JP2007136405A - Foaming solid flocculant for water treatment - Google Patents

Foaming solid flocculant for water treatment Download PDF

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JP2007136405A
JP2007136405A JP2005336689A JP2005336689A JP2007136405A JP 2007136405 A JP2007136405 A JP 2007136405A JP 2005336689 A JP2005336689 A JP 2005336689A JP 2005336689 A JP2005336689 A JP 2005336689A JP 2007136405 A JP2007136405 A JP 2007136405A
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flocculant
water treatment
foaming
water
solid
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JP4549962B2 (en
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Toshio Kawaguchi
俊夫 川口
Norio Yamamura
典男 山村
Keizo Ueda
桂三 上田
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Cf Hightech Kk
KANKYO RIKAGAKU KK
Tokuyama Corp
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KANKYO RIKAGAKU KK
Tokuyama Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a foaming solid flocculant which does not generate dust and rapidly foams and collapses to be dispersed when mixed in waste water. <P>SOLUTION: The foaming solid flocculant for water treatment comprises 50-90 wt.pts. of an inorganic flocculant such as aluminum sulfate and gypsum or of an organic floculant such as a polyacryl amide and a salt of a polyacrylic acid, 50-10 wt.pts. of a foaming agent such as sodium carbonate and sodium hydrogen carbonate, and 0.1-20 wt.pts. of calcium silicate as a forming auxiliary agent (a total amount of the flocculant and the foaming agent is 100 wt.pts.). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、水処理用の発泡性固形凝集剤に関する。より詳しくは、工業排水処理、産業排水処理、池、川等のヘドロおよびアオコ処理、上下水道の水処理およびアオコ処理、糞尿処理等の用途に使用される固形凝集剤に関する。   The present invention relates to a foamable solid flocculant for water treatment. More specifically, the present invention relates to a solid flocculant used for applications such as industrial wastewater treatment, industrial wastewater treatment, sludge and blue water treatment of ponds, rivers, water and sewage water treatment and blue water treatment, manure treatment, and the like.

凝集剤を用いて排水処理する場合、一般に使用されている凝集剤としては、硫酸アルミニウム、ポリ塩化アルミニウム、塩化鉄等に代表される無機系凝集剤と、ポリアクリルアミド等に代表される水溶性高分子からなる有機系凝集剤がある。   In the case of wastewater treatment using a flocculant, the commonly used flocculants include inorganic flocculants represented by aluminum sulfate, polyaluminum chloride, iron chloride and the like, and water-soluble high repellency represented by polyacrylamide and the like. There are organic flocculants composed of molecules.

無機系凝集剤は主に懸濁粒子の荷電を中和する効果があるため使用後の上澄液の透明度が良く、更に沈澱物から水分を分離し易いという特徴がある反面、生成するフロックが小さいため凝集速度が遅い事や、酸性物質である事が多く処理後にアルカリによる中和処理を行う必要があった。一方、有機系凝集剤は、一般的に高価であり、形成されるフロックは無機系の凝集剤を用いた場合に比して大きいが、懸濁粒子に対する吸着補集力に劣るため上澄液に濁りが残るといった問題や沈澱物フロックからの水分分離が難しいという欠点があった。従って、無機系凝集剤と有機系凝集剤を併用する処理方法が一般的である。この場合には、まず無機系凝集剤を添加した後に急速攪拌してマイクロフロック群を形成させた上で、次のステップで有機系凝集剤を添加し、緩速攪拌してより大きな凝集体群を形成させる処理方法が適応されている。この様に時間差を設けて2種類の凝集剤を別々に投入する方法は、手間が掛かり複数の凝集剤投入手段が必要となる他、設備面積が大きくなるだけでなく、装置自身も大きくなるという不利益があった。   Inorganic flocculants mainly have the effect of neutralizing the charge of suspended particles, so the transparency of the supernatant after use is good and the water content can be easily separated from the precipitate. Since it is small, the aggregation rate is slow or it is often an acidic substance, and it has been necessary to carry out a neutralization treatment with an alkali after the treatment. On the other hand, organic flocculants are generally expensive, and flocs formed are larger than when inorganic flocculants are used. There were problems such as turbidity remaining in the water and difficulty in separating water from the sediment floc. Therefore, a treatment method using both an inorganic flocculant and an organic flocculant is common. In this case, the inorganic flocculant is added first and then rapidly stirred to form a micro floc group. Then, the organic flocculant is added in the next step, and the flocculent group is stirred slowly to obtain a larger flocculant group. A processing method for forming is applied. In this way, the method of adding the two types of flocculants separately with a time difference is troublesome and requires a plurality of flocculant charging means, and not only the equipment area increases, but also the apparatus itself increases. There was a disadvantage.

一方、近年になってから、無機凝集剤と有機高分子凝集剤を混合した粉末状の凝集剤を用いる事が提案されている(特開2004−154726)。あるいは、石膏や人工ゼオライトあるいはセメントなどの比較的中性領域の材料を主成分とする無機系凝集剤についても提案されている。(特開平9−276604)
特開2004−154726号公報 特開平09−276604号公報
On the other hand, recently, it has been proposed to use a powdery flocculant in which an inorganic flocculant and an organic polymer flocculant are mixed (Japanese Patent Laid-Open No. 2004-154726). Alternatively, an inorganic flocculant mainly composed of a relatively neutral material such as gypsum, artificial zeolite, or cement has been proposed. (Japanese Patent Laid-Open No. 9-276604)
JP 2004-154726 A JP 09-276604 A

凝集剤を粉の形で水処理槽に投入する場合には、粉を一定間隔の時間と量で教習するための装置が高価になるだけでなく、装置内で棚つりなどの現象を発生し、供給がストップするなどのトラブルが時々発生するという問題があった。また、池や湖などで発生するアオコやヘドロ、工事現場での泥水などの凝集処理剤として現場で用いる際に、粉末状だと供給時に風で飛散するなどの恐れがあるだけでなく、広い範囲の地域に撒く事が出来ず手間がかかるという問題があった。更に、半導体工場などの粉塵を嫌う環境下では使えないため、防塵のための手段が望まれていた。
一方で、粉体を造粒化するためにはセルロースや水溶性高分子材料を結合剤に用いる方法が知られているが、この方法では、結合剤の添加量が多くなってしまい、固形材の強度が不十分であったり、凝集処理後に有機物が水中に残ってしまいCODやBODの値を上げ、返って汚染の原因になる恐れがあった。
When the flocculant is put into the water treatment tank in the form of powder, the equipment for learning the powder at regular intervals of time and quantity is not only expensive, but also causes phenomena such as shelves in the equipment. There was a problem that troubles such as supply stop occurred from time to time. In addition, when used on site as a coagulation treatment agent such as sea urchins and sludge generated in ponds and lakes, muddy water at construction sites, etc., if it is in powder form, it may not only be scattered by the wind at the time of supply, but also wide There was a problem that it was difficult to go to the area of the range and it took time. Further, since it cannot be used in an environment that dislikes dust, such as a semiconductor factory, a means for dust prevention has been desired.
On the other hand, in order to granulate powder, a method using cellulose or a water-soluble polymer material as a binder is known. However, in this method, the amount of binder added increases, and the solid material Insufficient strength or organic matter remains in the water after the coagulation treatment, raising the value of COD and BOD, which may cause contamination.

本発明者らは、これらの課題を解決すべく鋭意研究した結果、水処理用凝集剤成分、発泡剤、および成形助剤としての珪酸カルシウムを組み合わせて固形の水処理用凝集剤とすることによって前記の課題を解決させるに至った。   As a result of diligent research to solve these problems, the present inventors have combined a water treatment flocculant component, a foaming agent, and calcium silicate as a molding aid into a solid water treatment flocculant. It came to solve the said subject.

即ち、本発明は、水処理用凝集剤50〜90重量部、発泡剤50〜10重量部および珪酸カルシウム0.1〜20重量部(水処理用凝集剤と発泡剤の合計量を100重量部とする)を含有してなることを特徴とする水処理用発泡性固形凝集剤である。   That is, the present invention includes 50 to 90 parts by weight of a water treatment flocculant, 50 to 10 parts by weight of a foaming agent, and 0.1 to 20 parts by weight of calcium silicate (the total amount of the water treatment flocculant and the foaming agent is 100 parts by weight. A foamable solid aggregating agent for water treatment.

本発明の実施により、次のような効果がもたらされる。まず第1に、本発明の水処理用発泡性固形凝集剤は、排水に添加した際に、排水中に凝集剤成分を速やかにかつ均一に拡散することができる。これは、本発明の凝集剤を粉の状態で添加した時に比べて遜色のない凝集効果を発揮出来る。しかも、成型助剤などは凝集剤と一緒に沈降してしまうためBODやCODに悪影響を及ぼさない。更に、屋外で凝集剤を汚水に添加する際、例えば池や湖などに発生したアオコなどを凝集させる際にも粉塵を発生させる事無く添加する事が可能である。また、粉塵を嫌う半導体工場での排水処理にも問題なく使用することが出来る。   The following effects are brought about by implementation of the present invention. First, when the foamable solid flocculant for water treatment of the present invention is added to wastewater, the flocculant component can be quickly and uniformly diffused in the wastewater. This can exhibit an agglomeration effect comparable to when the flocculant of the present invention is added in a powder state. In addition, since the molding aid and the like settle together with the flocculant, BOD and COD are not adversely affected. Furthermore, when a flocculant is added to sewage outdoors, it can be added without generating dust even when agglomerates generated in ponds or lakes are agglomerated. In addition, it can be used for wastewater treatment in semiconductor factories that dislike dust.

本発明の水処理用発泡性固形凝集剤について以下具体的に説明する。   The foamable solid flocculant for water treatment of the present invention will be specifically described below.

本発明の水処理用発泡性固形凝集剤に配合される水処理用凝集剤としては、通常水処理に使用される粉体状の無機系または有機系の凝集剤が特に限定されず利用できる。   As the water treatment flocculant to be blended with the foamable solid flocculant for water treatment of the present invention, powdery inorganic or organic flocculants usually used for water treatment are not particularly limited and can be used.

具体的には、無機系凝集剤としては、硫酸アルミニウム、水酸化アルミニウム、アンモニウムミョウバン、カリミョウバン、アルミン酸ナトリウム、ポリ塩化アルミニウムなどのアルミニウム塩、塩化第一鉄、塩化第二鉄、ポリ硫酸鉄、シリカ鉄などの鉄塩、ニ水石膏、半水石膏などの石膏、人工または合成ゼオライトのナトリウム型、カルシウム型、鉄型など、天然ゼオライト、火山灰、石炭灰などの灰成分、セメントなどが挙げられ、これらの1種または2種以上を使用することも可能である。   Specifically, the inorganic flocculants include aluminum salts such as aluminum sulfate, aluminum hydroxide, ammonium alum, potassium alum, sodium aluminate, polyaluminum chloride, ferrous chloride, ferric chloride, polyiron sulfate. , Iron salt such as silica iron, gypsum such as dihydrate gypsum and hemihydrate gypsum, sodium type, calcium type and iron type of artificial or synthetic zeolite, natural zeolite, ash components such as volcanic ash and coal ash, cement etc. It is also possible to use one or more of these.

有機系凝集剤としては、水溶性の高分子物質、たとえば、ポリアクリルアミド、ポリアクリル酸塩、アクリルアミドとアクリル酸塩の共重合体、アルギン酸、アルギン酸塩、ポリビニルアルコール、CMC、MC(メチルセルロース)、アルギン酸塩、キサンタンガム、グアガム、HEC(ヒドロキシエチルセルロース)、ポリエチレンオキサイト、キトサン、寒天、ゼラチン、ポリマレイン酸、ポリスチレンスルホン酸塩、ポリビニルスルホン酸、ポリイミド、ポリアミン、ポリアクリル酸エステル等とこれらの変性物が挙げられ、これらの1種又は2種以上を使用することもできる。また、これらの共重合物を使用することも可能であり、アクリル酸ソーダとアクリルアミドの共重合物が特に好ましい。   Organic flocculants include water-soluble polymer materials such as polyacrylamide, polyacrylate, acrylamide and acrylate copolymer, alginic acid, alginate, polyvinyl alcohol, CMC, MC (methylcellulose), and alginic acid. Salt, xanthan gum, guar gum, HEC (hydroxyethyl cellulose), polyethylene oxide, chitosan, agar, gelatin, polymaleic acid, polystyrene sulfonate, polyvinyl sulfonic acid, polyimide, polyamine, polyacrylic acid ester, and the modified products thereof 1 type, or 2 or more types of these can also be used. Moreover, these copolymers can also be used, and a copolymer of sodium acrylate and acrylamide is particularly preferable.

無機系凝集剤と有機系凝集剤は単独あるいは組み合わせて使うことが可能であるが、無機系凝集剤を主体とする凝集剤が好ましい。具体的には、無機系凝集剤100重量部に対して有機系凝集剤0.1〜20重量部の範囲で組み合わせるのが好ましい。有機系凝集剤の含有量が多すぎると過剰な有機系凝集剤がフロックに取り込まれなくなり、処理水中に残存し、二次凝集の原因となることがある。少なすぎるとフロックの強度が弱くなり脱水しがたいフロックとなり、極端に少ない場合、フロックが微細となり、脱水不可能となる場合がある。   Inorganic flocculants and organic flocculants can be used alone or in combination, but flocculants mainly composed of inorganic flocculants are preferred. Specifically, it is preferable to combine in the range of 0.1 to 20 parts by weight of the organic flocculant with respect to 100 parts by weight of the inorganic flocculant. If the content of the organic flocculant is too large, excess organic flocculant is not taken into the floc and remains in the treated water, which may cause secondary aggregation. If the amount is too small, the floc strength becomes weak and difficult to dewater, and if it is extremely small, the floc becomes fine and may not be dewatered.

水処理用粉末凝集剤の製剤中における配合量は、特に限定されるものではないが、
凝集剤と発泡剤の合計100重量部に対して50〜90重量部である事が好ましい。下限より少なければ、凝集性能が不足してくるため好ましくなく、上限を超えると発泡性能が不足してくることになる。
The blending amount of the water treatment powder flocculant in the preparation is not particularly limited,
It is preferable that it is 50-90 weight part with respect to a total of 100 weight part of a coagulant | flocculant and a foaming agent. If it is less than the lower limit, the agglomeration performance is insufficient, which is not preferable. If the upper limit is exceeded, the foaming performance is insufficient.

本発明に使用する発泡剤としては、アルカリあるいはアルカリ土類の炭酸塩、例えば炭酸ナトリウム、炭酸水素ナトリウム、炭酸アンモニウム、炭酸カリウム、炭酸カルシウム、セスキ炭酸ナトリウムなどが挙げられ、単独または2種以上併用してもよい。この中でも、アルカリの炭酸塩が水中で溶解し易いため好適に用いられる。発泡剤は、水処理用凝集剤50〜90重量部に対して、発泡剤50〜10重量部の範囲で添加されて用いられる。発泡剤の添加量が少ないと発泡効果が少なくなり、多すぎると凝集効果が十分に得られなくなるため好ましくない。   Examples of the foaming agent used in the present invention include alkali or alkaline earth carbonates such as sodium carbonate, sodium hydrogen carbonate, ammonium carbonate, potassium carbonate, calcium carbonate, sodium sesquicarbonate, and the like. May be. Among these, alkali carbonates are preferably used because they are easily dissolved in water. A foaming agent is added and used in the range of 50-10 weight part of foaming agents with respect to 50-90 weight part of coagulants for water treatment. If the addition amount of the foaming agent is small, the foaming effect is reduced, and if it is too much, the aggregation effect cannot be obtained sufficiently, which is not preferable.

本発明の水処理用発泡性固形凝集剤においては、凝集処理工程で発泡剤による自己崩壊性が十分に得られない場合には、上記発泡剤に発泡助剤を組み合わせて配合するのが好ましい。該発泡助剤としては水溶性固体酸が好適に用いられる。水溶性固体酸からなる発泡助剤を発泡剤と併用することにより、水中に投下された固形凝集剤の発泡が促進され、その結果として錠剤の崩壊時間が大幅に短縮される事になる。   In the foamable solid flocculant for water treatment of the present invention, when sufficient self-disintegration by the foaming agent is not obtained in the aggregation treatment step, it is preferable to blend the foaming agent with a foaming aid. As the foaming aid, a water-soluble solid acid is preferably used. By using a foaming aid composed of a water-soluble solid acid in combination with a foaming agent, foaming of the solid flocculant dropped in water is promoted, and as a result, the disintegration time of the tablet is greatly shortened.

水溶性固体酸は特に限定されないが、例えば、クエン酸、コハク酸、フマル酸、マレイン酸、酒石酸、シュウ酸、リンゴ酸、アジピン酸、リン酸二水素ナトリウム、ホウ酸、リン酸二水素カリウム、などが挙げられる。また、これら水溶性固体酸は単独または2種以上を併用してもよい。発泡剤および発泡助剤の配合量は任意の配合で添加できるが、通常発泡剤100重量部に対して発泡助剤を10〜150重量部添加して用いられる。発泡助剤がこの添加量よりも少ないと十分な発泡補助効果が得られにくく、多すぎると空気中の水分を吸湿しやすくなり、使用前に発泡が起こるなどの恐れがあるため包装容器が高価なものになってしまう。   Although the water-soluble solid acid is not particularly limited, for example, citric acid, succinic acid, fumaric acid, maleic acid, tartaric acid, oxalic acid, malic acid, adipic acid, sodium dihydrogen phosphate, boric acid, potassium dihydrogen phosphate, Etc. These water-soluble solid acids may be used alone or in combination of two or more. The blending amount of the foaming agent and the foaming aid can be added by any formulation, but usually 10 to 150 parts by weight of the foaming aid is added to 100 parts by weight of the foaming agent. If the amount of foaming aid is less than this amount, it is difficult to obtain a sufficient foaming assistance effect, and if it is too much, moisture in the air tends to be absorbed and foaming may occur before use. It will become something.

本発明の水処理用発泡性固形凝集剤において、固形にし且つその形状を維持するために成形助剤が使用される。本発明においては数ある成型助剤の中で珪酸カルシウムを選択し使用したことに特徴がある。即ち、当該成型助剤として珪酸カルシウムが必須であり、更に該珪酸カルシウムの中でも、ジャイロライト型結晶構造、即ち2CaO・3SiO・nSiO・mH2O(但し、n、mは正の数)の結晶構造を有し、かつSiO2/CaOモル比が1.6〜4.2であり、平均粒径が100μ以下のものが添加量が少なくても成形助剤としての効果をもたらすだけでなく、成形圧力も低圧で成形できるため特に好ましい。 In the foamable solid aggregating agent for water treatment of the present invention, a molding aid is used in order to solidify and maintain its shape. The present invention is characterized in that calcium silicate is selected and used among a number of molding aids. That is, calcium silicate is essential as the molding aid, and among these calcium silicates, a gyrolite type crystal structure, that is, 2CaO · 3SiO 2 · nSiO 2 · mH 2 O (where n and m are positive numbers). And having an SiO 2 / CaO molar ratio of 1.6 to 4.2 and having an average particle size of 100 μm or less only has an effect as a molding aid even if the addition amount is small. In particular, the molding pressure is particularly preferable because molding can be performed at a low pressure.

このジャイロライト型結晶構造を有する珪酸カルシウムは、顕微鏡写真を撮る事によって確認が出来、該形状がバラの花びらに似た花弁状構造をしているものであり、一般には、「フローライト」(株式会社 トクヤマ製)と言う製品名で市販されている。この花弁状の結晶構造を有する珪酸カルシウムは、吸液性に優れているため固形凝集剤中に含まれる水分を取り込むことができ、特に湿気に弱い石膏などの成分を安定化することが可能となる点でも極めて好ましい成型助剤である。   This calcium silicate having a gyrolite-type crystal structure can be confirmed by taking a photomicrograph and has a petal-like structure whose shape resembles a rose petal. It is marketed under the product name “Made by Tokuyama Corporation”. This calcium silicate having a petal-like crystal structure is excellent in liquid absorbency and can take in moisture contained in the solid flocculant, and can stabilize components such as gypsum that is particularly sensitive to moisture. Therefore, it is a very preferable molding aid.

珪酸カルシウムの添加量としては、水処理用凝集剤と発泡剤の合計100重量部に対して、0.1〜20重量部、更に好ましくは0.1〜10重量部を添加して用いる事が好ましい。添加量がこの範囲よりも少ないと固形化が難しくなり、多過ぎると水中での崩壊性も低下するだけでなく、高価なものになってしまう。   As the addition amount of calcium silicate, 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight is added to 100 parts by weight of the total of the water treatment flocculant and the foaming agent. preferable. If the addition amount is less than this range, solidification becomes difficult, and if it is too much, not only the disintegration property in water is lowered, but also it becomes expensive.

本発明の水処理用発泡性固形凝集剤には、性能を損なわない限り、滑沢剤、凝集剤成分の安定化剤などの補助剤を添加してもよく、また一部担体を併用してもよい。滑沢剤としては、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸、滑石、水素添加植物油、タルクなどがあげられるが、ステアリン酸マグネシウム、ステアリン酸カルシウムが好ましい。   The foamable solid flocculant for water treatment of the present invention may contain an auxiliary agent such as a lubricant and a stabilizer for the flocculant component, as long as the performance is not impaired. Also good. Examples of the lubricant include magnesium stearate, calcium stearate, zinc stearate, stearic acid, talc, hydrogenated vegetable oil, talc and the like, and magnesium stearate and calcium stearate are preferable.

本発明の水処理用発泡性固形凝集剤は固形とすることが必須であるが、その形態は、造粒物あるいは錠剤のどちらでも構わない。本発明の水処理用発泡性固形凝集剤の固形化方法としては、転動造粒法、圧縮型造粒法、攪拌型造粒法、押し出し造粒法、破砕型造粒法などがあるが、凝集剤成分の中に無機系凝集材と有機系凝集材が混在している場合や石膏などの成分を含有している場合には、凝集剤の保存安定性の低下や凝集サイトの失活を避けるため乾式造粒法を用いる事が好ましい。錠剤を作製する場合には、直接打錠する方法だけでなく、一旦、上述した造粒法を用いて造粒したものを打錠する事も可能である。   The foamable solid aggregating agent for water treatment of the present invention must be solid, but the form may be either a granulated product or a tablet. Examples of the solidification method of the foamable solid flocculant for water treatment of the present invention include a rolling granulation method, a compression granulation method, a stirring granulation method, an extrusion granulation method, and a crushing granulation method. When the inorganic coagulant and organic coagulant are mixed in the coagulant component, or when components such as gypsum are included, the storage stability of the coagulant is reduced and the coagulation site is deactivated. In order to avoid this, it is preferable to use a dry granulation method. In the case of producing a tablet, it is possible not only to directly compress tablets but also to tablet once granulated using the granulation method described above.

水処理用発泡性固形凝集剤の使用方法としては、一般に用いる方法が何ら制限無く用いられる。例えば、円盤状に作製した錠剤を筒の中に複数の錠剤を積み重ねた状態で入れ、一定時間毎に錠剤を1つずつ水中に自動落下させる供給機を用いる事も可能である。この場合は、棚つりなどの現象も発生せず、安価な装置での供給が可能となる。また、錠剤を一つずつ袋で包装して保管し、海外などで飲料水の確保が難しい地域で、泥水などに投入し上澄みを飲用水とするなどの用途も考えられる。更に、池や湖などの広い地域に投下するためには、砲丸の形の固形物を作製し、バズーカ砲で打ち込む方法などが考えられる。この場合には、球状整粒機を用いた固形化により、目的の固形物が得られる。   As a method of using the foamable solid flocculant for water treatment, a generally used method is used without any limitation. For example, it is also possible to use a feeder in which tablets made in a disk shape are put in a state where a plurality of tablets are stacked in a cylinder, and the tablets are automatically dropped into water one by one at regular intervals. In this case, a phenomenon such as shelf hanging does not occur, and supply with an inexpensive device is possible. In addition, it may be possible to pack tablets one by one in bags and store them in mud or other places where it is difficult to secure drinking water overseas and use the supernatant as drinking water. Furthermore, in order to drop in a wide area such as a pond or a lake, a method of producing a solid material in a cannonball shape and driving it with a bazooka cannon is considered. In this case, the target solid is obtained by solidification using a spherical granulator.

本発明の水処理用発泡性凝集剤を使用して凝集処理する場合、必要な設備としては、汚水や汚泥と凝集沈降剤とを水槽中で攪拌翼を用いて攪拌する方法だけでなく、水流を渦巻き状のラインを通す事によって攪拌する方法や、水中ポンプ,水中ジェットポンプ,汚泥吸引車などが考えられる。特に、本発明の水処理用発泡性固形凝集剤は、従来に比べれば簡単な設備で使用可能であり、設備負担は大幅に軽減させることを可能とする画期的な発明である。   When coagulating using the foamable coagulant for water treatment of the present invention, the necessary equipment is not only a method of stirring sewage or sludge and coagulating sedimentation agent using a stirring blade in a water tank, A method of stirring by passing a spiral line, a submersible pump, a submersible jet pump, a sludge suction vehicle, etc. are conceivable. In particular, the foamable solid aggregating agent for water treatment of the present invention is an epoch-making invention that can be used with simple equipment as compared with the conventional one and can greatly reduce the equipment burden.

実施例1
以下に示す市販の水処理用凝集剤を入手し、発泡剤として炭酸水素ナトリウム、成形助剤として花弁状の結晶構造を有する珪酸カルシウム(製品名:フローライト、株式会社トクヤマ製)を混合して加圧下で成形し、水処理用発泡性固形凝集剤を得た。
市販凝集剤1「製品名:ZEOフロック」環境理化学株式会社製の石膏系凝集剤
市販凝集剤2「製品名:アクアフロックSL」人工ゼオライト系凝集剤(鈴木産業株式会社製)
市販凝集剤3「製品名:WITグラインダー」飛灰が主成分の凝集剤(株式会社WIT)
(フライアッシュ40%、硫酸カルシウム10%)
市販凝集剤4「製品名:きよまる君」火山灰由来の無機物を主成分とする凝集剤(株式会社柳生防水技研製)
市販凝集剤5「製品名:水夢」人工ゼオライト系凝集剤(株式会社ISAA製)
市販凝集剤6「製品名:ハイパー・フロック」ポリマーと無機質主成分の凝集剤(株式会社ホウショウEG製
市販凝集剤7「製品名:びわ湖瞬間凝集剤(サンプル)」セメント&人工ゼオライト系凝集剤(東亜工業株式会社製)
得られた錠剤を以下の基準で、水中での崩壊性と凝集能力を評価した。その結果を表1に示す。

1.錠剤化の有無
シリンダー式の加圧装置を用いて、40〜120kg/cm2で1分間加圧した後、サンプルを取り出して錠剤化の有無を確認した。
○印:錠剤になり、手で持っても壊れない。
×印:粉のままで錠剤化せず、取り出す時に崩れてしまう状態。

2.水中での崩壊性観察
20mlの水が入ったガラスサンプル瓶に上記水処理用固形凝集剤を投入し、静置したままで錠剤が崩壊して行く状態を観察した。
印:水中に投入された直後に発泡し、しかも水中で自ら上下に動き速やかに崩壊
印:水中に投入されてから速やかに発泡が始まり、数分以内に崩壊
△印:水中に投入されてしばらく経った後にゆっくりと崩壊が始まる。
×印:水中に投入されても発泡せず、長時間崩壊しない。

3.汚水に対する凝集能力
100mlの水が入ったPETボトル内にベントナイト1gを添加して懸濁させ、この懸濁液に上記水処理用固形凝集剤0.1gを投入し激しく30秒間攪拌した後に静置し様子を観察した。
◎印:静置により数分後にフロックが生成し、上澄液も透明な状態。
印:静置して数分後にフロックが生成するが、上澄液が若干不透明な状態。
印:静置してしばらくして小さなフロックが生成するが沈降が遅い。
×印:静置してもフロックが生成しない。
Example 1
Obtain the following commercially available water treatment flocculants and mix sodium hydrogen carbonate as a foaming agent and calcium silicate having a petal-like crystal structure as a molding aid (product name: Florite, manufactured by Tokuyama Corporation). Molding was performed under pressure to obtain a foamable solid flocculant for water treatment.
Commercially available flocculant 1 “Product name: ZEO Flock” Gypsum-based flocculant manufactured by Eco-Rikagaku Co., Ltd. Commercially available flocculant 2 “Product name: Aquafloc SL” artificial zeolite flocculant (manufactured by Suzuki Sangyo Co., Ltd.)
Commercial flocculant 3 “Product name: WIT grinder” Flour ash-based flocculant (WIT Co., Ltd.)
(Fly ash 40%, calcium sulfate 10%)
Commercial flocculant 4 “Product name: Kiyomaru-kun” Flocculant composed mainly of inorganic matter derived from volcanic ash (manufactured by Yagyu Waterproof Engineering Co., Ltd.)
Commercial flocculant 5 “Product name: Mizumu” artificial zeolite flocculant (ISAA Co., Ltd.)
Commercial flocculant 6 “Product name: Hyper Flock” polymer and flocculant of inorganic main component (commercial flocculant 7 manufactured by Hosho EG Co., Ltd. “Product name: Biwako instantaneous flocculant (sample)” Cement & artificial zeolite flocculant ( Toa Industries Co., Ltd.)
The tablets obtained were evaluated for disintegration in water and aggregating ability according to the following criteria. The results are shown in Table 1.

1. Presence / absence of tableting After applying pressure at 40 to 120 kg / cm 2 for 1 minute using a cylinder-type pressurizing apparatus, a sample was taken out and checked for tableting.
○ mark: It becomes a tablet and does not break even if it is held by hand.
X mark: The powder is not tableted and collapses when taken out.

2. Observation of disintegration in water The above-mentioned solid aggregating agent for water treatment was put into a glass sample bottle containing 20 ml of water, and the state in which the tablet disintegrated was observed while still standing.
Mark: foams immediately after being put into water, and moves up and down in water quickly. Collapses quickly: foaming starts immediately after being thrown into water, and collapses within a few minutes. After a while, the collapse begins slowly.
X mark: Even if thrown into water, it does not foam and does not collapse for a long time.

3. 1 g of bentonite is added to and suspended in a PET bottle containing 100 ml of water with agglomeration capacity for sewage, and 0.1 g of the above-mentioned solid aggregating agent for water treatment is added to this suspension and vigorously stirred for 30 seconds. The situation was observed.
◎: Flock is generated after a few minutes after standing, and the supernatant is also transparent.
Mark: Flock is formed after several minutes of standing, but the supernatant is slightly opaque.
Mark: Small flocs form after a while, but settling is slow.
X mark: No flocs are generated even when left standing.

Figure 2007136405
Figure 2007136405

実施例2
水処理用凝集剤として実施例1の代わりに表2に示す組成のものを調整し、発泡剤として炭酸水素ナトリウム、成形助剤としてフローライトを用い、錠剤化圧力40kg/cmで成型した後に錠剤化の有無、崩壊性、凝集性能を実施例1と同様な方法で評価した。その結果を表2に示す。
Example 2
After adjusting the composition shown in Table 2 instead of Example 1 as a flocculant for water treatment, using sodium bicarbonate as a foaming agent and fluorite as a molding aid, and molding at a tableting pressure of 40 kg / cm 2 The presence / absence of tableting, disintegration, and aggregation performance were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Figure 2007136405
Figure 2007136405

比較例1
実施例1のNo1について、成型助剤または発泡剤を使用しなかった時の評価結果を表3に示した。
Comparative Example 1
Table 3 shows the evaluation results when no molding aid or foaming agent was used for No1 of Example 1.

Figure 2007136405
Figure 2007136405

表3から明らかな様に、成型助剤としてフローライト(珪酸カルシウム)を使わない場合には凝集剤の錠剤化が出来ず、その結果として錠剤の崩壊性も評価することが出来なかった。一方、錠剤化前の粉について凝集性を調べてみたが凝集剤単独と比べて遜色は無かった。また、フローライトを凝集剤の成型助剤として使った場合には錠剤化することが出来たが、発泡剤(アルカリ炭酸塩)を使用しない場合には崩壊性が不十分であった。凝集剤を水中で崩壊させるために水溶性のポリマーとしてポリビニルピロリドンあるいは水溶性の塩として塩化カリウムを用いた場合には、錠剤化は可能であったが崩壊性は不十分であった。その結果として、凝集性も不十分な結果となった。   As is clear from Table 3, when fluorite (calcium silicate) was not used as a molding aid, the flocculant could not be tableted, and as a result, the disintegration of the tablet could not be evaluated. On the other hand, the cohesiveness of the powder before tableting was examined, but it was not inferior to that of the flocculant alone. Further, when fluorite was used as a coagulant forming aid, it could be tableted, but when no foaming agent (alkali carbonate) was used, disintegration was insufficient. When polyvinyl pyrrolidone was used as a water-soluble polymer or potassium chloride was used as a water-soluble salt in order to disintegrate the flocculant in water, tableting was possible but disintegration was insufficient. As a result, the cohesiveness was also insufficient.

これは、フローライトが花弁状の結晶構造を有する事により、錠剤する際に凝集剤ならびに発泡剤同士を繋ぎ留める効果を有しており、凝集時には凝集物と一緒にフロックを形成して水中から分離されるためと考えられる。更に、炭酸塩は水中で発泡するため凝集剤の助剤を急速に崩壊、分散させる効果を有しているが、一方、水溶性ポリマーや水溶性の塩は水中で溶解するのに時間がかかるだけでなく、発泡性が無いため凝集剤の崩壊性が不十分だったものと考えられる。   This has the effect of flocculating the flocculant and the foaming agent when tableting due to the fact that florite has a petal-like crystal structure. It is thought to be separated. Furthermore, carbonate foams in water, so it has the effect of rapidly disintegrating and dispersing the coagulant aid, while water-soluble polymers and water-soluble salts take time to dissolve in water. Moreover, it is considered that the disintegrating property of the flocculant was insufficient due to the lack of foamability.

比較例2
水処理用凝集剤として実施例1で使用した市販凝集剤1、発泡剤として炭酸水素ナトリウムを用い、成形助剤をフローライトに代えて結晶性セルロース(製品名セオラスFC-30、旭化成工業製)、無水リン酸水素カルシウム(製品名:フジカリン、富士化学工業製)、メタケイ酸アルミン酸マグネシウム(製品名:ノイシリン、富士化学工業製)を使用した場合の錠剤化の有無、崩壊性、凝集性能を実施例1と同様な方法で評価した。その結果を表4に示す。
Comparative Example 2
Commercially available flocculant 1 used in Example 1 as a water treatment flocculant, sodium hydrogen carbonate as a foaming agent, and crystalline cellulose (product name Theolas FC-30, manufactured by Asahi Kasei Kogyo Co., Ltd.) instead of fluorite as a molding aid , Presence or absence of tableting, disintegration, and aggregation performance when using anhydrous calcium hydrogen phosphate (product name: Fujicalin, manufactured by Fuji Chemical Industry Co., Ltd.), magnesium metasilicate magnesium aluminate (product name: Neusilin, manufactured by Fuji Chemical Industry Co., Ltd.) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Figure 2007136405
Figure 2007136405

表4から明らかな様に、凝集剤の成形助剤として、フローライト(珪酸カルシウム)の代わりに、賦形剤として知られている結晶セルロース、無水リン酸水素ナトリウムあるいはメタケイ酸アルミン酸マグネシウムを使った場合には、比較的低圧での成形時には添加量を25重量%まで上げても錠剤化することができず、高圧成形で始めて錠剤化することが出来た。この理由は定かではないが、表3の結果と同様にフローライトは花弁状の結晶性構造を有するために、錠剤化する際に凝集剤ならびに発泡剤同士を繋ぎ留める効果が優れていることによるものと考えられる。   As is apparent from Table 4, crystalline cellulose, anhydrous sodium hydrogen phosphate or magnesium aluminate metasilicate, which is known as an excipient, is used instead of fluorite (calcium silicate) as a coagulant forming aid. In this case, at the time of molding at a relatively low pressure, the tablet could not be formed even if the addition amount was increased to 25% by weight. The reason for this is not clear, but because the fluorite has a petal-like crystalline structure as in the results of Table 3, it has an excellent effect of holding together the flocculant and the foaming agent when tableting. It is considered a thing.

Claims (6)

水処理用凝集剤50〜90重量部、発泡剤50〜10重量部および珪酸カルシウム0.1〜20重量部(水処理用凝集剤と発泡剤の合計量を100重量部とする)を含有してなることを特徴とする水処理用発泡性固形凝集剤。   Contains 50 to 90 parts by weight of a water treatment flocculant, 50 to 10 parts by weight of a foaming agent, and 0.1 to 20 parts by weight of calcium silicate (the total amount of the water treatment flocculant and the foaming agent is 100 parts by weight). A foamable solid flocculant for water treatment, characterized in that 発泡補剤が、発泡剤100重量部に対して10〜150重量部含有されてなることを特徴とする請求項1記載の水処理用発泡性固形凝集剤。   The foaming solid aggregating agent for water treatment according to claim 1, wherein the foaming adjuvant is contained in an amount of 10 to 150 parts by weight per 100 parts by weight of the foaming agent. 水処理用凝集剤が、無機物を主成分とする粉末状の凝集剤であることを特徴とする請求項1または2記載の水処理用発泡性固形凝集剤。   3. The foamable solid aggregating agent for water treatment according to claim 1, wherein the aggregating agent for water treatment is a powdery aggregating agent mainly composed of an inorganic substance. 水処理用凝集剤が、石膏、セメントまたはゼオライトの少なくとも1種を主成分とする凝集剤であることを特徴とする請求項1または2記載の水処理用発泡性固形凝集剤。   3. The foamable solid flocculant for water treatment according to claim 1 or 2, wherein the flocculant for water treatment is a flocculant mainly composed of at least one of gypsum, cement or zeolite. 発泡剤が、アルカリの炭酸塩であることを特徴とする請求項1または2記載の水処理用発泡性固形凝集剤。   The foaming solid flocculant for water treatment according to claim 1 or 2, wherein the foaming agent is an alkali carbonate. 珪酸カルシウムが、花弁状構造を有する珪酸カルシウムであることを特徴とする請求項1または2記載の水処理用発泡性固形凝集剤。
The foamable solid flocculant for water treatment according to claim 1 or 2, wherein the calcium silicate is calcium silicate having a petal-like structure.
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JP2016073898A (en) * 2014-10-03 2016-05-12 デクセリアルズ株式会社 Water cleaning agent and water cleaning method
CN106794398A (en) * 2014-10-03 2017-05-31 迪睿合株式会社 Water scavengine agent and method for purifying water
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JP2018047471A (en) * 2018-01-05 2018-03-29 デクセリアルズ株式会社 Water cleaning agent, manufacturing method of water cleaning agent, and water cleaning method
JP2018103185A (en) * 2018-04-02 2018-07-05 デクセリアルズ株式会社 Water cleaning agent, manufacturing method of water cleaning agent, and water cleaning method
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