JP2014133229A - Method for removing suspended substances within an effluent - Google Patents

Method for removing suspended substances within an effluent Download PDF

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JP2014133229A
JP2014133229A JP2013252657A JP2013252657A JP2014133229A JP 2014133229 A JP2014133229 A JP 2014133229A JP 2013252657 A JP2013252657 A JP 2013252657A JP 2013252657 A JP2013252657 A JP 2013252657A JP 2014133229 A JP2014133229 A JP 2014133229A
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water
fine
wastewater
coarse
suspended
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JP6374157B2 (en
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Hiroshi Niekawa
拓 贄川
Shunsuke Arai
俊介 新井
Yuichiro Kato
加藤  雄一郎
Kazuhiro Kusumoto
和弘 楠元
Masahiro Shimase
正博 島瀬
Masaru Okunuki
優 奥貫
Shoji Fujita
将司 藤田
Dai Oyama
大 大山
Kazuji Maeda
和司 前田
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Nippon Steel Corp
Nippon Steel Eco Tech Corp
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Nippon Steel and Sumitomo Metal Corp
Nippon Steel and Sumikin Eco Tech Corp
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/48Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/484Treatment of water, waste water, or sewage with magnetic or electric fields using electromagnets
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide, by targeting a method for separating and removing, from an effluent including crude suspended substances (SS), the SS, a method for removing SS within an effluent extremely useful from an industrial standpoint and capable of yielding treated water of a favorable quality very quickly, of reducing the addition ratio of a flocculant, of significantly simplifying facilities, of reducing facility costs and maintenance and management costs, of reducing the cost of recycling a generated precipitate, and of avoiding problems attributed to inorganic flocculants.SOLUTION: The provided method for removing suspended substances within an effluent is a method for removing suspended substances within an effluent conceived for flocculating, precipitating, and removing suspended substances from an effluent by using a flocculant in which at least one type of organic flocculant is used as the flocculant and a state where at least crude suspended substances and fine suspended substances coexist in the co-presence of the organic flocculant within a body of turbulent water having a flow velocity of at least 0.5 m/sec is induced to arise so as to enable the flocculation and precipitation of the crude suspended substances and fine suspended substances in the course of an identical treatment and simultaneous removals of both.

Description

本発明は、廃水中の懸濁物質の除去処理方法に関し、より詳しくは、製鐵所において大量に発生する、粒径が50μm以上の金属粉や油分等の粗大な懸濁物質を含む廃水中から、有機凝集剤を利用して、これらの粗大な懸濁物質を含んだままの状態で懸濁物質を一挙に、速やかに、しかも極めて効率よく凝集沈降させ、これらを同時に除去することができるようにした廃水中の懸濁物質の除去処理技術に関する。   The present invention relates to a method for removing suspended solids from wastewater, and more specifically, wastewater containing a large amount of suspended matter such as metal powder or oil having a particle size of 50 μm or more, which is generated in large quantities in a steelworks. From the above, by using an organic flocculant, the suspended solids can be coagulated and settled quickly and extremely efficiently while containing these coarse suspended solids, and these can be removed simultaneously. The present invention relates to a technique for removing suspended substances in wastewater.

例えば、製鐵所において発生する廃水としては、連続鋳造工程における直接冷却廃水、圧延工程における直接冷却廃水、高炉、転炉、電炉工程における集塵廃水、屋外原料貯蔵ヤードから発生する雨水廃水などがあるが、その量は大量である。また、これらの廃水中には、下記に述べるように、いずれも、微細な懸濁物質のみならず、鉄等の金属粉や、水砕スラグ、石炭粉・コークス粉等の粒径が50μm以上の粗大な懸濁物質(以下、粗大SSとも呼ぶ)が含まれている。後述するように、このような廃水から懸濁物質を除去する場合は、先ず、粗大な懸濁物質を沈降分離等の方法で予め除去した後、除去後の廃水を種々の凝集剤を用いて更に処理して、粒径が50μmに満たない微細な懸濁物質(以下、微細SSとも呼ぶ)を、凝集沈降させて除去することが多い。   For example, wastewater generated at the ironworks includes direct cooling wastewater in the continuous casting process, direct cooling wastewater in the rolling process, dust collection wastewater in the blast furnace, converter, electric furnace process, rainwater wastewater generated from the outdoor raw material storage yard, etc. There is a large amount. Moreover, in these wastewaters, as described below, not only fine suspended substances, but also particle sizes of metal powder such as iron, granulated slag, coal powder and coke powder are 50 μm or more. Of coarse suspended solids (hereinafter also referred to as coarse SS). As will be described later, when removing suspended substances from such waste water, first, the coarse suspended substances are first removed in advance by a method such as sedimentation separation, and the removed waste water is then removed using various flocculants. In many cases, fine suspended substances (hereinafter also referred to as fine SS) having a particle size of less than 50 μm are removed by coagulation sedimentation.

図5は、廃水中に含有されている上記したような粗大SSと微細SSとを含む懸濁物質(SS)を除去処理する従来の方法の一例であり、鋼材圧延ラインの圧延工程における直接冷却廃水の処理の概要を模式的に示したものである。図5に示したように、直接冷却廃水は、SSを除去処理されて処理水となった後、再び直接冷却水として循環使用されている。したがって、その処理水は、懸濁物質の少ない、より清澄なものであることが望まれる。以下に、図5を参照して、従来行われている直接冷却廃水の処理の手順を説明する。先ず、圧延工程では、冷却水がスプレーノズル等から鋼材表面へ噴射されて、鋼材を冷却する。その際に使用された冷却水は、鋼材圧延ラインの下に作られた、図5中に1で示したスケールスルースと呼ばれる開放樋に流れ落ちる。これが、直接冷却廃水と呼ばれているものであり、種々の懸濁物質を含むものになる。具体的には、この直接冷却廃水中には、鋼材表面から剥がれ落ちたスケールと呼ばれる50μm以上の粒径を持つ大き目の懸濁物質や、鋳造や圧延に用いられるロールの軸用潤滑油や圧延油や、これらのロールと鋼材との摩擦により生じる微細な鉄粉等が含まれており、少なくとも粗大SSと微細SSとが混在したものとなっている。なお、鋼材製造ラインにおける連続鋳造工程で生じる直接冷却廃水も同様の性状のものであり、その処理も、上記と同様に行われることが多い。   FIG. 5 is an example of a conventional method for removing suspended matter (SS) containing coarse SS and fine SS as described above contained in wastewater, and is a direct cooling in a rolling process of a steel material rolling line. An outline of wastewater treatment is schematically shown. As shown in FIG. 5, the direct cooling wastewater is recycled as direct cooling water after the SS is removed to become treated water. Therefore, the treated water is desired to be clearer with less suspended matter. Below, with reference to FIG. 5, the procedure of the process of the direct cooling wastewater currently performed is demonstrated. First, in a rolling process, cooling water is sprayed on the steel material surface from a spray nozzle etc., and steel material is cooled. The cooling water used at that time flows down to an open soot called scale sluice indicated by 1 in FIG. This is called direct cooling wastewater and contains various suspended substances. Specifically, in this direct cooling wastewater, a large suspended substance having a particle size of 50 μm or more called a scale peeled off from the surface of the steel material, a roll shaft lubricating oil used for casting or rolling, or rolling Oil, fine iron powder generated by friction between these rolls and steel materials, and the like are included, and at least coarse SS and fine SS are mixed. In addition, the direct cooling waste water produced in the continuous casting process in the steel material production line has the same property, and the treatment is often performed in the same manner as described above.

上記でスケールスルース1に流れ落ちた大量の直接冷却廃水は、図5中に3で示したスケールピットと呼ばれる槽へと激しい流れによって排水されて、ピット内に貯溜される。スケールピットは、直接冷却廃水中に存在している粒径の大きなスケール(粗大SS)の沈殿分離を主目的としたものであり、Over Flow Rateが約10m/hr以上程度の比較的小さな槽である。   The large amount of directly cooled wastewater that has flowed down into the scale sluice 1 is drained by a violent flow into a tank called a scale pit indicated by 3 in FIG. 5 and stored in the pit. The scale pit is mainly intended for precipitation separation of large scale (coarse SS) having a large particle size that is present in the cooling wastewater directly. It is a relatively small tank with an Over Flow Rate of about 10 m / hr or more. is there.

先に述べたように、連続鋳造工程や圧延工程から発生する直接冷却廃水に対しての従来の処理では、先ず、このスケールピット3において、粒径の大きな懸濁物質(すなわち、粗大SS)を沈殿分離し、その後に、粗大SSを取り除いた廃水について、後段に設けた凝集沈殿設備8やろ過機9、更には電磁フィルター(不図示)等において、主に粒径50μmに満たない微粒子(すなわち、微細SS)を除去処理することが行われている。そして、上記のようにして粗大SSと微細SSを除去後、処理水を冷却塔4などに通水することで冷却して、再び直接冷却用水として工場へ給水するのが一般的である。   As described above, in the conventional treatment for the direct cooling wastewater generated from the continuous casting process or the rolling process, first, suspended matter having a large particle size (that is, coarse SS) is first formed in the scale pit 3. For the waste water from which the coarse SS has been separated after the precipitation separation, fine particles having a particle size of less than 50 μm (that is, in a coagulation sedimentation facility 8 or a filter 9 provided later, or an electromagnetic filter (not shown)) , The fine SS) is removed. Then, after removing the coarse SS and the fine SS as described above, the treated water is cooled by passing it through the cooling tower 4 or the like, and then supplied directly to the factory as cooling water again.

上記したようにして行われている従来の、直接冷却廃水からの懸濁物質の除去処理方法では、懸濁物質の沈降を効率よく行うことを目的として、凝集剤が使用されている。使用される凝集剤は、廃水の性状に応じて選択されており、更には各種の凝集剤を組み合わせて使用することが一般的になっている。例えば、鉄鋼圧延廃水の水処理方法に関する特許文献1では、鉄鋼圧延に使った水を回収してなる原水に、無機凝集剤であるポリ塩化アルミニウム(PAC)及び有機凝集剤を注入する工程を有することを前提とした上で、これらの注入量を調整することで、懸濁物質濃度を、より大幅且つ有利に低減させ得るとしている。また、特許文献2では、鉄鋼業等から生じる含油廃水を、PACで処理するにあたり、有機凝集剤であるカチオン系ディスパージョン型(共)重合体を添加し、次いで凝集沈澱処理及び脱水処理に付する方法が提案されている。また、特許文献3では、自動車工業廃水等の鉱油が混入した廃水において、特有のカチオン性有機凝集剤を添加した後、アニオン性有機凝集剤を添加し凝集させフロックを分離することが提案されている。   In the conventional method for removing suspended substances from directly cooled wastewater, which is performed as described above, a flocculant is used for the purpose of efficiently sedimenting suspended substances. The flocculant to be used is selected according to the properties of the wastewater, and it is common to use various flocculants in combination. For example, Patent Document 1 relating to a water treatment method for steel rolling wastewater has a step of injecting polyaluminum chloride (PAC), which is an inorganic flocculant, and an organic flocculant into raw water obtained by collecting water used for steel rolling. Based on this assumption, the concentration of suspended solids can be more greatly and advantageously reduced by adjusting these injection amounts. Further, in Patent Document 2, when oil-containing wastewater generated from the steel industry or the like is treated with PAC, a cationic dispersion type (co) polymer that is an organic flocculant is added, and then subjected to aggregation precipitation treatment and dehydration treatment. A method has been proposed. Patent Document 3 proposes to add a specific cationic organic flocculant to a wastewater mixed with mineral oil such as automobile industrial wastewater, and then add an anionic organic flocculant to aggregate and separate the flocs. Yes.

更に、特許文献4では、先に述べた圧延工程における直接冷却廃水の水処理方法において、無機凝集剤の硫酸バンドやPACを使用すると、冷却水中の硫酸イオンや塩素イオンが増加し、冷却水と接触する圧延機、ロール等の機器類の腐食を促進し、冷却水中に微細な酸化鉄(Fe23)を発生させるという問題があり、このような酸化鉄は、凝集処理によっても十分に除去することはできないとしている。そして、特許文献4に記載の技術では、その対策として、アンモニア、脂肪族第一アミン、脂肪族第二アミン又はアルキレンジアミンとエピクロルヒドリンとの重縮合物等のカチオン系有機凝集剤を用いて凝集処理し、該処理水に特有のスケール防止剤を添加することが有効であるとしている。 Furthermore, in Patent Document 4, in the water treatment method of direct cooling wastewater in the rolling process described above, when sulfuric acid bands or PACs of inorganic flocculants are used, sulfate ions and chlorine ions in the cooling water increase, and cooling water and There is a problem of promoting corrosion of equipment such as rolling mills and rolls in contact with each other and generating fine iron oxide (Fe 2 O 3 ) in the cooling water. It cannot be removed. And in the technique described in Patent Document 4, as a countermeasure, aggregation treatment is performed using a cationic organic flocculant such as ammonia, an aliphatic primary amine, an aliphatic secondary amine or a polycondensate of alkylenediamine and epichlorohydrin. However, it is said that it is effective to add a scale inhibitor specific to the treated water.

また、特許文献5には、製鐵所において発生する廃水の一つである転炉排ガス集塵水の処理に関し、湿式集塵器にて湿式集塵処理して得られるダストを含む集塵水を粗粒分離器に導入して粗粒ダストを分離した後、シックナーで凝集沈殿処理する際に、湿式集塵器の出口から該粗粒分離器の間の集塵水及び/又は粗粒分離器に高分子凝集剤を添加することが提案されている。そして、上記構成とすることで、粗粒分離器での粗粒ダストの回収率を高め、転炉排ガスダストのリサイクルコストの低減、リサイクル効率の向上を図ることができるとされている。   Further, Patent Document 5 relates to the treatment of converter exhaust gas dust collection water, which is one of waste water generated in a steelworks, and dust collection water containing dust obtained by wet dust collection processing using a wet dust collector. After separating coarse dust by introducing it into the coarse separator, when collecting and precipitating with a thickener, dust collection water and / or coarse separation between the coarse separators from the outlet of the wet precipitator It has been proposed to add a polymer flocculant to the vessel. And by setting it as the said structure, it is supposed that the recovery rate of the coarse-grain dust in a coarse-grain separator can be raised, the recycle cost of converter waste gas dust can be reduced, and the recycle efficiency can be improved.

特開2012−139633号公報JP 2012-139633 A 特開2008−006382号公報JP 2008-006382 A 特許第4072075号公報Japanese Patent No. 4072075 特許第3868521号公報Japanese Patent No. 3868521 特許第4134914号公報Japanese Patent No. 4134914

上記したように、例えば、製鐵所において大量に発生する直接冷却廃水中から懸濁物質を除去する処理では、無機系や有機系の各種凝集剤から選択された複数種類の凝集剤が使用されている。ここで、製鐵所における直接冷却廃水の量は大量であるため、凝集剤にかかる費用も多大になるので、より安価で、且つ少ない量で高い凝集沈降効率を達成する技術の開発が要望されている。また、従来の技術において、複数種類の凝集剤は別々に廃水に添加されるとしても、その添加地点は、通常は水処理設備内に入ってからである。例えば、図5に示した例において、水処理設備における最初の処理槽である先に述べたスケールピット3内に、粗大SSの沈殿をより早める目的で凝集剤を添加することも場合によってはあり得るが、この場合の凝集剤は、通常、無機凝集剤が用いられている。一方、有機凝集剤は、本来、微細SSを凝集させて大きなフロックとし凝集沈降するために用いられており、図5に示した例では、スケールピット3内で粗大SSを沈殿した後の、廃水中の微細SSを凝集沈殿させる目的で使用されている。具体的には、図5に示した例では、有機凝集剤は、凝集沈殿設備を構成する広大な沈殿池8に添加されている。そして、撹拌機を用いて、直接冷却廃水等の被処理水と凝集剤との混合を促進させる必要がある場合もある。混合を促進する方法としては、例えば、沈殿池内に撹拌機を設置してもよいが、沈殿池が広大な場合には、沈殿池の前段に撹拌槽を設け、該撹拌槽で予め被処理水と凝集剤とを混合させた後、沈殿池に導入するといったことが行われている。その場合は、使用する凝集剤にかかる費用に加えて、撹拌機や撹拌槽にかかる設備費及び維持費が別途必要となるので、撹拌機等の使用を伴わない処理方法の開発が望まれる。   As described above, for example, in the process of removing suspended substances from directly cooled wastewater generated in large quantities at a steelworks, multiple types of flocculants selected from various inorganic and organic flocculants are used. ing. Here, since the amount of direct cooling wastewater at the smelter is large, the cost for the flocculant becomes large. Therefore, development of a technology that achieves high coagulation sedimentation efficiency at a lower price and in a smaller amount is demanded. ing. Moreover, even if several types of flocculants are separately added to waste water in the prior art, the point of addition is usually after entering the water treatment facility. For example, in the example shown in FIG. 5, a flocculant may be added to the scale pit 3 described above, which is the first treatment tank in the water treatment facility, for the purpose of further precipitating the coarse SS. In this case, an inorganic flocculant is usually used as the flocculant. On the other hand, the organic flocculant is originally used to agglomerate fine SS to form a large floc and agglomerate and settle. In the example shown in FIG. 5, the waste water after the coarse SS is precipitated in the scale pit 3. It is used for the purpose of coagulating and precipitating fine SS inside. Specifically, in the example shown in FIG. 5, the organic flocculant is added to the vast sedimentation basin 8 that constitutes the coagulation sedimentation facility. And it may be necessary to accelerate | stimulate mixing with to-be-processed water, such as direct cooling wastewater, and a coagulant | flocculant using an agitator. As a method for promoting the mixing, for example, a stirrer may be installed in the settling basin. However, when the settling pond is very large, a stirrer tank is provided in front of the settling basin, and the water to be treated is previously stored in the stirrer tank. And a flocculant are mixed and then introduced into a settling basin. In that case, in addition to the cost for the coagulant to be used, the equipment cost and the maintenance cost for the stirrer and the stirring tank are required separately, and therefore development of a treatment method that does not involve the use of a stirrer or the like is desired.

また、従来の処理方法では、先に述べたように、スケールピット内で粗大SSを沈殿した後、粗大SSを取り除いた廃水について、凝集沈殿設備で処理を行っているため、沈殿池、または、その沈殿池の前段に設けられた撹拌槽に流入する廃水中の懸濁物質は、前述した通り、粒径50μmに満たない微粒子(微細SS)となっている。このため、種々の凝集剤を用いてフロックとしたとしても、その沈降速度は、大きくても2〜3m/hr程度であり、迅速なものではない。したがって、従来の処理方法では、この微細SSからなるフロックの沈降速度を下回るOver Flow Rateを持つ大きさの広大な沈殿池が必要となる。このことは、処理設備の規模が極めて大きくなることを意味している。   In the conventional treatment method, as described above, after the coarse SS is precipitated in the scale pit, the waste water from which the coarse SS has been removed is treated in the coagulation sedimentation facility. As described above, the suspended matter in the wastewater flowing into the stirring tank provided in the preceding stage of the settling basin is fine particles (fine SS) having a particle size of less than 50 μm. For this reason, even if it uses various flocculants as a floc, the sedimentation speed is about 2-3 m / hr at most, and it is not quick. Therefore, in the conventional treatment method, a large sedimentation basin having a size of Over Flow Rate that is lower than the sedimentation speed of flocs composed of the fine SS is required. This means that the scale of the processing facility becomes extremely large.

これに対し、連続鋳造工程や圧延工程から発生する直接冷却廃水のような、鉄を主成分とする懸濁物質を含む廃水の場合は、大きな沈殿池の代わりに、電磁フィルターやろ過機を懸濁物質の除去に用いることも行われている。図5に例示した設備では、沈殿池8を有する凝集沈殿設備と、ろ過機9を併用している。しかし、電磁フィルターやろ過機は、設備費がかかることに加えて、その維持管理が煩雑で高額である上に、これらに捕捉された懸濁物質を定期的に排出することを目的とした逆流洗浄が必須になる。そして、この逆流洗浄の廃水の処理には更に設備も薬品も必要となる。   On the other hand, in the case of wastewater containing suspended solids mainly composed of iron, such as direct cooling wastewater generated from continuous casting and rolling processes, an electromagnetic filter or filter is suspended instead of a large sedimentation basin. It is also used to remove turbid substances. In the facility illustrated in FIG. 5, the coagulation sedimentation facility having the sedimentation basin 8 and the filter 9 are used in combination. However, in addition to the equipment cost, electromagnetic filters and filters are cumbersome and expensive to maintain, and the backflow is intended to periodically discharge suspended substances captured by these filters. Cleaning is essential. Further, equipment and chemicals are required for the treatment of the waste water for backwashing.

また、前記した特許文献4に記載の技術においては、下記の課題がある。先に述べたように、連続鋳造工程や圧延工程から発生する直接冷却廃水における懸濁物質の除去では、通常、無機凝集剤のみ、または、無機凝集剤と有機凝集剤とを併用するため、無機凝集剤に由来するCl-やSO4 2-といった腐食性陰イオンが処理水に混入することが起こる。そして、一般的に、これらの処理水は冷却された後、再び冷却水として工場へ給水されるため、上記した腐食性陰イオンの濃度が冷却塔等で水分が蒸発することで上昇すると、循環系統の配管やスプレーノズルの腐食を促進する恐れがある。 Further, the technique described in Patent Document 4 has the following problems. As described above, in the removal of suspended substances in direct cooling wastewater generated from a continuous casting process or a rolling process, usually only an inorganic flocculant or an inorganic flocculant and an organic flocculant are used in combination. Corrosive anions such as Cl - and SO 4 2- derived from the flocculant may be mixed into the treated water. In general, after the treated water is cooled, it is supplied again to the factory as cooling water. Therefore, when the concentration of the corrosive anions increases as the water evaporates in the cooling tower or the like, There is a risk of accelerating corrosion of piping and spray nozzles in the system.

また、こうした直接冷却廃水における懸濁物質の除去処理では、油分と微細な鉄粉等の懸濁物質とが強固に吸着し合った高油分スラッジが沈殿池において大量に発生する。この高油分スラッジは、産業廃棄物として廃棄処理されるか、製鐵原料としてリサイクルされており、殆どの場合、濃縮、脱水する工程が必要となる。しかし、特開2002−275549号公報にも記載されているように、高油分スラッジは、濃縮不良や脱水不良が起こり易い上に、燃焼性が非常に悪いため、含まれる油分が焼結機内で充分に燃焼できずに油蒸気が発生し、排ガスの集塵装置内に蓄積されて自然発火や爆発を引き起こすことがあるという問題がある。   Moreover, in the removal processing of suspended solids in such directly cooled wastewater, a large amount of high oil sludge in which the oil and solid suspended solids such as fine iron powder are firmly adsorbed is generated in the sedimentation basin. This high oil content sludge is disposed of as industrial waste or recycled as a raw material for making koji, and in most cases, a step for concentration and dehydration is required. However, as described in Japanese Patent Application Laid-Open No. 2002-275549, high oil content sludge is liable to cause concentration failure and dewatering failure and is very flammable. There is a problem that oil vapor is generated without being able to burn sufficiently and accumulates in the exhaust gas dust collector, which may cause spontaneous ignition or explosion.

上記した高油分スラッジにおける濃縮不良や脱水不良といった課題に対する解決策としては、油分の含有量が少ない他のスラッジと混合させた後に濃縮脱水処理する方法や、焼却処理する方法がある。しかし、これらの方法は、高油分スラッジに混合させるための低油分スラッジの量に限りがある場合や、焼却炉の余力が大きくない場合は、採用することができないので、高油分スラッジの濃縮不良や脱水不良における問題に対する根本的な解決策とはなっていない。このため、従来の方法で大量に発生する高油分スラッジにおける課題の根本的な解決策を見出すことができれば、極めて有用である。   As a solution to the problems such as poor concentration and poor dehydration in the high oil sludge described above, there are a method of concentrating and dewatering after mixing with other sludge having a low oil content, and a method of incineration. However, these methods cannot be used when the amount of low oil sludge to be mixed with the high oil sludge is limited or when the remaining capacity of the incinerator is not large. And is not a fundamental solution to the problem of poor dehydration. For this reason, it would be extremely useful if a fundamental solution to the problem in the high oil content sludge generated in a large amount by the conventional method could be found.

また、前記した特許文献5に記載の技術は、上記に挙げた技術とは処理対象とする廃水が異なり、転炉排ガス集塵水の処理に関し、その目的は、微粒を凝集沈澱処理する前に粗粒分離器で行う粗粒ダストの分離の回収率を高めることである。この方法によっても、その後にシックナーで凝集沈殿処理して粗粒分離器で分離できない微粒を処理することを必須としており、粗粒分離器で分離した粗粒ダストの回収効率を高める以上の効果を得てはいない。さらに、その向上の程度は、粗粒分離器に高分子凝集剤を使用しない場合に比べて1.1〜1.3倍であるとされており、その向上効果は十分とは言い難い。これに対し、粗大な懸濁物質と微細な懸濁物質とを同時に一括して、しかも迅速に除去処理できる技術が開発されれば、極めて有用である。   In addition, the technique described in Patent Document 5 is different from the above-described technique in that the wastewater to be treated is different and relates to the treatment of the converter exhaust gas dust collection water. It is to increase the recovery rate of the coarse dust separation performed in the coarse separator. Even with this method, it is essential to treat the fine particles that cannot be separated with a coarse separator by aggregating and precipitating with a thickener, and this is more effective than increasing the recovery efficiency of coarse dust separated with the coarse separator. I don't get it. Furthermore, the degree of improvement is said to be 1.1 to 1.3 times that in the case where no polymer flocculant is used in the coarse-grain separator, and the improvement effect is hardly sufficient. On the other hand, it would be extremely useful if a technique capable of simultaneously removing a coarse suspended substance and a fine suspended substance at the same time and rapidly removing them was developed.

上記のような状況から、本発明者らは、特に、製鐵所において発生するような多様な懸濁物質を含む廃水中の懸濁物質を除去処理する方法において、下記の効果が得られ、しかも、少なくとも、廃水中の粗大な懸濁物質と微細な懸濁物質とを、さらには油分を含むものであったとしても、これらを、同時に一括して、スケールピット等のOver Flow Rateが10m/hr以上となる比較的小さな水槽で、分離、除去処理することを可能にする技術が提供できれば、極めて有用であると認識するに至った。製鐵所においては、例えば、循環使用されることが多い、連続鋳造工程や圧延工程から発生する直接冷却廃水等の懸濁物質を含有する各種廃水に対し、(1)簡略化された設備で処理して迅速に清澄な処理水を得ることができ、(2)維持管理費が低く、(3)できれば処理水への悪影響を生じ得る無機凝集剤を用いることなく、(4)廃水中に、金属やコークス等の懸濁物質に加えて油分が懸濁していたとしても、処理によってリサイクル困難なスラッジを発生しない、経済的で簡便な廃水中の懸濁物質の除去方法が望まれる。   From the situation as described above, the present inventors can obtain the following effects, particularly in the method for removing suspended substances in wastewater containing various suspended substances such as those generated in a steelworks, Moreover, even if it contains at least a coarse suspended substance and a fine suspended substance in the wastewater, and further contains an oil component, the Over Flow Rate such as a scale pit is 10 m at the same time. It has been recognized that it would be extremely useful if a technology that enables separation and removal treatment with a relatively small water tank of at least / hr could be provided. In the steelworks, for example, for various wastewater containing suspended solids such as direct cooling wastewater generated from continuous casting process and rolling process, which are often used in circulation, (1) With simplified equipment (2) Low maintenance costs, (3) If possible, without using inorganic flocculants that can adversely affect the treated water, (4) In the wastewater Even if oil is suspended in addition to suspended substances such as metal and coke, an economical and simple method for removing suspended substances in wastewater that does not generate sludge that is difficult to recycle by treatment is desired.

したがって、本発明は、例えば、前述したような製鐵所において発生する、粗大SSと微細SSとが併存している各種廃水中の懸濁物質を分離除去する際に下記のことを達成できる、工業上、極めて有用な廃水中の懸濁物質の除去処理方法を提供することを目的とする。すなわち、懸濁物質の除去処理に際し、粗大SSと微細SSとを同一の処理で凝集沈降させているにもかかわらず、別々に処理していた従来の処理方法で達成していたのと同等以上の清澄な水質の処理水を迅速に得ることができることに加え、同一に処理することを可能にすることで、凝集剤の総使用量を従来よりも低減することを可能とし、さらに、設備を大幅に簡略化することで設備費及び維持管理費を縮小でき、更に、発生する凝集沈降した沈殿物のリサイクル費の低減、場合によっては無機凝集剤を使用することに起因して処理水に混入される配管の腐食を促進する物質の低減をも達成できる技術の提供を可能とすることを目的とする。   Therefore, the present invention can achieve the following when, for example, separating and removing suspended substances in various wastewaters in which the coarse SS and the fine SS coexist, which occur in the steelworks as described above, An object of the present invention is to provide an industrially very useful method for removing suspended substances in wastewater. In other words, when the suspended solids are removed, the coarse SS and the fine SS are coagulated and settled by the same treatment, but the same or higher than that achieved by the conventional treatment method that has been treated separately. In addition to being able to quickly obtain treated water with a clear water quality, it is possible to reduce the total amount of flocculant used compared to the conventional method by making it possible to perform the same treatment. Equipment costs and maintenance costs can be reduced by greatly simplifying the process. Furthermore, the cost of recycling the aggregated and settled sediment generated is reduced. In some cases, it is mixed into the treated water due to the use of an inorganic flocculant. It is an object of the present invention to provide a technique capable of achieving reduction of substances that promote corrosion of pipes.

上記の目的は、下記の本発明によって達成される。すなわち、本発明は、凝集剤を用い、廃水中から懸濁物質を凝集沈降させて取り除くための廃水中の懸濁物質の除去処理方法であって、上記凝集剤として少なくとも1種の有機凝集剤を用い、少なくとも、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に、前記有機凝集剤が共存する状態を生じさせることで、前記粗大な懸濁物質と前記微細な懸濁物質とを同一の処理で凝集沈降させ、これらを同時に除去できるようにしたことを特徴とする廃水中の懸濁物質の除去処理方法を提供する。   The above object is achieved by the present invention described below. That is, the present invention is a method for removing suspended solids from wastewater by using a flocculant to remove suspended solids from the wastewater by coagulation and sedimentation, wherein at least one organic flocculant is used as the flocculant. A state in which at least a coarse suspended substance and a fine suspended substance coexist, the flow velocity is 0.5 m / second or more, and the organic flocculant coexists in turbulent water. The coarse suspended substance and the fine suspended substance are agglomerated and settled by the same treatment so that they can be removed at the same time. A processing method is provided.

上記した本発明の廃水中の懸濁物質の除去処理方法の好ましい形態としては、前記有機凝集剤を、粗大な懸濁物質と微細な懸濁物質とが併存している、流速が0.5m/秒以上で、且つ、乱流状態の廃水中に添加することで、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に前記有機凝集剤が共存する状態を生じさせている上記の廃水中の懸濁物質の除去処理方法が挙げられる。さらに、この廃水中の懸濁物質の除去処理方法において、前記廃水が、製鐵所において発生する廃水であり、前記有機凝集剤を廃水に添加する位置が、粗大な懸濁物質と微細な懸濁物質とが併存している廃水が発生する地点から水処理設備の入口付近に至るまでのいずれかの地点であることが挙げられる。   As a preferred embodiment of the above-described method for removing suspended solids from wastewater of the present invention, the organic flocculant contains a coarse suspended solid and a fine suspended solid, and a flow rate of 0.5 m. When added to wastewater in a turbulent state at a speed of more than 1 second / second, coarse suspended matter and fine suspended matter coexist, and the flow rate is at least 0.5 m / second, resulting in a turbulent state. And a method for removing suspended substances in the waste water, which causes the organic flocculant to coexist in the water. Further, in this method for removing suspended solids from wastewater, the wastewater is wastewater generated at a smelter, and the position where the organic flocculant is added to the wastewater is not limited to coarse suspended solids and fine suspension. It can be any point from the point where the wastewater where turbid substances coexist is generated to the vicinity of the entrance of the water treatment facility.

上記した本発明の廃水中の懸濁物質の除去処理方法の別の好ましい形態としては、前記粗大な懸濁物質と微細な懸濁物質とが併存した廃水になる前の用水に予め前記有機凝集剤を添加しておき、さらにこの水を使用することで、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に前記有機凝集剤が共存する状態を生じさせている廃水中の懸濁物質の除去処理方法が挙げられる。さらに、この廃水中の懸濁物質の除去処理方法において、前記廃水が、製鐵所において発生する廃水であり、前記粗大な懸濁物質と微細な懸濁物質とが併存した廃水になる前の用水が、前記粗大な懸濁物質と前記微細な懸濁物質とを、前記有機凝集剤の存在下、同一の処理で凝集沈降させて、これらを同時に除去処理した後に得られる処理水である、該処理水を循環使用する系で、該処理水への前記有機凝集剤の添加を、その使用基準を満たすまでに用水の処理がなされた地点から、該用水を使用する給水地点に至るまでのいずれかの地点で行う請求項4に記載の廃水中の懸濁物質の除去処理方法ことが挙げられる。   As another preferred embodiment of the above-described method for removing suspended substances in waste water of the present invention, the organic agglomeration is previously performed on the water before becoming waste water in which the coarse suspended substances and fine suspended substances coexist. By adding this agent and further using this water, coarse suspended substances and fine suspended substances coexist, and the flow rate is 0.5 m / second or more, and turbulent water Examples thereof include a method for removing suspended substances in wastewater that causes a state in which the organic flocculant coexists. Furthermore, in this method for removing suspended matter in wastewater, the wastewater is wastewater generated in a steelworks, and the wastewater before the coarse suspended matter and fine suspended matter coexist. Water is treated water obtained after coagulating and precipitating the coarse suspended substance and the fine suspended substance in the presence of the organic flocculant by the same treatment and removing them simultaneously. In the system that circulates and uses the treated water, the addition of the organic flocculant to the treated water is from the point where the water is treated until the use standard is satisfied to the water supply point where the water is used. The method for removing suspended substances in wastewater according to claim 4 performed at any point.

上記した本発明の廃水中の懸濁物質の除去処理方法の別の好ましい形態としては、更に、下記のことが挙げられる。前記粗大な懸濁物質が、粒径が50μm以上のものであり、前記微細な懸濁物質が、粒径が50μmに満たないものであり、且つ、これらの物質の併存状態が、微細な懸濁物質濃度に対する粗大な懸濁物質濃度の比(粗/微)が、その質量比で0.5以上であること;前記乱流状態の水のレイノズル数が、8000以上であること;前記有機凝集剤が、カチオン性又は両性の共重合体を主成分としてなり、該共重合体の重量平均分子量が100万〜1,300万であり、且つ、pH7におけるカチオンコロイド当量値が0.1meq/g以上であること;前記粗大な懸濁物質と前記微細な懸濁物質が、金属粉、水砕スラグ、石炭粉又はコークス粉の少なくともいずれかであり、場合によっては更にこれらいずれかの物質と油分とが併存していること;前記粗大な懸濁物質と前記微細な懸濁物質とを同一の処理で凝集沈降させた後に、さらに凝集沈降した沈殿物を除去することである。   Another preferred embodiment of the above-described method for removing suspended substances in wastewater of the present invention is as follows. The coarse suspended substance has a particle diameter of 50 μm or more, the fine suspended substance has a particle diameter of less than 50 μm, and the coexistence state of these substances is a fine suspension. The ratio of the coarse suspended solid concentration to the suspended solid concentration (rough / fine) is 0.5 or more in terms of mass ratio; the number of lay nozzles in the turbulent water state is 8000 or more; The flocculant has a cationic or amphoteric copolymer as a main component, the copolymer has a weight average molecular weight of 1,000,000 to 13 million, and a cation colloid equivalent value at pH 7 of 0.1 meq / the coarse suspended substance and the fine suspended substance are at least one of metal powder, granulated slag, coal powder or coke powder, and in some cases, any one of these substances Coexist with oil That is, after the coarse suspended substance and the fine suspended substance are coagulated and settled by the same treatment, the coagulated sediment is further removed.

本発明の廃水中の懸濁物質の除去処理方法において使用する有機凝集剤としては、特に限定されないが、例えば、下記に挙げるものを好適に使用することができる。更に、本発明では、このような有機凝集剤の他に無機凝集剤を併用しないように設計することが、より好ましい。
下記一般式(1)及び(2)を必須成分としてそれぞれ5モル%以上を含む原料モノマーから誘導されるカチオン性又は両性の共重合体を主成分としてなり、該共重合体の重量平均分子量が100万〜1,300万であり、且つ、pH7におけるカチオンコロイド当量値が0.1meq/g以上、より好ましくは、0.2meq/g以上であるものが挙げられる。

Figure 2014133229
Figure 2014133229
(上記式中の、R1、R2は、CH3又はC25を、R3は、H、CH3又はC25を表す。X-は、アニオン性対イオンを表す。) Although it does not specifically limit as an organic flocculant used in the removal processing method of the suspended matter in the wastewater of this invention, For example, the following can be used conveniently. Furthermore, in the present invention, it is more preferable to design so as not to use an inorganic flocculant in addition to such an organic flocculant.
The following general formulas (1) and (2) are essential components and a cationic or amphoteric copolymer derived from a raw material monomer each containing 5 mol% or more is a main component, and the weight average molecular weight of the copolymer is The cation colloid equivalent value at pH 7 is 0.1 meq / g or more, more preferably 0.2 meq / g or more.
Figure 2014133229
Figure 2014133229
(In the above formula, R 1 and R 2 represent CH 3 or C 2 H 5 , R 3 represents H, CH 3 or C 2 H 5. X represents an anionic counter ion.)

また、本発明の廃水中の懸濁物質の除去処理方法によって処理する廃水は、粗大な懸濁物質と微細な懸濁物質とが併存した状態にあるものであればいずれのものも対象とすることができるが、例えば、大量処理が必要となる下記に挙げるような廃水を、処理対象とすることができる。本発明の廃水中の懸濁物質の除去処理方法は、例えば、製鐵所の連続鋳造工程における鋼材の直接冷却廃水、製鐵所の圧延工程における鋼材の直接冷却廃水、製鐵所の高炉、転炉、電炉工程における集塵廃水、製鐵所の屋外原料貯蔵ヤードから発生する雨水廃水、製鐵所の高炉滓から水砕を得る際に発生する冷却廃水等の処理に好適に用いることができる。   In addition, waste water treated by the method for removing suspended solids from waste water according to the present invention is applicable to any waste water in which coarse suspended solids and fine suspended solids coexist. However, for example, wastewater as described below that requires a large amount of treatment can be treated. The method for removing suspended substances in wastewater of the present invention includes, for example, direct cooling wastewater of steel in a continuous casting process of a steelworks, direct cooling wastewater of steel in a rolling process of a steelworks, a blast furnace of a steelworks, Dust collection wastewater in the converter, electric furnace process, rainwater wastewater generated from the outdoor raw material storage yard of the steelworks, and cooling wastewater generated when water granulation is obtained from the blast furnace water of the steelworks it can.

本発明によれば、例えば、製鐵所等において発生する、粗大SSと微細SSとが併存している各種廃水中の懸濁物質を分離除去する際に、例えば、Over Flow Rateが10m/hr以上の比較的小さな槽のみで、粗大SSと微細SSとを同一の処理で、従来技術で処理した場合と比べてSSをより速やかに沈降させることができ、しかも、得られる処理水を、これらの懸濁物質を別々に処理していた従来の処理方法で達成していたのと同等以上の清澄な水質のものにできる、工業上、極めて有用な廃水中の懸濁物質の除去処理方法が提供される。すなわち、本発明の処理プロセスを採用することで、粗大SSと微細SSとを同一の処理で、しかも従来技術と比べて明らかに迅速に凝集沈降させることが可能になったことで、凝集剤の総使用量を従来よりも低減することが可能になり、更に設備を大幅に簡略化することもできるので、設備費及び維持管理費を縮小でき、これらに加えて、発生する凝集沈降した沈殿物のリサイクル費の低減、無機凝集剤を使用することに起因して処理水に混入される配管の腐食を促進する物質の低減をも達成できる。また、本発明の処理プロセスによって得られる処理水は、従来の処理方法で達成していたのと同等以上の清澄な水質を示すので、そのまま循環使用することが可能であり、さらに、発生する凝集沈降した沈殿物は、水離れのよい取り扱い易いものになるといった利点もあり、沈殿物の処理にかかる費用を従来の方法の場合よりも大幅に低減できるという効果も得られる。   According to the present invention, for example, when the suspended matter in various wastewaters in which a large SS and a fine SS coexist are separated and removed, for example, the Over Flow Rate is 10 m / hr. With only the above relatively small tanks, the SS can be settled more quickly than in the case where the coarse SS and the fine SS are processed in the same process as in the prior art. There is an industrially extremely useful method for removing suspended solids from wastewater that can be made to have a clear water quality equivalent to or better than that achieved by conventional treatment methods that have been separately treated. Provided. In other words, by adopting the treatment process of the present invention, it is possible to coagulate and settle coarse SS and fine SS in the same treatment, and more clearly compared to the prior art. It is possible to reduce the total amount of use compared to the conventional method, and furthermore, the equipment can be greatly simplified, so that the equipment cost and the maintenance cost can be reduced. It is also possible to achieve a reduction in recycling costs and a reduction in substances that promote corrosion of piping mixed into treated water due to the use of an inorganic flocculant. In addition, the treated water obtained by the treatment process of the present invention exhibits a clear water quality equivalent to or higher than that achieved by the conventional treatment method, and thus can be recycled as it is, and further agglomerates are generated. The settled sediment has the advantage that it is easy to handle with good water separation, and the cost for processing the sediment can be greatly reduced as compared with the conventional method.

本発明の懸濁物質の除去処理方法を、連続鋳造工程の直接冷却廃水処理に適用した場合の好適な一例を示す模式図である。It is a schematic diagram which shows a suitable example at the time of applying the removal processing method of the suspended solids of this invention to the direct cooling wastewater process of a continuous casting process. 本発明の懸濁物質の除去処理方法を、連続鋳造工程の直接冷却廃水処理に適用した場合の別の好適な一例を示す模式図(実施例1)である。It is a schematic diagram (Example 1) which shows another suitable example at the time of applying the removal processing method of the suspended solids of this invention to the direct cooling wastewater process of a continuous casting process. 本発明の懸濁物質の除去処理方法を、熱間圧延工程の直接冷却廃水処理に適用した場合の別の好適な一例を示す模式図(実施例4及び5)である。It is a schematic diagram (Examples 4 and 5) which shows another suitable example at the time of applying the removal processing method of the suspended solids of this invention to the direct cooling wastewater process of a hot rolling process. 本発明の懸濁物質の除去処理方法に対する比較例(熱間圧延工程)を示す模式図である。It is a schematic diagram which shows the comparative example (hot rolling process) with respect to the removal processing method of the suspended solids of this invention. 従来の熱間圧延工程の直接冷却廃水に対する懸濁物質の除去処理方法の模式図である。It is a schematic diagram of the removal processing method of the suspended solid with respect to the direct cooling wastewater of the conventional hot rolling process.

以下、好ましい実施の形態を挙げて本発明を更に詳細に説明する。本発明者らは、先に述べた従来技術の課題を解決すべく鋭意検討を行った結果、無機凝集剤の使用を停止する一方で、有機凝集剤を添加した際に、或いは、有機凝集剤の添加が行われた以降に、該有機凝集剤と、粗大SSと微細SSとが、流速が0.5m/秒以上と速く、且つ、乱流状態となる中に共存する状態を生じさせる、という極めて単純な方法によって、廃水中に存在している、或いは、廃水中に存在することとなる、粗大SSと微細SSとを同一の処理で、極めて効率よく迅速に凝集沈降させることができる、という従来技術の常識を覆す驚くべき事実を見出して本発明を達成した。この結果、上記した本発明の処理方法によれば、従来の懸濁物質の除去処理方法と比較して、下記に挙げる種々の効果を得ることができる。まず、従来、粗大SSの沈降の促進に用いていた無機凝集剤の使用の必要がなく、また、粗大SSの処理の後段で微細SSを取り除く必要がなくなるので、そのための設備が不要となり、その結果、従来処理の場合よりも、設備費及び維持管理費を縮小できる。更に、粗大SSと微細SSとを同一の処理で、極めて迅速にこれらのSSを凝集沈降させることができることに加え、その沈殿物は、従来の処理で生じていた汚泥とは全く異なり、脱水性が良好で、油分の含有率も低いため、その後の処理が極めて容易であり、沈殿物の処理のために従来の処理で必要のあった設備費及び維持管理費が大幅に削減できる。更に、得られる処理水は、無機凝集剤の使用に起因して混入する塩素イオンや硫酸イオンの問題がないことに加え、従来の懸濁物質の除去処理方法で得られた処理水と同等以上の清澄な水質であり、懸濁物質の残留が極めて少ないものであり、後段で、更に微細SSを取り除くことなく良好な冷却水として再利用できる画期的なものである。   Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. As a result of intensive studies to solve the problems of the prior art described above, the present inventors stopped using the inorganic flocculant, while adding the organic flocculant, or the organic flocculant After the addition of the organic flocculant, the coarse SS and the fine SS, the flow velocity is as fast as 0.5 m / second or more, and a state of coexistence in a turbulent state is generated, By a very simple method, it is possible to agglomerate and sediment very efficiently and quickly with the same treatment of coarse SS and fine SS existing in wastewater or existing in wastewater. The present invention has been accomplished by finding the surprising fact that overturns the common sense of the prior art. As a result, according to the treatment method of the present invention described above, various effects listed below can be obtained as compared with the conventional suspension material removal treatment method. First, it is not necessary to use an inorganic flocculant that has been used to promote sedimentation of coarse SS, and it is not necessary to remove fine SS after the treatment of coarse SS. As a result, the equipment cost and the maintenance cost can be reduced as compared with the case of the conventional processing. Furthermore, in addition to being able to agglomerate and settle these SSs very quickly with the same treatment of coarse SS and fine SS, the precipitate is completely different from the sludge produced by the conventional treatment and is dewatering. Since the oil content is low and the oil content is low, the subsequent treatment is extremely easy, and the equipment cost and maintenance cost required for the conventional treatment for the treatment of the precipitate can be greatly reduced. Furthermore, the treated water obtained has no problem of chlorine ions and sulfate ions mixed due to the use of the inorganic flocculant, and at least equivalent to the treated water obtained by the conventional method for removing suspended solids. This is an epoch-making thing that can be reused as good cooling water without removing fine SS at a later stage.

より具体的には、本発明の廃水中の懸濁物質の除去処理方法では、少なくとも1種の有機凝集剤を用い、少なくとも、粗大なSSと微細SSとが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に、前記有機凝集剤が共存する状態を生じさせることで、上記した優れた作用・効果が得られる。   More specifically, in the method for removing suspended solids in wastewater of the present invention, at least one organic flocculant is used, at least coarse SS and fine SS coexist, and the flow rate is 0. By producing a state in which the organic flocculant coexists in turbulent water at 5 m / second or more, the above-described excellent actions and effects can be obtained.

先に述べたように、製鐵所において発生する廃水では、通常、粒径が50μm以上のものを粗大SS、粒径が50μmに満たないものを微細SSとして扱い、粗大SSを取り除いた廃水に対し、後段で、微細SSを凝集沈殿等の処理をしてこれらを処理しているが、本願発明では、これらの粗大SSと微細SSとを同一の処理で凝集沈降させ、これらを同時に除去できるようにしたことを特徴としている。処理する廃水中における粗大SSと微細SSとの併存状態は特に限定されないが、本発明者らの検討によれば、微細SS濃度に対する粗大SS濃度の比(粗/微)が、その質量比で0.5以上である廃水であれば、これらを一緒に安定した状態で良好に処理することができることがわかった。また、本発明者らの検討によれば、微細SS濃度に対する粗大SS濃度の比(粗/微)は、0.5以上であればよく、むしろ大きい場合に良好な処理ができ、例えば、微細SS濃度に対する粗大SS濃度の比が100程度であっても問題なく処理できる。本発明者らが確認したところ、製鐵所において発生する廃水の、微細SS濃度に対する粗大SS濃度の比(粗/微)は、懸濁物質の比重にもよるが、例えば、その大半が、5〜100程度或いは10〜70程度であった。さらに、本発明者らの検討によれば、これらのいずれの廃水に対しても、本発明の処理方法を適用することで、廃水中の異なる大きさの懸濁物質を、同一の処理で、例えば、Over Flow Rateが10m/hr以上の比較的小さな槽のみで、極めて迅速に沈降させることができ、これに加えてその処理水は、従来の処理では容易に達成することができなかった清澄なものとなる。   As described above, wastewater generated at a smelter is usually treated as coarse SS with a particle size of 50 μm or more, and as fine SS with a particle size of less than 50 μm. On the other hand, in the latter stage, the fine SS is treated by agglomeration and precipitation. However, in the present invention, these coarse SS and fine SS can be coagulated and settled by the same treatment, and these can be removed simultaneously. It is characterized by doing so. Although the coexistence state of coarse SS and fine SS in the wastewater to be treated is not particularly limited, according to the study by the present inventors, the ratio of coarse SS concentration to fine SS concentration (rough / fine) is the mass ratio. It was found that if the waste water is 0.5 or more, these can be treated well together in a stable state. Further, according to the study by the present inventors, the ratio of the coarse SS concentration to the fine SS concentration (coarse / fine) may be 0.5 or more, and if it is rather large, good processing can be performed. Even if the ratio of the coarse SS concentration to the SS concentration is about 100, it can be processed without any problem. As a result of confirmation by the present inventors, the ratio of coarse SS concentration to fine SS concentration (coarse / fine) of wastewater generated in the smelter depends on the specific gravity of the suspended matter. It was about 5-100 or about 10-70. Furthermore, according to the study by the present inventors, by applying the treatment method of the present invention to any of these wastewaters, suspended substances of different sizes in the wastewater can be treated with the same treatment. For example, in a relatively small tank with an Over Flow Rate of 10 m / hr or more, it can be settled very quickly, and in addition to this, the treated water cannot be easily achieved by the conventional treatment. It will be something.

本発明で規定する「流速が0.5m/秒以上で、且つ、乱流状態」が意味するところは、有機凝集剤の使用状態を、従来の撹拌しながらの緩やかな流動状態の中で処理するのでなく、本発明の顕著な効果が得られる激しい流動状態に、粗大なSSと微細SSと有機凝集剤とを共存させることを意味している。流速が0.5m/秒以上の速さで流動している状態であればよいが、より好ましくは、流速が1.0m/秒以上の速さで流動している状態となることが好ましい。更に、その流動状態が、乱流状態であることを要するが、より具体的には、水のレイノズル数が8000以上、更に好ましくは、水のレイノズル数が10000以上である状態となっている水の中に、粗大なSSと微細SSとが併存し、更に有機凝集剤が共存する状態を生じさせればよい。本発明の上記構成は、従来の懸濁物の処理方法の場合のように撹拌設備等を別に設けて達成する必要がなく、下記に述べるように、工場内で生じている廃水の激しい流れを懸濁物質の除去処理に巧みに利用することで達成できるので、その設備的なメリットは極めて大きい。   The meaning of “flow velocity of 0.5 m / second or more and turbulent state” as defined in the present invention means that the use state of the organic flocculant is treated in the conventional gentle flow state while stirring. Instead, it means that coarse SS, fine SS, and organic coagulant coexist in a vigorous fluid state where the remarkable effects of the present invention are obtained. The flow rate may be in a state of flowing at a speed of 0.5 m / second or more, but more preferably, the flow rate is in a state of flowing at a speed of 1.0 m / second or more. Further, the flow state needs to be a turbulent flow state. More specifically, the number of water lay nozzles is 8000 or more, and more preferably, the number of water lay nozzles is 10,000 or more. The coarse SS and the fine SS may coexist, and the organic coagulant may coexist. The above-described configuration of the present invention does not need to be achieved by providing a separate agitation facility or the like as in the case of the conventional suspension treatment method, and, as described below, the intense flow of wastewater generated in the factory. Since it can be achieved by skillfully using the suspended matter removal process, the equipment advantage is extremely large.

本発明で規定する上記した水の状態を生じさせる方法としては、例えば、下記(1)のそのような状態の廃水中に有機凝集剤を添加する方法や、下記(2)の、粗大なSSと微細SSとが併存した廃水になる前の用水に、予め有機凝集剤を添加する方法が挙げられる。   Examples of a method for producing the above-described water state defined in the present invention include a method of adding an organic flocculant to waste water in such a state as described in (1) below, and a coarse SS as described in (2) below. And a method of adding an organic flocculant in advance to the water before becoming wastewater in which the fine SS is coexisted.

(1)有機凝集剤を、粗大なSSと微細SSとが併存している、流速が0.5m/秒以上で、且つ、乱流状態の廃水中に添加する。その場合における有機凝集剤の好ましい添加の位置としては、粗大なSSと微細SSとが併存している廃水が発生する地点から水処理設備の入口付近に至るまでのいずれかの地点が挙げられる。
(2)粗大なSSと微細SSとが併存した廃水になる前の用水に予め前記有機凝集剤を添加しておき、さらにこの水を使用することで、粗大なSSと微細SSとが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に前記有機凝集剤が共存する状態を生じさせる。その場合における有機凝集剤の添加の位置の一例としては、粗大なSSと微細SSとが併存した廃水になる前の用水が、前記粗大なSSと微細SSとを、前記有機凝集剤の存在下、同一の処理で凝集沈降させて、これらを同時に除去処理した後に得られる処理水を循環使用する系において、前記有機凝集剤の添加を、その使用基準を満たすまでに用水の処理がなされた地点から、該用水を使用する給水地点に至るまでのいずれかの地点で行うことが挙げられる。
(1) An organic flocculant is added to waste water in a turbulent state where a coarse SS and a fine SS coexist, the flow rate is 0.5 m / second or more. In this case, a preferable addition position of the organic flocculant includes any point from the point where the waste water where coarse SS and fine SS coexist to the vicinity of the inlet of the water treatment facility.
(2) The organic flocculant is added in advance to the water before becoming waste water in which coarse SS and fine SS coexist, and by using this water, coarse SS and fine SS coexist. In addition, the organic flocculant coexists in turbulent water at a flow rate of 0.5 m / second or more. As an example of the position of addition of the organic flocculant in that case, the water before becoming the waste water in which the coarse SS and the fine SS coexist is converted into the coarse SS and the fine SS in the presence of the organic flocculant. In a system that circulates and uses treated water obtained after coagulating and settling in the same treatment and removing these simultaneously, the point where the water was treated until the addition of the organic flocculant satisfies the use standard To the water supply point where the water is used.

上記(1)及び(2)について、製鐵所の連続鋳造工程や圧延工程において発生する直接冷却廃水を例にとって具体的に説明すれば、上記(1)でいう「粗大なSSと微細SSとが併存している廃水の発生地点から水処理設備の入口付近に至るまでのいずれかの地点」とは、以下の地点を含むものである。先ず、冷却水がスプレーノズル等から鋼材表面へ噴射されて、鋼材を冷却した時点で、冷却水は直接冷却廃水となるので、この地点が「廃水の発生地点」である。また、「廃水の発生地点から水処理設備の入口付近に至るまでのいずれかの地点」は、鋼材を冷却後、直接冷却廃水となってスケールスルースと呼ばれる開放樋に流れ落ちて、この開放樋を流れて、水処理設備であるスケールピットに至るので、この間の一連の地点とその近傍の地点を意味している。   As for the above (1) and (2), the direct cooling wastewater generated in the continuous casting process and rolling process of the steelworks will be specifically described as an example. "Any point from the point where the wastewater coexists to the vicinity of the entrance of the water treatment facility" includes the following points. First, when cooling water is sprayed from the spray nozzle or the like onto the surface of the steel material to cool the steel material, the cooling water becomes direct cooling waste water, so this point is a “waste water generation point”. In addition, “any point from the point where the wastewater is generated to the vicinity of the entrance of the water treatment facility”, after cooling the steel material, directly becomes cooling wastewater and flows down into an open rod called scale sluice. It flows to the scale pit, which is a water treatment facility, meaning a series of points in the meantime and nearby points.

上記したことから、本発明において、有機凝集剤の添加は、粗大なSSと微細SSとが併存している廃水となっているスケールスルースに流れ落ちる地点で行っても、スケールスルースのいずれかの地点で行っても、スケールピットに排水される直前の激しい流れの中に添加させても、スケールピット入口付近に添加しても、スケールピットポンプのサクション付近に添加してもよい。   As described above, in the present invention, the addition of the organic flocculant is performed at a point where the coarse SS and the fine SS coexist in the wastewater in which the coarse SS and the fine SS coexist. Or may be added in the vigorous stream immediately before being drained into the scale pit, added near the scale pit inlet, or added near the suction of the scale pit pump.

また、上記(2)でいう「その使用基準を満たすまでに用水の処理がなされた地点から、該用水の給水地点に至るまでのいずれかの地点」とは、スケールピット以降、沈殿池、ろ過機、電磁フィルター等の懸濁物質の除去設備の出口地点(すなわち処理水の排出口)から、冷却塔を通じて、上記した廃水の発生地点まで、及び、スケールピット下流側からスケールスルースへと循環流を生じさせるスケールピットポンプのサクション近傍から、先に説明した廃水の発生地点までを意味している。   In addition, the “any point from the point where the water is treated before the use standard is met to the point where the water is supplied” as referred to in the above (2) refers to the sedimentation basin, the filtration tank after the scale pit Circulating flow from the exit point of the suspended solids removal equipment such as the machine, electromagnetic filter, etc. (that is, the treated water discharge port) to the waste water generation point through the cooling tower and from the downstream side of the scale pit to the scale sluice It means from the vicinity of the suction of the scale pit pump that generates the water to the waste water generation point described above.

本発明者らの検討によれば、少なくとも1種類の有機凝集剤を用い、特に、該有機凝集剤が、粗大なSSと微細SSとが併存し、水と共に激しく流動している状態の中に共存する状態を生じさせると、高い効果が得られることがわかった。より具体的には、有機凝集剤を、粗大SS及び微細SSと激しい混合状態で共存させた場合に、有機凝集剤の凝結・凝集・沈降効果がより顕著に発揮され、粗大SSと微細SSが同一の処理で、従来技術では達成できていなかった速度で速やかに凝集沈降して、その上澄み液が従来にない清澄なものとなることを見出した。更に、これらが共存した状態で、激しく流動している時間がある程度確保された方がより高い効果が得られることと、添加作業の容易性から、例えば、図1中に2で示したように、スケールスルースのスケールピット3からできるだけ遠い地点で有機凝集剤を添加することが好ましいこともわかった。このように構成すれば、例えば、直接冷却廃水がスケールスルースを流れていくいずれの地点でも、有機凝集剤と粗大SSと微細SSとが激しい混合状態となる。その結果、驚くべきことに、スケールピット3に排出された時点で、直接冷却廃水中の粗大SSと微細SSとを含む懸濁物質は、凝結・凝集中である、または既に凝結・凝集しているため、沈殿物と清澄な処理水とに速やかに分離する。また、例えば、図1に例示したような、処理水を冷却水として循環使用する系において、スケールピット3からできるだけ遠い地点として、例えば、先に説明した廃水の発生地点の前の、得られた処理水を用水に使用することとなる給水地点に至るまでを選択し、廃水になる前の用水に有機凝集剤を添加することも有効である。勿論、処理水を循環使用する系でなくても、用水に予め有機凝集剤を添加し、当該用水を使用することで、本発明で規定する「有機凝集剤が、粗大なSSと微細SSとが併存し、水と共に激しく流動している状態の中に共存する状態を生じさせる」ものであってもよい。   According to the study by the present inventors, at least one kind of organic flocculant is used, and in particular, the organic flocculant is in a state in which coarse SS and fine SS coexist and fluidly flows with water. It was found that a high effect can be obtained by creating a coexisting state. More specifically, when the organic flocculant coexists with the coarse SS and fine SS in a vigorous mixed state, the coagulation / aggregation / sedimentation effect of the organic flocculant is more prominent, and the coarse SS and fine SS It has been found that the same treatment quickly causes aggregation and sedimentation at a rate that could not be achieved by the prior art, and that the supernatant liquid becomes clearer than before. Furthermore, for example, as indicated by 2 in FIG. 1, for example, as shown in FIG. 1, the higher effect can be obtained by ensuring a certain amount of time during which the fluids are flowing vigorously in the coexistence state and the ease of the addition work. It was also found that it is preferable to add the organic flocculant at a point as far as possible from the scale pit 3 of the scale sluice. If comprised in this way, an organic flocculant, coarse SS, and fine SS will be in a vigorous mixing state in any point where cooling wastewater flows through a scale sluice, for example. As a result, surprisingly, when discharged into the scale pit 3, the suspended matter containing coarse SS and fine SS directly in the cooling wastewater is coagulating / aggregating, or has already coagulated / aggregated. Therefore, it separates quickly into precipitate and clear treated water. Further, for example, in a system in which treated water is circulated and used as cooling water as illustrated in FIG. 1, the point as far as possible from the scale pit 3 is obtained, for example, before the waste water generation point described above. It is also effective to select up to the water supply point where the treated water will be used for the service water, and to add the organic flocculant to the service water before becoming the waste water. Of course, even if it is not a system in which treated water is circulated, an organic flocculant is added to the service water in advance, and by using the water, the “organic flocculant is defined as coarse SS and fine SS. May coexist and produce a coexisting state in a state of flowing vigorously with water ".

本発明者らは、これらの理由について、有機凝集剤を上記したような地点で、廃水或いは用水に添加すると激しく混合され、その状態で、まず、有機凝集剤が、共存している粗大SSに対して特に高い凝集効果、更に強い凝結効果を示し、その結果、粗大SSの凝結・凝集が速やかに生じ、その際に、併存している微細SSが、この有機凝集剤によって形成された粗大な凝集物内に取り込まれ、これらのことによって、同一処理による速やかで効率のよい良好な凝集沈降という本発明の優れた効果が得られたものと考えている。特に、廃水が溝や液路内を流動している場合は、微細SSが廃水内を活発に動いているので、微細SSが、粗大な凝集物内により取り込まれやすくなったものと推論している。更に、このようなメカニズムで得られたと考えられる、本発明の処理方法によって得られる凝集した沈降・沈殿物は、従来の、凝集剤を添加して沈殿槽内に沈降させることで得られた汚泥とは明らかに異なり、脱水性がよく、油分の含有率も低い。このため、その後の処理が極めて容易なものになり、従来、沈降・沈殿物の2次処理にかかっていたコストの大幅な低減が可能になる。   For these reasons, the inventors of the present invention are mixed vigorously when the organic flocculant is added to waste water or irrigation water at the points as described above, and in this state, first, the organic flocculant is mixed with the coarse SS where it coexists. On the other hand, it exhibits a particularly high agglomeration effect and a stronger agglomeration effect. As a result, agglomeration and agglomeration of coarse SS occur rapidly, and at this time, the coexisting fine SS is formed by the coarse agglomerate formed by this organic flocculant It is considered that the excellent effect of the present invention of quick and efficient good aggregation and sedimentation by the same treatment was obtained by being taken into the aggregates. In particular, when the wastewater is flowing in a ditch or liquid channel, the fine SS is actively moving in the wastewater, so it is inferred that the fine SS is more easily taken up by coarse aggregates. Yes. Further, the aggregated sediment / precipitate obtained by the treatment method of the present invention, which is considered to be obtained by such a mechanism, is sludge obtained by adding a flocculant and allowing it to settle in a sedimentation tank. This is clearly different from the above, and it has good dehydration and low oil content. For this reason, subsequent processing becomes extremely easy, and it is possible to significantly reduce the cost conventionally required for the secondary treatment of sedimentation / precipitate.

本発明で使用する有機凝集剤としては、特に限定されず、例えば、アクリル系、ポリアミン系、およびジアリルアンモニウム系の化合物から選ばれる有機凝集剤を用いることができる。本発明者らの検討によれば、下記に挙げる有機凝集剤を用いれば、より顕著な効果が得られる。具体的には、下記一般式(1)及び(2)を必須成分としてそれぞれ5モル%以上を含む原料モノマーから誘導されるカチオン性又は両性の共重合体を主成分としてなり、該共重合体の重量平均分子量が100万〜1,300万であり、且つ、pH7におけるカチオンコロイド当量値が0.1meq/g以上であるものを用いることが有効である。

Figure 2014133229
Figure 2014133229
(上記式中の、R1、R2は、CH3又はC25を、R3は、H、CH3又はC25を表す。X-は、アニオン性対イオンを表す。) The organic flocculant used in the present invention is not particularly limited. For example, an organic flocculant selected from acrylic, polyamine and diallylammonium compounds can be used. According to the study by the present inventors, a more remarkable effect can be obtained by using the organic flocculants listed below. Specifically, a cationic or amphoteric copolymer derived from a raw material monomer containing 5 mol% or more of each of the following general formulas (1) and (2) as an essential component is the main component. It is effective to use those having a weight average molecular weight of 1 million to 13 million and a cation colloid equivalent value at pH 7 of 0.1 meq / g or more.
Figure 2014133229
Figure 2014133229
(In the above formula, R 1 and R 2 represent CH 3 or C 2 H 5 , R 3 represents H, CH 3 or C 2 H 5. X represents an anionic counter ion.)

本発明で有機凝集剤として利用することができる上記したカチオン性の共重合体は、上記式(1)及び式(2)で表されるモノマーをそれぞれ5モル%以上含む原料モノマーから、その重量平均分子量及びpH7におけるカチオンコロイド当量値が、本発明で規定する範囲内となるようにすることで誘導できる。具体的には、特許第2779732号公報に記載の合成方法が利用できる。また、両性の共重合体は、例えば、特許第3352835号公報に記載されているように、上記式(1)及び(2)で表されるカチオン性モノマーに、その他のモノマーとしてイタコン酸やアクリル酸等のアニオン性モノマーを適宜混合して原料モノマーとすることで、同様の方法で得ることができる。   The above-mentioned cationic copolymer that can be used as an organic flocculant in the present invention is obtained from the raw material monomers each containing 5 mol% or more of the monomers represented by the above formulas (1) and (2). The average molecular weight and the cation colloid equivalent value at pH 7 can be derived by being within the ranges defined in the present invention. Specifically, the synthesis method described in Japanese Patent No. 2777732 can be used. In addition, amphoteric copolymers include, for example, a cationic monomer represented by the above formulas (1) and (2), and other monomers such as itaconic acid and acrylic as described in Japanese Patent No. 3352835. It can be obtained by the same method by appropriately mixing an anionic monomer such as an acid to obtain a raw material monomer.

上記式(1)で示されるモノマーの代表的なもとしては、アクリロイルオキシエチルトリメチルアンモニウムクロリド、ジメチルアミノエチルアクリレートの塩酸塩等が挙げられる。また、式(2)で示されるモノマーの代表例としては、アクリロイルオキシエチルジメチルベンジルアンモニウムクロリドが挙げられる。これらのモノマーと共重合可能な他のモノマーとしては、(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド等が挙げられる。   Typical examples of the monomer represented by the formula (1) include acryloyloxyethyltrimethylammonium chloride, hydrochloride of dimethylaminoethyl acrylate, and the like. A typical example of the monomer represented by the formula (2) is acryloyloxyethyldimethylbenzylammonium chloride. Examples of other monomers copolymerizable with these monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.

本発明者らは、上記したような原料モノマーから得られる有機凝集剤について詳細に検討した結果、本発明の目的をより高レベルで安定して達成させるためには、上記したような原料モノマーから得られるカチオン性又は両性の共重合体が、下記の要件を満たすものであることを要することを見出した。具体的には、上記した有機凝集剤の場合は、上記原料モノマーから誘導される共重合体の中でも、重量平均分子量が100万〜1,300万であり、且つ、pH7におけるカチオンコロイド当量値が0.1meq/g以上であるであることが好ましい。その、より好ましい範囲は、重量平均分子量とカチオンコロイド当量値との兼ね合いによっても異なるが、重量平均分子量が200万〜1100万であり、且つ、pH7におけるカチオンコロイド当量値が0.2〜1.9meq/gである弱カチオン〜強カチオンのものを使用するとよい。   As a result of detailed studies on the organic flocculants obtained from the raw material monomers as described above, the present inventors have found that the above-mentioned raw material monomers are used in order to stably achieve the object of the present invention at a higher level. It has been found that the obtained cationic or amphoteric copolymer needs to satisfy the following requirements. Specifically, in the case of the organic flocculant described above, among the copolymers derived from the raw material monomers, the weight average molecular weight is 1 million to 13 million, and the cation colloid equivalent value at pH 7 is It is preferably 0.1 meq / g or more. The more preferable range varies depending on the balance between the weight average molecular weight and the cation colloid equivalent value, but the weight average molecular weight is 2 million to 11 million, and the cation colloid equivalent value at pH 7 is 0.2 to 1. A weak cation to a strong cation of 9 meq / g may be used.

重量平均分子量が上記範囲内よりも小さ過ぎると十分なSS除去効果が得られず、一方、大き過ぎるとその粘度が上昇し、使用し難くなる。上記カチオンコロイド当量値は、有機凝集剤中のカチオン密度、すなわち、カチオン性を示す官能基の量を示すものである。本発明に使用する有機凝集剤のカチオンコロイド当量値は、コロイド滴定法により測定した値であるが、ポリビニル硫酸カリウム溶液で滴定する方法で求めた値である。   If the weight average molecular weight is too smaller than the above range, a sufficient SS removal effect cannot be obtained. On the other hand, if the weight average molecular weight is too large, the viscosity increases and it becomes difficult to use. The cation colloid equivalent value indicates the cation density in the organic flocculant, that is, the amount of the functional group exhibiting cationic property. The cation colloid equivalent value of the organic flocculant used in the present invention is a value measured by a colloid titration method, but is a value obtained by a titration method using a polyvinyl potassium sulfate solution.

上記に例示した有機凝集剤は、カチオン性のものであるが、本発明はこれに限定されるものでなく、対象とする廃水によってはアニオン性やノニオン性の有機凝集剤を使用することもできる。例えば、本発明者らの検討によれば、転炉からの集塵廃水の場合は、カチオン性の有機凝集剤を用いた場合よりも、アニオン性の有機凝集剤を用いた方が大きな効果が得られる。また、石炭ヤードの雨水排水などからの石炭・コークス等の炭素系の粉塵を含有する廃水を処理する場合には、微アニオン性或いはノニオン性の有機凝集剤の使用が適している。   The organic flocculants exemplified above are cationic, but the present invention is not limited to this, and anionic or nonionic organic flocculants can be used depending on the wastewater to be treated. . For example, according to the study by the present inventors, in the case of dust collection wastewater from a converter, it is more effective to use an anionic organic flocculant than to use a cationic organic flocculant. can get. In addition, when treating wastewater containing carbon-based dust such as coal and coke from rainwater drainage in a coal yard, the use of a slightly anionic or nonionic organic flocculant is suitable.

本発明者らの検討によれば、上記した共重合体を主成分とする有機凝集剤を、例えば、製鐵工場の熱間圧延工程から大量に排出される、鉄粉等の金属や圧延油等の油分が懸濁した、粗大SSと微細SSとが併存して浮遊している状態の直接冷却廃水に、該処理廃水に対して0.1mg/L以上、例えば、2mg/L程度と微少量添加するだけで、廃水中の懸濁物質が速やかに凝集沈降して、しかも、その上澄みは、目視において濁りの見られない極めて清澄なものになる。これに対し、この有機凝集剤を、従来のように、予め廃水中から粗大SSを除去した後に行う凝集沈降処理に使用した場合には、上記したような顕著な効果は得られず、微細SSが凝集沈降する傾向はみられるものの、その上澄みは、目視において濁りがあり、明らかに十分なものではなかった。このことは、上記した有機凝集剤によってもたらされるより本発明の顕著な凝結・凝集・沈降効果は、微細なSSと共に、粒径が50μm以上の粗大なSSが併存している場合に発揮されるものであり、粗大SSと微細SSとが併存して浮遊している状態の廃水を処理することが重要であることを示している。   According to the study by the present inventors, the above-described organic flocculant mainly composed of a copolymer is discharged from a metal such as iron powder or rolling oil, for example, in a large amount from a hot rolling process of a steelmaking factory. Directly cooled wastewater in which coarse SS and fine SS coexist and suspended, in which oil components such as oil are suspended, is 0.1 mg / L or more with respect to the treated wastewater, for example, about 2 mg / L. Just by adding a small amount, the suspended matter in the wastewater quickly aggregates and settles, and the supernatant becomes very clear with no turbidity observed visually. On the other hand, when this organic flocculant is used for the coagulation sedimentation treatment performed after removing coarse SS from wastewater in advance as in the prior art, the remarkable effect as described above cannot be obtained, and the fine SS Although there was a tendency to flocculate and settle, the supernatant was turbid with the naked eye and apparently not sufficient. This is because the remarkable coagulation / coagulation / sedimentation effect of the present invention brought about by the organic coagulant described above is exhibited when a fine SS and a coarse SS having a particle size of 50 μm or more coexist. This indicates that it is important to treat waste water in a state where coarse SS and fine SS coexist and float.

更に、本発明者らの検討によれば、上記有機凝集剤は、先に述べたように、例えば、上記熱間圧延工程からの直接冷却廃水が、水処理設備である「スケールピット」に至るまでの廃水が激しく流動している「スケールスルース」と呼ばれている溝や液路に添加するとより高い効果が得られる。すなわち、製鐵所において発生する廃水中の懸濁物質には、比重の大きな鉄粉が多く含まれているため、懸濁物質の沈降を防止する必要があり、このスケールスルースの流れは1〜5m/秒程度と極めて速いものとなっている。本発明者らの検討によれば、この速い廃水の流れ中に有機凝集剤を単に添加するだけで、先に述べた本発明で規定する要件を満たし、その結果、本発明の顕著な効果を得ることができる。また、先にも述べたように、この場合に、有機凝集剤を、水処理設備である「スケールピット」に対してより上流側に添加することがより効果的である。特に、上記有機凝集剤の添加を廃水の発生地点の近傍で行うことで、「スケールスルース」を経由して「スケールピット」に至るまでの廃水が激しく流動している状態の時間をより長く確保できるようになるが、このようにした方が、本発明のより高い効果を得ることができる。これらのことは、有機凝集剤を添加する場合は、廃水が激しく流動している場所に添加し、有機凝集剤と、粗大SS及び微細SSを激しい混合状態で反応させた方が、該有機凝集剤を使用したことによる凝結・凝集・沈降効果が、より速やかにより顕著に発揮されることを示している。先述したように、スケールスルースと呼ばれている溝や液路では、廃水が速い流れの中で激しく流動しており、例えば、水処理設備に廃水が導入される前のこの地点を巧みに利用すれば、別途、撹拌装置等の設備を設ける必要がなく、有機凝集剤を添加する地点を適宜に設計するという簡便な手段によって、後述する工業上、極めて優れた種々の効果を得ることが可能になる。このため、本発明で規定する要件を達成するためには、従来のスケールスルースと呼ばれている溝や液路のままでも勿論よいが、場合によっては、例えば、溝や液路内に障害物や回転羽等を設置するといった方法で、流れがより乱流となるように工夫してもよい。いずれにしても、本発明の廃水中の懸濁物質の除去処理方法においては、有機凝集剤と、除去処理の対象である粗大SSおよび微細SSを激しい混合状態で反応させることがより好ましく、このようにすれば、有機凝集剤の使用量を低減できるとともに、添加した有機凝集剤によって、より高い凝結・凝集・沈降効果を得ることができる。   Further, according to the study by the present inventors, the organic flocculant is, as described above, for example, the direct cooling wastewater from the hot rolling process reaches the “scale pit” which is a water treatment facility. A higher effect can be obtained if it is added to a groove or liquid channel called “scale sluice” where the waste water up to this point is flowing vigorously. That is, since the suspended solids generated in the wastewater contain a large amount of iron powder having a large specific gravity, it is necessary to prevent sedimentation of the suspended solids. It is extremely fast, about 5 m / sec. According to the study by the present inventors, the organic flocculant is simply added to the flow of this fast wastewater, and the requirements specified in the present invention are satisfied. As a result, the remarkable effects of the present invention are achieved. Can be obtained. Further, as described above, in this case, it is more effective to add the organic flocculant to the “scale pit” that is the water treatment facility more upstream. In particular, by adding the organic flocculant in the vicinity of the wastewater generation point, it will ensure a longer time for the wastewater to flow violently until it reaches the “scale pit” via the “scale sluice”. Although it becomes possible to do so, the higher effect of the present invention can be obtained. When organic flocculant is added, it is better to add the organic flocculant to the place where the wastewater is flowing vigorously and react the organic flocculant with coarse SS and fine SS in a vigorous mixed state. It shows that the coagulation / aggregation / sedimentation effect due to the use of the agent is more rapidly and more prominently exhibited. As mentioned earlier, in the grooves and liquid channels called scale sluice, wastewater flows violently in a fast flow, for example, skillfully using this point before the wastewater is introduced into the water treatment facility If this is the case, it is not necessary to separately provide equipment such as a stirrer, and various industrially excellent effects described later can be obtained by a simple means of appropriately designing the point where the organic flocculant is added. become. For this reason, in order to achieve the requirements defined in the present invention, it is of course possible to keep the grooves and liquid paths called conventional scale sluice, but in some cases, for example, obstacles in the grooves and liquid paths Alternatively, the flow may be devised so that the flow becomes more turbulent by a method such as installing a rotating wing or the like. In any case, in the method for removing suspended substances in waste water of the present invention, it is more preferable to react the organic flocculant with the coarse SS and fine SS that are the targets of the removal treatment in a vigorous mixed state. By doing so, the amount of the organic flocculant used can be reduced, and a higher coagulation / aggregation / sedimentation effect can be obtained by the added organic flocculant.

本発明の特徴は、少なくとも、粗大なSSと微細なSSとが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に、有機凝集剤が共存する状態を生じさせることにあるが、有機凝集剤を添加する地点を、上記に挙げたような各地点とすることで、本発明で規定する上記要件を容易に満足する処理ができる。本発明の処理方法によれば、上記した極めて簡便な方法によって、以下に挙げる工業上極めて有用な種々の効果が得られる。本発明の処理方法によって得られる主な効果、またはメリットを4つ述べる。   The feature of the present invention is that at least coarse SS and fine SS coexist, and the flow velocity is 0.5 m / second or more, and the organic coagulant coexists in turbulent water. However, by setting the point where the organic flocculant is added to each of the points as mentioned above, it is possible to easily satisfy the above-mentioned requirements defined in the present invention. According to the treatment method of the present invention, the following industrially extremely useful effects can be obtained by the above-described extremely simple method. Four main effects or merits obtained by the processing method of the present invention will be described.

(1)水処理プロセスの簡略化
有機凝集剤の添加地点を工夫するだけで、廃水中の粗大なSSと微細なSSが有機凝集剤とよく混合されることで、微細な鉄粉や油と粒径の大きなスケールとが極めて速やかに凝集し、沈降させることができ、従来は、粗大な懸濁物質を処理するためのスケールピットでは除去できなかった微細な鉄粉や油も、スケールピット、またはそれに類する比較的小さい槽で沈殿分離でき、スケールピットの出側で、従来と同等或いはそれ以上のレベルまで懸濁物質の混入を低減した清浄な処理水が得られる、簡易且つ迅速な処理が可能になる。
上記の結果、従来の廃水中の微細なSSの除去処理において必要とされていた、沈殿池やろ過機、電磁フィルターといった、微細鉄粉や油の分離設備が不要となる。これに伴い、撹拌機や、ろ過機や電磁フィルターを使用した場合に必要となっていた逆流洗浄排水処理設備も不要となる。
また、本発明の廃水中の懸濁物質の除去処理方法では無機凝集剤が不要となることから、そのためのタンクやポンプ、撹拌機、送液ライン等の設備も不要となる。
したがって、製鐵所において大量に発生する、粗大なSSと微細なSSとが共存している状態の廃水に対して、新たに懸濁物質の除去処理設備を建設する場合には、上記に関連した設備スペース、及び建設費が大幅に削減できる。
(2)維持管理費の縮小
沈殿池やろ過機が不要となり、スケールピットの出側から処理水を冷却塔へ直接送水できるため、必要なポンプの台数を減らすことができ、電気代を含む維持管理費が大幅に縮小できる。
(3)腐食の低減
本発明の廃水中の懸濁物質の除去処理方法では無機凝集剤を必要としないため、ポリ塩化アルミニウムや、硫酸バンド等に代表される無機凝集剤に含まれる、腐食性陰イオンである、Cl-や、SO4 2-が処理水中に混入することを著しく低減できる。このため、凝集沈殿、及び冷却処理した処理水を、再度工場へ給水する場合、その配管系等、ならびに生産する鋼材表面の腐食を軽減することが可能となる。
(4)鉄スラッジのリサイクル促進
本発明の廃水中の懸濁物質の除去処理方法を採用し、粗大なSSと微細なSSとを同一の処理で凝集沈降させたことによってスケールピットにおいて発生する、粒径の大きなスケール、微細な鉄粉、及び油からなるスラッジは、脱水性と濃縮性がよく、重量あたりの油含有率が小さいため、その運搬及びリサイクルが簡便にできる。
(1) Simplification of water treatment process By simply devising the addition point of the organic flocculant, coarse SS and fine SS in the wastewater are well mixed with the organic flocculant, so that fine iron powder and oil Scales with large particle sizes can agglomerate and settle very quickly, and fine iron powder and oil that could not be removed with scale pits for treating coarse suspended solids, Or it can be separated and settled in a relatively small tank similar to that, and on the exit side of the scale pit, clean treated water can be obtained with reduced suspended matter contamination to the same or higher level as before. It becomes possible.
As a result, the fine iron powder and oil separation facilities such as a sedimentation basin, a filter, and an electromagnetic filter, which are required in the conventional process for removing fine SS in wastewater, are not required. In connection with this, the backwashing waste water treatment equipment required when using a stirrer, a filter, and an electromagnetic filter becomes unnecessary.
Moreover, since the inorganic flocculant is unnecessary in the method for removing suspended solids from wastewater according to the present invention, facilities such as a tank, a pump, a stirrer, and a liquid feed line are not required.
Therefore, when constructing a new facility for removing suspended solids from wastewater that is generated in large quantities at a steelworks and coexists with coarse SS and fine SS, Equipment space and construction costs can be greatly reduced.
(2) Reduction of operation and maintenance costs No sedimentation basin or filter is required, and treated water can be sent directly from the exit side of the scale pit to the cooling tower, reducing the number of necessary pumps and maintaining electricity costs. Administrative costs can be significantly reduced.
(3) Reduction of corrosion Since the inorganic flocculant is not required in the method for removing suspended solids in the waste water of the present invention, the corrosiveness contained in inorganic flocculants represented by polyaluminum chloride and sulfuric acid band. It is possible to remarkably reduce the presence of anions, such as Cl - and SO 4 2-, in the treated water. For this reason, when the coagulated sediment and the treated water cooled are supplied again to the factory, it is possible to reduce the corrosion of the piping system and the surface of the steel material to be produced.
(4) Promotion of recycling of iron sludge Occurred in scale pits by adopting the method for removing suspended substances in wastewater of the present invention, and coagulating and sedimenting coarse SS and fine SS by the same treatment, A sludge composed of a large particle size scale, fine iron powder, and oil has good dewaterability and concentration, and has a low oil content per weight, and therefore can be easily transported and recycled.

図1は、本発明の廃水中の懸濁物質の除去処理方法を連続鋳造工程の直接冷却廃水処理に適用した場合の好適な一実施形態を示す模式図である。図1に示したように、連続鋳造工程から発生する直接冷却廃水は、連続鋳造ラインからスケールスルース1に流れ落ち、廃水は、スケールスルース1の内部を激しく流動しながら、スケールピット3へと移動する。図1に示した例では、有機凝集剤2が、直接冷却廃水が流動していくスケールスルース1の最上流部分で添加されている。それ故、有機凝集剤2と直接冷却廃水は、スケールスルース1内の激しい流れの中で混合され、スケールピット3内に排水される。その結果、スケールピット3内では、廃水中のスケール、微粒鉄粉、油の凝結・凝集したものが極めて速やかに沈降分離される。そのため、スケールピット3内の上澄水は清澄なものとなるので、そのまま上澄水を冷却塔4へ揚水する。最後に、冷却塔4で冷却されて得られた処理水は、直接冷却水として再び工場へ給水される。   FIG. 1 is a schematic view showing a preferred embodiment when the method for removing suspended substances in wastewater of the present invention is applied to direct cooling wastewater treatment in a continuous casting process. As shown in FIG. 1, the directly cooled wastewater generated from the continuous casting process flows down from the continuous casting line to the scale sluice 1, and the wastewater moves to the scale pit 3 while vigorously flowing inside the scale sluice 1. . In the example shown in FIG. 1, the organic flocculant 2 is added at the most upstream part of the scale sluice 1 through which the cooling wastewater flows directly. Therefore, the organic flocculant 2 and the directly cooled wastewater are mixed in a vigorous flow in the scale sluice 1 and drained into the scale pit 3. As a result, in the scale pit 3, the scale, fine iron powder, and agglomerated and agglomerated oil in the wastewater are settled and separated very quickly. Therefore, since the supernatant water in the scale pit 3 becomes clear, the supernatant water is pumped to the cooling tower 4 as it is. Finally, the treated water obtained by cooling in the cooling tower 4 is supplied to the factory again as direct cooling water.

実施例と比較例を挙げて本発明をより具体的に説明するが、これらの実施例により本発明が限定されるものではない。   EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

<確認試験例>
まず、粗大SSと微細SSとを同一の処理で凝集沈降させることの優位性について、下記のようにして確認試験を行った。検討には、図4に示した従来の熱間圧延工程において発生する、スケールピット3への流入水を採水し、これを確認試験に使用した。具体的には、採水したスケールピット流入水を2つに分け、一方のスケールピット流入水はそのままの状態で試験に用い、他方のスケールピット流入水は、その中の粒径50μm以上のSS(粗大SS)を除去したものを用いた。上記したそれぞれの水に対して、後述する実施例で使用した有機凝集剤を同量添加してよく混合した後、複数の同じ形状の縦長の筒状容器内にそれぞれ同量ずつ入れて、一番長いもので20分間となるように静置させて、各時点における沈降状態を観察した。そして、沈降状態を客観的に評価するため、静置時間の異なる処理水を、筒状容器の底面から一定の高さから採水し、採水したそれぞれの水(処理水)について、JIS K0102に則して、SS濃度を分析した。
<Example of confirmation test>
First, the confirmation test was performed as follows about the superiority of coagulating and sedimenting coarse SS and fine SS by the same treatment. In the examination, water flowing into the scale pit 3 generated in the conventional hot rolling process shown in FIG. 4 was collected and used for the confirmation test. Specifically, the sampled scale pit inflow water is divided into two, and one scale pit inflow water is used as it is for the test, and the other scale pit inflow water is an SS having a particle size of 50 μm or more. What removed (coarse SS) was used. Add the same amount of the organic flocculant used in the examples described later to each of the water described above and mix well, then put the same amount into each of the plurality of vertically long cylindrical containers of the same shape. The longest one was allowed to stand for 20 minutes, and the sedimentation state at each time point was observed. Then, in order to objectively evaluate the sedimentation state, treated water having different standing times is collected from a certain height from the bottom surface of the cylindrical container, and each collected water (treated water) is JIS K0102. The SS concentration was analyzed according to

表1に、上記の試験結果を示した。その結果、表1に示した通り、本発明で規定している、粗大SSと微細SSとを同一に処理した「粗大SSありの系」と、従来の処理で行われている「粗大SSなしの系」では、その沈降速度に大きな違いがあることが確認された。例えば、SS濃度が15mg/lの処理水を得る場合の沈降時間が、「粗大SSありの系」では、僅か2分間で済むのに対し、従来の処理で行われている「粗大SSなしの系」では8分間必要であった。このことから、本発明で規定した、粗大SSと微細SSとを同一に処理する「粗大SSありの系」とすることで、従来の方法に比べてSSを極めて迅速に沈降させることができることが確認された。   Table 1 shows the test results. As a result, as shown in Table 1, the “system with coarse SS” in which the coarse SS and the fine SS are treated in the same manner as defined in the present invention, and “no coarse SS” used in the conventional process are used. It was confirmed that there is a big difference in the sedimentation rate in For example, the sedimentation time for obtaining treated water with an SS concentration of 15 mg / l is only 2 minutes in the “system with coarse SS”, whereas “no coarse SS” used in the conventional treatment is required. The "system" required 8 minutes. From this, it is possible to precipitate SS very quickly as compared with the conventional method by using the “system with coarse SS” that treats coarse SS and fine SS identically defined in the present invention. confirmed.

Figure 2014133229
Figure 2014133229

上記した、従来より行われている「粗大SSなしの系」で処理した場合と、本発明で新たに行った「粗大SSありの系」で処理した場合の比較試験で、SSの沈降速度に顕著な差が生じた理由について、本発明者らは、「粗大SSありの系」で処理した場合は、粗大SSと微細SSとが共存する状態の被処理水へ有機凝集剤を添加することで、両SSの凝集体が速やかに生成されたことで、その沈降速度が、従来技術で「粗大SSなしの系」の処理を行う前に行われている粗大SSのみの処理の場合と同程度以上になったためと考えている。   In the comparison test between the above-described case of processing with the “system without coarse SS” conventionally performed and the case of processing with the “system with coarse SS” newly performed in the present invention, the sedimentation rate of SS was increased. Regarding the reason for the remarkable difference, the present inventors added an organic flocculant to the water to be treated in a state where the coarse SS and the fine SS coexist when the treatment is performed in the “system with coarse SS”. Thus, since the aggregates of both SSs were rapidly formed, the sedimentation rate was the same as in the case of the treatment with only the coarse SS performed before the processing of the “system without coarse SS” in the prior art. I think that it was because of over.

上記した確認試験の結果から、従来の「粗大SSなしの系」で処理する場合には、粗大SSの処理には比較的小さな槽(例えば、設計Over Flow Rate:10〜50m/hr程度)であるスケールピットを使用し、その後の微細SSの処理には、大きな沈殿槽(例えば、設計Over Flow Rate:0.5〜4.0m/hr程度)を用い、場合によっては更にろ過機等が必要であったのに対し、本発明で規定した「粗大SSありの系」を適用することで、上記したスケールピットのような比較的小さな槽のみを使用することで、従来の処理法と同等以上の処理水質が得られることが示唆された。つまり、上記した試験結果は、本発明で新たに規定する「粗大SSありの系」での処理によって、従来技術の「粗大SSなしの系」で行われていた、凝集沈殿処理によっては決して得ることができなかった顕著な効果が達成されることを確認した。   From the result of the above-described confirmation test, when processing with the conventional “system without coarse SS”, the coarse SS is processed in a relatively small tank (for example, design Over Flow Rate: about 10 to 50 m / hr). A large sedimentation tank (for example, design Over Flow Rate: about 0.5 to 4.0 m / hr) is used for the subsequent processing of fine SS using a certain scale pit. On the other hand, by applying the “system with coarse SS” defined in the present invention, by using only a relatively small tank such as the scale pit described above, it is equal to or more than the conventional processing method. It was suggested that the quality of treated water was obtained. In other words, the test results described above are never obtained by the coagulation sedimentation treatment performed in the “system without coarse SS” of the prior art by the treatment in the “system with coarse SS” newly defined in the present invention. It was confirmed that a remarkable effect that could not be achieved was achieved.

<実施例1、2、比較例1>
本実施例の概要を図2に示した。本実施例では、図1に示したものと同様に、連続鋳造工程において発生するスプレー系冷却廃水に対して、有機凝集剤2をスプレー系冷却廃水が流動していくスケールスルース1の最上流部分で添加した。そして、スケールピット3で得た上澄み水を、電磁フィルター5で処理後に、冷却塔4で冷却し、再度、冷却水として使用した。本実施例では、有機凝集剤2として、前記した一般式(1)及び(2)で表される2種類のモノマーを必須成分として、それぞれ20モル%ずつ含む原料モノマーから誘導した、アクリルアミド/[2−(アクリロイルオキシ)エチル]ベンジルジメチルアンモニウム・クロリド/[2−(アクリロイルオキシ)エチル]トリメチルアンモニウム・クロリド共重合体(モル比=60/20/20)を主成分とするカチオン性のものを用いた。その重量平均分子量は300万であり、pH7におけるカチオンコロイド当量値が0.6〜1.0meq/g程度であるものを用いた。そして、スケールスルース1内の廃水に対し、該有機凝集剤を、0mg/l(無添加)、1mg/l、2mg/lとなるように連続添加した。なお、上記で処理したスプレー系冷却廃水における粗大SSと微細SSとの比(粗/微)は、その質量比で、5〜20程度であった。
<Examples 1 and 2 and Comparative Example 1>
The outline of this example is shown in FIG. In the present embodiment, similar to that shown in FIG. 1, the uppermost stream portion of the scale sluice 1 in which the spray cooling wastewater flows through the organic flocculant 2 with respect to the spray cooling wastewater generated in the continuous casting process. Added at. And the supernatant water obtained by the scale pit 3 was processed by the electromagnetic filter 5, cooled by the cooling tower 4, and used again as cooling water. In this example, the organic flocculant 2 was derived from a raw material monomer containing 20 mol% each of the two types of monomers represented by the general formulas (1) and (2) as essential components. A cationic compound mainly composed of 2- (acryloyloxy) ethyl] benzyldimethylammonium chloride / [2- (acryloyloxy) ethyl] trimethylammonium chloride copolymer (molar ratio = 60/20/20). Using. The weight average molecular weight was 3 million, and the cation colloid equivalent value at pH 7 was about 0.6 to 1.0 meq / g. Then, the organic flocculant was continuously added to the waste water in the scale sluice 1 so as to be 0 mg / l (no addition), 1 mg / l, and 2 mg / l. In addition, ratio (rough / fine) of coarse SS and fine SS in the spray system cooling wastewater processed above was about 5-20 in the mass ratio.

そして、上記の処理後に、JIS K0102に則して、スプレー戻水6(処理水A)、スプレー直送水7(処理水B)のSS濃度及びn−Hex抽出物質濃度(油分)を測定した。尚、ここでいうスプレー戻水とは、スケールピット3の出側の水(上澄み水)のことであり、スプレー直送水とは電磁フィルター5で処理後に、冷却された水(処理後の冷却水)のことである。また、比較例1として、有機凝集剤を添加しない場合についても、SS濃度及びn−Hex抽出物質濃度(油分)を測定した。   And after said process, according to JISK0102, SS density | concentration and the n-Hex extract substance density | concentration (oil content) of the spray return water 6 (process water A) and the spray direct water 7 (process water B) were measured. In addition, spray return water here is the water (supernatant water) of the exit side of scale pit 3, and spray direct feed water is the water cooled after processing with the electromagnetic filter 5 (cooling water after a process). ). Further, as Comparative Example 1, the SS concentration and the n-Hex extract substance concentration (oil content) were also measured when no organic flocculant was added.

表2に、上記の有機凝集剤の添加試験の結果を示した。実施例1として、有機凝集剤を1mg/lとなるように添加することで、スプレー戻水のSS濃度は19mg/l、n−Hex抽出物質濃度は5mg/lになり、無添加時(比較例1)と比べ、両汚濁物質の濃度が半減することを確認した。また、スプレー直送水においては、SS濃度が10mg/l、n−Hex抽出物質濃度が4mg/lという良好な水質が得られた。   Table 2 shows the results of the above-described organic flocculant addition test. As Example 1, the organic flocculant was added to 1 mg / l, so that the SS concentration of spray return water was 19 mg / l and the n-Hex extract substance concentration was 5 mg / l. Compared to Example 1), it was confirmed that the concentrations of both pollutants were halved. Moreover, in spray direct water, good water quality with an SS concentration of 10 mg / l and an n-Hex extract concentration of 4 mg / l was obtained.

更に、実施例2として、有機凝集剤を2mg/lとなるようにして添加した以外は上記と同様にして試験したところ、スプレー戻水のSS濃度は9mg/lになり、n−Hex抽出物質濃度は2mg/lになった。このスプレー戻水水質は、有機凝集剤の添加濃度が1mg/lで後段の電磁フィルター5で処理を行ったスプレー直送水と同等の水質である。したがって、有機凝集剤を2mg/lになるように添加した場合は、電磁フィルター5による処理を停止しても、良好な水質を維持可能であると考えられる。   Further, as Example 2, when tested in the same manner as above except that the organic flocculant was added to 2 mg / l, the SS concentration of spray return water was 9 mg / l, and the n-Hex extract substance The concentration was 2 mg / l. The water quality of the spray return water is the same as that of the direct spray water treated with the electromagnetic filter 5 at the subsequent stage when the addition concentration of the organic flocculant is 1 mg / l. Therefore, when an organic flocculant is added so that it may become 2 mg / l, even if the process by the electromagnetic filter 5 is stopped, it is thought that favorable water quality can be maintained.

Figure 2014133229
Figure 2014133229

<実施例3>
本実施例では、従来のスケールピット3の後段に設ける処理設備を停止することが可能か否かを判断することを目的として、最も水質が悪化すると考えられる、スケール揚げ時の処理水質の悪化の有無を確認した。スケール揚げとは、スケールピット底層に堆積する沈殿物であるスケールスラッジをクラム重機で浚渫することである。スケール揚げ時には、堆積していたスケールの巻揚げが発生するため、一時的な水質の悪化が起こると考えられる。本実施例では、実施例1の場合と同様の構成とし、廃水量に対して、2mg/lとなるようにスケールスルース上流で有機凝集剤を連続添加して処理した。
<Example 3>
In the present embodiment, for the purpose of determining whether or not it is possible to stop the treatment facility provided in the subsequent stage of the conventional scale pit 3, it is considered that the water quality is most deteriorated. The presence or absence was confirmed. Scale frying refers to dripping scale sludge, which is sediment deposited in the bottom layer of the scale pit, with a crumb heavy machine. At the time of scale frying, since the scales that have been accumulated are wound up, it is considered that the water quality temporarily deteriorates. In this example, the same constitution as in Example 1 was used, and the organic flocculant was continuously added upstream of the scale sluice so that the amount of wastewater was 2 mg / l.

スケール揚げの開始直後(開始5分後)、終了間際(終了10分前)、終了後(終了5分後)のスプレー戻水のSS及びn−Hex抽出物質の濃度を測定した。表3に、このスケール揚げ時における水質確認試験の結果をまとめて示した。スプレー戻水のSSは7〜8mg/l、n−Hex抽出物質は2mg/lとなり、最も水質が悪化すると考えられる、スケール揚げ時の前後でも、水質変動がほとんど見られないことを確認した。以上の結果から、発明の廃水中の懸濁物質の除去処理方法を採用することで、従来、必要とされていたスケールピット後段の処理設備は、停止可能になると判断した。   Immediately after the start of scale frying (5 minutes after the start), just before the end (10 minutes before the end), and after the end (5 minutes after the end), the concentrations of SS and n-Hex extract substances in the spray return water were measured. Table 3 summarizes the results of the water quality confirmation test when the scale was deep-fried. The SS of the spray return water was 7-8 mg / l, the n-Hex extract was 2 mg / l, and it was confirmed that the water quality was hardly changed even before and after the scale frying, which is thought to be the worst in water quality. From the above results, it was determined that the treatment facility after the scale pit, which was conventionally required, can be stopped by adopting the method for removing suspended solids from wastewater according to the invention.

Figure 2014133229
Figure 2014133229

<実施例4、5、比較例2>
実施例4、5と比較例2では、製鋼工程でつくられた鋼片を熱間圧延する際に、ロール冷却、鋼材や鋼片の冷却やスケール落としなどに使用された水(直接冷却廃水)を対象とした。
先ず、比較のために、図4に示した、上記の対象水に対する通常の懸濁物質の除去処理であるプロセスで処理し、これを比較例2とした。具体的には、先ず、スケールピット3において無機凝集剤2’を添加すると共に、粗大スケールを沈降分離し、その後段に配置した沈殿池8において微粒の懸濁物質と油分を除去後、冷却塔4で冷却処理して処理水を得、これを冷却水とした。この場合の処理水A(6)と、処理水B(7)を分析し、これらの結果を表4と表5に示した。
<Examples 4 and 5 and Comparative Example 2>
In Examples 4 and 5 and Comparative Example 2, when hot-rolling the steel slabs produced in the steelmaking process, water used for roll cooling, cooling of steel and steel slabs, scale reduction, etc. (direct cooling wastewater) Targeted.
First, for comparison, it was processed by the process shown in FIG. 4 which is a process for removing suspended substances from the target water, and this was designated as Comparative Example 2. Specifically, first, the inorganic flocculant 2 ′ is added to the scale pit 3, and the coarse scale is settled and separated, and after removing suspended fine particles and oil in the settling basin 8 arranged in the subsequent stage, the cooling tower The water was cooled at 4 to obtain treated water, which was used as cooling water. The treated water A (6) and treated water B (7) in this case were analyzed, and the results are shown in Tables 4 and 5.

実施例4、5として、図3に示したプロセスで、有機凝集剤の添加量を変えた以外は同様にして廃水中の懸濁物質の除去処理を行った。具体的には、図3に示した通り、スケールピット3への無機凝集剤の添加をすることなく、実施例1及び実施例2と同様に、スケールスルース1の上流に有機凝集剤2を添加した。そして、スケールピット3の出側の処理水Aを分析した。処理水のSS濃度及びn−Hex抽出物質濃度の分析は、JIS K0102に準拠して行い、試験結果を表4に示した。   As Examples 4 and 5, in the process shown in FIG. 3, the suspended solids in the wastewater were removed in the same manner except that the amount of the organic flocculant added was changed. Specifically, as shown in FIG. 3, the organic flocculant 2 is added upstream of the scale sluice 1 in the same manner as in Examples 1 and 2 without adding the inorganic flocculant to the scale pit 3. did. And the treated water A of the exit side of the scale pit 3 was analyzed. The analysis of the SS concentration of the treated water and the n-Hex extract substance concentration was performed according to JIS K0102, and the test results are shown in Table 4.

表4に示した通り、有機凝集剤を添加したことにより、処理水AのSS及びn−Hex抽出物質は、比較例2の処理に比べて良好に除去できた。また、実施例4の方法で処理した処理水AのSS濃度は16mg/lであり、n−Hex抽出物質濃度は2mg/lであった。更に、実施例5の方法で処理した処理水AのSS濃度は4mg/lであり、n−Hex抽出物質濃度は1mg/lであった。これらの結果から、比較例2における処理水Aよりも水質が改善できた。   As shown in Table 4, by adding the organic flocculant, SS and n-Hex extract material of the treated water A could be removed better than the treatment of Comparative Example 2. Further, the SS concentration of the treated water A treated by the method of Example 4 was 16 mg / l, and the n-Hex extract substance concentration was 2 mg / l. Furthermore, the SS concentration of the treated water A treated by the method of Example 5 was 4 mg / l, and the n-Hex extract substance concentration was 1 mg / l. From these results, the water quality was improved as compared with the treated water A in Comparative Example 2.

Figure 2014133229
Figure 2014133229

また、表4に示した実施例4、5の処理水Aと、図4で示した比較例2の従来の処理方法で処理した結果得られた処理水Bの水質を表5に示したが、これらを比較すると、実施例4、5の処理水Aは、比較例2の処理水Bに比べ、SS及びn−Hex抽出物質の濃度が同等以下であった。このことから、無機凝集剤を添加せずとも、スケールスルースに有機凝集剤を添加することにより、沈殿池を除外しても従来と同等以下まで汚濁物質を除去できると考えられる。   Table 5 shows the water quality of the treated water A of Examples 4 and 5 shown in Table 4 and the treated water B obtained as a result of treatment by the conventional treatment method of Comparative Example 2 shown in FIG. When these were compared, the treated water A of Examples 4 and 5 was less than or equal to the concentration of SS and n-Hex extract material compared to the treated water B of Comparative Example 2. From this, it is considered that by adding the organic flocculant to the scale sluice without adding the inorganic flocculant, the pollutant can be removed to the same level or lower even if the sedimentation basin is excluded.

Figure 2014133229
Figure 2014133229

<参考例6>
本発明をより明確にするため、薬剤を添加する水の流速やレイノルズ数が、薬剤の効果に与える影響について、圧延工場の直接冷却廃水を対象とした室内試験で、その流速条件を8通りに設定し、その処理水SS濃度を比較して評価し、本発明で規定する要件の意味するところについての確認を行った。その結果、表6に示したように、想定流速が0.5m/秒を超えると大幅に処理水濁度の改善が確認され、それ以上想定流速を上げても処理水濁度の改善効果は小さいことを確認した。
<Reference Example 6>
In order to clarify the present invention, the influence of the flow rate and Reynolds number of the water to which the chemical is added on the effect of the chemical is tested in laboratory tests for direct cooling wastewater of the rolling mill in eight ways. It was set, the treated water SS concentration was compared and evaluated, and the meaning of the requirements defined in the present invention was confirmed. As a result, as shown in Table 6, when the assumed flow rate exceeds 0.5 m / sec, the treatment water turbidity is greatly improved. Even if the assumed flow rate is increased further, the effect of improving the treatment water turbidity is I confirmed it was small.

Figure 2014133229
Figure 2014133229

以上の結果から、表6に示されているように、本発明の処理方法を適用する場合は、必要量の有機凝集剤を適宜な位置で添加することで、粗大なSSと微細なSSとが併存し、有機凝集剤が共存している状態が、少なくとも流速が0.5m/秒以上で、且つ、レイノルズ数8000以上の乱流状態の水の中に生じている場合に、望ましくは、流速が1.0m/秒以上で、且つ、レイノルズ数10000以上の乱流状態の水の中に生じている場合に、本発明の効果が顕著に認められることが確認できた。このため、本発明の処理方法を適用する際には、廃水の発生地点から、廃水が移動して処理設備に入るまでの各地点における廃水の流速及びレイノルズ数を測定し、上記において好適な結果が得られることが確認された測定値を有する地点を把握し、その上で、粗大なSSと微細なSSとが併存し、有機凝集剤が共存している状態となるように、有機凝集剤を添加する地点を決定することが好ましい。   From the above results, as shown in Table 6, when applying the treatment method of the present invention, by adding a necessary amount of organic flocculant at an appropriate position, coarse SS and fine SS And the coexistence of the organic flocculant occurs in turbulent water having a flow velocity of at least 0.5 m / second and a Reynolds number of 8000 or more. It was confirmed that the effect of the present invention is remarkably observed when the flow velocity is 1.0 m / second or more and the turbulent flow state water has a Reynolds number of 10,000 or more. For this reason, when applying the treatment method of the present invention, the flow rate and Reynolds number of the wastewater at each point from the point where the wastewater occurs until the wastewater moves and enters the treatment facility are measured. The organic flocculant is obtained so that the coarse SS and the fine SS coexist, and the organic flocculant coexists. It is preferable to determine the point at which is added.

本発明の活用例としては、製鐵所の連続鋳造工程における鋼材の直接冷却廃水、製鐵所の圧延工程における鋼材の直接冷却廃水、製鐵所の高炉、転炉、電炉工程における集塵廃水、製鐵所の屋外原料貯蔵ヤードから発生する雨水廃水、製鐵所の高炉滓から水砕スラグを得る際に発生する冷却廃水といった、粗大なSSと微細なSSとが併存している状態の大量の廃水から、有機凝集剤を添加する位置を工夫するといった極めて簡便な方法で、粗大なSSと微細なSSとを同一の処理で、極めて迅速に凝集沈降させて取り除くことができることが挙げられる。上記のように構成することで、従来の処理で必要とされてきた微細SSの処理のための沈殿池といった設備や、これに伴う運転や維持管理が不要となり、極めて経済的な処理が可能になるので、その利用が期待される。また、粗大なSSと微細なSSとを同一の処理で凝集沈降させた場合の上澄み水は、従来の方法で処理した場合の処理水と比較して、目視でも懸濁物質の残留が少なくなったことが明確に分かる濁りのない清澄なものであり、更に、従来の無機凝集剤を使用した方法において懸念されていた混入した塩素イオン等による悪影響の問題も事実上なく、そのまま、再度冷却水として利用することができるので、この点からも極めて経済的である。更に、有機凝集剤と粗大な懸濁物質と微細な懸濁物質とが凝結・凝集してなる沈殿物(スケールスラッジ)は、取り扱い易く、クラム重機で浚渫することができ、しかも強固に凝結したものとなるので、当該作業の際における、上澄み液の水質への影響も小さく、これによって、沈殿物の処理が大幅に簡略化できるので、この点でも極めて経済的な処理が可能になる。上記したように、本発明の処理方法は、有機凝集剤を添加する地点を変更するといった極めて簡便なものでありながら、従来の方法と比べて、粗大なSSと微細なSSとを分けて処理する必要がなく、これによって、使用する凝集剤の種類や量を低減でき、更には、微細な懸濁物質の凝集沈殿に要していた広大な沈殿槽を不要とすることも可能であり、また、沈殿物の処理が極めて簡便になり、電磁フィルターやろ過機等の設備も不要とできる可能性があり、従来の処理方法を根底から覆し、極めて大きな経済的な効果をもたらすことが期待できる。本発明の処理方法は、粗大なSSと微細なSSとが併存している状態のいずれの廃水に対しても適用することが可能であるが、処理する廃水の量が極めて多い、製鐵所において発生する懸濁物質を含む廃水に適用した場合に、特に多大な効果が期待できる。   Examples of utilization of the present invention include direct cooling wastewater for steel in the continuous casting process of the steelworks, direct cooling wastewater for steel in the rolling process of the steelworks, dust collection wastewater in the blast furnace, converter, and electric furnace processes of the steelworks Coarse SS and fine SS, such as rainwater wastewater generated from the outdoor raw material storage yard of the steelworks and cooling wastewater generated when granulated slag is obtained from the blast furnace pit of the steelworks From a large amount of wastewater, it is possible to remove coarse SS and fine SS by coagulation sedimentation very quickly by the same treatment by an extremely simple method such as devising the position where the organic flocculant is added. . By configuring as described above, facilities such as a sedimentation basin for processing fine SS, which has been required in the conventional processing, and the operation and maintenance associated therewith are unnecessary, and extremely economical processing is possible. Therefore, its use is expected. In addition, the supernatant water in the case where coarse SS and fine SS are coagulated and settled by the same treatment is less visually suspended than the treated water obtained by the conventional method. It is clear that there is no turbidity, and there is virtually no problem of adverse effects due to mixed chlorine ions, etc., which has been a concern in conventional methods using inorganic flocculants. From this point, it is extremely economical. Furthermore, the sediment (scale sludge) formed by agglomeration / aggregation of organic flocculant, coarse suspended solids and fine suspended solids is easy to handle, can be dredged with crumb heavy machinery, and solidified firmly. Therefore, the influence of the supernatant liquid on the water quality during the operation is small, and the treatment of the precipitate can be greatly simplified. In this respect, an extremely economical treatment is possible. As described above, the treatment method of the present invention is extremely simple, such as changing the point at which the organic flocculant is added, but the coarse SS and the fine SS are separately treated as compared with the conventional method. This makes it possible to reduce the type and amount of the flocculant to be used, and it is also possible to eliminate the need for a vast sedimentation tank required for the coagulation and precipitation of fine suspended substances. In addition, the treatment of the precipitate becomes very simple, and there is a possibility that facilities such as an electromagnetic filter and a filter may be unnecessary, and it can be expected that the conventional treatment method will be completely covered and a very large economic effect will be brought about. . The treatment method of the present invention can be applied to any wastewater in which coarse SS and fine SS coexist, but the amount of wastewater to be treated is extremely large. When applied to wastewater containing suspended solids generated in the process, a particularly great effect can be expected.

1:スケールスルース(開放樋)
2:有機凝集剤
2’:無機凝集剤
3:スケールピット
4:冷却塔
5:電磁フィルター
6:スプレー戻水(処理水A)
7:スプレー直送水(処理水B)
8:沈殿池
9:ろ過機
1: Scale sluice (open)
2: Organic flocculant 2 ': Inorganic flocculant 3: Scale pit 4: Cooling tower 5: Electromagnetic filter 6: Spray return water (treated water A)
7: Direct spray water (treated water B)
8: Sedimentation basin 9: Filter

Claims (10)

凝集剤を用い、廃水中から懸濁物質を凝集沈降させて取り除くための廃水中の懸濁物質の除去処理方法であって、
上記凝集剤として少なくとも1種の有機凝集剤を用い、
少なくとも、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に、前記有機凝集剤が共存する状態を生じさせることで、前記粗大な懸濁物質と前記微細な懸濁物質とを同一の処理で凝集沈降させ、これらを同時に除去できるようにしたことを特徴とする廃水中の懸濁物質の除去処理方法。
A method for removing suspended solids from wastewater by using a flocculant to remove suspended solids from the wastewater by coagulation and sedimentation,
Using at least one organic flocculant as the flocculant,
At least a coarse suspended substance and a fine suspended substance coexist, and a flow rate of 0.5 m / second or more causes a state in which the organic flocculant coexists in turbulent water. In this way, the coarse suspended substance and the fine suspended substance are coagulated and settled by the same treatment, and these can be removed at the same time.
前記有機凝集剤を、粗大な懸濁物質と微細な懸濁物質とが併存している、流速が0.5m/秒以上で、且つ、乱流状態の廃水中に添加することで、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に前記有機凝集剤が共存する状態を生じさせている請求項1に記載の廃水中の懸濁物質の除去処理方法。   By adding the organic flocculant to waste water in a turbulent flow state where a coarse suspended substance and a fine suspended substance coexist, the flow rate is 0.5 m / second or more, The suspension material and the fine suspension material coexist, and the flow rate is 0.5 m / second or more, and the organic coagulant coexists in the turbulent water. A method for removing suspended substances in wastewater as described in 1. 前記廃水が、製鐵所において発生する廃水であり、
前記有機凝集剤を廃水に添加する位置が、粗大な懸濁物質と微細な懸濁物質とが併存している廃水が発生する地点から水処理設備の入口付近に至るまでのいずれかの地点である請求項2に記載の廃水中の懸濁物質の除去処理方法。
The waste water is waste water generated in a steelworks,
The position where the organic flocculant is added to the wastewater is at any point from the point where the wastewater where coarse suspended substances and fine suspended substances coexist to the vicinity of the entrance of the water treatment facility. The method for removing suspended substances in wastewater according to claim 2.
前記粗大な懸濁物質と微細な懸濁物質とが併存した廃水になる前の用水に予め前記有機凝集剤を添加しておき、さらにこの水を使用することで、粗大な懸濁物質と微細な懸濁物質とが併存し、且つ、流速が0.5m/秒以上で、乱流状態の水の中に前記有機凝集剤が共存する状態を生じさせている請求項1に記載の廃水中の懸濁物質の除去処理方法。   The organic flocculant is added in advance to the water before becoming the waste water in which the coarse suspended substance and the fine suspended substance coexist, and by using this water, the coarse suspended substance and the fine suspended substance are used. The waste water according to claim 1, wherein the organic flocculant coexists in the turbulent water at a flow rate of 0.5 m / second or more. Method for removing suspended solids. 前記廃水が、製鐵所において発生する廃水であり、
前記粗大な懸濁物質と微細な懸濁物質とが併存した廃水になる前の用水が、前記粗大な懸濁物質と前記微細な懸濁物質とを、前記有機凝集剤の存在下、同一の処理で凝集沈降させて、これらを同時に除去処理した後に得られる処理水を循環使用する系で、前記有機凝集剤の添加を、その使用基準を満たすまでに用水の処理がなされた地点から、該用水を使用する給水地点に至るまでのいずれかの地点で行う請求項4に記載の廃水中の懸濁物質の除去処理方法。
The waste water is waste water generated in a steelworks,
In the presence of the organic flocculant, the irrigation water before the waste water in which the coarse suspended substance and the fine suspended substance coexist is the same in the presence of the organic flocculant. In a system that circulates and uses treated water obtained after coagulating and sedimenting by treatment and removing these simultaneously, the addition of the organic flocculant is performed from the point where the water is treated until the use standard is satisfied. The method for removing suspended substances in wastewater according to claim 4, wherein the method is performed at any point up to a water supply point where water is used.
前記粗大な懸濁物質が、粒径が50μm以上のものであり、前記微細な懸濁物質が、粒径が50μmに満たないものであり、且つ、これらの物質の併存状態が、微細な懸濁物質濃度に対する粗大な懸濁物質濃度の比(粗/微)が、その質量比で0.5以上である請求項1〜5のいずれか1項に記載の廃水中の懸濁物質の除去処理方法。   The coarse suspended substance has a particle diameter of 50 μm or more, the fine suspended substance has a particle diameter of less than 50 μm, and the coexistence state of these substances is a fine suspension. The removal of suspended matter in wastewater according to any one of claims 1 to 5, wherein the ratio of coarse suspended substance concentration to turbid substance concentration (rough / fine) is 0.5 or more in terms of mass ratio. Processing method. 前記乱流状態の水のレイノズル数が、8000以上である請求項1〜6のいずれか1項に記載の廃水中の懸濁物質の除去処理方法。   The number of lay nozzles of the water in the turbulent flow state is 8000 or more. The method for removing suspended substances in wastewater according to any one of claims 1 to 6. 前記有機凝集剤が、カチオン性又は両性の共重合体を主成分としてなり、該共重合体の重量平均分子量が100万〜1,300万であり、且つ、pH7におけるカチオンコロイド当量値が0.1meq/g以上である請求項1〜7のいずれか1項に記載の廃水中の懸濁物質の除去処理方法。   The organic flocculant contains a cationic or amphoteric copolymer as a main component, the copolymer has a weight average molecular weight of 1,000,000 to 13 million, and a cation colloid equivalent value at pH 7 is 0.00. It is 1 meq / g or more, The removal processing method of the suspended solids in wastewater of any one of Claims 1-7. 前記粗大な懸濁物質と前記微細な懸濁物質が、金属粉、水砕スラグ、石炭粉又はコークス粉の少なくともいずれかであり、場合によっては更にこれらいずれかの物質と油分とが併存している請求項1〜8のいずれかに1項記載の廃水中の懸濁物質の除去処理方法。   The coarse suspended substance and the fine suspended substance are at least one of metal powder, granulated slag, coal powder, and coke powder, and in some cases, any of these substances and oil components may coexist. The method for removing suspended substances in wastewater according to any one of claims 1 to 8. 前記粗大な懸濁物質と前記微細な懸濁物質とを同一の処理で凝集沈降させた後に、さらに凝集沈降した沈殿物を除去する請求項1〜9のいずれか1項に記載の廃水中の懸濁物質の除去処理方法。   The waste water according to any one of claims 1 to 9, wherein the coarse suspended substance and the fine suspended substance are coagulated and settled by the same treatment, and then the coagulated sediment is further removed. A method for removing suspended solids.
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