JP6837403B2 - Water treatment method for wastewater containing oil and water treatment equipment for wastewater containing oil - Google Patents
Water treatment method for wastewater containing oil and water treatment equipment for wastewater containing oil Download PDFInfo
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- JP6837403B2 JP6837403B2 JP2017163453A JP2017163453A JP6837403B2 JP 6837403 B2 JP6837403 B2 JP 6837403B2 JP 2017163453 A JP2017163453 A JP 2017163453A JP 2017163453 A JP2017163453 A JP 2017163453A JP 6837403 B2 JP6837403 B2 JP 6837403B2
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Description
本発明は、油分を含む排水の処理方法と、油分を含む排水の処理装置に関する。 The present invention relates to a method for treating wastewater containing oil and a device for treating wastewater containing oil.
油分を含む排水は、業種を問わず、工場や事業所などで大量に発生する。そのため、より効率的な油分を含む排水の処理方法の確立が望まれている。 Wastewater containing oil is generated in large quantities in factories and business establishments regardless of the type of industry. Therefore, it is desired to establish a more efficient method for treating wastewater containing oil.
一般的に、油分を含む排水の処理方法として、凝集加圧浮上処理が知られている。凝集加圧浮上処理では、まず、無機凝集剤とアニオン性有機高分子凝集剤により、油分を凝集させ、フロックを形成させる。次に、加圧浮上槽内で、空気を溶解させた加圧水を注入することにより、加圧浮上槽表面にフロックを浮上させる。加圧浮上槽表面に浮上したフロスは掻き寄せ機で系外に排出される。しかしながら、凝集加圧浮上処理には、下記のような課題がある。 Generally, a coagulation pressure flotation treatment is known as a method for treating wastewater containing oil. In the coagulation pressure flotation treatment, first, the oil content is coagulated by the inorganic coagulant and the anionic organic polymer coagulant to form flocs. Next, the flocs are levitated on the surface of the pressurized flotation tank by injecting pressurized water in which air is dissolved in the pressurized flotation tank. The floss that has floated on the surface of the pressurized flotation tank is discharged to the outside of the system by a scraper. However, the coagulation pressure flotation treatment has the following problems.
（１）無機凝集剤とアニオン性有機高分子凝集剤の２種類を使用するため、各薬品のタンク、溶解槽、供給ポンプなどの設備が増える。また、各薬品の注入率を適正に制御する手間が増える。 (1) Since two types of coagulant, an inorganic coagulant and an anionic organic polymer coagulant, are used, equipment such as a tank, a dissolution tank, and a supply pump for each chemical is increased. In addition, the time and effort required to properly control the injection rate of each chemical is increased.
（２）無機凝集剤には、凝集効果を発揮できるｐＨ範囲があり、酸やアルカリを使用して、ｐＨを調整する必要がある。また、無機凝集剤は酸性であるため、注入した量に応じて、アルカリが必要となる。 (2) The inorganic flocculant has a pH range capable of exerting a flocculation effect, and it is necessary to adjust the pH by using an acid or an alkali. Moreover, since the inorganic flocculant is acidic, alkali is required depending on the amount injected.
（３）無機凝集剤中の金属に由来した汚泥が発生するため、その分汚泥量が増える。 (3) Since sludge derived from the metal in the inorganic flocculant is generated, the amount of sludge increases accordingly.
（４）汚泥の含水率は９４〜９７％と高いので、発生する汚泥容積が大きくなる。このため、別途、脱水処理設備が必要であり、汚泥を別の凝集剤を使って、再度凝集させて脱水処理を行う必要がある。 (4) Since the water content of sludge is as high as 94 to 97%, the volume of sludge generated increases. Therefore, a separate dewatering treatment facility is required, and it is necessary to re-coagulate the sludge using another coagulant to perform the dewatering treatment.
上記のような凝集加圧浮上の課題に対して、無機凝集剤とアニオン性有機高分子凝集剤の代わりに、カチオン性の有機高分子凝集剤を使用する凝集加圧浮上処理が公知になっている。 In response to the above-mentioned problems of coagulation and pressure levitation, coagulation and pressure levitation treatment using a cationic organic polymer flocculant instead of the inorganic coagulant and the anionic organic polymer flocculant has become known. There is.
特許文献１にはカチオン系高分子凝集剤を用いた含油排水の処理方法が開示されており、油分を含む汚れ成分が界面活性剤にて微細に分散せしめられた含油排水を、ｐＨ値が８より大きく、１２より小さな値となり、且つ温度が５０℃以下となるように調整した状態で、かかる排水中に、ジメチルアミノエチルアクリレート系ポリマ若しくはジメチルアミノエチルメタクリレート系ポリマからなり、且つイオン性を示す官能基を有するユニットが全ユニットの６０モル％以上である高カチオン系高分子凝集剤を、１００〜１０００ｍｇ／Ｌの範囲の濃度となる量において添加して、該排水中に分散した汚れ成分を凝集させ、該汚れ成分の凝集体からなる汚泥を形成させることによって、該排水を、該汚れ成分と水分とに分離する。 Patent Document 1 discloses a method for treating oil-impregnated wastewater using a cationic polymer flocculant, and has a pH value of 8 for oil-containing wastewater in which dirt components including oil are finely dispersed with a surfactant. It is composed of a dimethylaminoethyl acrylate-based polymer or a dimethylaminoethyl methacrylate-based polymer and exhibits ionicity in such wastewater in a state where the value is larger, less than 12, and the temperature is adjusted to 50 ° C. or lower. A highly cationic polymer flocculant in which the number of units having functional groups is 60 mol% or more of the total units is added in an amount having a concentration in the range of 100 to 1000 mg / L to remove the dirt component dispersed in the waste water. The wastewater is separated into the dirt component and water by aggregating and forming a sludge composed of agglomerates of the dirt component.
上記のカチオン性有機高分子凝集剤を使用した凝集加圧浮上処理では、無機凝集剤とアニオン性有機高分子凝集剤の２種類の薬品する必要はなく、カチオン系高分子凝集剤のみを使った一回の操作により上記（１）〜（３）の課題は解決されるが（特許文献１の段落００１１）、依然として、上記（４）の課題は解決されない。また、カチオン性有機高分子凝集剤による油分の凝集処理では、さらに下記のような課題が生じることが分かった。 In the coagulation pressure levitation treatment using the above-mentioned cationic organic polymer flocculant, it is not necessary to use two kinds of chemicals, an inorganic coagulant and an anionic organic polymer flocculant, and only a cationic polymer flocculant is used. Although the above-mentioned problems (1) to (3) can be solved by one operation (paragraph 0011 of Patent Document 1), the above-mentioned problem (4) is still not solved. Further, it was found that the agglomeration treatment of oils with a cationic organic polymer flocculant causes the following problems.
（５）カチオン性有機高分子凝集剤で油分を含む排水を凝集させると、油分やカチオン性有機高分子凝集剤の粘着性・粘性に起因してフロックの粘着性が増加し、凝集槽、凝集槽の撹拌機、加圧浮上槽、配管などの処理装置にフロックが付着するトラブルが起こる。さらには、このような付着トラブルによって凝集不良や分離不良が起こる。 (5) When wastewater containing oil is agglomerated with a cationic organic polymer flocculant, the stickiness of flocs increases due to the adhesiveness and viscosity of the oil and the cationic organic polymer flocculant, and the flocculation tank and agglomeration Problems such as flocs adhering to processing devices such as tank stirrers, pressurized flotation tanks, and piping occur. Furthermore, such adhesion troubles cause poor aggregation and poor separation.
（６）排水中からの油分の除去率は不十分な場合がある。 (6) The removal rate of oil from wastewater may be insufficient.
本発明の目的は、特に、上記（４）〜（６）の課題を同時に解決できる水処理方法及び水処理装置を提供することである。より詳しくは、本発明の目的は、上記（４）の課題に対して、汚泥の含水率を低減し、発生する汚泥量を削減することができる水処理方法及び水処理装置を提供することである。 An object of the present invention is, in particular, to provide a water treatment method and a water treatment apparatus capable of simultaneously solving the above problems (4) to (6). More specifically, an object of the present invention is to provide a water treatment method and a water treatment apparatus capable of reducing the water content of sludge and reducing the amount of sludge generated in response to the above problem (4). is there.
また、本発明の目的は、汚泥の含水率を低減し、発生する汚泥量を削減することにより、後段の脱水処理を不要とし、脱水処理で使用される凝集剤を不要とする水処理方法を提供することである。 Another object of the present invention is to provide a water treatment method that eliminates the need for the dewatering treatment in the subsequent stage and does not require the coagulant used in the dewatering treatment by reducing the water content of the sludge and reducing the amount of sludge generated. To provide.
また、本発明の目的は、上記（５）の課題に対し、カチオン性有機高分子凝集剤、油分を含む被処理水、凝集条件を適切に選択し、フロック粘着性のトラブルを回避する水処理方法を提供することである。更に、上記（６）の課題に対して、油分の除去率が高い水処理方法を提供することも目的とする。 Further, an object of the present invention is to solve the problem of (5) above by appropriately selecting a cationic organic polymer flocculant, water to be treated containing oil, and coagulation conditions to avoid problems with flock adhesiveness. To provide a method. Further, it is also an object of the present invention to provide a water treatment method having a high oil removal rate for the above-mentioned problem (6).
上記課題を解決するために、本発明は以下の構成とすることができる。 In order to solve the above problems, the present invention can have the following configuration.
（Ｉ）本発明の水処理方法は、油分を含む被処理水に、カチオン性有機高分子凝集剤を加えて混合し、フロックを含む被処理水を形成するフロック形成工程と、前記フロックを含む被処理水を、当該フロックと分離液とに固液分離する固液分離工程とを有し、カチオン性有機高分子凝集剤を加える前の被処理水に、天然高分子系油除去剤と合成高分子系油除去剤のいずれか一方又は両方からなる油除去剤を添加することを特徴とする。 (I) The water treatment method of the present invention includes a floc forming step of adding a cationic organic polymer flocculant to the water to be treated containing oil and mixing the water to form the water to be treated containing flocs, and the flocs. It has a solid-liquid separation step of solid-liquid separation of the water to be treated into the floc and the separation liquid, and is synthesized with a natural polymer oil remover in the water to be treated before adding the cationic organic polymer flocculant. It is characterized by adding an oil removing agent composed of either one or both of the high molecular weight oil removing agents.
（ＩＩ）好ましいカチオン性有機高分子凝集剤は、全原料モノマーに占めるカチオン性モノマーの割合が５０モル％以上であり、カチオン性有機高分子凝集剤を純水に２ｇ/Ｌの割合で溶解した溶液を、温度２５℃、６０分−１の回転速度で測定した粘度が２００ｍＰａ・ｓ以上である。 (II) The preferable cationic organic polymer flocculant has a ratio of the cationic monomer to the total raw material monomer of 50 mol% or more, and the cationic organic polymer flocculant is dissolved in pure water at a ratio of 2 g / L. The viscosity of the solution measured at a temperature of 25 ° C. and a rotation speed of 60 minutes-1 is 200 mPa · s or more.
（ＩＩＩ）好ましい天然高分子系油除去剤はセルロース系物質である。 (III) A preferable natural polymer oil remover is a cellulosic substance.
（ＩＶ）短繊維状セルロース系物質と粉末状セルロース系物質のいずれか一方又は両方を用いることができる。 (IV) Either one or both of the short fibrous cellulosic substance and the powdered cellulosic substance can be used.
（Ｖ）固液分離工程としては、１ｋＰａ〜２００ｋＰａの圧力で加圧しながら固液分離する機械的固液分離工程が好ましい。 As the solid-liquid separation step (V), a mechanical solid-liquid separation step of solid-liquid separation while pressurizing at a pressure of 1 kPa to 200 kPa is preferable.
（ＶＩ）フロック形成工程では、撹拌機の回転速度を２０分−１〜３００分−１に設定した凝集槽で、前記被処理水と前記カチオン性有機高分子凝集剤とを混合することができる。 In the (VI) floc forming step, the water to be treated and the cationic organic polymer flocculant can be mixed in a coagulation tank in which the rotation speed of the stirrer is set to 20 minutes-1 to 300 minutes- 1. ..
（ＶＩＩ）前記凝集槽での被処理水の滞留時間は５分以上が好ましい。 (VII) The residence time of the water to be treated in the coagulation tank is preferably 5 minutes or more.
（ＶＩＩＩ）本発明は、更に水処理装置に関するものであって、その水処理装置は、油分を含む被処理水に、天然高分子系油除去剤と合成高分子系油除去剤のいずれか一方又は両方から選択される油除去剤が供給される貯槽と、前記貯槽から供給される被処理水に、カチオン性有機高分子凝集剤を添加し、撹拌する凝集槽と、前記凝集槽から供給される被処理水を、汚泥と分離液とに固液分離する固液分離装置とを備えることを特徴とする。 (VIII) The present invention further relates to a water treatment apparatus, wherein the water treatment apparatus comprises either a natural polymer oil remover or a synthetic polymer oil remover in water to be treated containing oil. A coagulation tank to which an oil removing agent selected from both of them is supplied, a coagulation tank to which a cationic organic polymer flocculant is added and stirred to the water to be treated supplied from the storage tank, and a coagulation tank to be supplied from the coagulation tank. It is characterized by comprising a solid-liquid separation device that solid-liquid separates the water to be treated into sludge and a separation liquid.
（ＩＸ）水処理装置には、更に、油除去剤を供給する第１の供給手段と、カチオン性有機高分子凝集剤を供給する第２の供給手段と、カチオン性有機高分子凝集剤を供給する前に、被処理水に油除去剤を供給させる制御手段とを設置することができる。 The (IX) water treatment apparatus is further supplied with a first supply means for supplying the oil removing agent, a second supply means for supplying the cationic organic polymer flocculant, and a cationic organic polymer flocculant. Before this, a control means for supplying the oil removing agent to the water to be treated can be installed.
（Ｘ）水処理装置には、貯槽と凝集槽との間に混和槽を設置することも可能であり、油除去剤を供給すべきタイミングで、第１の供給手段が油除去剤を貯槽と混和槽の一方又は両方に供給するよう制御手段を設定することができる。 (X) In the water treatment device, it is also possible to install an admixture tank between the storage tank and the coagulation tank, and when the oil remover should be supplied, the first supply means uses the oil remover as the storage tank. The control means can be set to supply one or both of the mixing tanks.
本発明によれば、油分を含む被処理水の水処理において、汚泥の含水率を低減し、発生する汚泥量を削減することができる。また、後段の脱水処理と、その脱水処理で使用される凝集剤を不要にすることができる。更に、フロックの粘着性によるトラブルも回避できる。 According to the present invention, in the water treatment of water to be treated containing oil, the water content of sludge can be reduced and the amount of sludge generated can be reduced. In addition, the subsequent dehydration treatment and the flocculant used in the dehydration treatment can be eliminated. Furthermore, troubles due to the stickiness of the flocs can be avoided.
図１は本発明を模式的に示すフローシートであり、本発明の水処理方法及び水処理装置は、油分を含む被処理水を処理対象とし、この被処理水に天然高分子系油除去剤と合成高分子系油除去剤のいずれか一方又は両方から選択される油除去剤を添加し、更にカチオン性有機高分子凝集剤を添加してフロックを形成した後、フロックが形成された被処理水を、汚泥（フロック）と分離液とに固液分離する。以下、本発明を更に具体的に説明するが、本発明は特定の具体例に限定されるものではない。 FIG. 1 is a flow sheet schematically showing the present invention, and the water treatment method and the water treatment apparatus of the present invention target water to be treated containing oil, and a natural polymer oil remover is added to the water to be treated. An oil remover selected from one or both of the synthetic polymer oil remover and the synthetic polymer oil remover is added, and a cationic organic polymer flocculant is further added to form flocs, and then the flocs are formed. Water is solid-liquid separated into sludge (flock) and separation liquid. Hereinafter, the present invention will be described in more detail, but the present invention is not limited to a specific specific example.
［処理対象］
処理の対象となる被処理水は油分を含む排水であれば特に限定されない。例えば、食品加工工場、食品製造工場、機械工場、自動車工場など各種工場で発生する排水を挙げることができる。また、ショッピングセンタ、レストラン、スーパーマーケット、ホテル、病院などの各種施設で発生する排水（例：厨房排水）を挙げることができる。また、被処理水は、油分以外の有機物や無機物を含んでもよい。
[Processing object]
The water to be treated is not particularly limited as long as it is wastewater containing oil. For example, wastewater generated in various factories such as food processing factories, food manufacturing factories, machine factories, and automobile factories can be mentioned. In addition, wastewater generated in various facilities such as shopping centers, restaurants, supermarkets, hotels, and hospitals (eg, kitchen wastewater) can be mentioned. Further, the water to be treated may contain organic substances and inorganic substances other than oil.
油分とは常温で液体の油のみならず、常温で固体の脂肪、即ち、油脂類全般を示す。例えば、油分としては、植物油、動物油、鉱物油などの１種以上を挙げることができる。一般的に、排水中の油分の濃度は、ヘキサン抽出物質（ＪＩＳ Ｋ０１０２）として測定される。 The oil content refers not only to oils that are liquid at room temperature, but also to fats that are solid at room temperature, that is, fats and oils in general. For example, as the oil content, one or more kinds such as vegetable oil, animal oil, and mineral oil can be mentioned. Generally, the concentration of oil in wastewater is measured as a hexane extractant (JIS K0102).
植物油としては、サフラワー油、大豆油、菜種油、パーム油、パーム核油、綿実油、ヤシ油、米糠油、ゴマ油、ヒマシ油、亜麻仁油、オリーブ油、桐油、椿油、落花生油、カポック油、カカオ油、木蝋、ヒマワリ油、コーン油などが挙げられる。動物油としてはイワシ油、ニシン油、イカ油、サンマ油などの魚油、肝油、鯨油、牛脂、牛酪脂、馬油、豚脂、羊脂などが挙げられる。これらの植物油、動物油は単独またはそれらの組み合わせのいずれでも良い。 Vegetable oils include saflower oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, cottonseed oil, palm oil, rice bran oil, sesame oil, castor oil, flaxseed oil, olive oil, tung oil, camellia oil, peanut oil, capoc oil, and coconut oil. , Wood wax, sunflower oil, coconut oil and the like. Examples of animal oils include fish oils such as sardine oil, herring oil, squid oil, and saury oil, cod liver oil, whale oil, beef tallow, beef tallow, horse oil, lard, and sheep fat. These vegetable oils and animal oils may be used alone or in combination thereof.
一方、鉱物油としては、各種潤滑油、スピンドル油、冷凍機油、ダイナモ油、タービン油、マシン油、船用内燃機関潤滑油、ガソリンエンジン潤滑油、ディーゼルエンジン潤滑油、シリンダー油、マリンエンジン油、ギヤー油、切削油、絶縁油、自動変速機油、圧縮機油、油圧作動油、圧延油等が挙げられる。 On the other hand, as mineral oils, various lubricating oils, spindle oils, refrigerating machine oils, dynamo oils, turbine oils, machine oils, internal combustion engine lubricating oils for ships, gasoline engine lubricating oils, diesel engine lubricating oils, cylinder oils, marine engine oils, gears Examples thereof include oil, cutting oil, insulating oil, automatic transmission oil, compressor oil, hydraulic hydraulic oil, rolling oil and the like.
その他に、原油、重油、軽油、揮発油、各種廃油等を挙げることができる。従って、本発明の処理対象は、上記のような各種工場や各種施設からの排水に限定されず、海面、河川或いは湖水等に流出した油類、水産加工場、畜産加工場、金属圧延工場、金属の加工工場等から排出される含油排水やその他排水も処理対象とすることができる。 In addition, crude oil, heavy oil, light oil, volatile oil, various waste oils and the like can be mentioned. Therefore, the treatment target of the present invention is not limited to the wastewater from various factories and facilities as described above, but oils that have flowed out to the sea surface, rivers, lake water, etc., fishery processing plants, livestock processing plants, metal rolling plants, etc. Oil-impregnated wastewater and other wastewater discharged from metal processing factories can also be treated.
上記被処理水に添加する油除去剤としては、天然物高分子系油除去剤、合成高分子系油除去剤のうち、１種以上を選択して使用する。以下、具体的に説明する。 As the oil remover to be added to the water to be treated, one or more of a natural polymer oil remover and a synthetic polymer oil remover are selected and used. Hereinafter, a specific description will be given.
［天然高分子系油除去剤（親水性物質）］
天然高分子系油除去剤は、天然物又は天然物由来の親水性物質であれば特に限定されず、天然物からの抽出物、天然物の精製品、天然物の加工品（化学修飾、変性）、天然物の再生品なども含まれる。なお、親水性物質とは、化学構造中に水酸基やアミド基などの親水基（親水性部分）を有し、水分散性を有するものであれば特に限定されず、２種以上の親水性物質を混合したものもよい。
[Natural polymer oil remover (hydrophilic substance)]
The natural polymer oil remover is not particularly limited as long as it is a natural product or a hydrophilic substance derived from the natural product, and is an extract from the natural product, a refined product of the natural product, or a processed product of the natural product (chemical modification, modification). ), Recycled natural products are also included. The hydrophilic substance is not particularly limited as long as it has a hydrophilic group (hydrophilic portion) such as a hydroxyl group or an amide group in its chemical structure and has water dispersibility, and is two or more kinds of hydrophilic substances. May be mixed.
しかし、親水性物質が水溶性の場合、油の取り込み能力が劣る上、フロックの回収も困難になるので、常温で水に溶解する水溶性物質を用いる場合、その含有量は油除去剤全体の５０質量％未満が好ましい。最も好ましい親水性物質は、水分散性に優れてはいるが、常温の水には溶解しない物質であって、特に好ましくは、化学構造中に親水性部分と疎水性部分の両方を有するものである。具体的には、親水性物質はセルロース系物質とタンパク質系物質とから選択される。 However, when the hydrophilic substance is water-soluble, the ability to take in oil is inferior and it is difficult to recover flocs. Therefore, when a water-soluble substance that dissolves in water at room temperature is used, the content of the water-soluble substance is the total content of the oil remover. It is preferably less than 50% by mass. The most preferable hydrophilic substance is a substance having excellent water dispersibility but not soluble in water at room temperature, and particularly preferably a substance having both a hydrophilic part and a hydrophobic part in the chemical structure. is there. Specifically, the hydrophilic substance is selected from a cellulosic substance and a protein-based substance.
従来から油の吸着剤として親油性の合成繊維や合成樹脂粉末が使用されていることは公知であるが、これらを連続した水処理系に使用した場合、表面に親水性が無いため水中の油分を完全に吸着しないことがあり、水面に浮上して堆積し除去に手間がかかるなども問題があった。本発明者らの検討によればセルロース系物質のように親水性部分を有する物質は、水中への分散性が優れているにもかかわらず油分の除去効果が高く、また、フロック中に均一に分散するので、フロック脱水性も優れていることが判明した。 It is known that lipophilic synthetic fibers and synthetic resin powders have been used as oil adsorbents in the past, but when these are used in a continuous water treatment system, the oil content in water is not hydrophilic because the surface is not hydrophilic. May not be completely adsorbed, and there is also a problem that it floats on the surface of the water and accumulates, which takes time and effort to remove. According to the study by the present inventors, a substance having a hydrophilic portion such as a cellulosic substance has a high oil-removing effect despite its excellent dispersibility in water, and is uniformly distributed during flocs. Since it disperses, it was found that the floc dehydration property is also excellent.
天然高分子系油除去剤は短繊維状、粉体のいずれの形状のものでも使用可能である。ここで、短繊維状とは、細長の糸状に形成された状態を示し、水とフロック中への分散性を考慮すると、その長さは０．０１ｍｍ〜５０ｍｍ程が好ましく、より好ましくは０．１ｍｍ〜２０ｍｍ、最も好ましくは５ｍｍ〜１０ｍｍ程度である。 The natural polymer oil remover can be used in either a short fibrous form or a powder form. Here, the short fibrous form means a state formed in the form of an elongated thread, and the length thereof is preferably about 0.01 mm to 50 mm, more preferably 0., in consideration of dispersibility in water and flocs. It is about 1 mm to 20 mm, most preferably about 5 mm to 10 mm.
天然高分子系油除去剤として最も好ましい物質はセルロース系物質であり、油除去剤としては、セルロース系物質を５０質量％以上含むものを用いることが好ましく、最も好ましくは実質的にセルロース系物質からなる油除去剤を用いる。 The most preferable substance as a natural polymer oil remover is a cellulosic substance, and the oil remover preferably contains 50% by mass or more of a cellulosic substance, and most preferably substantially from a cellulosic substance. Use an oil remover.
ここで、セルロースとは、一般にβ-グルカン骨格を有し、ＯＨ基等の親水基を有する天然高分子を意味するが、本発明に用いるセルロース系物質は親水性を保持していれば、上記セルロースの加工品（化学修飾、変性、再生品）をも含む広い概念である。具体的にはレーヨン繊維、アセテート繊維、木綿、麻等が挙げられる。これらのうち被処理水への分散性の点からレーヨン繊維が好ましい。ただし、セルロースエーテルのような水溶性セルロースは、油除去剤全体の５０質量％未満に含有量を抑えることが好ましく、より好ましい含有量は１０質量％未満であり、最も好ましくは水溶性セルロースを実質的に使用しない。 Here, cellulose generally means a natural polymer having a β-glucan skeleton and having a hydrophilic group such as an OH group, but the cellulosic substance used in the present invention is described above as long as it retains hydrophilicity. It is a broad concept that also includes processed cellulose products (chemically modified, modified, recycled products). Specific examples thereof include rayon fiber, acetate fiber, cotton and hemp. Of these, rayon fiber is preferable from the viewpoint of dispersibility in water to be treated. However, the content of water-soluble cellulose such as cellulose ether is preferably suppressed to less than 50% by mass of the total oil remover, more preferably the content is less than 10% by mass, and most preferably the water-soluble cellulose is substantially contained. Do not use as a target.
また、天然高分子系油除去剤は、上記親水性物質を含むものであれば天然物をそのまま用いることもできる。具体的には、天然物の粉体としてピーナッツ殻、コーヒー豆殻、おが屑、かんな屑、木材チップ、バーク、おから、水苔、ピートモス、やし殻、もみ殻、米ぬか、小麦ふすまを挙げることができる。また、古紙の粉砕物も使用可能である。 Further, as the natural polymer oil remover, a natural product can be used as it is as long as it contains the above hydrophilic substance. Specifically, natural powders include peanut husks, coffee bean husks, sawdust, planer husks, wood chips, bark, okara, water moss, peat moss, coconut husks, rice husks, rice bran, and wheat bran. Can be done. Also, crushed waste paper can be used.
天然高分子系油除去剤としては、上記セルロース系物質以外にも、絹、羊毛等のタンパク質系物質も用いることができるし、タンパク系物質とセルロース系物質を混合して用いることもできる。更に、これらの天然高分子系油除去剤の炭化物も同様の効果が得られる。 As the natural polymer oil remover, in addition to the above-mentioned cellulosic substance, a protein-based substance such as silk or wool can be used, or a protein-based substance and a cellulosic substance can be mixed and used. Further, the carbides of these natural polymer oil removers also have the same effect.
［合成高分子系油除去剤（親油性物質）］
合成高分子系油除去剤は、石油などの化石原料から合成される親油性物質であれば特に限定されない。具体的には、化学構造中に炭化水素鎖（例：長鎖アルキル基、長鎖アリール基）のような親油性部分を有するものであれば特に限定されないが、水分散性の観点からは、疎水性部分と親水性部分の両方を有するものが好ましい。
[Synthetic polymer oil remover (lipophilic substance)]
The synthetic polymer oil remover is not particularly limited as long as it is a lipophilic substance synthesized from a fossil raw material such as petroleum. Specifically, it is not particularly limited as long as it has a lipophilic portion such as a hydrocarbon chain (eg, long-chain alkyl group, long-chain aryl group) in the chemical structure, but from the viewpoint of water dispersibility, it is not particularly limited. Those having both a hydrophobic portion and a hydrophilic portion are preferable.
例えば、ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、エチレン−プロピレンコポリマ、オレフィン−ノルボルネンコポリマ、ポリブテン等のポリオレフィン、ポリ塩化ビニル、ポリ酢酸ビニル等のビニル系重合体、ＰＥＴ、ＰＢＴ等の芳香族ポリエステル、ナイロン６、ナイロン６，６等のポリアミド、ポリ乳酸、ポリサクシニックブチレート等の脂肪族ポリエステル、ポリウレタン、ポリオール、ポリエステルポリオール、ポリカーボネート等から１種以上を選択して用いる。 For example, polyolefins such as polyethylene, isotactic polypropylene, syndiotactic polypropylene, ethylene-propylene copolyma, olefin-norbornencopolyma, polybutene, vinyl polymers such as polyvinyl chloride and polyvinyl acetate, and aromatics such as PET and PBT. One or more kinds are selected and used from polyester, polyamide such as nylon 6, nylon 6,6, aliphatic polyester such as polylactic acid and polysuccinic butyrate, polyurethane, polyol, polyester polyol, polycarbonate and the like.
合成高分子系油除去剤の形状としては、上記天然高分子系油除去剤と同様、短繊維状、粉体状いずれも使用可能である。粉体としては、高分子鎖の絡み合いまたは三次元的な架橋構造のネットワークの中に油分を分子レベルで抱き込む吸油性ポリマを０．１ｍｍから約５ｍｍに無定形に粉砕した粉末も使用可能である。このような吸油性ポリマとしては、例えばスチレン・ブタジエン系熱可塑性エラストマー、アクリレートコポリマ、ポリノルボルネン系エラストマー、多孔性ビニル系ポリマなどがある。 As the shape of the synthetic polymer oil remover, both short fibrous form and powder form can be used as in the case of the above natural polymer oil remover. As the powder, it is also possible to use a powder obtained by amorphously crushing an oil-absorbing polymer that embraces oil at the molecular level in a network of entangled polymer chains or a three-dimensional crosslinked structure from 0.1 mm to about 5 mm. is there. Examples of such oil-absorbing polymers include styrene-butadiene thermoplastic elastomers, acrylate copolymers, polynorbornene elastomers, and porous vinyl polymers.
更に、油除去剤としては、親水性の天然高分子系物質（天然繊維、古紙粉砕物等）の表面を疎水化処理したものを用いることもできる。 Further, as the oil remover, a hydrophilic natural polymer substance (natural fiber, crushed waste paper, etc.) whose surface is hydrophobized can also be used.
［カチオン性有機高分子凝集剤］
−種類
カチオン性有機高分子凝集剤としては、カチオン性モノマーの単独重合体又は共重合体、カチオン性モノマーとノニオン性モノマーとの共重合体、カチオン性モノマーとアニオン性モノマーとの共重合体などから１種以上を選択して用いることができる。本発明では、ポリ塩化アルミニウム、ポリ硫酸第二鉄などの無機凝集剤と明確に区別するため、有機高分子凝集剤と記載するが、一般的には単に高分子凝集剤と称される。
[Cationic organic polymer flocculant]
-Types Cationic organic polymer flocculants include homopolymers or copolymers of cationic monomers, copolymers of cationic monomers and nonionic monomers, copolymers of cationic monomers and anionic monomers, etc. One or more of them can be selected and used. In the present invention, in order to clearly distinguish it from inorganic flocculants such as polyaluminum chloride and ferric sulfate, it is described as an organic polymer flocculant, but it is generally simply referred to as a polymer flocculant.
カチオン性モノマーとしては、ジアルキルアミノアルキル（メタ）アクリレート又はこれらの中和塩、３級塩若しくは４級塩などから１種以上を選択して用いることができる。例えば、ジメチルアミノエチル（メタ）アクリレート又はこれらの中和塩、３級塩若しくは４級塩などが挙げられる。これらの中でもジメチルアミノエチル（メタ）アクリレートの４級塩が好ましく、より好ましくはアンモニウム塩である。 As the cationic monomer, one or more of dialkylaminoalkyl (meth) acrylates, neutralized salts thereof, tertiary salts, quaternary salts and the like can be selected and used. For example, dimethylaminoethyl (meth) acrylate, a neutralized salt thereof, a tertiary salt or a quaternary salt, and the like can be mentioned. Among these, a quaternary salt of dimethylaminoethyl (meth) acrylate is preferable, and an ammonium salt is more preferable.
ノニオン性モノマーとしては、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、（メタ）アクリロニトリル、酢酸ビニルなどから１種以上を選択して用いることができる。アニオン性モノマーとしては、（メタ）アクリル酸、（メタ）アクリル酸ナトリウム、イタコン酸、マレイン酸、フマル酸、２−（メタ）アクリルアミド−メチルプロパンスルホン酸、及びこれらの金属塩又はアンモニウム塩などから１種以上を選択して用いることができる。 As the nonionic monomer, one or more kinds can be selected and used from (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, vinyl acetate and the like. Anionic monomers include (meth) acrylic acid, sodium (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, 2- (meth) acrylamide-methylpropanesulfonic acid, and metal salts or ammonium salts thereof. One or more types can be selected and used.
なお、（メタ）アクリレートはアクリレートとメタクリレートの両方を含む概念であり、（メタ）アクリル酸はアクリル酸とメタクリル酸の両方を含む概念であり、更に、（メタ）アクリルアミドはアクリルアミドとメタクリルアミドの両方を含む概念である。 Note that (meth) acrylate is a concept containing both acrylate and methacrylate, (meth) acrylic acid is a concept containing both acrylic acid and methacrylic acid, and (meth) acrylamide is a concept containing both acrylamide and methacrylamide. Is a concept that includes.
また、カチオン性有機高分子凝集剤としては、非アミジン系高分子凝集剤に加え、アミジン単位を有するアミジン系高分子凝集剤を使用することが可能であり、アミジン系高分子凝集剤と非アミジン系高分子凝集剤を混合した高分子凝集剤も使用することができる。 Further, as the cationic organic polymer flocculant, in addition to the non-amidine polymer flocculant, an amidine polymer flocculant having an amidine unit can be used, and the amidine polymer flocculant and the non-amidine polymer flocculant can be used. A polymer flocculant mixed with a polymer flocculant can also be used.
カチオン性有機高分子凝集剤の態様は特に限定されず、例えば、粉末状、液状（ディスパージョン、エマルジョン）などが挙げられる。 The mode of the cationic organic polymer flocculant is not particularly limited, and examples thereof include powder and liquid (dispersion, emulsion).
−カチオン度
上述したように、原料モノマーの種類や凝集剤の態様は限定されるものではないが、本発明は、全モノマー単位（ユニット）中にカチオン性モノマーが５０ｍｏｌ％以上含有された凝集剤、すなわち、カチオン度が５０ｍｏｌ％以上のカチオン性有機高分子凝集剤を用いる。すなわち、本発明に用いられるカチオン性有機高分子凝集剤は、カチオン性モノマーを５０ｍｏｌ％以上含む原料モノマーを重合して製造され、より好ましいカチオン性モノマーの量は６０ｍｏｌ％以上であり、さらに好ましくは７０ｍｏｌ％以上、特に８０ｍｏｌ％以上である。
-Cativity As described above, the type of raw material monomer and the mode of the flocculant are not limited, but in the present invention, the flocculant containing 50 mol% or more of the cationic monomer in all the monomer units (units). That is, a cationic organic polymer flocculant having a cationic degree of 50 mol% or more is used. That is, the cationic organic polymer flocculant used in the present invention is produced by polymerizing a raw material monomer containing 50 mol% or more of a cationic monomer, and a more preferable amount of the cationic monomer is 60 mol% or more, more preferably. It is 70 mol% or more, particularly 80 mol% or more.
更に、実質カチオン性モノマーからなる（１００ｍｏｌ％）カチオン性有機高分子凝集剤を使用することもできる。なお、カチオン度は、凝集剤の原料モノマーに含まれるカチオン性モノマーの割合（ｍｏｌ％）として定義することができる。 Further, a (100 mol%) cationic organic polymer flocculant composed of a substantially cationic monomer can also be used. The degree of cation can be defined as the ratio (mol%) of the cationic monomer contained in the raw material monomer of the flocculant.
一般的に、排水中に含まれる油分は、界面活性剤やアルカリ成分によって、排水中に細かく分散し、油分粒子の表面は負に帯電している。一般的な汚濁物質のゼータ電位に比べて、油分粒子のゼータ電位は著しく低く、通常のカチオン性有機高分子凝集剤を加えても、フロックは形成されないか、フロックが形成されても機械的な固液分離に耐えられる強いフロックは形成されない。 Generally, the oil contained in the wastewater is finely dispersed in the wastewater due to the surfactant and the alkaline component, and the surface of the oil particles is negatively charged. Compared to the zeta potential of general pollutants, the zeta potential of oil particles is significantly lower, and even if a normal cationic organic polymer flocculant is added, flocs are not formed, or even if flocs are formed, they are mechanical. Strong flocs that can withstand solid-liquid separation are not formed.
一方、カチオン度が５０モル％以上のカチオン性有機高分子凝集剤を加えて混合すると、大きく正に帯電した（正の電荷密度が高い）分子鎖が排水中に細かく分散した油分を捕捉し、機械的な固液分離に耐えられる強いフロックを形成することができる。 On the other hand, when a cationic organic polymer flocculant having a cationic content of 50 mol% or more is added and mixed, a large positively charged (high positive charge density) molecular chain captures oil finely dispersed in wastewater. It is possible to form strong flocs that can withstand mechanical solid-liquid separation.
−分子量
カチオン性有機高分子凝集剤の分子量は特に限定されないが、分子量が５００万以上であることが好ましく、より好ましくは６００万以上、特に７００万以上、その中でも８００万以上であることが好ましい。なお、この分子量は、固有粘度法で測定、算出された値であり、その測定、算出法の詳細は「ポリマー凝集剤 使用の手引き」の１１２〜１１６頁（東京都下水道サービス株式会社、平成１４年３月発行）に記載されている。
-Molecular weight The molecular weight of the cationic organic polymer flocculant is not particularly limited, but the molecular weight is preferably 5 million or more, more preferably 6 million or more, particularly 7 million or more, and 8 million or more among them. .. This molecular weight is a value measured and calculated by the intrinsic viscosity method, and the details of the measurement and calculation method are described on pages 112 to 116 of "Guide for Using Polymer Coagulant" (Tokyo Metropolitan Sewerage Service Co., Ltd., 2002). (Issued in March of the year).
上述したように、排水中の油分は排水中に細かく分散しているので、通常のカチオン性有機高分子凝集剤を加えても、フロック形成は形成され難いか、フロックが形成されても機械的な固液分離に耐えられる強いフロックは形成されない。一方、カチオン度が５０モル％以上であることに加え、分子量が５００万以上のカチオン性有機高分子凝集剤を用いると、長い分子鎖が排水中に細かく分散した油分を捕捉し、機械的な固液分離に耐えられるより強いフロックを形成することができる。 As mentioned above, since the oil in the wastewater is finely dispersed in the wastewater, it is difficult to form flocs even if ordinary cationic organic polymer flocculants are added, or even if flocs are formed, they are mechanical. Strong flocs that can withstand solid-liquid separation are not formed. On the other hand, when a cationic organic polymer flocculant having a molecular weight of 5 million or more is used in addition to having a cation degree of 50 mol% or more, a long molecular chain traps finely dispersed oil in wastewater and mechanically. It is possible to form stronger flocs that can withstand solid-liquid separation.
−粘度
分子量と同じ観点から、カチオン性有機高分子凝集剤の特性を溶液粘度で定義することもできる。具体的には、カチオン性有機高分子凝集剤を純水に１ｇ／Ｌで溶解したときの水溶液の粘度は、１００ｍＰａ・ｓ以上が好ましく、より好ましくは１２０ｍＰａ・ｓ以上、特に好ましくは１５０ｍＰａ・ｓ以上である。
-Viscosity The properties of the cationic organic polymer flocculant can also be defined by the solution viscosity from the same viewpoint as the molecular weight. Specifically, the viscosity of the aqueous solution when the cationic organic polymer flocculant is dissolved in pure water at 1 g / L is preferably 100 mPa · s or more, more preferably 120 mPa · s or more, and particularly preferably 150 mPa · s. That is all.
また、カチオン性有機高分子凝集剤を純水に２ｇ／Ｌで溶解した場合、その水溶液の粘度は、２００ｍＰａ・ｓ以上であることが好ましく、より好ましくは２２０ｍＰａ・ｓ以上、特に好ましくは２５０ｍＰａ・ｓ以上である。 When the cationic organic polymer flocculant is dissolved in pure water at 2 g / L, the viscosity of the aqueous solution is preferably 200 mPa · s or more, more preferably 220 mPa · s or more, and particularly preferably 250 mPa · s. s or more.
なお、上記粘度は、濃度が１ｇ/Ｌと２ｇ/Ｌのいずれの場合も、Ｂ形粘度計、ＪＩＳ Ｋ７１１７−１：１９９９の附属書１（参考）に記載されているスピンドルＳＢ２号を使用し、２５℃、６０ｍｉｎ−１の回転速度で測定した値である。スピンドルはロータとも呼ばれる。 For the above viscosity, the spindle SB2 described in Annex 1 (reference) of JIS K7117-1: 1999 is used for the B-type viscometer regardless of the concentration of 1 g / L or 2 g / L. , 25 ° C., 60 min -1 rotation speed. The spindle is also called a rotor.
−溶媒
カチオン性有機高分子凝集剤は、好ましくは溶媒に溶解又は分散させた凝集剤溶液として使用する。この溶媒は特に限定されないが、例えば、純水（蒸留水も含む）、水道水、工業用水、地下水、各種排水処理の処理水、海水などから１種以上を選択して用いることができる。カチオン性有機高分子凝集剤の凝集力を最大限発揮させる観点からは、純水、水道水を使用することが好ましい。一方、経済性の観点からは、工場用水、地下水、各種排水処理の処理水を使用することが好ましい。但し、以上は例示であり、これらに限定されるものではない。
-Solvent The cationic organic polymer flocculant is preferably used as a flocculant solution dissolved or dispersed in a solvent. The solvent is not particularly limited, but for example, one or more of pure water (including distilled water), tap water, industrial water, groundwater, treated water for various wastewater treatments, seawater, and the like can be selected and used. From the viewpoint of maximizing the cohesive force of the cationic organic polymer flocculant, it is preferable to use pure water or tap water. On the other hand, from the viewpoint of economy, it is preferable to use factory water, groundwater, and treated water for various wastewater treatments. However, the above is an example, and the present invention is not limited to these.
［その他の薬剤］
本発明は、上記の油除去剤とカチオン性有機高分子凝集剤以外の薬剤の使用を何ら制限するものではない。具体的には、カチオン性有機高分子凝集剤を添加する前に、公知の無機凝集剤や有機高分子凝結剤（カチオン性有機高分子凝集剤よりも低分子量の凝集剤）などの１種以上の薬剤を添加することもできる。
[Other drugs]
The present invention does not limit the use of agents other than the above-mentioned oil remover and cationic organic polymer flocculant. Specifically, before adding the cationic organic polymer flocculant, one or more of known inorganic flocculants and organic polymer coagulants (coagulants having a lower molecular weight than the cationic organic polymer flocculants). Drugs can also be added.
無機凝集剤としては硫酸バンド、ポリ塩化アルミニウム（ＰＡＣ）、塩化アルミニウム、ポリ硫酸第２鉄（ポリ鉄）、硫酸第２鉄、塩化第２鉄あるいはこれらの混合物が使用可能である。有機高分子凝結剤としては縮合系ポリアミン、ジシアンジアミド・ホルマリン縮合物、ポリエチレンイミン、ポリビニルイミダリン、ポリビニルピリジン、ジアリルアミン塩・二酸化硫黄共重合体、ポリジメチルジアリルアンモニウム塩、ポリジメチルジアリルアンモニウム塩・二酸化硫黄共重合体、ポリジメチルジアリルアンモニウム塩・アクリルアミド共重合体、ポリジメチルジアリルアンモニウム塩・ジアリルアミン塩酸塩誘導体共重合体、アリルアミン塩重合体などが挙げられる。 As the inorganic flocculant, a sulfate band, polyaluminum chloride (PAC), aluminum chloride, polyferric sulfate (polyiron), ferric sulfate, ferric chloride or a mixture thereof can be used. As an organic polymer coagulant, condensing polyamine, dicyandiamide / formalin condensate, polyethyleneimine, polyvinylimidazolin, polyvinylpyridine, diallylamine salt / sulfur dioxide copolymer, polydimethyldialylammonium salt, polydimethyldialylammonium salt / sulfur dioxide Examples thereof include a copolymer, a polydimethyldiallyl ammonium salt / acrylamide copolymer, a polydimethyldiallyl ammonium salt / diallylamine hydrochloride derivative copolymer, and an allylamine salt polymer.
縮合系ポリアミンの具体例としては、アルキレンジクロライドとアルキレンポリアミンとの縮合物、アニリンとホルマリンの縮合物、アルキレンジアミンとエピクロルヒドリンとの縮合物、アンモニアとエピクロルヒドリンとの縮合物などが挙げられる。エピクロルヒドリンと縮合するアルキレンジアミンとしては、ジメチルアミン、ジエチルアミン、メチルプロピルアミン、メチルブチルアミン、ジブチルアミンなどが挙げられる。 Specific examples of the condensation polyamine include a condensate of alkylene dichloride and alkylene polyamine, a condensate of aniline and formarin, a condensate of alkylenediamine and epichlorohydrin, and a condensate of ammonia and epichlorohydrin. Examples of the alkylene diamine that condenses with epichlorohydrin include dimethylamine, diethylamine, methylpropylamine, methylbutylamine, and dibutylamine.
しかしながら、本発明の水処理方法及び水処理装置では上記薬剤は必須ではなく、油除去剤とカチオン性有機高分子凝集剤のみの使用も可能である。 However, the above-mentioned chemicals are not essential in the water treatment method and the water treatment apparatus of the present invention, and it is possible to use only the oil remover and the cationic organic polymer flocculant.
次に、本発明の水処理装置を具体的に説明する。 Next, the water treatment apparatus of the present invention will be specifically described.
［水処理装置］
図２、３は第１例、第２例の水処理装置１ａ、１ｂを示している。これら水処理装置１ａ、１ｂは、油除去剤を被処理水に添加する前段の装置と、カチオン性有機高分子凝集剤を被処理水に添加する後段の装置とを備えていれば特に限定されない。
[Water treatment equipment]
2 and 3 show the water treatment devices 1a and 1b of the first example and the second example. These water treatment devices 1a and 1b are not particularly limited as long as they include a first-stage device for adding an oil removing agent to the water to be treated and a second-stage device for adding a cationic organic polymer flocculant to the water to be treated. ..
例えば、水処理装置１ａ、１ｂは、油除去剤を添加する貯槽１１と、カチオン性有機高分子凝集剤を添加する凝集槽２１とを有しており（図２、３）、必要に応じて貯槽１１と凝集槽２１の間には混和槽２５等の他の装置を設置してもよい（図３）。好ましくは、貯槽１１と凝集槽２１には撹拌機を設置する。 For example, the water treatment devices 1a and 1b have a storage tank 11 to which an oil removing agent is added and a coagulation tank 21 to which a cationic organic polymer flocculant is added (FIGS. 2 and 3), if necessary. Another device such as a mixing tank 25 may be installed between the storage tank 11 and the coagulation tank 21 (FIG. 3). Preferably, a stirrer is installed in the storage tank 11 and the coagulation tank 21.
油除去剤、カチオン性有機高分子凝集剤などの薬剤の供給手段として、一台以上の供給手段（第１、第２の供給手段１５、１７）を設置し、必要であれば任意の箇所に、被処理水や薬剤供給用の送液手段（ポンプ１３、１４）を設置する。更に、水処理装置１ａ、１ｂの内部又は外部に制御手段５を設置し、これら供給手段１５、１７、送液手段１３、１４、撹拌機を、制御手段５で制御することもできる。 One or more supply means (first and second supply means 15 and 17) are installed as means for supplying chemicals such as an oil remover and a cationic organic polymer flocculant, and if necessary, at any location. , Install liquid feeding means (pumps 13 and 14) for supplying water to be treated and chemicals. Further, the control means 5 can be installed inside or outside the water treatment devices 1a and 1b, and the supply means 15, 17, the liquid feeding means 13, 14, and the stirrer can be controlled by the control means 5.
この水処理装置１ａ、１ｂでは、被処理水は貯槽１１、任意の混和槽２５、凝集槽２１を記載した順番で通過し、薬剤が添加されるが、凝集槽２１の下流側には更に固液分離装置３１ａ、３１ｂが設置されており、凝集槽２１で形成されたフロックは、固液分離装置３１ａ、３１ｂで分離される。 In the water treatment devices 1a and 1b, the water to be treated passes through the storage tank 11, the arbitrary mixing tank 25, and the coagulation tank 21 in the order described, and the chemical is added, but the water is further solidified on the downstream side of the coagulation tank 21. Liquid separation devices 31a and 31b are installed, and the flocs formed in the coagulation tank 21 are separated by the solid-liquid separation devices 31a and 31b.
この固液分離装置３１ａ、３１ｂは特に限定されないが、重力式沈殿処理設備や加圧浮上装置よりも、加圧、遠心力、減圧（真空排気）又はこれらの組み合わせで機械的に固液分離する装置が好ましい。例えば、従来から汚泥濃縮に用いる濃縮機や汚泥処理などに使用する脱水機を固液分離装置３１ａ、３１ｂに用いることが可能である。濃縮機は特に限定されないが、例えば、スクリュー濃縮機、ベルト濃縮機、遠心濃縮機、楕円板型濃縮機などを単独又は組み合わせて使用することができる。脱水機は特に限定されないが、後述する固液分離後の更なる脱水に用いるものと同じ種類の装置を用いることができる。 The solid-liquid separation devices 31a and 31b are not particularly limited, but mechanically solid-liquid separation is performed by pressurization, centrifugal force, decompression (vacuum exhaust), or a combination thereof, rather than a gravity-type precipitation treatment facility or a pressurized flotation device. The device is preferred. For example, a concentrator conventionally used for sludge concentration and a dehydrator used for sludge treatment can be used for the solid-liquid separation devices 31a and 31b. The concentrator is not particularly limited, and for example, a screw concentrator, a belt concentrator, a centrifugal concentrator, an elliptical plate concentrator, and the like can be used alone or in combination. The dehydrator is not particularly limited, but the same type of apparatus used for further dehydration after solid-liquid separation described later can be used.
図４、５は第１例、第２例の固液分離装置３１ａ、３１ｂを示す部分断面図であり、同じ部材には同じ符号を付して説明を省略する。固液分離装置３１ａ、３１ｂは、フロック９を連続処理するフロック移動手段３５を有している。フロック移動手段３５は、例えば、回転ロールのようなベルト駆動手段３７と、ベルト駆動手段３７に架け渡されたベルト３６とを有しており、フロック９はフロック投入口３３を介してベルト上３６上に供給される。 4 and 5 are partial cross-sectional views showing the solid-liquid separation devices 31a and 31b of the first example and the second example, and the same members are designated by the same reference numerals and the description thereof will be omitted. The solid-liquid separation devices 31a and 31b have a flock moving means 35 that continuously processes the flock 9. The flock moving means 35 has, for example, a belt driving means 37 such as a rotary roll and a belt 36 bridged to the belt driving means 37, and the flock 9 is placed on the belt 36 via the flock input port 33. Supplied on.
ベルト３６の一部又は全部はろ布で構成されており、フロック９は移動の間に水分が固液分離され、分離液はベルト３６下方の捕捉手段３４に補足され、分離したフロック９（汚泥）は排出口３９から排出される。汚泥を排出後のベルト３６はフロック投入口３３側へ戻り、フロック９が再度供給されるが、フロック投入口３３側に戻る前に、洗浄管３８からの洗浄水を散布し、ベルト３６を洗浄してもよい。 A part or all of the belt 36 is made of a filter cloth, and the flock 9 is solid-liquid separated during movement, and the separated liquid is captured by the trapping means 34 below the belt 36 and separated flock 9 (sludge). Is discharged from the discharge port 39. After the sludge is discharged, the belt 36 returns to the flock inlet 33 side and the flock 9 is supplied again, but before returning to the flock inlet 33 side, the cleaning water from the cleaning pipe 38 is sprayed to wash the belt 36. You may.
このように、上記固液分離装置３１ａ、３１ｂはいずれも固液分離処理の連続処理に適しているが、より好ましくは第２例の固液分離装置３１ｂのように、加圧手段４１を設置する（図５）。加圧手段４１はフロック９を加圧（圧搾）する装置であって、例えば、排出口３９の手前に配置された１枚以上の加圧板４２を有している。 As described above, both the solid-liquid separation devices 31a and 31b are suitable for continuous solid-liquid separation processing, but more preferably, the pressurizing means 41 is installed as in the solid-liquid separation device 31b of the second example. (Fig. 5). The pressurizing means 41 is a device that pressurizes (squeezes) the flocs 9, and has, for example, one or more pressurizing plates 42 arranged in front of the discharge port 39.
加圧板４２は鉛直面からフロック投入口３３側へ傾斜し、その下端とベルト３６との間には隙間があり、その隙間を通過する際に、フロック９が加圧板４２でベルト３６に押し付けられて加圧（圧搾）される。このときの加圧圧力は、隙間の大きさ、加圧板４２の傾斜角度及び枚数、フロック９の移動速度及び供給量等を加圧条件とし、１以上の加圧条件を変更することで、調整することができる。 The pressure plate 42 is inclined from the vertical surface toward the flock inlet 33 side, and there is a gap between the lower end thereof and the belt 36, and when passing through the gap, the flock 9 is pressed against the belt 36 by the pressure plate 42. Is pressurized (squeezed). The pressurizing pressure at this time is adjusted by changing one or more pressurizing conditions with the size of the gap, the inclination angle and the number of pressurizing plates 42, the moving speed of the flocs 9 and the supply amount as the pressurizing conditions. can do.
なお、加圧手段４１は加圧板４２に限定されず、加圧ロールのような他の形状の加圧部材を用いてもよい。いずれの場合も、加圧手段４１により、フロック９の含水率を効率良く低下させることができる。フロック９に加える圧力は装置や固液分離条件により適宜変更可能であるが、２００ｋＰａ以下が好ましく、特に１ｋＰａ〜１５０ｋＰａが好ましく、その中でも１ｋＰａ〜１００ｋＰａが好ましく、より好ましくは１０ｋＰａ以上であり、更に好ましくは１５ｋＰａ以上であり、特に好ましくは２０ｋＰａ以上である。上記圧力は、第２例の固液分離装置３１ｂの場合は加圧板４２の加圧条件で調整することができるし、スクリュープレス脱水機の場合は、スクリューの回転数や出口の開度を調整して内部圧力を調整することができる。 The pressurizing means 41 is not limited to the pressurizing plate 42, and a pressurizing member having another shape such as a pressurizing roll may be used. In either case, the pressurizing means 41 can efficiently reduce the water content of the floc 9. The pressure applied to the floc 9 can be appropriately changed depending on the apparatus and solid-liquid separation conditions, but is preferably 200 kPa or less, particularly preferably 1 kPa to 150 kPa, particularly preferably 1 kPa to 100 kPa, more preferably 10 kPa or more, and further preferably. Is 15 kPa or more, and particularly preferably 20 kPa or more. In the case of the solid-liquid separation device 31b of the second example, the pressure can be adjusted by the pressure condition of the pressure plate 42, and in the case of the screw press dehydrator, the rotation speed of the screw and the opening degree of the outlet are adjusted. The internal pressure can be adjusted.
なお、上記水処理装置１ａ、１ｂでは、フロック形成用の凝集槽２１と固液分離装置３１ａ、３１ｂとを別装置としたが、遠心脱水機のように、フロック形成工程と固液分離工程を同時に行う装置を採用することもできる。 In the water treatment devices 1a and 1b, the floc forming tank 21 and the solid-liquid separating devices 31a and 31b are separate devices, but the floc forming step and the solid-liquid separation step are performed like a centrifugal dehydrator. It is also possible to adopt a device that performs at the same time.
更に、被処理水から固液分離した後のフロック９（汚泥）を、汚泥処理などに使用する脱水機で更に脱水処理することも可能である。この脱水に用いる脱水機は特に限定されず、従来から汚泥脱水に使用される脱水機を用いることができる。具体的には、スクリュープレス脱水機、ベルトプレス脱水機、遠心脱水機、多重円板型脱水機、多重板型スクリュープレス脱水機、回転加圧脱水機、真空脱水機、楕円板型脱水機などを用いることができる。 Further, the floc 9 (sludge) after solid-liquid separation from the water to be treated can be further dehydrated by a dehydrator used for sludge treatment or the like. The dehydrator used for this dehydration is not particularly limited, and a dehydrator conventionally used for sludge dehydration can be used. Specifically, screw press dehydrator, belt press dehydrator, centrifugal dehydrator, multiple disk type dehydrator, multiple plate type screw press dehydrator, rotary pressure dehydrator, vacuum dehydrator, elliptical plate dehydrator, etc. Can be used.
次に、上記水処理装置１ａ、１ｂを用いた水処理方法について説明する。 Next, a water treatment method using the water treatment devices 1a and 1b will be described.
［水処理方法］
先ず、天然高分子系油除去剤と合成高分子系油除去剤の少なくとも一方を含む油除去剤を第１の供給手段１５に収容しておき、カチオン性有機高分子凝集剤を第２の供給手段１７に収容しておく。これら供給手段は特に限定されず、公知の供給手段を用いることが可能であり、その接続先も特に限定されないが、第１の供給手段１５は凝集槽２１よりも上流側の装置、好ましくは貯槽１１に接続しておき、第２の供給手段１７はそれよりも下流側に接続しておく。
[Water treatment method]
First, an oil remover containing at least one of a natural polymer oil remover and a synthetic polymer oil remover is housed in the first supply means 15, and a cationic organic polymer flocculant is supplied to the second supply means 15. It is housed in means 17. These supply means are not particularly limited, and a known supply means can be used, and the connection destination thereof is not particularly limited, but the first supply means 15 is a device on the upstream side of the coagulation tank 21, preferably a storage tank. It is connected to 11, and the second supply means 17 is connected to the downstream side of the second supply means 17.
上述した被処理水は、先ず貯槽１１へ供給される。制御手段５には、供給量、供給速度、供給時期などの１以上の供給条件が設定されており、被処理水の供給が開始されると、制御手段５は第１の供給手段１５からの油除去剤の供給を開始し、被処理水には所定の供給条件で油除去剤が添加されることになる。 The water to be treated described above is first supplied to the storage tank 11. One or more supply conditions such as a supply amount, a supply speed, and a supply timing are set in the control means 5, and when the supply of the water to be treated is started, the control means 5 is sent from the first supply means 15. The supply of the oil remover is started, and the oil remover is added to the water to be treated under predetermined supply conditions.
貯槽１１の下流側に混和槽２５を設置する場合、第１の供給手段１５を混和槽２５に接続することも可能であり、より好ましくは貯槽１１と混和槽２５の両方に接続しておく（図３）。制御手段５は、油除去剤を供給すべきタイミング、例えば、被処理水の供給が開始されたときに、貯槽１１と混和槽２５のいずれか一方又は両方へ油除去剤を供給するよう設定されている。従って、被処理水には、油除去剤が１回で供給されるか、複数回に分けて供給される。 When the mixing tank 25 is installed on the downstream side of the storage tank 11, the first supply means 15 can be connected to the mixing tank 25, and more preferably, it is connected to both the storage tank 11 and the mixing tank 25 (). Figure 3). The control means 5 is set to supply the oil removing agent to one or both of the storage tank 11 and the mixing tank 25 at the timing when the oil removing agent should be supplied, for example, when the supply of the water to be treated is started. ing. Therefore, the oil removing agent is supplied to the water to be treated at one time or in a plurality of times.
なお、ｐＨ調整用の中和剤（酸・アルカリ）や、無機凝集剤を使用する場合は、これらの薬剤は凝集槽２１よりも上流側、例えば貯槽１１や混和槽２５で添加するが、無機凝集剤を使用する場合は、油除去剤を添加した後であって、カチオン性有機高分子凝集剤を添加する前の被処理水に無機凝集剤を添加する。また、２種以上の油除去剤を使用する場合、これら油除去剤は被処理水に一緒に添加してもよいし、別々に添加してもよい。 When a neutralizing agent (acid / alkali) for pH adjustment or an inorganic coagulant is used, these agents are added upstream of the coagulation tank 21, for example, in the storage tank 11 or the mixing tank 25, but are inorganic. When a flocculant is used, the inorganic flocculant is added to the water to be treated after the oil remover is added and before the cationic organic polymer flocculant is added. When two or more kinds of oil removers are used, these oil removers may be added to the water to be treated together or separately.
少なくとも１種の油除去剤が添加された被処理水は、凝集槽２１へ供給される。凝集槽２１には第２の供給手段１７が接続されている。第二の供給手段１７は特に限定されないが、ポンプ１４等に加え、溶解槽１８を設置してカチオン性有機高分子凝集剤の溶液を収容してもよい。第２の供給手段１７に収容したカチオン性有機高分子凝集剤は、そのまま、または、水などの溶媒に溶解、分散もしくは希釈した溶液として被処理水に添加される。 The water to be treated to which at least one oil removing agent has been added is supplied to the coagulation tank 21. A second supply means 17 is connected to the coagulation tank 21. The second supply means 17 is not particularly limited, but in addition to the pump 14 and the like, a dissolution tank 18 may be installed to accommodate the solution of the cationic organic polymer flocculant. The cationic organic polymer flocculant contained in the second supply means 17 is added to the water to be treated as it is or as a solution dissolved, dispersed or diluted in a solvent such as water.
好ましい実施形態では、凝集槽２１に撹拌手段が設置されており、カチオン性有機高分子凝集剤が添加された被処理水を撹拌混合し、油分及び懸濁物質を凝集させ、フロックを形成する。 In a preferred embodiment, a stirring means is installed in the coagulation tank 21, and the water to be treated to which the cationic organic polymer flocculant is added is stirred and mixed to aggregate the oil and the suspended substance to form flocs.
撹拌羽根などの回転により撹拌混合する場合、フロック成長のためには、その撹拌速度（回転速度）は２０ｍｉｎ−１〜３００ｍｉｎ−１（回/分）が好ましく、特に３０ｍｉｎ−１〜２００ｍｉｎ−１が好ましく、その中でも特に４０ｍｉｎ−１〜１５０ｍｉｎ−１が好ましい。 If stirring and mixing by rotation, such as stirring blades, for floc growth, the stirring speed (rotation speed) is preferably from 20min -1 ~300min -1 (times / min), in particular 30min -1 ~200min -1 preferably, preferred is particularly 40min -1 ~150min -1 among them.
被処理水がフロック形成工程に供される時間、すなわち、フロック形成に関る装置に留まる滞留時間は、１分〜３０分が好ましく、より好ましくは３分〜２０分、特に好ましくは５分〜１５分である。例えば、被処理水を凝集槽２１に連続して供給する連続式撹拌処理の場合、凝集槽２１の容積（複数槽の場合、合計容積）を、凝集槽２１へ供給する溶液（被処理水等）の供給速度（体積/分）で除した値が滞留時間となる。 The time during which the water to be treated is subjected to the floc forming step, that is, the residence time in the device involved in floc forming is preferably 1 minute to 30 minutes, more preferably 3 minutes to 20 minutes, and particularly preferably 5 minutes to. 15 minutes. For example, in the case of continuous stirring treatment in which the water to be treated is continuously supplied to the coagulation tank 21, the volume of the coagulation tank 21 (in the case of a plurality of tanks, the total volume) is supplied to the coagulation tank 21 (water to be treated, etc.). ) Divided by the supply rate (volume / minute) is the residence time.
フロック形成装置の種類や台数は特に限定されず、高速撹拌機が設置された高速撹拌槽、低速撹拌機が設置された低速撹拌槽などの２台以上の撹拌槽（凝集槽）でフロック形成装置を構成してもよい。この場合、被処理水とカチオン性有機高分子凝集剤を高速撹拌槽で撹拌した後、さらに低速撹拌槽で撹拌する。 The type and number of flock forming devices are not particularly limited, and two or more agitating tanks (coagulation tanks) such as a high-speed stirring tank equipped with a high-speed stirrer and a low-speed stirring tank equipped with a low-speed stirrer May be configured. In this case, the water to be treated and the cationic organic polymer flocculant are stirred in a high-speed stirring tank, and then further stirred in a low-speed stirring tank.
高速撹拌槽で被処理水中にカチオン性有機高分子凝集剤を均一分散させ、次に低速撹拌槽でフロックを成長させることで、より大きなフロックを形成させることが可能であり、その結果、ろ過性のよい、強固なフロックを得ることができる。 Larger flocs can be formed by uniformly dispersing the cationic organic polymer flocculant in the water to be treated in a high-speed stirring tank and then growing the flocs in a low-speed stirring tank, resulting in filterability. You can get a good and strong flock.
高速撹拌とは、３００ｍｉｎ−１以上の撹拌を示し、低速撹拌とは３００ｍｉｎ−１よりも遅い撹拌を示す。 High-speed agitation means agitation of 300 min -1 or more, and low-speed agitation means agitation slower than 300 min -1.
いずれの場合も、油分を含む有機物は油除去剤に取り込まれ後に、カチオン性有機高分子凝集剤によりフロックが形成されるので、油分の除去率が高いだけではなく、強固なフロックが形成される。また、カチオン度が高く、分子量が大きい有機高分子凝集剤を使用した場合、油分のみならず、カチオン性有機高分子凝集剤がフロックの粘着性を増加させる原因にもなったが、油除去剤の使用によりフロックの粘着性が抑制される。 In either case, after the organic matter containing oil is taken up by the oil remover, flocs are formed by the cationic organic polymer flocculant, so that not only the oil removal rate is high but also strong flocs are formed. .. In addition, when an organic polymer flocculant having a high degree of cation and a large molecular weight was used, not only the oil content but also the cationic organic polymer flocculant caused an increase in the adhesiveness of flocs, but the oil remover The stickiness of the flocs is suppressed by the use of.
従って、フロック９は機械的な固液分離で破壊され難く、フロックの粘着性による装置トラブルも抑制されるので、上記のような固液分離装置３１ａ、３１ｂを用いて、水分を効率良く除去することができる。従って、固液分離装置３１ａ、３１ｂの後段に別の脱水装置や脱水工程を設けなくても、汚泥の含水率を低下させることができる。
以下、実施例により本発明をより具体的に説明する。
Therefore, the flocs 9 are not easily destroyed by mechanical solid-liquid separation, and device troubles due to the stickiness of the flocs are suppressed. Therefore, the solid-liquid separation devices 31a and 31b as described above are used to efficiently remove water. be able to. Therefore, the water content of sludge can be reduced without providing a separate dewatering device or dewatering step after the solid-liquid separation devices 31a and 31b.
Hereinafter, the present invention will be described in more detail with reference to Examples.
［実施例１］
本試験では、被処理水にカチオン性有機高分子凝集剤を加えて混合し、フロックを形成した。次に、フロックを含む被処理水をフロック（＝汚泥）と分離液に固液分離した。本試験では、油除去剤を用いることで、油除去率が向上し、汚泥の含水率が低減できることを確認した。
[Example 1]
In this test, a cationic organic polymer flocculant was added to the water to be treated and mixed to form flocs. Next, the water to be treated containing flocs was solid-liquid separated into flocs (= sludge) and a separation solution. In this test, it was confirmed that the oil removal rate can be improved and the water content of sludge can be reduced by using an oil remover.
試験では、下記表１に示すように、食品製造工場排水Ｆ１を使用した。油除去剤には、古紙粉砕物、レーヨン繊維、ポリエチレンテレフタレート繊維（ＰＥＴ繊維）を使用した。有機高分子凝集剤には、カチオン性有機高分子凝集剤ｐｃ１（カチオン度：８５ｍｏｌ％、分子量：９００万）を使用した。凝集剤溶液のカチオン性有機高分子凝集剤の溶解濃度は１ｇ／Ｌとした。 In the test, as shown in Table 1 below, the food manufacturing factory wastewater F1 was used. As the oil remover, crushed waste paper, rayon fiber, and polyethylene terephthalate fiber (PET fiber) were used. As the organic polymer flocculant, the cationic organic polymer flocculant pc1 (cationic degree: 85 mol%, molecular weight: 9 million) was used. The dissolution concentration of the cationic organic polymer flocculant in the flocculant solution was 1 g / L.
試験手順の詳細は以下の通りである。容器に１Ｌの被処理水を分取し、下記表１に記載した注入量で油除去剤を加え、撹拌機（回転速度１００ｍｉｎ−１、撹拌時間５ｍｉｎ）で被処理水と油除去剤を混合した。次に、下記表１に記載した注入量でカチオン性有機高分子凝集剤を加え、撹拌機（回転速度５０ｍｉｎ−１、撹拌時間１０ｍｉｎ）で油除去剤を含む被処理水とカチオン性有機高分子凝集剤を混合し、フロックを形成させた。なお、表１の注入量は、凝集剤溶液としてではなく、カチオン性有機高分子凝集剤としての量を示す。 The details of the test procedure are as follows. 1 L of water to be treated is separated into a container, an oil remover is added at the injection amount shown in Table 1 below, and the water to be treated and the oil remover are mixed with a stirrer (rotation speed 100 min -1, stirring time 5 min). did. Next, the cationic organic polymer flocculant was added at the injection amount shown in Table 1 below, and the water to be treated containing the oil remover and the cationic organic polymer were used in a stirrer (rotation speed 50 min -1, stirring time 10 min). The flocculant was mixed to form flocs. The injection amount in Table 1 shows the amount as a cationic organic polymer flocculant, not as a flocculant solution.
次に、ふるい（目開き１ｍｍ）と加圧板（圧力５０ｋＰａ）を使用して、フロックを含む被処理水をフロック（＝汚泥）と分離液（＝処理水）に固液分離した。最後に、処理水のＳＳ及びヘキサン抽出物質と、汚泥の含水率とを測定した。 Next, using a sieve (opening 1 mm) and a pressure plate (pressure 50 kPa), the water to be treated containing flocs was solid-liquid separated into flocs (= sludge) and a separation liquid (= treated water). Finally, the SS and hexane extracts of the treated water and the water content of the sludge were measured.
比較例として、油除去剤を添加しない試験、アニオン性有機高分子凝集剤ｐａ１（カアニオン度：１５ｍｏｌ％、分子量：１,９００万）を使用した試験をそれぞれ行った。試験結果を表１に示す。これらの試験結果から、被処理水に油吸着剤を添加することで、油除去率を向上させることができ、汚泥の含水率を低減させることが可能であることが確認された。 As a comparative example, a test without adding an oil removing agent and a test using an anionic organic polymer flocculant pa1 (canian degree: 15 mol%, molecular weight: 19 million) were carried out. The test results are shown in Table 1. From these test results, it was confirmed that the oil removal rate can be improved and the water content of sludge can be reduced by adding an oil adsorbent to the water to be treated.
［実施例２］
本試験では、フロックを形成して固液分離をする工程において、種類の異なるカチオン性有機高分子凝集剤を使用し、処理性能を比較した。
[Example 2]
In this test, different types of cationic organic polymer flocculants were used in the step of forming flocs and performing solid-liquid separation, and the treatment performance was compared.
試験では、食品製造工場排水（Ｆ２）を使用した。油除去剤には、古紙粉砕物を使用した。有機高分子凝集剤には、カチオン性有機高分子凝集剤ｐｃ１〜ｐｃ４を使用した。カチオン性有機高分子凝集剤ｐｃ１〜ｐｃ４はジメチルアミノエチルアクリレート四級アンモニウム塩とアクリルアミドとの共重合体である。カチオン性有機高分子凝集剤の溶解濃度はいずれも１ｇ／Ｌとした。 In the test, food manufacturing plant wastewater (F2) was used. A crushed waste paper was used as the oil remover. As the organic polymer flocculant, the cationic organic polymer flocculants pc1 to pc4 were used. The cationic organic polymer flocculants pc1 to pc4 are copolymers of dimethylaminoethyl acrylate quaternary ammonium salt and acrylamide. The dissolution concentration of the cationic organic polymer flocculants was 1 g / L.
試験手順の詳細は以下の通りである。容器に１Ｌの被処理水を分取し、表２に記載した注入量で油除去剤を加え、撹拌機（回転速度１００ｍｉｎ−１、撹拌時間５ｍｉｎ）で被処理水と油除去剤を混合した。次に、表２に記載の注入量でカチオン性有機高分子凝集剤を加え、撹拌機（回転速度５０ｍｉｎ−１、撹拌時間１０ｍｉｎ）で油除去剤を含む被処理水とカチオン性有機高分子凝集剤を混合し、フロックを形成させた。次に、ふるい（目開き１ｍｍ）を使用して、フロックを含む被処理水を汚泥と分離液（＝処理水）に固液分離した。最後に、処理水のヘキサン抽出物質を測定した。 The details of the test procedure are as follows. 1 L of water to be treated was dispensed into a container, an oil remover was added at the injection amount shown in Table 2, and the water to be treated and the oil remover were mixed with a stirrer (rotation speed 100 min -1, stirring time 5 min). .. Next, the cationic organic polymer flocculant was added at the injection amount shown in Table 2, and the water to be treated containing the oil remover and the cationic organic polymer flocculant were aggregated with a stirrer (rotation speed 50 min -1, stirring time 10 min). The agents were mixed to form flocs. Next, using a sieve (opening 1 mm), the water to be treated containing flocs was solid-liquid separated into sludge and a separation liquid (= treated water). Finally, the hexane extract of the treated water was measured.
試験結果を表２に示す。これらの試験結果から、有機高分子凝集剤のカチオン度（全モノマーに対するカチオン性モノマーの割合）が５０モル％以上である場合に、大きなフロックが形成され、処理水のヘキサン抽出物質の低減が可能であった。また、カチオン性有機高分子凝集剤の分子量が４００万より大きい場合に、大きなフロックが形成され、処理水のヘキサン抽出物質を低減可能であった。 The test results are shown in Table 2. From these test results, when the cationicity (ratio of cationic monomer to total monomer) of the organic polymer flocculant is 50 mol% or more, large flocs are formed and the hexane extract substance of the treated water can be reduced. Met. Further, when the molecular weight of the cationic organic polymer flocculant was larger than 4 million, large flocs were formed, and the hexane extract substance in the treated water could be reduced.
［実施例３］
上記実施例１、２では、フロック形成工程と固液分離工程とを、所定量（１Ｌ）ずつ処理するバッチ方式としたが、実施例３では連続式とした。但し、油除去剤は被処理水に予め添加した。
[Example 3]
In Examples 1 and 2, the floc forming step and the solid-liquid separation step were batch-processed by a predetermined amount (1 L), but in Example 3, a continuous method was used. However, the oil remover was added to the water to be treated in advance.
すなわち、油除去剤を含む被処理水とカチオン性有機高分子凝集剤を連続的に凝集槽に供給して混合し、フロックを形成させると共に、フロックが形成された被処理水を凝集槽から連続して排出して固液分離装置へ供給し、連続的に固液分離した。 That is, the water to be treated containing the oil removing agent and the cationic organic polymer flocculant are continuously supplied to the coagulation tank and mixed to form flocs, and the water to be treated on which the flocs are formed is continuously supplied from the flocculation tank. Then, it was discharged and supplied to a solid-liquid separator, and solid-liquid separation was performed continuously.
この試験では、食品製造工場排水（Ｆ３）を使用した。油除去剤には、古紙粉砕物を使用した。カチオン性有機高分子凝集剤としては、上記表１、表２のカチオン性有機高分子凝集剤ｐｃ１を使用した。カチオン性有機高分子凝集剤の溶解濃度は２ｇ／Ｌとした。 In this test, food manufacturing plant effluent (F3) was used. A crushed waste paper was used as the oil remover. As the cationic organic polymer flocculant, the cationic organic polymer flocculant pc1 shown in Tables 1 and 2 above was used. The dissolution concentration of the cationic organic polymer flocculant was 2 g / L.
試験手順の詳細は以下の通りである。被処理水の貯槽（容量：１ｍ３）に油除去剤を表３に記載した濃度で添加し、混合した。次に、撹拌機が設置された凝集槽（容積：３２Ｌ）に、油除去剤を含む被処理水（流量：５Ｌ／ｍｉｎ）、カチオン性有機高分子凝集剤の溶液（流量：０．１５Ｌ／ｍｉｎ）を供給し、撹拌機（回転速度：６０ｍｉｎ−１）で被処理水とカチオン性有機高分子凝集剤を混合してフロックを形成させた。 The details of the test procedure are as follows. An oil remover was added to a storage tank (capacity: 1 m 3 ) of water to be treated at the concentration shown in Table 3 and mixed. Next, in a coagulation tank (volume: 32 L) in which a stirrer is installed, water to be treated (flow rate: 5 L / min) containing an oil remover and a solution of a cationic organic polymer coagulant (flow rate: 0.15 L / min). Min) was supplied, and the water to be treated and the cationic organic polymer flocculant were mixed with a stirrer (rotation speed: 60 min -1) to form flocs.
次に、機械的固液分離装置３１ｂ（図５）を使用して、フロックを含む被処理水をフロック（＝汚泥）と分離液（＝処理水）に固液分離した。機械的固液分離装置上部の加圧板の圧力は５ｋＰａとした。最後に、処理水のヘキサン抽出物質、汚泥の含水率を測定した。比較例として、油除去剤を添加しない試験を実施した。 Next, using the mechanical solid-liquid separation device 31b (FIG. 5), the water to be treated containing flocs was solid-liquid separated into flocs (= sludge) and separation liquid (= treated water). The pressure of the pressure plate on the upper part of the mechanical solid-liquid separator was 5 kPa. Finally, the water content of the hexane extract substance and sludge of the treated water was measured. As a comparative example, a test was conducted in which no oil remover was added.
試験結果を表３に示す。これらの試験結果から、油除去剤を添加することにより、フロックを加圧することにより、処理水のヘキサン抽出物質を低減でき、汚泥の含水率を低減できた。 The test results are shown in Table 3. From these test results, it was possible to reduce the hexane extract substance of the treated water and reduce the water content of sludge by pressurizing the flocs by adding an oil remover.
１ａ、１ｂ：水処理装置、 ５：制御手段、 ９：フロック、 １１：貯槽、 １３、１４：ポンプ、 １５：第１の供給手段、 １７：第２の供給手段、 １８：溶解槽、 ２１：凝集槽、 ２５：混和槽、 ３１ａ、３１ｂ：固液分離装置、 ３３：フロック投入口、 ３４：捕捉手段、 ３５：フロック移動手段、 ３６：ベルト、 ３７：ベルト駆動手段、 ３８：洗浄管、 ３９：排出口、 ４１：加圧手段、 ４２：加圧板 1a, 1b: Water treatment device, 5: Control means, 9: Flock, 11: Storage tank, 13, 14: Pump, 15: First supply means, 17: Second supply means, 18: Dissolution tank, 21: Coagulation tank, 25: Mixing tank, 31a, 31b: Solid-liquid separator, 33: Flock inlet, 34: Capturing means, 35: Flock moving means, 36: Belt, 37: Belt driving means, 38: Cleaning pipe, 39 : Discharge port, 41: Pressurizing means, 42: Pressurizing plate
Claims (6)
前記フロックを含む被処理水を、当該フロックと分離液とに固液分離する固液分離工程と、を有する、油分を含む排水の水処理方法であって、
前記カチオン性有機高分子凝集剤を加える前の被処理水に、天然高分子系油除去剤と合成高分子系油除去剤のいずれか一方又は両方からなる油除去剤を添加し、
前記カチオン性有機高分子凝集剤は、全原料モノマーに占めるカチオン性モノマーの割合が５０モル％以上であり、前記カチオン性有機高分子凝集剤を純水に２ｇ/Ｌの割合で溶解した溶液を、温度２５℃、６０分 −１ のＢ型粘度計の回転速度で測定した粘度が２００ｍＰａ・ｓ以上であり、
前記固液分離工程は、１ｋＰａ〜２００ｋＰａの圧力で加圧しながら固液分離する機械的固液分離工程であることを特徴とする油分を含む排水の水処理方法。 Water to be treated containing oil is mixed by adding a cationic organic polymer flocculant having a molecular weight of 5 million or more without adding an anionic polymer having a weight average molecular weight of at least 1 million. Flock forming process to form
A method for treating oil-containing wastewater, which comprises a solid-liquid separation step of solid-liquid separating the floc-containing water to be treated into the floc and a separation liquid.
An oil remover consisting of one or both of a natural polymer oil remover and a synthetic polymer oil remover is added to the water to be treated before the cationic organic polymer flocculant is added.
The cationic organic polymer flocculant is prepared by dissolving the cationic organic polymer flocculant in pure water at a ratio of 2 g / L, wherein the ratio of the cationic monomer to the total raw material monomers is 50 mol% or more. The viscosity measured at the rotation speed of a B-type viscometer at a temperature of 25 ° C. and 60 minutes- 1 is 200 mPa · s or more.
The solid-liquid separation step is a mechanical solid-liquid separation step of solid-liquid separation while pressurizing at a pressure of 1 kPa to 200 kPa, which is a method for treating water containing oil-containing wastewater.
前記貯槽から供給される被処理水に、分子量が５００万以上であって、全原料モノマーに占めるカチオン性モノマーの割合が５０モル％以上であり、純水に２ｇ/Ｌの割合で溶解した溶液を、温度２５℃、６０分 −１ のＢ型粘度計の回転速度で測定した粘度が２００ｍＰａ・ｓ以上のカチオン性有機高分子凝集剤を添加し、撹拌する凝集槽と、
前記凝集槽から供給される被処理水を、汚泥と分離液とに固液分離する固液分離装置であって、汚泥に１ｋＰａ〜１００ｋＰａの圧力を加えて圧搾する加圧手段を有する固液分離装置と、
前記貯槽と前記凝集槽との間に設けられた混和槽と、
前記貯槽または前記被処理水へ前記油除去剤を供給する第１の供給手段と、
前記凝集槽へ前記カチオン性有機高分子凝集剤を供給する第２の供給手段と、
前記カチオン性有機高分子凝集剤を供給する前に、前記被処理水に油除去剤を供給させる制御手段であって、前記被処理水の供給が開始されたときに前記油除去剤を前記貯槽と前記混和槽の少なくとも一方に供給するよう、前記第１の供給手段を制御する制御手段と、
を有し、
前記貯槽、前記被処理水および前記凝集槽の何れにも少なくとも１００万の重量平均分子量を有するアニオン性ポリマーを供給する供給手段は供えられておらず、
前記貯槽と前記凝集槽との間に、固液分離のための装置が設けられていないことを特徴とする、油分を含む排水の水処理装置。 A storage tank in which an oil remover selected from one or both of a natural polymer oil remover and a synthetic polymer oil remover is supplied to the water to be treated containing oil.
A solution in which the molecular weight of the water to be treated supplied from the storage tank is 5 million or more , the ratio of the cationic monomer to the total raw material monomers is 50 mol% or more, and the solution is dissolved in pure water at a ratio of 2 g / L. A coagulation tank in which a cationic organic polymer flocculant having a viscosity of 200 mPa · s or more measured at a rotation speed of a B-type viscometer at a temperature of 25 ° C. for 60 minutes- 1 is added and stirred.
The treated water supplied from the flocculation tank, a solid-liquid separation device for solid-liquid separation and sludge and the separation liquid, solid-liquid separation with a pressure means for squeezing by applying pressure of 1kPa~100kPa sludge Equipment and
An admixture tank provided between the storage tank and the coagulation tank,
A first supply means for supplying the oil removing agent to the storage tank or the water to be treated, and
A second supply means for supplying the cationic organic polymer flocculant to the coagulation tank,
It is a control means for supplying the oil removing agent to the water to be treated before supplying the cationic organic polymer flocculant, and the oil removing agent is supplied to the storage tank when the supply of the water to be treated is started. And a control means for controlling the first supply means so as to supply to at least one of the mixing tanks.
Have,
None of the storage tank, the water to be treated, or the coagulation tank is provided with a supply means for supplying an anionic polymer having a weight average molecular weight of at least 1 million.
A water treatment device for wastewater containing oil, characterized in that a device for solid-liquid separation is not provided between the storage tank and the coagulation tank.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01274807A (en) * | 1988-04-28 | 1989-11-02 | Sanai Fujita | Coagulant containing animal bone, and its production and using the coagulant |
| US5200086A (en) * | 1991-08-20 | 1993-04-06 | Nalco Chemical Company | Emulsion destabilization and treatment |
| JPH0796284A (en) * | 1993-09-29 | 1995-04-11 | Kurita Water Ind Ltd | Treatment of oil-containing waste water |
| CA2264803A1 (en) * | 1996-10-03 | 1998-04-09 | Cytec Technology Corp. | Aqueous dispersions |
| JP2000328048A (en) * | 1999-05-17 | 2000-11-28 | Teruo Kato | Agent and process for separating oil |
| CN100537455C (en) * | 2006-08-15 | 2009-09-09 | 中国石油天然气股份有限公司 | Ternary combination flooding produced liquid oil-containing sewage treatment technique |
| JP2008173610A (en) * | 2007-01-22 | 2008-07-31 | Mhi Environment Engineering Co Ltd | Waste liquid treating method and waste liquid treatment system |
| JP5867125B2 (en) * | 2012-02-06 | 2016-02-24 | 三菱レイヨン株式会社 | Coagulation treatment method for oil-containing cleaning wastewater |
| JP6152108B2 (en) * | 2012-08-22 | 2017-06-21 | Ｍｔアクアポリマー株式会社 | Polymer flocculant, method for producing the same, and sludge dewatering method using the same |
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