処理水の濁度を測定する濁
度測定手段と、 該濁度測定手段によって測定された濁度に応じて、該原
水供給手段から該晶析反応糟に供給される該原水の量を
制御する原水供給制御手段、および／または該晶析用薬
液供給手段から該晶析反応糟に供給される該晶析用薬液
の量を制御する晶析用薬液供給制御手段とをさらに具備
する前記晶析反応装置。1. A crystallization reaction tank for discharging treated water in which seed crystals are filled and a crystallization target component in raw water is reduced, and raw water supply means for supplying the raw water to the crystallization reaction tank. A crystallization solution supply means for supplying a crystallization solution to the crystallization reaction vessel; and a treated water circulation means for returning at least a portion of the treated water discharged from the crystallization reaction vessel to the crystallization reaction vessel. A turbidity measuring means for measuring the turbidity of the treated water discharged from the crystallization reaction vessel; and supplying the raw water in accordance with the turbidity measured by the turbidity measuring means. Raw water supply control means for controlling the amount of the raw water supplied to the crystallization reaction tank from the means, and / or the amount of the crystallization chemical supplied to the crystallization reaction tank from the crystallization chemical liquid supply means The crystallization reaction device, further comprising a crystallization chemical liquid supply control means for controlling the crystallization reaction solution.
を晶析反応糟に供給し、該晶析反応糟の内部の種晶上に
該晶析対象成分と、該晶析用薬液に含まれる晶析反応成
分との反応物を析出させることにより、晶析対象成分が
低減された処理水を生じさせ、該晶析反応糟から排出さ
れる該処理水の少なくとも一部を該晶析反応糟に返送す
る晶析処理方法において、 該晶析反応糟から排出される該処理水の濁度を測定し、
該濁度が許容値以上となった場合に、該晶析反応糟への
原水供給量を低減させ、および／または該晶析反応糟へ
の晶析用薬液供給量を低減させる前記晶析処理方法。2. A raw water containing a component to be crystallized and a chemical solution for crystallization are supplied to a crystallization reactor, and the component to be crystallized and the crystallization component are placed on a seed crystal inside the crystallization reactor. By precipitating a reaction product with the crystallization reaction component contained in the chemical solution, treated water in which the crystallization target component is reduced is generated, and at least a part of the treated water discharged from the crystallization reaction tank is subjected to the treatment. In the crystallization treatment method of returning to the crystallization reaction vessel, the turbidity of the treated water discharged from the crystallization reaction vessel is measured,
When the turbidity becomes equal to or more than an allowable value, the crystallization treatment for reducing the supply amount of raw water to the crystallization reaction tank and / or reducing the supply amount of a chemical solution for crystallization to the crystallization reaction tank. Method.
水を該晶析反応糟に間欠的に供給するか、低減された流
量で連続的に供給することにより行われる請求項２記載
の晶析処理方法。3. The raw water supply to the crystallization reactor is reduced by intermittently supplying raw water to the crystallization reactor or by continuously supplying the raw water at a reduced flow rate. The crystallization treatment method described in the above.
が、晶析用薬液を該晶析反応糟に間欠的に供給するか、
低減された流量で連続的に供給することにより行われる
請求項２記載の晶析処理方法。4. The method according to claim 1, wherein the supply amount of the crystallization solution to the crystallization reactor is reduced by intermittently supplying the crystallization solution to the crystallization reactor.
3. The crystallization treatment method according to claim 2, wherein the crystallization treatment is performed by continuously supplying at a reduced flow rate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006281057A (en) * | 2005-03-31 | 2006-10-19 | Kurita Water Ind Ltd | Method and apparatus for treating fluorine-containing wastewater |
| JP2010284593A (en) * | 2009-06-11 | 2010-12-24 | Kurita Water Ind Ltd | Method for recovering water and metal from washing wastewater in electroplating |
| JP2011104454A (en) * | 2009-11-12 | 2011-06-02 | Mitsubishi Heavy Ind Ltd | Wastewater treating apparatus and wastewater treating method |
| CN105339063A (en) * | 2013-06-26 | 2016-02-17 | 奥加诺株式会社 | Crystallization reactor |
| CN115340125A (en) * | 2022-09-02 | 2022-11-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Online judgment method for hydrolysis plus seed crystal quality |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000024673A (en) * | 1998-07-08 | 2000-01-25 | Nishihara Environ Sanit Res Corp | Pretreating device of reverse osmotic membrane separation device |
-
2001
- 2001-03-30 JP JP2001100082A patent/JP4842450B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000024673A (en) * | 1998-07-08 | 2000-01-25 | Nishihara Environ Sanit Res Corp | Pretreating device of reverse osmotic membrane separation device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006281057A (en) * | 2005-03-31 | 2006-10-19 | Kurita Water Ind Ltd | Method and apparatus for treating fluorine-containing wastewater |
| JP2010284593A (en) * | 2009-06-11 | 2010-12-24 | Kurita Water Ind Ltd | Method for recovering water and metal from washing wastewater in electroplating |
| JP2011104454A (en) * | 2009-11-12 | 2011-06-02 | Mitsubishi Heavy Ind Ltd | Wastewater treating apparatus and wastewater treating method |
| CN105339063A (en) * | 2013-06-26 | 2016-02-17 | 奥加诺株式会社 | Crystallization reactor |
| CN115340125A (en) * | 2022-09-02 | 2022-11-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Online judgment method for hydrolysis plus seed crystal quality |
| CN115340125B (en) * | 2022-09-02 | 2023-10-13 | 攀钢集团攀枝花钢铁研究院有限公司 | On-line judging method for quality of hydrolyzed added seed crystal |
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| Publication number | Publication date |
|---|---|
| JP4842450B2 (en) | 2011-12-21 |
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