JP2013198830A - Recovering and removing method and recovering and removing apparatus for object to be removed in wastewater - Google Patents

Recovering and removing method and recovering and removing apparatus for object to be removed in wastewater Download PDF

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JP2013198830A
JP2013198830A JP2012066996A JP2012066996A JP2013198830A JP 2013198830 A JP2013198830 A JP 2013198830A JP 2012066996 A JP2012066996 A JP 2012066996A JP 2012066996 A JP2012066996 A JP 2012066996A JP 2013198830 A JP2013198830 A JP 2013198830A
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wastewater
recovery
electrode pair
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water
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Hiroyuki Umezawa
浩之 梅沢
Etsuji Tachiki
悦二 立木
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Panasonic Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a method capable of recovering and removing an object to be removed in wastewater in good purity, and an apparatus used for it.SOLUTION: A method for recovering and removing an object to be removed in wastewater includes steps of: generating a hydroxide ion by immersing at least a pair of electrodes into wastewater or filtered water for applying a voltage to the pair of electrodes; aggregating the object to be removed in the wastewater by bringing the hydroxide ion into contact with the wastewater to be treated containing the object to be removed; and filtering the aggregated object to be removed. An apparatus for recovering and removing an object to be removed in wastewater includes: an electrolytic cell having at least a pair of electrodes for generating an hydroxide ion by electrolyzing wastewater or filtered water; a water injection pump for sending the wastewater or filtered water containing the hydroxide ion to a treatment tank; the treatment tank connected to the water injection pump and capable of storing the wastewater to be treated containing the object to be removed; and a filtration membrane.

Description

本発明は、排水中の被除去物を純度よく回収除去することが可能な方法と、当該方法に用いられる回収除去装置に関する。   The present invention relates to a method capable of recovering and removing an object to be removed in waste water with high purity, and a recovery and removal apparatus used in the method.

現在、産業廃棄物を減らすこと、また産業廃棄物を分別し再利用することまたは産業廃棄物を自然界に放出させないことは、エコロジーの観点から重要なテーマであり、２１世紀の企業課題である。   At present, reducing industrial waste, separating and reusing industrial waste, or not releasing industrial waste to the natural world is an important theme from the viewpoint of ecology and is a corporate issue in the 21st century.

この産業廃棄物の中には、被除去物が含まれた色々な流体がある。これらは、汚水、排水、廃液等の色々な言葉で表現されているが、以下、水や薬品等の流体中に被除去物である物質が含まれているものを排水と呼び説明する。   Among these industrial wastes, there are various fluids containing the objects to be removed. These are expressed in various words such as sewage, drainage, and waste liquid. Hereinafter, a substance that is a substance to be removed in a fluid such as water or chemicals will be referred to as drainage.

これらの排水は、濾過処理装置等で前記被除去物が除去され、排水がきれいな流体となり再利用されることが比較的多い一方で、分別された被除去物は、産業廃棄物として処理されることが多い。   In these wastewaters, the removal target is removed by a filtration processing device or the like, and the wastewater is relatively often reused as a clean fluid. On the other hand, the separated removal target is treated as industrial waste. There are many cases.

被除去物を除去する従来の方法としては、たとえば、半導体のＣＭＰ工程から排出されるコロイド排水では、凝集剤等を添加して微粒子を凝集させて粒子径を増大させ膜分離が行われている。   As a conventional method for removing an object to be removed, for example, in a colloid waste water discharged from a CMP process of a semiconductor, a flocculant is added to agglomerate fine particles to increase a particle diameter to perform membrane separation. .

具体的には、特許文献１には、コロイド状の被除去物を含むコロイド溶液に、ＰＡＣ（ポリ塩化アルミニウム）、Ａｌ2（ＳＯ4）3（硫酸バンド）等の凝集剤や、ＨＣｌ（塩酸）、ＮａＯＨ（水酸化ナトリウム）等のｐＨ調整剤を添加して被除去物の凝集粒子を生成させ、これをフィルタでろ過することが開示されている。 Specifically, Patent Document 1 discloses that a colloid solution containing a colloidal object to be removed includes a flocculant such as PAC (polyaluminum chloride) and Al 2 (SO 4 ) 3 (sulfuric acid band), and HCl (hydrochloric acid). ), A pH adjusting agent such as NaOH (sodium hydroxide) is added to produce aggregated particles of an object to be removed, and this is filtered through a filter.

特許文献２および３には、ＣＭＰ工程から発生した被除去物が含まれると共に濃縮された流体中に、ハロゲンイオンを含む化合物等の導電率調整剤やｐＨ調整剤を添加し、電解によってシリカと鉄イオンが化合した高分子化合物である凝集剤をまず生成させ、この凝集剤を用いて流体中の被除去物を凝集させて、ろ過することが開示されている。   In Patent Documents 2 and 3, a conductivity adjusting agent such as a compound containing a halogen ion or a pH adjusting agent is added to a concentrated fluid containing an object to be removed generated from the CMP process, and silica is obtained by electrolysis. It is disclosed that a flocculant, which is a polymer compound in which iron ions are combined, is first generated, and a substance to be removed in the fluid is agglomerated using the flocculant and filtered.

しかしながら、上記の凝集剤、ｐＨ調整剤、導電率調整剤のような排水成分以外の成分は、異物と言えるものである。排水にこのような異物を添加する場合には、回収した被除去物を含むスラッジ中に異物が多量に混入して、回収した被除去物の純度が再利用基準値未満にまで低下してしまう。このため、エコロジーの観点から被除去物が再利用されることが望ましいのにもかかわらず、スラッジの再利用が困難になるという問題があった。   However, components other than the drainage component such as the above-mentioned flocculant, pH adjuster, and conductivity adjuster can be said to be foreign matters. When such foreign matter is added to the wastewater, a large amount of foreign matter is mixed in the sludge containing the collected removal object, and the purity of the collected removal object falls below the reuse standard value. . For this reason, there is a problem that it is difficult to reuse sludge, although it is desirable that the object to be removed is reused from the viewpoint of ecology.

特許第３５５７１９７号公報Japanese Patent No. 3557197 特許第４２３３４８５号公報Japanese Patent No. 4233485 特許第４２３３４８４号公報Japanese Patent No. 4233484

上記従来技術の問題点に鑑み、本発明は、排水中から被除去物を純度よく回収除去することが可能な方法、およびそれに用いる装置を提供することを目的とする。   In view of the above-described problems of the conventional technology, an object of the present invention is to provide a method capable of recovering and removing an object to be removed from waste water with high purity, and an apparatus used therefor.

本発明は、排水またはろ過処理水に少なくとも１対の電極対を浸漬し、前記電極対に電圧を印加して水酸化物イオンを生成させる工程、
前記水酸化物イオンを、被除去物を含む処理すべき排水と接触させて、処理すべき排水中の被除去物を凝集させる工程、および
凝集した被除去物を、ろ過処理する工程を含む、
排水中の被除去物の回収除去方法である。 The present invention includes a step of immersing at least one electrode pair in waste water or filtered water, and applying hydroxide to the electrode pair to generate hydroxide ions.
A step of bringing the hydroxide ions into contact with wastewater to be treated containing a substance to be removed, and aggregating the substance to be removed in the wastewater to be treated; and a step of filtering the aggregated substance to be removed.
This is a method for recovering and removing objects to be removed from waste water.

本発明はまた、排水またはろ過処理水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対を備えた電解槽、
前記電解槽に接続され、水酸化物イオンを含む排水またはろ過処理水を処理槽に送液するための注水ポンプ、
前記注水ポンプに接続され、被除去物を含む処理すべき排水を貯留可能な処理槽、および
ろ過膜を有する、
排水中の被除去物の回収除去装置である。 The present invention also provides an electrolytic cell comprising at least one electrode pair for electrolyzing waste water or filtered water to generate hydroxide ions,
A water injection pump connected to the electrolytic cell, for feeding wastewater containing hydroxide ions or filtered water to the treatment tank,
A treatment tank connected to the water injection pump, capable of storing wastewater to be treated including the object to be removed, and a filtration membrane;
This is a device for recovering and removing objects to be removed from waste water.

本発明はまた、被除去物を含む処理すべき排水を貯留可能な処理槽、
当該処理槽内に設けられ、排水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対、および
ろ過膜を有する、
排水中の被除去物の回収除去装置である。 The present invention also provides a treatment tank capable of storing wastewater to be treated including the object to be removed,
Provided in the treatment tank, having at least one electrode pair for electrolyzing waste water to generate hydroxide ions, and a filtration membrane;
This is a device for recovering and removing objects to be removed from waste water.

本発明によれば、従来のように異物成分を添加することなく、排水中の被除去物の微粒子を凝集させてろ過処理することができるため、被除去物の純度を低下させることなく、被除去物を再利用可能なスラッジ等として回収することができる。   According to the present invention, it is possible to agglomerate and remove the fine particles of the object to be removed in the wastewater without adding a foreign substance component as in the prior art. The removed product can be recovered as reusable sludge or the like.

本発明の回収除去方法の実施に用いる実施の態様１の回収除去装置の構成図1 is a configuration diagram of a recovery / removal apparatus according to an embodiment 1 used for carrying out the recovery / removal method of the present invention. 本発明の回収除去方法の実施に用いる実施の態様２の回収除去装置の構成図Configuration diagram of the recovery / removal apparatus according to the second embodiment used for carrying out the recovery / removal method of the present invention

本発明の方法は、排水またはろ過処理水に少なくとも１対の電極対を浸漬し、前記電極対に電圧を印加して水酸化物イオンを生成させる工程、
前記水酸化物イオンを、被除去物を含む処理すべき排水と接触させて、処理すべき排水中の被除去物を凝集させる工程、および
凝集した被除去物を、ろ過処理する工程を含む、
排水中の被除去物の回収除去方法である。 The method of the present invention comprises immersing at least one electrode pair in waste water or filtered water, and applying hydroxide to the electrode pair to generate hydroxide ions.
A step of bringing the hydroxide ions into contact with wastewater to be treated containing a substance to be removed, and aggregating the substance to be removed in the wastewater to be treated; and a step of filtering the aggregated substance to be removed.
This is a method for recovering and removing objects to be removed from waste water.

本発明の方法の望ましい一実施の態様では、前記電極対に、不溶性電極対を用いる。   In a preferred embodiment of the method of the present invention, an insoluble electrode pair is used as the electrode pair.

本発明の方法の望ましい別の実施の態様では、前記電極対の少なくとも１つの電極に、鉄電極を用いる。   In another desirable embodiment of the method of the present invention, an iron electrode is used as at least one electrode of the electrode pair.

本発明の方法の望ましい一実施の態様では、前記電極対の各電極の極性の切り替えを行う。   In a preferred embodiment of the method of the present invention, the polarity of each electrode of the electrode pair is switched.

本発明の方法の望ましい一実施の態様では、前記被除去物が、コロイド粒子を含む。   In a desirable embodiment of the method of the present invention, the object to be removed includes colloidal particles.

本発明の方法の望ましい一実施の態様は、被除去物をろ過した処理水の、濁度および／または導電率を測定し、得られた濁度および／または導電率の値に応じて、水酸化物イオンの濃度を調整する工程をさらに含む。   One desirable embodiment of the method of the present invention is to measure the turbidity and / or conductivity of the treated water obtained by filtering the material to be removed, and depending on the obtained turbidity and / or conductivity value, The method further includes the step of adjusting the concentration of oxide ions.

別の側面から、本発明の第１の装置は、排水またはろ過処理水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対を備えた電解槽、
前記電解槽に接続され、水酸化物イオンを含む排水またはろ過処理水を処理槽に送液するための注水ポンプ、
前記注水ポンプに接続され、被除去物を含む処理すべき排水を貯留可能な処理槽、および
ろ過膜を有する、
排水中の被除去物の回収除去装置である。 From another aspect, the first apparatus of the present invention is an electrolytic cell comprising at least one electrode pair for electrolyzing waste water or filtered water to generate hydroxide ions,
A water injection pump connected to the electrolytic cell, for feeding wastewater containing hydroxide ions or filtered water to the treatment tank,
A treatment tank connected to the water injection pump, capable of storing wastewater to be treated including the object to be removed, and a filtration membrane;
This is a device for recovering and removing objects to be removed from waste water.

本発明の第１の装置の望ましい一実施の態様は、前記処理槽内に配置され、水酸化物イオンを含む排水またはろ過処理水と、被除去物を含む処理すべき排水とを混合するための混合槽をさらに有する。   One desirable embodiment of the first apparatus of the present invention is arranged in the treatment tank, for mixing waste water containing hydroxide ions or filtered water and waste water to be treated containing an object to be removed. The mixing tank is further provided.

本発明の第２の装置は、被除去物を含む処理すべき排水を貯留可能な処理槽、
当該処理槽内に設けられ、排水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対、および
ろ過膜を有する、
排水中の被除去物の回収除去装置である。 The second apparatus of the present invention is a treatment tank capable of storing wastewater to be treated including an object to be removed,
Provided in the treatment tank, having at least one electrode pair for electrolyzing waste water to generate hydroxide ions, and a filtration membrane;
This is a device for recovering and removing objects to be removed from waste water.

本発明の第２の装置の望ましい一実施の態様は、前記処理槽内に配置され、内部に前記電極対が配置されており、被除去物を含む処理すべき排水が供給されて当該排水を電解するための電解混合槽をさらに有する。   A desirable embodiment of the second apparatus of the present invention is arranged in the treatment tank, the electrode pair is arranged in the inside thereof, and waste water to be treated including an object to be removed is supplied to discharge the waste water. It further has an electrolytic mixing tank for electrolysis.

本発明の第１および第２の装置の望ましい一実施の態様では、前記ろ過膜が、前記処理槽内であって排水に浸漬される位置に配置されている。このとき、より望ましい一実施の態様は、前記処理槽内であって、前記ろ過膜の下部に散気管をさらに有する。   In a desirable embodiment of the first and second apparatuses of the present invention, the filtration membrane is disposed in a position where it is immersed in waste water in the treatment tank. At this time, a more desirable embodiment is in the treatment tank, and further has a diffuser tube below the filtration membrane.

本発明の第１および第２の装置の望ましい一実施の態様では、前記電極対が、不溶性電極対である。   In a desirable embodiment of the first and second devices of the present invention, the electrode pair is an insoluble electrode pair.

本発明の第１および第２の装置の望ましい別の実施の態様では、前記電極対の少なくとも１つの電極が、鉄電極である。   In another desirable embodiment of the first and second devices of the invention, at least one electrode of the electrode pair is an iron electrode.

本発明の第１および第２の装置の望ましい一実施の態様は、導電率計および／または濁度計をさらに有する。   One desirable embodiment of the first and second devices of the present invention further comprises a conductivity meter and / or a turbidimeter.

以下、本発明の具体的な実施の形態について図面を参照しながら説明する。   Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

（実施の形態１）
実施の形態１では、上記本発明の第１の装置を使用して本発明の回収除去方法が実施される。当該装置の構成例を図１に示す。 (Embodiment 1)
In Embodiment 1, the recovery and removal method of the present invention is carried out using the first apparatus of the present invention. A configuration example of the apparatus is shown in FIG.

処理される排水５は、たとえば、電子産業から排出される、水がシリコン、シリカ、セリア、炭化珪素、カーボンブラックなどを被除去物として含む排水である。これらの被除去物は、おおよそ０．０５μｍ〜０．３μｍ程度の粒径の微粒子であり、これらの微粒子は通常の排水処理である凝集沈殿や、遠心分離などでは、処理することが困難で純水製造などで使用されるＵＦろ過処理（限外ろ過処理）などの高度な処理が必要とされる。本発明の回収除去方法は、特にコロイド粒子（ここでは、動的光散乱法により測定される粒径が１０ｎｍ〜１μｍの微粒子をコロイド粒子とする）を除去するのに適している。   The wastewater 5 to be treated is, for example, wastewater that is discharged from the electronics industry and contains silicon, silica, ceria, silicon carbide, carbon black, and the like as objects to be removed. These objects to be removed are fine particles having a particle size of about 0.05 μm to 0.3 μm, and these fine particles are difficult to be treated by agglomeration and precipitation such as ordinary wastewater treatment or centrifugal separation. Advanced treatment such as UF filtration (ultrafiltration) used in water production is required. The recovery and removal method of the present invention is particularly suitable for removing colloidal particles (here, fine particles having a particle diameter of 10 nm to 1 μm measured by a dynamic light scattering method are used as colloidal particles).

まず、電解槽９に、最初は、被除去物を含む排水を注入する。一度本発明の回収除去方法が実施された場合には、平膜２でろ過処理され、ろ過ポンプ６から排出されるろ過処理水１６の一部を、流量調整バルブ１５を介して電解槽９へ供給する。ろ過処理水１６を電解に用いる場合には、排水５から被除去物がろ過分離されているため、安定した電解が可能であるという利点がある。なお、電解槽９には、ろ過処理水１６を供給することなく、常に排水を注入しても構わない。   First, wastewater containing an object to be removed is injected into the electrolytic cell 9 at first. Once the recovery and removal method of the present invention is carried out, a portion of the filtered water 16 that is filtered by the flat membrane 2 and discharged from the filtration pump 6 is transferred to the electrolytic cell 9 via the flow rate adjusting valve 15. Supply. In the case of using the filtered water 16 for electrolysis, there is an advantage that stable electrolysis is possible because the object to be removed is filtered and separated from the waste water 5. In addition, you may always inject | pour waste_water | drain into the electrolytic cell 9, without supplying the filtered water 16. FIG.

電解槽９には、電圧を印加して水酸化物イオンを生成させる電解用電極対として第１の電極１０と第２の電極１１が浸漬されている。電極対へ電解制御装置１２より任意の直流電圧を印加し、排水５またはろ過処理水１６を電気分解し、水酸化物イオンを生成させる。ここでは、電極対１０、１１には、溶解性電極である鉄電極を用いており、水酸化物イオンが陰極近傍で発生し、陽極からは、陽イオンとして鉄イオンが溶出し、水酸化鉄水溶液が生成する。なお、電極対１０、１１に、不溶性電極を用いても構わないが本実施の形態では溶解性電極が適している。電極は１対に限らず、複数対使用してもよい。   In the electrolytic cell 9, a first electrode 10 and a second electrode 11 are immersed as an electrode pair for electrolysis that generates a hydroxide ion by applying a voltage. An arbitrary DC voltage is applied to the electrode pair from the electrolysis control device 12 to electrolyze the waste water 5 or the filtered water 16 to generate hydroxide ions. Here, an iron electrode which is a soluble electrode is used for the electrode pairs 10 and 11, hydroxide ions are generated in the vicinity of the cathode, and iron ions are eluted as cations from the anode. An aqueous solution is formed. Although insoluble electrodes may be used for the electrode pairs 10 and 11, a soluble electrode is suitable in this embodiment. The electrodes are not limited to a single pair, and a plurality of pairs may be used.

排水を電解する場合には、電極表面に不純物が付着することがある。また、電解により、鉄電極が溶解して消耗する。このような場合、電解制御装置１２によって電極１０、１１の極性の切り替えを行えば、電極表面に付着した不純物を除去したり、溶解性電極を用いた電解を長時間実施することができる。   When electrolyzing waste water, impurities may adhere to the electrode surface. In addition, the iron electrode is dissolved and consumed by electrolysis. In such a case, if the polarity of the electrodes 10 and 11 is switched by the electrolysis control device 12, impurities attached to the electrode surface can be removed, or electrolysis using a soluble electrode can be performed for a long time.

電解槽９と処理槽１は、注水ポンプ８を介して接続されており、水酸化鉄水溶液（水酸化物イオンを含む排水またはろ過処理水）が、処理槽１内に注入される。一方で、処理すべき排水５も、処理槽１に注入される。ここで、処理槽１は、槽内に混合槽３を有しており、水酸化鉄水溶液、および排水５が混合槽３内において混合され、水酸化物イオンが処理すべき排水５と接触する。混合槽３の使用によれば、予め排水５中の水酸化物イオン濃度を均一にしてから、排水５および水酸化物イオンを処理槽１全体に供給することにより、水酸化物イオン濃度の制御が容易になるという効果が得られる。   The electrolytic bath 9 and the treatment bath 1 are connected via a water injection pump 8, and an aqueous iron hydroxide solution (drainage or filtered water containing hydroxide ions) is injected into the treatment bath 1. On the other hand, the waste water 5 to be treated is also poured into the treatment tank 1. Here, the processing tank 1 has the mixing tank 3 in the tank, and the aqueous iron hydroxide solution and the waste water 5 are mixed in the mixing tank 3 and the hydroxide ions come into contact with the waste water 5 to be treated. . According to the use of the mixing tank 3, the hydroxide ion concentration in the waste water 5 is made uniform in advance, and then the waste water 5 and the hydroxide ions are supplied to the entire processing tank 1, thereby controlling the hydroxide ion concentration. The effect that it becomes easy is acquired.

被除去物が、たとえば、０．１μｍ程度の平均粒子径のカーボンブラックなどの微粒子の場合、微粒子はコロイド粒子であり、電荷を持つためお互いに反発しあい、排水中に分散した状態となっている。   For example, when the object to be removed is a fine particle such as carbon black having an average particle diameter of about 0.1 μm, the fine particle is a colloidal particle and repels each other because of electric charge, and is dispersed in the waste water. .

この電荷を持った微粒子に、水酸化物イオン、および場合によりこれと対となる陽イオン（ここでは鉄イオン）が近づき、微粒子の電荷を中和することにより、微粒子同士は凝集し、粒子径が増大した凝集粒子となる。このとき、凝集粒子の粒子径は数十倍にもなり得、平膜２の孔径より大きくなって、平膜２の表面に堆積し、ろ過分離が可能となる。   The fine particles with electric charge approach the hydroxide ions and, in some cases, the cation (in this case, iron ions) paired with the fine particles. Becomes an aggregated particle having increased. At this time, the particle diameter of the agglomerated particles can be several tens of times larger than the pore diameter of the flat membrane 2 and is deposited on the surface of the flat membrane 2 and can be separated by filtration.

ろ過ポンプ６により被除去物の微粒子が凝集した排水を平膜２を介して排出することによって、ろ過分離が行われる。ここで、平膜２は、処理槽１内であって排水に浸漬される位置に配置されている。これにより、凝集粒子が大きくなりすぎないうちにろ過されるので、水酸化物イオンの注入量を容易に最適化することができるという効果が得られる。平膜２の孔径は被除去物の粒子径を元に設定される。たとえば、平膜２の孔径を０．２５μｍとすると、それ以下の微粒子はろ過分離することができず、ろ過処理水は濁った水質になるおそれがあるので、この孔径よりも小さい孔径を採用することが推奨される。なお、ここでは膜として平膜２を用いているが、膜の形状はこれに限られず、円筒膜等種々の形状の膜を用いることができる。   Filtration separation is performed by discharging the waste water in which fine particles of the object to be removed are aggregated by the filtration pump 6 through the flat membrane 2. Here, the flat membrane 2 is disposed in the treatment tank 1 at a position where it is immersed in the waste water. As a result, since the aggregated particles are filtered before becoming too large, an effect of easily optimizing the injection amount of hydroxide ions can be obtained. The pore diameter of the flat membrane 2 is set based on the particle diameter of the object to be removed. For example, when the pore diameter of the flat membrane 2 is 0.25 μm, fine particles smaller than that cannot be separated by filtration, and the filtered water may become turbid water quality. Therefore, a pore diameter smaller than this pore diameter is adopted. It is recommended. Here, the flat membrane 2 is used as the membrane, but the shape of the membrane is not limited to this, and membranes of various shapes such as a cylindrical membrane can be used.

処理槽１に浸漬された平膜２の下部には、エアーポンプ７と接続された散気管４が設けられている。散気管４を介して気体を供給することにより、平膜２近傍の水酸化物イオン濃度および粒子濃度が均一化されたり、平膜２表面に付着した微粒子が再分散されたり、平膜２表面に堆積した微粒子の離脱が促進されるため、凝集効果とろ過性能を向上させることができる。   A diffuser tube 4 connected to an air pump 7 is provided below the flat membrane 2 immersed in the treatment tank 1. By supplying gas through the air diffuser 4, the hydroxide ion concentration and the particle concentration in the vicinity of the flat membrane 2 are made uniform, the fine particles adhering to the surface of the flat membrane 2 are redispersed, or the surface of the flat membrane 2 Since the detachment of the fine particles accumulated on the surface is promoted, the aggregation effect and filtration performance can be improved.

ろ過ポンプ６の後段には、水質を計測するセンサーとして、導電率計１３および濁度計１４などが取り付けられている。これらの計器が示す値により導電率の上昇や濁度の上昇などを検出することで、印加電圧を調整したり、電解の停止または注水ポンプの停止によって水酸化物イオンの供給を停止したりして、水酸化物イオンの濃度を調整することができる。これにより、ろ過処理水１６が所定の水質の範囲に入るように容易に制御ができるので、ろ過分離の性能、回収スラッジの純度を容易に監視することができる。特に本願発明では、イオンの作用によって、被除去物を凝集させるために、水酸化物イオン濃度の調整目的には、導電率計の使用が適している。   A conductivity meter 13 and a turbidimeter 14 are attached to the subsequent stage of the filtration pump 6 as sensors for measuring water quality. By detecting the increase in conductivity or turbidity based on the values indicated by these instruments, the applied voltage can be adjusted, or the supply of hydroxide ions can be stopped by stopping the electrolysis or water injection pump. Thus, the concentration of hydroxide ions can be adjusted. Thereby, since it can control easily so that the filtration water 16 may enter into the range of predetermined | prescribed water quality, the performance of filtration separation and the purity of collection | recovery sludge can be monitored easily. In particular, in the present invention, the use of a conductivity meter is suitable for the purpose of adjusting the hydroxide ion concentration in order to agglomerate the object to be removed by the action of ions.

ろ過処理によって清浄なろ過処理水１６を得ることができる。一方で、処理槽１内の被除去物の濃度が所定の濃度を超えたら、ろ過操作を停止し、被除去物の凝集物を沈殿させる。その後、処理槽１より排出ポンプ１８を介して回収スラッジ１９を回収することができる。   Clean filtered water 16 can be obtained by filtration. On the other hand, when the concentration of the object to be removed in the treatment tank 1 exceeds a predetermined concentration, the filtration operation is stopped and the aggregate of the object to be removed is precipitated. Thereafter, the recovered sludge 19 can be recovered from the processing tank 1 via the discharge pump 18.

（実施の形態２）
実施の形態２では、上記本発明の第２の装置を使用して本発明の回収除去方法が実施される。当該装置の構成例を図２に示す。 (Embodiment 2)
In Embodiment 2, the recovery and removal method of the present invention is carried out using the second apparatus of the present invention. A configuration example of the apparatus is shown in FIG.

実施の形態２については、実施の態様１と異なる点のみ説明する。その他の点については実施の形態１と同様である。図２において、図１と同様の構成および要素については、同じ参照符号を使用する。   In the second embodiment, only points different from the first embodiment will be described. Other points are the same as in the first embodiment. 2, the same reference numerals are used for the same components and elements as those in FIG.

実施の形態２で使用される除去装置は、電極対１０、１１が処理槽内に設けられている点、および前記電解槽と混合槽に代えて電解混合槽１７を設置している点で実施の形態１の除去装置と異なっている。   The removal apparatus used in Embodiment 2 is implemented in that the electrode pairs 10 and 11 are provided in the treatment tank, and that an electrolytic mixing tank 17 is provided instead of the electrolytic tank and the mixing tank. This is different from the removal apparatus of the first embodiment.

図２に示すように、処理槽１内に電解槽と混合槽をかねた電解混合槽１７を設置すると、電解で生成するイオンを直接排水５に接触させることができ、また、装置自体をコンパクトにすることができる。   As shown in FIG. 2, when an electrolytic mixing tank 17 that also serves as an electrolytic tank and a mixing tank is installed in the processing tank 1, ions generated by electrolysis can be directly brought into contact with the drainage 5 and the apparatus itself is compact. Can be.

ここでは、電極１０、１１に不溶性電極を用いている。不溶性電極を用いた場合には、ろ過処理水に電極由来の不純物が含まれることが無いため、ろ過処理水の純度を容易に排水基準値以下とすることができ、本実施の形態においては不溶性電極の使用が望ましい。不溶性電極としては、たとえば、Ｐｔ電極、Ｐｔを含む化合物の電極、Ｐｔ又はＰｔ化合物で被覆された電極等を用いることができる。微粒子が直接的に電極に接触するため、電極が劣化する可能性がある。これに対し、ダイヤモンドが塗布されたダイヤモンド電極などを用いることで、電極の劣化を進みにくくすることもできる。なお、本実施の形態においても鉄電極等の溶解性電極を用いてもよい。   Here, insoluble electrodes are used for the electrodes 10 and 11. When an insoluble electrode is used, since the filtered water does not contain impurities derived from the electrode, the purity of the filtered water can be easily reduced below the drainage standard value, and insoluble in this embodiment. The use of electrodes is desirable. As the insoluble electrode, for example, a Pt electrode, an electrode of a compound containing Pt, an electrode coated with Pt or a Pt compound, or the like can be used. Since the fine particles directly contact the electrode, the electrode may be deteriorated. On the other hand, by using a diamond electrode coated with diamond or the like, the deterioration of the electrode can be made difficult to proceed. Note that a soluble electrode such as an iron electrode may also be used in this embodiment.

処理すべき排水５が電解混合槽１７に注入されると、槽内に配置された電極近傍で発生する水酸化物イオン、および場合により陽イオン（水素イオン）によって、微粒子の電荷が中和されることにより、微粒子同士が凝集し、ろ過するのに十分なまでに粒子径が増大した凝集粒子となる。   When the waste water 5 to be treated is injected into the electrolytic mixing tank 17, the charge of the fine particles is neutralized by hydroxide ions generated in the vicinity of the electrodes arranged in the tank, and possibly cations (hydrogen ions). As a result, the fine particles are aggregated and become aggregated particles having a particle diameter increased enough to be filtered.

本発明の回収除去方法は、このように、被除去物の粒子を凝集させるために異物成分を添加する従来方法とは異なり、電解により生じるイオンの電荷を利用して被除去物を凝集させている。このため、回収される被除去物の純度を低下させることなく、被除去物を再利用可能なスラッジ等として回収することができる。また、ろ過処理水の方も高純度で回収することができ、再利用が可能である。   Unlike the conventional method of adding a foreign substance component to agglomerate particles of the object to be removed, the recovery and removal method of the present invention agglomerates the object to be removed by utilizing the charge of ions generated by electrolysis. Yes. Therefore, the object to be removed can be recovered as reusable sludge or the like without reducing the purity of the object to be recovered. Further, the filtered water can also be recovered with high purity and can be reused.

なお、本発明は、上記の実施の態様に限られず、本発明の趣旨を逸脱しない範囲内で当該発明の属する技術の分野における通常の知識を有する者によって各種変更及び修正が可能である。   The present invention is not limited to the above-described embodiments, and various changes and modifications can be made by persons having ordinary knowledge in the technical field to which the present invention belongs without departing from the spirit of the present invention.

本発明にかかる排水中の被除去物の回収除去方法および装置は、従来のように異物成分を添加することなく、排水中の被除去物の微粒子を凝集させてろ過処理することができるため、被除去物の純度を低下させることなく、被除去物を再利用可能なスラッジ等として回収することができ、電子産業分野等から発生する排水の処理に有用である。   Since the method for recovering and removing the object in the waste water according to the present invention can filter the agglomerated fine particles of the object in the waste water without adding a foreign component as in the prior art, The material to be removed can be recovered as reusable sludge or the like without reducing the purity of the material to be removed, which is useful for the treatment of wastewater generated from the electronics industry.

１ 処理槽
２ 平膜
３ 混合槽
４ 散気管
５ 排水
６ ろ過ポンプ
７ エアーポンプ
８ 注水ポンプ
９ 電解槽
１０ 第１の電極
１１ 第２の電極
１２ 電解制御装置
１３ 導電率計
１４ 濁度計
１５ 流量調整バルブ
１６ ろ過処理水
１７ 電解混合槽
１８ 排出ポンプ
１９ 回収スラッジ DESCRIPTION OF SYMBOLS 1 Treatment tank 2 Flat membrane 3 Mixing tank 4 Aeration pipe 5 Drainage 6 Filtration pump 7 Air pump 8 Water injection pump 9 Electrolysis tank 10 1st electrode 11 2nd electrode 12 Electrolysis control apparatus 13 Conductivity meter 14 Turbidimeter 15 Flow rate Adjustment valve 16 Filtered water 17 Electrolytic mixing tank 18 Discharge pump 19 Collected sludge

Claims (15)

排水またはろ過処理水に少なくとも１対の電極対を浸漬し、前記電極対に電圧を印加して水酸化物イオンを生成させる工程、
前記水酸化物イオンを、被除去物を含む処理すべき排水と接触させて、処理すべき排水中の被除去物を凝集させる工程、および
凝集した被除去物を、ろ過処理する工程を含む、
排水中の被除去物の回収除去方法。 Immersing at least one electrode pair in drainage or filtered water and applying a voltage to the electrode pair to generate hydroxide ions;
A step of bringing the hydroxide ions into contact with wastewater to be treated containing a substance to be removed, and aggregating the substance to be removed in the wastewater to be treated; and a step of filtering the aggregated substance to be removed.
A method for collecting and removing objects to be removed from wastewater. 前記電極対に、不溶性電極対を用いる請求項１に記載の回収除去方法。   The recovery and removal method according to claim 1, wherein an insoluble electrode pair is used as the electrode pair. 前記電極対の少なくとも１つの電極に、鉄電極を用いる請求項１に記載の回収除去方法。   The recovery and removal method according to claim 1, wherein an iron electrode is used as at least one electrode of the electrode pair. 前記電極対の各電極の極性の切り替えを行う請求項１〜３のいずれか１項に記載の回収除去方法。   The recovery and removal method according to any one of claims 1 to 3, wherein the polarity of each electrode of the electrode pair is switched. 前記被除去物が、コロイド粒子を含む請求項１〜４のいずれか１項に記載の回収除去方法。   The recovery and removal method according to claim 1, wherein the object to be removed includes colloidal particles. 被除去物をろ過した処理水の、濁度および／または導電率を測定し、得られた濁度および／または導電率の値に応じて、水酸化物イオンの濃度を調整する工程をさらに含む請求項１〜５のいずれか１項に記載の回収除去方法。   The method further includes the step of measuring the turbidity and / or conductivity of the treated water obtained by filtering the material to be removed and adjusting the concentration of hydroxide ions according to the obtained turbidity and / or conductivity value. The recovery removal method of any one of Claims 1-5. 排水またはろ過処理水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対を備えた電解槽、
前記電解槽に接続され、水酸化物イオンを含む排水またはろ過処理水を処理槽に送液するための注水ポンプ、
前記注水ポンプに接続され、被除去物を含む処理すべき排水を貯留可能な処理槽、および
ろ過膜を有する、
排水中の被除去物の回収除去装置。 An electrolytic cell comprising at least one electrode pair for electrolyzing waste water or filtered water to generate hydroxide ions;
A water injection pump connected to the electrolytic cell, for feeding wastewater containing hydroxide ions or filtered water to the treatment tank,
A treatment tank connected to the water injection pump, capable of storing wastewater to be treated including the object to be removed, and a filtration membrane;
Equipment for collecting and removing objects to be removed from wastewater. 前記処理槽内に配置され、水酸化物イオンを含む排水またはろ過処理水と、被除去物を含む処理すべき排水とを混合するための混合槽をさらに有する請求項７に記載の回収除去装置。   The recovery / removal device according to claim 7, further comprising a mixing tank disposed in the processing tank for mixing wastewater or filtered water containing hydroxide ions and wastewater to be processed containing a substance to be removed. . 被除去物を含む処理すべき排水を貯留可能な処理槽、
当該処理槽内に設けられ、排水を電解して水酸化物イオンを発生させるための少なくとも１対の電極対、および
ろ過膜を有する、
排水中の被除去物の回収除去装置。 A treatment tank capable of storing wastewater to be treated including the object to be removed;
Provided in the treatment tank, having at least one electrode pair for electrolyzing waste water to generate hydroxide ions, and a filtration membrane;
Equipment for collecting and removing objects to be removed from wastewater. 前記処理槽内に配置され、内部に前記電極対が配置されており、被除去物を含む処理すべき排水が供給されて当該排水を電解するための電解混合槽をさらに有する請求項９に記載の回収除去装置。   The electrolysis mixing tank which is arrange | positioned in the said process tank, the said electrode pair is arrange | positioned inside, and has further supplied the waste_water | drain which should be processed including a to-be-removed object, and electrolyzes the said waste_water | drain. Recovery and removal equipment. 前記ろ過膜が、前記処理槽内であって排水に浸漬される位置に配置されている請求項７〜１０のいずれか１項に記載の回収除去装置。   The recovery / removal device according to any one of claims 7 to 10, wherein the filtration membrane is disposed in a position in the treatment tank and immersed in waste water. 前記処理槽内であって、前記ろ過膜の下部に散気管をさらに有する請求項１１に記載の回収除去装置。   The recovery / removal apparatus according to claim 11, further comprising a diffuser tube in the processing tank and below the filtration membrane. 前記電極対が、不溶性電極対である請求項７〜１２のいずれか１項に記載の回収除去装置。   The recovery / removal device according to claim 7, wherein the electrode pair is an insoluble electrode pair. 前記電極対の少なくとも１つの電極が、鉄電極である請求項７〜１２のいずれか１項に記載の回収除去装置。   The recovery / removal apparatus according to claim 7, wherein at least one electrode of the electrode pair is an iron electrode. 導電率計および／または濁度計をさらに有する請求項７〜１４のいずれか１項に記載の回収除去装置。   The recovery and removal apparatus according to claim 7, further comprising a conductivity meter and / or a turbidity meter.
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