JP4465431B2 - Inorganic powdery water treatment flocculant and various sludge / polluted wastewater treatment methods - Google Patents
Inorganic powdery water treatment flocculant and various sludge / polluted wastewater treatment methods Download PDFInfo
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本発明は、各種汚泥廃水、各種汚濁廃水の水処理用無機系粉末凝集剤に関し、より詳細には、各種の建設汚泥、河川・港湾等の浚渫汚泥、浄水場汚泥、工場排水汚泥等の汚泥廃水及び各種の工事、建設現場で発生する汚濁廃水の水処理に用いられて、沈降清澄速度を一層早めて濾過排水方法を著しく簡素化させることができる低廉でハンドリング性に優れる無機系粉末状の水処理用凝集剤及びその無機系凝集剤を用いる各種汚泥廃水及び各種汚濁廃水を簡便、低処理コストで処理する各種廃水の水処理方法にも関する。 The present invention relates to various sludge wastewater and inorganic powder flocculants for water treatment of wastewater, and more specifically, various construction sludge, dredged sludge from rivers, ports, etc., sludge from water purification plants, factory wastewater sludge, etc. It is used for the treatment of wastewater and various wastewater generated at construction sites, and it is an inexpensive inorganic powder that can be used to treat the wastewater at a construction site. The present invention also relates to a water treatment method for treating various wastewaters, which treats various sludge wastewaters and various polluted wastewaters using the water treatment flocculant and the inorganic flocculants in a simple and low treatment cost.
従来から、下水処理場等におけうる下水の汚泥廃水、し尿及び有機性産業汚泥廃水は、高度に水処理されて河川、海等に排出されている。また、地盤改良、トンネル掘削、ビル建設現場等で発生する工事・建設汚濁（又は泥奨）廃水や、河川、港湾等の工事現場で発生する浚渫泥奨や、各種産業における工場廃水浄化設備等で発生する各種産業汚濁廃水も、それぞれ高度に水処理されてリサイクル又はリユース用水として利用又は、河川、海等に排出されている。このように、社会活動及び各種の産業活動を行うには、大量の水が使用されている。しかも、使用後には、日常の生活環境、自然環境である河川や海にそのまま排出できない各種の汚泥廃水、各種の汚濁廃水を大量に発生させている。 Conventionally, sewage sludge wastewater, human waste, and organic industrial sludge wastewater that can be used in sewage treatment plants and the like have been highly treated and discharged into rivers, seas, and the like. Also, ground improvement, tunnel excavation, construction / contamination waste (or mud award) wastewater generated at building construction sites, dredging mud aspiration at construction sites such as rivers and harbors, factory wastewater purification equipment in various industries, etc. Various industrial polluted wastewater generated in Japan is highly treated and used as water for recycling or reuse, or discharged into rivers, seas, and the like. Thus, a large amount of water is used to perform social activities and various industrial activities. Moreover, after use, a large amount of various sludge wastewater and various polluted wastewater that cannot be discharged as they are into the daily living environment and natural rivers and seas are generated.
従って、このような生活環境、社会環境で発生する生活廃水や、産業廃水や又は工場廃水等は、大量で、しかも、広域的に散在して発生することから、そのまま放置・汚染させたら地域の生活環境や自然環境を広域的に汚染・崩壊させてしまう。そこで、従来からそれぞれ発生地の終末処理場で水処理用凝集剤等を用いながら処理されて、リサイクル・リユース用水として、又は河川、海等に排出されている。 Therefore, domestic wastewater, industrial wastewater, factory wastewater, etc. generated in such living and social environments are generated in large quantities and scattered over a wide area. It will contaminate and collapse the living environment and the natural environment over a wide area. Therefore, it has been conventionally treated at a terminal treatment plant at the place of occurrence using a water treatment flocculant or the like, and is discharged as water for recycling or reuse, or into rivers, seas, and the like.
従来からこのような汚泥・汚濁廃水の終末処理に使用される水処理用凝集剤は、これら汚泥・汚濁廃水中に浮遊する混濁浮遊物を効果的に沈降させて清澄な廃水にさせる終末処理には不可欠な処理剤である。また、このような終末処理場において使用されている凝集剤は、処理対照となるのが廃水で、その処理方法からして、従来から著しく低廉で、持ち運び性がよく、使用時におけるハンドリング性がよく、しかも、使用量が少なく低処理コストを可能にさせることが求められている。 Conventionally, the flocculant for water treatment used for the final treatment of such sludge / polluted wastewater is used for the final treatment to effectively settle the suspended suspended matters floating in the sludge / polluted wastewater into a clear wastewater. Is an indispensable treatment agent. In addition, the flocculant used in such a final treatment plant is wastewater as a treatment control, and has been remarkably inexpensive and portable since its treatment method. In addition, there is a demand for enabling a low processing cost with a small amount of use.
このような状況下に従来から使用されている水処理凝集剤には、硫酸バンド、ポリ塩化アルミニウム（ＰＡＣ）、塩化アルミニウム、塩化第二鉄、ポリ硫酸第二鉄（ポリ鉄）等の無機系凝集剤が挙げられ、また、通常、ノニオン系、アニオン系、カチオン系の有機高分子凝集剤が組合わせて、汚泥廃水、汚濁廃水の水処理に使用されている。しかしながら、これらの凝集剤は、単に汚泥・汚濁廃水に添加させれば、浮遊混濁物が、凝集・沈降・清澄化される簡便で、且つ短時間で清澄化・排水処理されるものでないのが一般的である。 Water treatment flocculants conventionally used under such circumstances include inorganic systems such as sulfate band, polyaluminum chloride (PAC), aluminum chloride, ferric chloride, polyferric sulfate (polyiron), etc. There are flocculants, and nonionic, anionic, and cationic organic polymer flocculants are usually used in combination with sludge wastewater and polluted wastewater. However, if these flocculants are simply added to sludge / polluted wastewater, suspended turbid materials are not easily flocculated / settled / clarified, and are not clarified / drained in a short time. It is common.
更に詳述すれば、その処理行程、処理方法は、各種廃水の発生状況、汚泥・汚濁物の種類、濁度等にもよるが、無機凝集剤の単独又は２種以上の組合せ添加、又は高分子凝集剤種との組合せ添加、又はこれら凝集剤添加時のアルカリ剤等によるｐＨ調整、又はこれら凝集剤添加時の撹拌速度等のように、単純で、簡便な処理工程でないのが実状である。例えば、［特許文献１］には、その処理工程として、有機性汚泥に硫酸バンド、ポリ塩化アルミニウム（ＰＡＣ）、塩化アルミニウム、ポリ硫酸第二鉄（ポリ鉄）等の従来から使用されている無機凝集剤の単独又は２種以上を組み合わせて添加させ、次いで、有機高分子凝集剤を添加させて脱水ろ過するに当たって、ｐＨを４以下になるまで無機凝集剤を添加させた後、アルカリ剤を添加させてｐＨを４〜７に調整し、次いで両性高分子凝集剤を添加させて、浮遊汚泥汚濁物を低含水率のろ過ケーキとして処理される汚泥の脱水方法が記載されている。 More specifically, the treatment process and treatment method depend on the state of generation of various wastewaters, the type of sludge / pollutant, turbidity, etc., but the inorganic flocculant is added alone or in combination of two or more, or high In reality, it is not a simple and easy processing step, such as combination addition with molecular flocculant species, pH adjustment with an alkali agent when adding these flocculants, or stirring speed when adding these flocculants. . For example, in [Patent Document 1], as the treatment step, inorganic materials conventionally used such as organic sludge such as sulfate band, polyaluminum chloride (PAC), aluminum chloride, and ferric sulfate (polyiron) are used. Add the flocculant alone or in combination of two or more, then add the organic flocculant, add the inorganic flocculant until the pH is 4 or less, and then add the alkali agent. The sludge dewatering method is described in which the pH is adjusted to 4 to 7 and then the amphoteric polymer flocculant is added to treat the suspended sludge sludge as a low moisture content filter cake.
また、［特許文献３］には、商業用、事務用、家庭用等に広く使用されている感圧接着紙を含む古紙を再生処理して得られる粘着物を含有する再生パルプの処理方法として、この再生パルプ中に微分散されている粘着物を表面に吸着し、懸濁粒子を増大させる作用を発揮させる吸油量が４０ｍｌ／１００ｇ以上であるベントナイト、活性白土等の無機凝集剤を添加させて、パルプ濃度２〜８重量％の懸濁液とした後、１時間以上撹拌処理してパルプ濃度１〜２重量％に希釈した懸濁液をスクリーン処理する、又はパルプ濃度０．５〜１重量％に希釈させた懸濁液をクリーナー処理して粘着物を除去する再生パルプの処理方法が記載されている。 [Patent Document 3] describes a method for treating recycled pulp containing a pressure-sensitive adhesive obtained by reclaiming waste paper containing pressure-sensitive adhesive paper widely used for commercial, office, household, etc. In addition, an inorganic flocculant such as bentonite or activated clay with an oil absorption amount of 40 ml / 100 g or more that exerts the action of adsorbing the adhesive substance finely dispersed in the recycled pulp to the surface and increasing the suspended particles is added. Then, after making a suspension with a pulp concentration of 2 to 8% by weight, the suspension processed by stirring for 1 hour or more and diluted to a pulp concentration of 1 to 2% by weight is screened, or the pulp concentration is 0.5 to 1 A method for treating recycled pulp is described in which a suspension diluted to% by weight is subjected to a cleaner treatment to remove stickies.
また、［特許文献４］には、パルプ、製紙工業廃水の汚泥に硫酸バンド、塩化第二鉄、硫酸第一鉄、ポリ硫酸鉄等の無機凝集剤を添加させ、ｐＨ５〜８コントロール下に、カチオン及びアニオンの組合わせ高分子凝集剤のコントロール添加下に処理するパルプ又は製紙工業の汚泥廃水の凝集脱水処理方法が記載されている。 In addition, in [Patent Document 4], an inorganic flocculant such as sulfate band, ferric chloride, ferrous sulfate, and polyiron sulfate is added to sludge of pulp and paper industry wastewater, and under pH 5-8 control, A method for coagulation and dewatering treatment of pulp or paper industry sludge wastewater treated under the controlled addition of a combination of cationic and anionic polymeric flocculants is described.
また、［特許文献５］には、下水道処理場、し尿処理場で発生する有機性汚泥の脱水性を向上させ、無機凝集剤の使用量を減らし、回収される脱水ケーキ焼却灰増加を抑制させる汚泥焼却灰を利用する有機性汚泥の凝集脱水処理法が提案されている。すなわち、下水場汚泥に、シリカ、アルミナ、酸化鉄、カルシア、マグネシア、リン酸分を含む汚泥焼却灰の塩酸水焼却灰スラリーを添加し、次いで無機凝集剤の塩化第二鉄水溶液と、メタクリレート系カチオン性又はメタクリレート系両性高分子凝集剤を添加させて、凝集・脱水・ろ過処理する凝集脱水処理法である。 In [Patent Document 5], the dewaterability of organic sludge generated in sewerage treatment plants and human waste treatment plants is improved, the amount of inorganic flocculant is reduced, and the increase in recovered dewatered cake incineration ash is suppressed. An agglomeration dewatering method for organic sludge using sludge incineration ash has been proposed. That is, the sludge incineration ash slurry of silica sludge incineration ash containing silica, alumina, iron oxide, calcia, magnesia, phosphoric acid content is added to the sewage sludge, then ferric chloride aqueous solution of inorganic flocculant and methacrylate system This is an agglomeration and dehydration method in which a cationic or methacrylate amphoteric polymer flocculant is added to agglomerate, dehydrate and filter.
また、［特許文献６］には、浄水（上水）処理場における凝集沈殿処理水中に残留するアルミニウムイオンがアルツハイマ症の一要因との指摘から、アルミニウム系無機凝集剤であるＰＡＣ、硫酸バンドに代えて、しかも、水酸化物を形成しないマンガンイオン（ＭｎイオンをＳＳとして分離できないため）であるため、Ｍｎ／Ｆｅ量比が９×１０−４以下（凝集処理水中に、飲料水水質基準の快適水質基準：１０μｇ／リットル以下とされている。）である新規な高純度第二鉄系無機凝集剤が提案されている。また、この高純度第二鉄系無機凝集剤は、工業用水処理分野においても、残留アルミニウムイオンの同様な観点から、また、マンガン汚染のおそれがなく、しかも、従来から設けられている特別にマンガン除去処理工程を必要としない好適な無機凝集剤であると記載されている。[Patent Document 6] states that aluminum ions remaining in the coagulation sedimentation treatment water at the water purification (clean water) treatment plant are one factor of Alzheimer's disease. Instead, since it is a manganese ion that does not form a hydroxide (because Mn ions cannot be separated as SS), the Mn / Fe amount ratio is 9 × 10 −4 or less (in the agglomerated treated water, Comfortable water quality standard: 10 μg / liter or less)), a novel high-purity ferric inorganic flocculant has been proposed. In addition, this high-purity ferric inorganic flocculant is also used in the industrial water treatment field from the same viewpoint of residual aluminum ions, there is no risk of manganese contamination, and the specially provided manganese It is described as a suitable inorganic flocculant that does not require a removal treatment step.
また、［特許文献７］には、処理水に対して、急速撹拌下に無機凝集剤を添加させて濁質分をマイクロフロックにさせた後、高分子凝集剤を添加させて凝集沈殿処理を行い、次いでろ過処理させて浄水処理にするに際して、高分子凝集剤の添加後における凝集フロックの流動電流を測定し、それに基づいて高分子凝集剤の添加量をコントロールする浄水処理方法が提案されている。 In [Patent Document 7], an inorganic flocculant is added to the treated water under rapid stirring to make the turbid component into micro floc, and then a polymer flocculant is added to perform the coagulation precipitation treatment. A water purification treatment method has been proposed in which the flow current of the coagulation flocs after the addition of the polymer flocculant is measured and the addition amount of the polymer flocculant is controlled based on the measured flow current after the addition of the polymer flocculant. Yes.
以上のような状況にあって、各種の建設汚泥、河川、港湾等の浚渫汚泥、浄水場汚泥、工場等における汚泥・汚濁廃水は、自然環境や、生活環境を汚染させることから、そのまま河川や、海等へ排出させたり、リユース用水としてリサイクルできない。そのために、従来から、それぞれの終末処理場で水処理凝集剤等を用いて河川や、海に排水できる清澄な廃水に処理されている。また、既に上述した如く［特許文献１］〜［特許文献５］、［特許文献７］からも理解されるように、このような廃水の処理方法においては、用いる凝集剤はコスト的にも著しく低廉であって、また、その処理工程は著しく簡便で低コストな処理方法であることが望まれる。しかも、処理後に新たに発生するろ過ケーキの発生量の抑制・取り扱いが容易であることが望まれる。また、特に［特許文献６］からも明らかなように残留Ａｌイオンに対する課題をクリアさせても、従来から用いられている無機凝集剤は、低廉でなければならないが故に凝集剤として使用することで、新たにＭｎイオン汚染を発生させることも事実である。 Under such circumstances, various construction sludge, dredged sludge from rivers, harbors, water purification plant sludge, sludge and polluted wastewater from factories, etc. contaminate the natural environment and living environment. It cannot be discharged into the sea or recycled as reused water. Therefore, conventionally, it has been treated into clear wastewater that can be drained into rivers or the sea using a water treatment flocculant or the like at each terminal treatment plant. Moreover, as already described above, as can be understood from [Patent Document 1] to [Patent Document 5] and [Patent Document 7], in such a wastewater treatment method, the coagulant used is remarkably costly. It is desirable that the process is inexpensive and the process is extremely simple and low-cost. Moreover, it is desirable that the amount of filter cake newly generated after the treatment can be easily suppressed and handled. In addition, as is clear from [Patent Document 6], even if the problem with respect to residual Al ions is cleared, conventionally used inorganic flocculants must be inexpensive, so they can be used as flocculants. It is also a fact that Mn ion contamination is newly generated.
以上のように廃水処理には、従来から技術的にも、コスト的にも未だ未解決な課題が多く、また、発生量が大量で、また、発生場所も広域的に散在して発生し、更には、発生する汚泥・汚濁廃水によって、必ずしも一様に処理できない傾向にあることから、未だ必ずしも満足される処理方法が提供されていないことも事実である。 As described above, wastewater treatment has many problems that have not been solved yet, both technically and in terms of cost. The amount of wastewater generated is large, and the locations of occurrence are scattered over a wide area. Furthermore, since there is a tendency that the generated sludge and polluted wastewater cannot be uniformly treated, it is also true that a satisfactory treatment method has not yet been provided.
特に、汚泥・汚濁廃水を沈降清澄化させる水処理用無機系凝集剤には、従来から、通常、凝集用主剤及び高分子凝集剤を含めての凝集助剤とを組み合わせて用いられている。すなわち、従来から硫酸第二鉄、塩化第二鉄、ポリ硫酸第二鉄（ポリ鉄）等の鉄塩系の凝集剤のみでは、十分な凝集効果が得られず、また、消石灰等を併用してｐＨ調整を要したりする傾向にあり、また、硫酸アルミ塩・硫酸鉄塩の塩基性混和凝集剤や、ポリ塩化アルミニウム（ＰＡＣ）や、珪酸アルカリ水溶液の珪酸ゾル（又はコロイダルシリカ）等の液状凝集剤も、単独使用では一長一短があって万能ではない。また、これら従来からの無機系凝集剤は、何れも「水和反応」→「ゾル・ゲル化」→「フロック凝集化」等の作用は、廃水のｐＨ領域に依存して、すなわち鉄イオン及びアルミイオン等のゼータ電位の調整下に凝集剤としての作用を発揮させる。従って、従来からこのような浮遊分散する汚泥・汚濁物の「凝集・フロック・沈降」化には、ゼータ電位との関連付け下に実績評価がなされている。その実績評価として、フロック化促進効果及びフロック粒径を増大化させるためから、それぞれ、アニオン性、カチオン性、ノニオン性等の高分子凝集剤を組み合わせて、架橋作用を発揮させる高分子凝集剤の併用が不可欠であることも事実である。 In particular, inorganic coagulants for water treatment that settle and clarify sludge / polluted wastewater have been conventionally used in combination with a coagulant aid including a coagulant main agent and a polymer coagulant. In other words, conventional iron salt-type flocculants such as ferric sulfate, ferric chloride, and polyferric sulfate (polyiron) alone cannot provide a sufficient agglomeration effect. PH adjustment is required, and the basic admixing flocculants of aluminum sulfate and iron sulfate, polyaluminum chloride (PAC), and silicic acid sol (or colloidal silica) of alkali silicate aqueous solution, etc. Liquid flocculants are not universal because of their merits and demerits. In addition, these conventional inorganic flocculants all have an action such as “hydration reaction” → “sol / gelation” → “floc agglomeration” depending on the pH range of wastewater, that is, iron ions and It acts as a flocculant under the control of zeta potential such as aluminum ions. Therefore, in the past, performance evaluation has been made in association with the zeta potential for such agglomeration / floc / sedimentation of sludge and pollutants that float and disperse. As a result evaluation, in order to increase the flocking promoting effect and the floc particle size, a polymer flocculant that exhibits a crosslinking action by combining polymer flocculants such as anionic, cationic, and nonionic, respectively. It is also true that a combination is essential.
以上から、本発明の目的は、地域生活圏及び産業圏から発生する各種の生活廃水、産業廃水の処理に、フロック形成速度が大きく、また、最終到達フロック粒径が大きく、沈降速度を速くして、上澄み液とスラッジとの分離が短時間であって、しかも、処理工程がより簡便な処理を可能にさせ、且つ低廉で取扱い容易な凝集剤であることを特徴とする無機系粉末状の各種廃水の水処理用凝集剤を提供することである。 From the above, the object of the present invention is to increase the floc formation speed, increase the final floc particle size, and increase the sedimentation speed in the treatment of various domestic and industrial wastewater generated from the local living area and industrial area. In addition, the inorganic liquid powder is characterized in that the separation of the supernatant liquid and the sludge is a short time, and the processing step enables a simpler processing, and is an inexpensive and easy-to-handle flocculant. It is to provide a flocculant for water treatment of various wastewater.
また、本発明の他の目的は、このようなフロック形成速度が大きく、最終到達フロック粒径が大きく、沈降速度が速く、上澄液とスラッジとの分離が短時間にさせる無機系粉末状凝集剤を用いて、各種汚泥廃水及び各種汚濁廃水を簡便で、しかも、低コストで処理できる水処理方法を提供することである。 In addition, another object of the present invention is such an inorganic powdery agglomeration that has such a large floc formation rate, a large final floc particle size, a high sedimentation rate, and a short separation of the supernatant and sludge. It is to provide a water treatment method that can treat various sludge wastewater and various polluted wastewater easily and at low cost by using an agent.
そこで、本発明者らが、既に特許出願済みの特願０３−２０４１２６号において、各種の建設汚泥、河川、港湾等の浚渫汚泥、浄水場汚泥、工場排水汚泥等で発生する高含水率でドロドロ状（又はヘドロ状）で取扱い搬送・運搬し難い各種の汚泥を、取扱い容易な形状に凝集固結化させ、再汚泥化させない高含水率汚泥の固化処理材を提案している。 Therefore, the inventors of the present invention have already applied for a patent in Japanese Patent Application No. 03-204126 with a high moisture content generated in various types of construction sludge, dredged sludge in rivers, harbors, water purification plant sludge, factory wastewater sludge, etc. We propose a high moisture content sludge solidification material that coagulates and consolidates various sludges that are difficult to handle, transport and transport in the form of sludge (or sludge), and does not re-sludge.
本発明者らが提案済みの固化処理材とは、
（１）各種の廃水を処理させて発生する高含水率のろ過ケーキや、自然沈降及び沈降堆積の高含水率の汚泥、浚渫汚泥に、極めて容易に分散混合することができ、汚泥を取扱い容易な形状に凝集化させ、固結化させる無機系の固化処理材である。
（２）しかも、使用することで、環境汚染・環境保全等に係わって、再汚染を発生させない更にはコスト的にも低廉な素材から構成されている。
（３）そのために、各種の環境規制をクリヤし、各種の産業に利用され排出・回収される産業排出材等の低廉な素材を有効にリユースさせた無機質固化処理材である。
（４）そこで、その主配合成分が、従来から各種の工業から排出・回収されている代表的な工業廃材であって、火力発電所等の排煙脱硫処理で副生する排煙石膏や、製紙工場の焼却ダスト、鋳物砂の取扱い業からの使用済み鋳物砂の焼成再生処理時に回収される微硅砂等の著しく低廉で、再使用しても環境的にも極めて安全性の高い無機質素材である。
例えば、製紙工場から排出される焼却ダストは、国内で約１００，０００ｔ／Ｍ以上で、これは紙の抄紙工程で使用されるタルク，カオリン，アルミナ，シリカ等の添料としての粘土鉱物等の無機質成分が、パルプ繊維と共に濾過処理されて回収される含水ケーキ状物を約８５０℃で焼成させ副性する焼却ダストで、ダイオキシンや、有害金属を含まず、既に焼成汚泥肥料としても認可されているクリーンな工業廃材である。
（５）しかも、配合されている、製紙工場の焼成炉から捕収されるシリカ、アルミナ、マグネシア及びカルシアを主成分に含有する粉末状の焼成ダストは、無機質吸水性硬化促進材として作用し、特にその他有機質成分を全く含まないＪＩＳ Ｋ５１０１．１９法の吸油量測定法に準拠させて求まる吸水量が５０〜９０ｍｌ／１００ｇの範囲にあって、優れた吸水作用を発揮する素材である。
（６）また、その産業廃材が、特に水質汚濁防止法で定める排出基準としての、カドミ、全シアン、有機リン、六価クロム、鉛、ヒ素、総水銀、アルキル水銀、ジクロロメタン、ＰＣＢ等の有害成分の含有基準を全てクリヤする素材でもある。The solidification material proposed by the inventors is
(1) It is very easy to disperse and mix with high-water content filter cakes generated by treating various wastewaters, natural water sedimentation and sedimentation high-water content sludge, and sludge, and easy to handle sludge. It is an inorganic solidified material that is agglomerated and consolidated into various shapes.
(2) In addition, it is made of a material that does not cause re-contamination and is low in cost due to environmental pollution and environmental conservation.
(3) To that end, it is an inorganic solidification treatment material that has cleared various environmental regulations and has effectively reused inexpensive materials such as industrial waste materials that are used and discharged / recovered in various industries.
(4) Therefore, the main compounding ingredients are typical industrial waste materials that have been discharged and collected from various industries, and flue gas gypsum by-produced by flue gas desulfurization treatment at thermal power plants, Inorganic materials that are extremely inexpensive, reusable and environmentally safe, such as incineration dust from paper mills, fine sand collected from used casting sand from the foundry sand handling industry is there.
For example, incineration dust discharged from paper mills is about 100,000 t / M or more in Japan, and this includes clay minerals as additives for talc, kaolin, alumina, silica, etc. used in paper making processes. An incinerated dust that is a by-product of burning a water-containing cake recovered by filtration with pulp fibers at about 850 ° C. It does not contain dioxins or harmful metals and has already been approved as a calcined sludge fertilizer. Clean industrial waste.
(5) Moreover, the powdered baked dust containing silica, alumina, magnesia, and calcia as the main components, which is collected from the baking furnace of the paper mill that is blended, acts as an inorganic water-absorbing hardening accelerator, In particular, it is a material that exhibits an excellent water-absorbing action when it has a water absorption of 50 to 90 ml / 100 g determined according to the oil absorption measurement method of JIS K5101.19, which does not contain any other organic components.
(6) In addition, the industrial waste materials are harmful, such as cadmium, total cyanide, organophosphorus, hexavalent chromium, lead, arsenic, total mercury, alkyl mercury, dichloromethane, PCB, etc. as emission standards specified by the Water Pollution Control Law. It is also a material that clears all the content standards of ingredients.
そこで、本発明者らは、これらの知見に着目して上記課題を解決するために、高含水率の汚泥ケーキの前駆体として発生した懸濁物（ＳＳ）濃度が８，５００ｍｇ／リットルで浮遊する汚濁廃水に、既に本発明者らが提案した粉末状の汚泥固化処理材を添加・撹拌処理をした結果、汚泥ケーキに対して作用したと同様に粉末状で、吸水性で、撹拌分散性で、凝集性等が活かされて、汚濁廃水中の浮遊懸濁物が効果的に凝集・沈降されることを見出して、本発明を完成させるに至った。 Therefore, in order to solve the above-mentioned problems by paying attention to these findings, the present inventors suspended the suspended matter (SS) generated as a precursor of the sludge cake having a high water content at 8,500 mg / liter. As a result of adding and stirring the powdery sludge solidification material already proposed by the present inventors to the polluted wastewater, the powdered, water-absorbing, stirring and dispersible as well as acting on the sludge cake Thus, the present inventors have completed the present invention by finding that the coagulability and the like are utilized and the suspended suspension in the polluted wastewater is effectively aggregated and settled.
すなわち、本発明が提供する水処理用凝集剤の第一の特徴が、シリカ、アルミナ、マグネシア及びカルシア成分を主成分として含有する吸水量が５０〜９０ｍｌ／１００ｇの範囲にある無機粉末（１）と、シリカ成分が６５〜８０重量％で、平均粒子径１５〜１５０μｍで、吸水量が２０〜４０ｍｌ／１００ｇの範囲にある硅砂粉末（２）と、半水石膏粉末（３）及び高分子凝集剤（４）とを含有し、しかも、高分子凝集剤（４）以外の主配合剤である無機粉末（１）、硅砂粉末（２）及び半水石膏粉末（３）の何れもが水不溶性で粉末状の無機質配合成分である。
また、その第二の特徴が、主配合剤として粉末状に混合配合されている無機粉末（１）、硅砂粉末（２）、半水石膏粉末（３）及び高分子凝集剤（４）との合計含有量１００重量部当たり、唯一、水可溶性である原子価が３価以上である金属塩無機粉末（５）が０．０５〜２０重量部の範囲で含有するワンパックタイプであって、各種の汚泥・汚濁廃水に用いることができる無機系粉末凝集剤である。That is, the first feature of the water treatment flocculant provided by the present invention is that the water absorption amount containing silica, alumina, magnesia and calcia components as main components is in the range of 50 to 90 ml / 100 g of inorganic powder (1) Silica sand powder (2) having a silica component of 65 to 80% by weight, an average particle size of 15 to 150 μm and a water absorption of 20 to 40 ml / 100 g, hemihydrate gypsum powder (3) and polymer agglomeration In addition, all of inorganic powder (1), cinnabar powder (2) and hemihydrate gypsum powder (3), which are main compounding agents other than polymer flocculant (4), are water-insoluble. It is a powdery inorganic compounding component.
The second feature is that the inorganic powder (1), cinnabar powder (2), hemihydrate gypsum powder (3) and polymer flocculant (4) mixed and blended in powder form as the main compounding agent. It is a one-pack type in which the metal salt inorganic powder (5) whose water-soluble valence is not less than 3 is contained in the range of 0.05 to 20 parts by weight per 100 parts by weight of the total content, It is an inorganic powder flocculant that can be used for sludge and polluted wastewater.
また、本発明によれば、高速攪拌下にある活性汚泥法で処理されて懸濁物（ＳＳ）濃度が５０〜２０，０００ｍｇ／リットルの廃水１０００ｍｌ当たり、請求項１に載するワンパックタイプの水処理用無機系粉末凝集剤を、１００〜３０，０００ｐｐｍの範囲で、しかも、少なくとも一段法で添加させ、次いで、緩速攪拌後の静置下に懸濁物（ＳＳ）濃度が１０〜５０ｐｐｍ以下の清澄水にできることを特徴とする汚泥廃水の処理方法を提供する。 In addition, according to the present invention, the one-pack type of the one-pack type that is treated by the activated sludge method under high-speed stirring and has a suspension (SS) concentration of 50 to 20,000 mg / liter of waste water of 1000 ml. An inorganic powder flocculant for water treatment is added in the range of 100 to 30,000 ppm, and at least in one step, and then the suspension (SS) concentration is 10 to 50 ppm under still standing after slow stirring. Provided is a sludge wastewater treatment method characterized by being made into the following clear water.
更にはまた、本発明によれば、高速攪拌下にある各種の工事現場で発生する懸濁物（ＳＳ）濃度が５０〜２０，０００ｍｇ／リットルである１次沈降槽中の汚濁廃水１０００ｍｌ当たり、請求項５に記載するワンパックタイプの水処理用無機系粉末凝集剤を１００〜３０，０００ｐｐｍの範囲で、しかも、少なくとも一段法で添加させ、次いで、緩速攪拌後の静置下に懸濁物（ＳＳ）濃度が１０〜５０ｐｐｍ以下の清澄水にできることを特徴とする汚濁廃水の処理方法を提供する。 Furthermore, according to the present invention, per 1000 ml of contaminated wastewater in the primary sedimentation tank having a suspension (SS) concentration generated at various construction sites under high speed stirring of 50 to 20,000 mg / liter, The one-pack type inorganic powder flocculant for water treatment according to claim 5 is added in the range of 100 to 30,000 ppm and at least in one step, and then suspended under static stirring. Provided is a method for treating polluted wastewater, characterized in that it can be clarified water having an object (SS) concentration of 10 to 50 ppm or less.
以上から、本発明によって提供される水処理凝集剤は、数種の粉末状の無機質成分からなり、しかも、従来の無機凝集剤とは著しく相違するほぼ水不溶性の数種の無機成分がワンパックタイプに混合された取扱い容易な水処理用凝集剤である。また、この水処理用凝集剤は、各種の汚泥廃水又は汚濁廃水に、「強撹拌下に一段法で添加」させた後、「緩撹拌下」後の「静置下」に廃水中に浮遊する懸濁物に対して、ワンパックタイプの無機質粉末状凝集剤が、「分散接触」→「吸水吸引収束」及び／又は「吸水水和収束」→「フロック凝集化」及び「フロック粒径の成長化」→「沈降清澄化」等の作用が効果的に発揮させる従来の無機凝集剤とは、著しく相違する新規なワンパックタイプの水処理用の無機系粉末凝集剤である。 From the above, the water treatment flocculant provided by the present invention is composed of several kinds of powdery inorganic components, and several kinds of almost water-insoluble inorganic components that are significantly different from conventional inorganic flocculants are in one pack. Easy-to-handle water treatment flocculant mixed in type. In addition, this flocculant for water treatment is added to various sludge wastewater or polluted wastewater by “one-step addition under strong stirring”, and then floated in wastewater after “under gentle stirring”. One-pack type inorganic powder flocculant is added to the suspension to be “dispersed contact” → “water absorption suction convergence” and / or “water absorption hydration convergence” → “floc aggregation” and “floc particle size”. It is a novel one-pack type inorganic powder flocculant for water treatment that is significantly different from the conventional inorganic flocculant that effectively exerts actions such as “growth” → “precipitation clarification”.
このようなワンパックタイプに粉末混合された配合剤のそれぞれが発揮させる詳細な作用効果は不明であるが、ワンパックタイプであることで、以下の（ｉ）〜（ｉｖ）なる作用効果が、並行及び／又は時間差下に組み合わされて処理効果を進行するものと言える。
（ｉ）：吸水量が５０〜９０ｍｌ／１００ｇの範囲にある無機粉末（１）、吸水量が２０〜４０ｍｌ／１００ｇの範囲にある硅砂粉末（２）とは、「強撹拌下」に素早く水親和性を発揮させて、浮遊する懸濁物に「分散接触」→「吸水吸引収束」させる。
（ｉｉ）：半水石膏粉末（３）は、「強撹拌下」に素早く水親和性及び／又は２水化の水和反応を発揮させて、浮遊する懸濁物に「分散接触」→「吸水水和収束」させる。
（ｉｉｉ）：唯一の水可溶性である原子価２以上の金属塩無機粉末（５）と架橋作用を発揮する高分子凝集剤（４）とが、「強撹拌下」に素早く、「分散溶解」→「イオン接触」して浮遊する懸濁物の電荷を調整させて、「緩撹拌下」に「フロック凝集化」→「フロック粒径の増大化」を発揮させる。なお、本発明におけるこの水可溶性金属塩無機粉末（５）は、廃水中に分散して容易に不溶性の水和物に転化する。
（ｉｖ）：「静置下」に水不溶性で従来には見られない程の高比重である無機粉末成分（１）〜（３）が発揮する「重力沈降性」も作用して、浮遊する懸濁物を効果的に「沈降清澄化」させる。Although the detailed action and effect exhibited by each of the compounding agents powder-mixed in such a one-pack type is unknown, the following effects (i) to (iv) are obtained by being a one-pack type. It can be said that the processing effect progresses in combination in parallel and / or under a time difference.
(I): The inorganic powder (1) having a water absorption of 50 to 90 ml / 100 g and the cinnabar powder (2) having a water absorption of 20 to 40 ml / 100 g are water quickly under “strong stirring”. Demonstrate the affinity to “disperse contact” → “water absorption and suction convergence” to the suspended suspension.
(Ii): The hemihydrate gypsum powder (3) exhibits a water affinity and / or dihydration hydration reaction quickly under “strong stirring”, and “dispersion contact” → “ "Water absorption hydration converges".
(Iii): The only water-soluble metal salt inorganic powder (2) having a valence of 2 or more and the polymer flocculant (4) exhibiting a crosslinking action are rapidly “dispersed and dissolved” under “strong stirring”. → “Ion contact” is used to adjust the charge of the suspended suspension, and under “slow agitation”, “floc agglomeration” → “increase in floc particle size” is exhibited. In addition, this water-soluble metal salt inorganic powder (5) in this invention disperse | distributes in a wastewater, and converts into an insoluble hydrate easily.
(Iv): “Gravity sedimentation” exerted by the inorganic powder components (1) to (3), which is water-insoluble and has a high specific gravity that cannot be seen in the past, also acts and floats. Effectively “precipitates” the suspension.
また、従来からの廃水の水処理行程は、各種廃水の発生状況、汚泥・汚濁物の種類、濁度等によって、無機凝集剤の単独又は２種以上の組合せ添加、又は高分子凝集剤種との組み合せ添加、又はこれら凝集剤添加時のアルカリ剤等によるｐＨ調整、又はこれら凝集剤添加時の撹拌速度の組合わせ等から、通常、単純・簡便でない多段の処理工程を余儀なくされていた各種の汚泥・汚濁廃水を、このよう作用効果を発揮させる本発明によるワンパックタイプの水処理用無機系粉末凝集剤は、一段の添加工程で沈降清澄化できる簡便、低処理コストを可能にさせる新規な廃水の水処理方法を提供することができる。 In addition, the conventional wastewater treatment process is based on the state of various wastewater generation, the type of sludge / contaminant, the turbidity, etc. From the combination addition of these, or the pH adjustment with an alkali agent at the time of adding these flocculants, or the combination of the stirring speed at the time of adding these flocculants, etc. The one-pack type inorganic powder flocculant for water treatment according to the present invention, which exhibits sludge / polluted wastewater in this way, is a novel and easy-to-set and low treatment cost that can be settled and clarified in a single addition step. A method for treating wastewater can be provided.
また、このような特徴を発揮させるワンパックタイプの水処理用無機系粉末凝集剤によって凝集沈降される汚泥・汚濁沈降物は、例えば、濁度ＳＳ濃度５，０００〜２０，０００ｐｐｍ範囲の汚濁廃水に対して、本発明の水処理用無機系粉末凝集剤５，０００〜１５，０００ｐｐｍ範囲の添加処理で得られる重力脱水物の水分（％）は、６５〜７３であって、通常、加圧脱水処理されることから、例えば、ベルトプレスの多段加圧条件０．２Ｋｇ／ｃｍ２→０．５Ｋｇ／ｃｍ２→１．０Ｋｇ／ｃｍ２（各１分加重下）の加圧脱水物の水分（％）は、５３．１〜５３．８の含水物として沈降処理される。このような事実から、本発明によるほぼ水不溶性の無機系粉末配合剤からなる凝集剤は、脱水性の良好な汚濁沈降物を形成させる効果を発揮させる。Moreover, the sludge and the polluted sediment that are coagulated and settled by the one-pack type inorganic powder flocculant for water treatment that exhibits such characteristics are, for example, polluted wastewater having a turbidity SS concentration of 5,000 to 20,000 ppm. On the other hand, the water content (%) of the gravity dehydrated product obtained by the addition treatment in the range of 5,000 to 15,000 ppm of the inorganic powder aggregating agent for water treatment of the present invention is 65 to 73 and is usually pressurized. Since the dehydration process is performed, for example, the moisture content of the pressure dehydrated product under the belt press multi-stage pressurization condition 0.2 kg / cm 2 → 0.5 kg / cm 2 → 1.0 kg / cm 2 (each under 1 minute load) (%) Is settled as a hydrous material of 53.1 to 53.8. From these facts, the flocculant comprising the almost water-insoluble inorganic powder compounding agent according to the present invention exhibits the effect of forming a polluted sediment having good dewaterability.
以下に、本発明によるワンパックタイプの水処理用無機系粉末凝集剤について、その実施に係わる最良形態を更に説明する。 Below, the best form concerning the implementation is further demonstrated about the inorganic type powder flocculant for water treatments of the one pack type by this invention.
既に上述する如く、本発明による汚泥廃水及び汚濁廃水用の水処理凝集剤は、「強撹拌下」に素早く水親和性を発揮させて、浮遊する懸濁物に「分散接触」→「吸水吸引収束」させる吸水量が５０〜９０ｍｌ／１００ｇの範囲にある無機粉末（１）と、吸水量が２０〜４０ｍｌ／１００ｇの範囲にある硅砂粉末（２）と、「強撹拌下」に素早く水親和性及び２水化の水和反応を発揮させて、浮遊する懸濁物に「分散接触」→「吸水水和収束」させる半水石膏粉末（３）と、「強撹拌下」に素早く「分散溶解」→「イオン接触」して浮遊する懸濁物の電荷を調整させて、「緩撹拌下」に「フロック凝集化」及び「フロック成長」させる唯一の水可溶性である原子価３以上の金属塩無機粉末（５）［以後、単に金属塩無機粉末（５）と記すこともある。］及び可溶して架橋作用を発揮させる高分子凝集剤（４）とが、「各種粉末状機能性配合材」と「吸水・吸引・収束・凝集の作用効果」とがワンパックタイプ化されていることを特徴とする無機系粉末状の新規な廃水用の水処理凝集剤である。 As already mentioned above, the water treatment flocculant for sludge wastewater and polluted wastewater according to the present invention quickly exhibits water affinity under “strong stirring”, and “dispersion contact” → “water absorption suction” on the suspended suspension. Convergent ”water absorption amount in the range of 50-90 ml / 100 g, inorganic powder (1) in the range of water absorption amount of 20-40 ml / 100 g, and quick water affinity under“ strong stirring ” Hemihydrate gypsum powder (3), which makes the suspension and “hydration hydration reaction” and “dispersion contact” → “water absorption and hydration convergence” to the suspended suspension, quickly “disperse under strong stirring” The only water-soluble metal with a valence of 3 or more that adjusts the electric charge of the suspended suspension by “dissolution” → “ionic contact” and “floc agglomerates” and “floc grows” under “slow agitation” Salt-inorganic powder (5) [hereinafter simply referred to as metal salt-inorganic powder (5) That. ] And a polymer flocculant (4) that dissolves and exhibits a cross-linking action, and "various powdery functional compounding materials" and "effects of water absorption / suction / convergence / aggregation" are made into one pack type It is a novel water treatment flocculant for inorganic waste water, characterized in that it is an inorganic powder.
このように数種の異なる粉末状配合剤が水処理用凝集剤としてワンパックタイプ化されていることは、従来の水処理用凝集剤とは異なる新規なものである。また、既に上述する如くの作用効果を発揮させる本発明のワンパックタイプの水処理用凝集剤においては、特に主配合剤でもある吸水量が５０〜９０ｍｌ／１００ｇの範囲にあるシリカ、アルミナ、マグネシア及びカルシアを主成分に含有する無機粉末（１）と、シリカ成分が６５〜８０重量％で、平均粒子径１５〜１５０μｍで吸水量が２０〜４０ｍｌ／１００ｇの範囲にある硅砂粉末（２）に係わって、その吸水量が、必ずしも格別高吸水性ではなく、例えば、ベントナイトのような高吸水量（ｍｌ／１００ｇ）の水膨潤性層状粘土鉱物や、高吸油価（ｍｌ／１００ｇ）の微粉シリカでないことも特徴と言える。 The fact that several different powdered compounding agents are made into a one-pack type as a water treatment flocculant is a novel one that is different from conventional water treatment flocculants. Further, in the one-pack type water treatment flocculant of the present invention that exhibits the effects as described above, silica, alumina, magnesia whose water absorption is in the range of 50 to 90 ml / 100 g, which is also the main compounding agent, is particularly preferred. In addition, inorganic powder (1) containing calcia as a main component, and silica sand powder (2) having a silica component of 65 to 80% by weight, an average particle size of 15 to 150 μm, and a water absorption of 20 to 40 ml / 100 g. Therefore, the water absorption is not necessarily particularly high water absorption. For example, water-swelling layered clay minerals with high water absorption (ml / 100 g) such as bentonite, and fine powder silica with high oil absorption (ml / 100 g). It can also be said that it is not.
すなわち、高吸水性であるがベントナイトの如く水膨潤性で、また、同じく高吸油量で高吸水性を発揮する微粉シリカ等は、吸水後、いずれもゲル状の粘弾粘調状物になって、反面、懸濁浮遊物の凝集沈降を著しく阻害させる傾向にある。従って、本発明における無機粉末（１）及び硅砂粉末（２）係わる吸水量は、撹拌分散下に汚泥・汚濁廃水中に素早く分散して、懸濁浮遊物に「分散接触」→「吸水水和収束」を発揮させる水親和性であることを示すものと言える。 In other words, finely divided silica that is highly water-absorbing but water-swelling like bentonite, and also exhibits high water absorption with a high oil absorption amount, becomes a gel-like viscoelastic viscose after water absorption. On the other hand, it tends to significantly inhibit the aggregation and sedimentation of suspended suspensions. Therefore, the water absorption amount related to the inorganic powder (1) and cinnabar powder (2) in the present invention is quickly dispersed in sludge / contaminated wastewater with stirring and dispersed, and "dispersed contact" → "water absorption hydration" It can be said that it shows water affinity that exhibits “convergence”.
そこで、本発明においては、必ずしも限定されないが、無機粉末（１）として、好ましくは、無機粉末（１）が製紙工場の焼成炉から捕収される粉末状の焼成ダストが適宜好適に使用される。また、硅砂粉末（２）として、好ましくは、鋳物砂取扱い業から発生する使用済み鋳物砂の焼成硅砂粉末が適宜好適に配合剤として使用することができる。いずれの配合剤も粉末状であって、撹拌下の廃水中への分散・拡散性に優れ、しかも、優れる水親和性を発揮させる低廉な配合剤である。 Therefore, in the present invention, although not necessarily limited, as the inorganic powder (1), preferably, a powdered baking dust in which the inorganic powder (1) is collected from a baking furnace of a paper mill is suitably used. . In addition, as the cinnabar powder (2), preferably, a calcined cinnabar powder of used foundry sand generated from the foundry sand handling industry can be suitably used as a compounding agent. Each of the compounding agents is in a powder form, and is an inexpensive compounding agent that is excellent in dispersibility and diffusibility in agitation waste water and exhibits excellent water affinity.
また、上述する粉末状で、水分散性で、吸水性又は水親和性である無機粉末（１）及び硅砂粉末（２）係わって、その互いの吸水量から発揮させる両者配合材は、粉末状の吸水性無機質配合剤と、粉末状の吸水性無機質配合助剤としての配合組合わせである。本発明において、無機粉末（１）として、上記する製紙工場の焼成炉から捕収される焼成ダストは、粉末状のシリカ、アルミナ、マグネシア及びカルシアを主成分に含有し、吸水量が５０〜９０ｍｌ／１００ｇの範囲にある。既に上述するように、粉末状で撹拌下に分散・拡散して、水親和性で、吸水性を発揮させる過程が、汚泥・汚濁廃水中に浮遊する懸濁物に「強撹拌下」系に素早く「分散接触」→「吸水吸引収束」を適宜効果的に作用させると思われる。また、高温下の焼成炉からの焼成ダストとして捕収されることから、本発明においては、成分的にも極めて再汚染性のないクリーンで低廉な優れた工業廃材のリユース配合剤である。また、その粉末粒度は、撹拌下の分散性、吸水性又は水親和性を効果的に発揮させることから、好ましくは、平均粒子径が２０〜４００μｍの範囲にあることが好適である。 In addition, the above-mentioned powder, water dispersible, water-absorbing or water-affinity inorganic powder (1) and cinnabar powder (2) are both in the form of powder. The water-absorbing inorganic compounding agent and a powdery water-absorbing inorganic compounding aid are combined. In the present invention, as the inorganic powder (1), the calcined dust collected from the calcining furnace of the paper mill described above contains powdered silica, alumina, magnesia and calcia as main components, and has a water absorption of 50 to 90 ml. / 100g. As already mentioned above, the process of dispersing and diffusing in a powdery state with stirring, water affinity, and water absorption is a "strongly stirring" system for suspensions suspended in sludge and polluted wastewater. It seems that “dispersed contact” → “water absorption / suction convergence” is effectively acted quickly and appropriately. Further, since it is collected as calcined dust from a calcining furnace at a high temperature, in the present invention, it is a clean, inexpensive and excellent industrial waste reuse compounding agent that is extremely free from re-contamination. Moreover, since the powder particle size effectively exhibits dispersibility, water absorption or water affinity under stirring, the average particle size is preferably in the range of 20 to 400 μm.
また、本発明において、硅砂粉末（２）として上記する鋳物砂取扱い業から発生する使用済み鋳物砂の焼成硅砂粉末は、低廉で、水不溶性で、再汚染性のないシリカ成分が６５〜８０重量％で、好ましくは、平均粒子径が１５〜１５０μｍで、より好ましくは１００μｍ以下であって、しかも、吸水量が２０〜４０ｍｌ／１００ｇの範囲にあるように、特に水親和性で、水分散性の粉末状配合剤として適宜好適に使用される。 Further, in the present invention, the fired cinnabar powder of the used foundry sand generated from the above-mentioned foundry sand handling business as the cinnabar powder (2) is inexpensive, water-insoluble, and contains 65 to 80 wt. %, Preferably an average particle size of 15 to 150 μm, more preferably 100 μm or less, and water absorption in the range of 20 to 40 ml / 100 g, in particular water affinity and water dispersibility. It is suitably used as a powdery compounding agent.
また、本発明に用いる半水石膏粉末（３）は、既に上述する如く、「強撹拌下」に素早く「半水石膏」→「２水石膏」化なる水和反応を発揮させる変化過程が、浮遊する懸濁物に「分散接触」→「吸水水和収束」させる作用を発揮させると理解される。その半水石膏粉末（３）も低廉な素材であることが望まれ、好ましくは、火力発電所で大量に副生する排煙脱硫石膏を、半水化させた粉末石膏が適宜好適に用いられる。また、その粉末粒度は、撹拌下の分散性、２水化の水和反応性から、好ましくは、平均粒子径が４０〜４００μｍの範囲にあれば好適である。 In addition, as already described above, the hemihydrate gypsum powder (3) used in the present invention has a changing process that quickly exhibits a hydration reaction of “semihydrate gypsum” → “2 hydrogypsum” under “strong stirring”. It is understood that the suspended suspension exerts the action of “dispersing contact” → “water absorption and hydration convergence”. The hemihydrate gypsum powder (3) is also desired to be an inexpensive material. Preferably, a powder gypsum obtained by semi-hydrating flue gas desulfurization gypsum produced as a by-product in a thermal power plant is suitably used. . The powder particle size is preferably in the range of 40 to 400 μm from the viewpoint of dispersibility under stirring and hydration reactivity of dihydration.
また、本発明に用いる唯一水可溶性で、原子価が３価以上である水可溶性金属塩無機粉末（５）としては、従来から凝集剤として使用されている硫酸第二鉄、塩化第二鉄、ポリ硫酸第二鉄（ポリ鉄）、特開０２−０７９００３号に提案する高純度第二鉄塩等や、硫酸バンド、硫酸アルミ塩・硫酸鉄塩の塩基性混和アルミ塩や、ポリ塩化アルミニウム（ＰＡＣ）等が挙げられる。本発明において、好ましくは、低廉で、粉末ワンパック化が容易で、しかも、廃水中に分散させて容易に水不溶性の水和物に転化する観点から硫酸バンド、ポリ塩化アルミニウム（ＰＡＣ）等の金属アルミニウム塩粉末の１種又は２種混合物を適宜好適に用いることができる。 Moreover, as the water-soluble metal salt inorganic powder (5) that is the only water-soluble and has a valence of 3 or more used in the present invention, ferric sulfate, ferric chloride, which have been conventionally used as a flocculant, Polyferric sulfate (polyiron), high-purity ferric salt proposed in Japanese Patent Application Laid-Open No. 02-079003, etc., basic admixed aluminum salts of sulfate bands, aluminum sulfate / iron sulfate, polyaluminum chloride ( PAC) and the like. In the present invention, a sulfate band, polyaluminum chloride (PAC), etc. are preferable from the viewpoint of low cost, easy powder one-pack formation, and dispersion into waste water to easily convert to a water-insoluble hydrate. One or two kinds of metallic aluminum salt powder can be suitably used as appropriate.
なお、このような無機塩凝集剤を用いることによる既に上述したＭｎイオン汚染に関しては、本発明において、例えば、金属塩無機粉末（５）として従来から市販されている水処理用の凝集剤硫酸バンド［通常、Ｍｎイオンの最大含有量は５０ｐｐｍである粉末硫酸バンド中（Ａｌ２（ＳＯ４）３・１２Ｈ２Ｏ）である。］を用いた場合、本発明による水処理用無機系粉末凝集剤を１００〜３０，０００ｐｐｍの範囲で添加処理すると、処理水中に排出されるＭｎイオン量は、０．５ｐｐｂ〜０．１５ｐｐｍの範囲（飲料水水質基準の快適水質基準：Ｍｎイオンが１０μｇ／リットル以下とされている。）になると言える。また、Ａｌイオンのアルツハイマ症要因に係わって、その添加処理時におけるＡｌ２Ｏ３で表すＡｌイオンの添加量は、水処理用無機系粉末凝集剤を１００〜３０，０００ｐｐｍの範囲で、０．８８２〜２６４．６ｐｐｍの範囲になるが、そのほぼ全量が水不溶化のＡｌ水和物であるフロック沈降物として消費されて、処理水中へのＡｌイオン排出はないと言える。Incidentally, regarding the Mn ion contamination already described above by using such an inorganic salt flocculant, in the present invention, for example, a flocculant sulfuric acid band for water treatment that is conventionally commercially available as a metal salt inorganic powder (5). [Usually, the maximum content of Mn ions is in powdered sulfuric acid band (Al 2 (SO 4 ) 3 · 12H 2 O) of 50 ppm. When the inorganic powder flocculant for water treatment according to the present invention is added in the range of 100 to 30,000 ppm, the amount of Mn ions discharged into the treated water is in the range of 0.5 ppb to 0.15 ppm. It can be said that (comfortable water quality standard of drinking water quality standard: Mn ion is 10 μg / liter or less). In addition, in relation to the Alzheimer's disease factor of Al ions, the amount of Al ions represented by Al 2 O 3 during the addition treatment is in the range of 100 to 30,000 ppm of the inorganic powder flocculant for water treatment, and is 0.00. Although it is in the range of 882 to 264.6 ppm, it can be said that almost the entire amount is consumed as a floc sediment which is a water-insolubilized Al hydrate, and Al ions are not discharged into the treated water.
また、本発明によるワンパックタイプの無機系粉末凝集剤として、無機粉末（１）、硅砂粉末（２）、半水石膏粉末（３）及び原子価２以上の水可溶性金属塩無機粉末（５）に、高分子凝集剤（４）を組合わせ配合させる作用効果は、既に説明済みであるが、水分散下で、これら無機配合剤との作用効果をよる効果的に発揮させることから、好ましくは、アニオン性の高分子凝集剤であることが好適である。また、本発明において、その高分子凝集剤は、他の配合材と同様に、粉末状であることにより吸水性を発揮させて、素早く凝集剤としての［フロック−凝集］化作用を汚泥・汚濁粒子に及ぼさせることができる。本発明において、その平均粒子径は、好ましくは６０〜２００μｍである。また、本発明の凝集剤の配合剤機能からして、粉末状にすることでその溶解性（２０℃での溶解度が０．０１ｇ／１００ｍｌ以上）も加わって、その添加量も少量でよい。従って、その粒子径も下限値６０μｍ以下にする必要がなく、単に粉砕コストを要すだけである。そこで、粉末状の高分子凝集剤として、好ましくは、その適正ｐＨが弱酸性〜アルカリ性で、適正使用系が無機系で、また、その効果の凝集・沈殿性等からアニオン系又はノニオン系で、同様の理由から、より好ましくは、アニオン系が好適で、例えば、アニオン系；ポリアクリル酸ソーダ、ポリスルホメチル化ポリアクリドアミド、また、ノニオン系；ポリアクリドアミド、ポリエチレンｐキサイドが挙げられる。高分子凝集剤の添加量は、０．０５〜０．５ｍｇ／リットルで、使用上の規制値は、処理水中の残留アクリルアミドモノマーとして、０．００００５ｍｇ／リットル以下であることから、本発明の粉末凝集剤中のアクリルアミドモノマーは、理論上０．００５ｗｔ％以下であることが重要である。 Further, as the one-pack type inorganic powder flocculant according to the present invention, inorganic powder (1), cinnabar powder (2), hemihydrate gypsum powder (3), and water-soluble metal salt inorganic powder having a valence of 2 or more (5) In addition, the effect of combining and blending the polymer flocculant (4) has already been explained, but it is preferable to effectively exhibit the effect of these inorganic compounding agents under water dispersion. An anionic polymer flocculant is preferred. Further, in the present invention, the polymer flocculant, like other compounding materials, exhibits water absorption by being in the form of powder, so that the [floc-aggregation] action as a flocculant can be quickly achieved as sludge / pollution. Can affect the particles. In the present invention, the average particle diameter is preferably 60 to 200 μm. In addition, from the function of the compounding agent of the flocculant of the present invention, its solubility (solubility at 20 ° C. of 0.01 g / 100 ml or more) is added by making it into a powder form, and the addition amount may be small. Therefore, the particle size does not need to be lower than the lower limit of 60 μm, and only the pulverization cost is required. Therefore, as the powdery polymer flocculant, preferably, the appropriate pH is weakly acidic to alkaline, the proper use system is inorganic, and the anionic or nonionic due to the aggregation and precipitation of the effect, For the same reason, an anionic system is more preferable, for example, anionic system; polyacrylic acid soda, polysulfomethylated polyacylamide, and nonionic system: polyacridamide, polyethylene poxide. . The amount of the polymer flocculant added is 0.05 to 0.5 mg / liter, and the regulation value for use is 0.00005 mg / liter or less as residual acrylamide monomer in the treated water. It is important that the acrylamide monomer in the flocculant is theoretically 0.005 wt% or less.
なお、本発明によるワンパックタイプの無機系粉末凝集剤として、無機粉末（１）、硅砂粉末（２）、半水石膏粉末（３）及び原子価３以上の水可溶性金属塩無機粉末（５）に、更に組合わせ配合させる高分子凝集剤（４）の作用効果も、本発明においては重視され、その作用効果を効果的に発揮させるため、より好ましくはアニオン系ポリマーを適宜好適に配合するものである。すなわち、水質汚濁されている廃水には懸濁粒子と呼ばれる微細粒子が多く含まれている。その微細粒子とはたんぱく質やベントナイトのようなコロイド粒子（１００ｍμ〜１μｍ）部分が相当含まれている。このような微細粒子はゼーター電位により粒子間の静電気反発力（クーロン斥力）により互いに反発して、なかなか凝結し難い特徴がある。広い有効ｐＨ領域を持つアニオン系ポリマーは、特に本発明による無機系粉末凝集剤との相乗効果が発揮される。また、既に上述するように、廃水中の浮遊懸濁微粒子に対して「強攪拌下」に無機系粉末凝集剤が「イオン接触」すると同時に、コロイド粒子の界面電位を中和し、粒子間の反発力を弱め、粒子間引力が増す状態となり小フロックを作る。更に、この小フロックはアニオン系ポリマーによって吸着架橋が進み、粗大フロックの生成に繋がるものと推察される。また、浮遊懸濁粒子の他にこの無機系粉末粒子自身もアニオン系ポリマーによる吸着架橋が速やかに進み、粗大フロックの生成要因になっていると思われる。 As the one pack type inorganic powder flocculant according to the present invention, inorganic powder (1), cinnabar powder (2), hemihydrate gypsum powder (3), and water-soluble metal salt inorganic powder (5) having a valence of 3 or more. Further, the effect of the polymer flocculant (4) to be further combined and blended is also emphasized in the present invention, and more preferably an anionic polymer is suitably blended in order to effectively exhibit the function and effect. It is. In other words, the wastewater that is contaminated with water contains many fine particles called suspended particles. The fine particles include a substantial amount of colloidal particles (100 mμ to 1 μm) such as protein and bentonite. Such fine particles are repelled by electrostatic repulsive force (Coulomb repulsive force) between particles due to the zeta potential, and have a characteristic that it is difficult to condense. An anionic polymer having a wide effective pH region exhibits a synergistic effect with the inorganic powder flocculant according to the present invention. In addition, as already mentioned above, the inorganic powder flocculant “ionic contact” with “strong stirring” with respect to the suspended fine particles in the wastewater, and at the same time, neutralizes the interfacial potential of the colloidal particles, The repulsive force is weakened, and the attractive force between particles increases, creating a small flock. Furthermore, it is assumed that the small flocs are adsorbed and cross-linked by the anionic polymer, leading to the formation of coarse flocs. In addition to the suspended suspended particles, the inorganic powder particles themselves are thought to be a cause of the generation of coarse flocs due to the rapid progress of adsorption crosslinking by the anionic polymer.
＜第１の水処理用無機系粉末凝集剤＞
以上から、本発明において、ワンパックタイプの「第１の水処理用無機系粉末凝集剤」として、ワンパックタイプ化させるに際して、重量部数で表して、無機粉末（１）が２０〜８０重量部で、好ましくは沈降速度の観点から、５０重量部以下で、また、硅砂粉末（２）が５〜５０重量部で、好ましくは沈降速度の観点から、３０重量部以下で、また、半水石膏粉末（３）が１〜５０重量部で、好ましくは凝集速度の観点から、１０〜２５重量部で、また、高分子凝集剤（４）が０．０５〜５重量部で、好ましくは形成フロックサイズの観点から、０．５〜３重量部で、及び水可溶性の金属塩無機粉末（５）が０．０５〜２０重量部で、好ましくは処理水のｐＨの観点から、０．５〜１０重量部であって、従来から周知の機械的混合法で適宜容易にワンパックタイプの水処理用無機系粉末凝集剤にすることができる。<First inorganic powder flocculant for water treatment>
From the above, in the present invention, when the one-pack type “first inorganic powder flocculant for water treatment” is formed into a one-pack type, the inorganic powder (1) is expressed in 20 to 80 parts by weight. Preferably, from the viewpoint of sedimentation speed, 50 parts by weight or less, and the silica sand powder (2) is from 5 to 50 parts by weight, preferably from the viewpoint of sedimentation speed, 30 parts by weight or less, and hemihydrate gypsum. Powder (3) is 1 to 50 parts by weight, preferably 10 to 25 parts by weight from the viewpoint of aggregation rate, and polymer flocculant (4) is 0.05 to 5 parts by weight, preferably formed floc From the viewpoint of size, 0.5 to 3 parts by weight, and the water-soluble metal salt inorganic powder (5) is 0.05 to 20 parts by weight, preferably from the viewpoint of the pH of the treated water, 0.5 to 10 parts. It is part by weight and is appropriately determined by a conventionally known mechanical mixing method. It can be a one pack type water treatment inorganic powder flocculant easily.
本発明においては、上記する「第１の水処理用無機系粉末凝集剤」を、活性汚泥法で処理された、例えば、下水処理場、食品加工場、製紙工場等で発生する余剰汚泥、混合汚泥、消化汚泥、生汚泥の懸濁物（ＳＳ）濃度が５０〜２０，０００ｍｇ／リットルの廃水１０００ｍｌ当たり、高速攪拌下に１００〜３０，０００ｐｐｍの添加量で、好ましくは、５００〜２０，０００ｐｐｍの添加量で、少なくとも一段で添加させ、次いで、緩速攪拌後の静置下に懸濁物（ＳＳ）濃度が１０〜５０ｐｐｍ以下の清澄水に処理することができる。なお、上記高速攪拌下とは、１２０〜１６０ｒｐｍ範囲の撹拌速度であって、また、緩速攪拌とは、４０〜６０ｒｐｍの範囲の撹拌速度であって、このような処理方法で、緩速攪拌後、６分以下の静置時間で各種の汚泥廃水を処理することができる。 In the present invention, the “first water treatment inorganic powder flocculant” described above is treated by the activated sludge method, for example, surplus sludge generated in a sewage treatment plant, food processing plant, paper mill, etc., mixed The amount of suspension (SS) of sludge, digested sludge, and raw sludge is from 100 to 30,000 ppm, preferably from 500 to 20,000 ppm, per 1000 ml of wastewater having a concentration of 50 to 20,000 mg / liter while stirring at high speed. In an addition amount of at least one step, the suspension (SS) concentration can be treated in a clear water having a concentration of 10 to 50 ppm or less under still stirring after slow stirring. The high-speed stirring is a stirring speed in the range of 120 to 160 rpm, and the slow stirring is a stirring speed in the range of 40 to 60 rpm. Thereafter, various sludge wastewaters can be treated with a standing time of 6 minutes or less.
＜第２の水処理用無機系粉末凝集剤＞
また、本発明においては、必要に応じて、半水石膏粉末（３）と同様に水和反応性を発揮する平均粒子径３０〜１００μｍの軽焼マグネシア粉末を配合剤として組み合わせすることができる。廃水の種類によっては、既に上述した無機粉末（１）、硅砂粉末（２）、半水石膏粉末（３）、高分子凝集剤（４）及び原子価３以上の水可溶性金属塩無機粉末（５）に、更に軽焼マグネシア粉末（６）をワンパックに配合させてなる「第２の水処理用無機系粉末凝集剤」を提供することができる。<Second inorganic powder flocculant for water treatment>
Moreover, in this invention, the light-burning magnesia powder with an average particle diameter of 30-100 micrometers which exhibits hydration reactivity similarly to hemihydrate gypsum powder (3) can be combined as a compounding agent as needed. Depending on the type of waste water, the inorganic powder (1), cinnabar powder (2), hemihydrate gypsum powder (3), polymer flocculant (4), and water-soluble metal salt inorganic powder having a valence of 3 or more (5) In addition, a “second inorganic powder flocculant for water treatment” obtained by further blending lightly-burned magnesia powder (6) into one pack can be provided.
すなわち、本発明においては、上記「第１の水処理用無機系粉末凝集剤」１００重量当たり、軽焼マグネシア粉末が０．０１〜５０重量部の範囲で、好ましくは有効ｐＨの観点から、２〜２０重量部を含有することを特徴とする水処理用無機系粉末凝集剤である。本発明においては、より速やかに水和反応をして２水石膏化する半水石膏粉末（３）に比べ、軽焼マグネシア粉末（６）は、より緩慢な水和反応下に水和反応物を生成させ、且つ半水石膏粉末（３）の２水化水和に比べ、軽焼マグネシア粉末（６）の「ＭｇＯ」→「Ｍｇ（ＯＨ）２」なる水和化のｐＨ領域が、より塩基度領域である相違が、廃水の種類に対して、より好ましい凝集効果を発揮させることができる。尚、上記する有効ｐＨとはｐＨ１０．５〜６．５である。That is, in the present invention, the light-burned magnesia powder is in the range of 0.01 to 50 parts by weight per 100 parts by weight of the “first inorganic powder flocculant for water treatment”, preferably 2 in terms of effective pH. It is an inorganic powder flocculant for water treatment characterized by containing -20 weight part. In the present invention, the light-burned magnesia powder (6) is more hydrated than the hemihydrate gypsum powder (3), which is more quickly hydrated and converted into dihydrated gypsum. In comparison with the dihydrate hydration of the hemihydrate gypsum powder (3), the hydrated pH region of “MgO” → “Mg (OH) 2 ” of the light calcined magnesia powder (6) is more The difference which is a basicity area | region can exhibit a more preferable aggregation effect with respect to the kind of waste water. The effective pH described above is pH 10.5 to 6.5.
すなわち、各種の建設、河川、港湾工事現場、浄水場等で発生する懸濁物（ＳＳ）濃度が５０〜２０，０００ｍｇ／リットルである１次沈降槽中の汚濁廃水（又は汚濁用水）１０００ｍｌ当たり、高速攪拌下に上記する「第２の水処理用無機系粉末凝集剤」を１００〜３０，０００ｐｐｍの範囲で、少なくとも一段で添加させ、次いで、緩速攪拌後の静置下に懸濁物（ＳＳ）濃度が１０〜５０ｐｐｍ以下の清澄水にすることを特徴とする汚濁廃水の処理方法である。なお、上記高速攪拌下とは、１２０〜１６０ｒｐｍの範囲の撹拌速度であって、また、緩速攪拌とは、４０〜６０ｒｐｍの範囲の撹拌速度であって、このような処理方法で、緩速攪拌後、６分以下の静置時間で各種の汚濁廃水（又は汚濁用水）を処理することができる。 That is, per 1000 ml of polluted wastewater (or water for pollution) in the primary sedimentation tank with a suspended solid (SS) concentration of 50 to 20,000 mg / liter generated in various constructions, rivers, harbor construction sites, water purification plants, etc. The above-mentioned “second inorganic powder flocculant for water treatment” is added in a range of 100 to 30,000 ppm in at least one stage under high-speed stirring, and then the suspension is left to stand after slow stirring. (SS) A method for treating polluted wastewater, characterized in that clear water having a concentration of 10 to 50 ppm or less is used. The high-speed stirring is a stirring speed in the range of 120 to 160 rpm, and the slow stirring is a stirring speed in the range of 40 to 60 rpm. After stirring, various types of contaminated waste water (or water for pollution) can be treated in a standing time of 6 minutes or less.
＜第３の水処理用無機系粉末凝集剤＞
また、本発明によれば、必要に応じてこれらの第１及び第２の水処理用無機系粉末凝集剤に、予め硫酸第１鉄塩粉末をワンパック状に配合させた「第３の水処理用無機系粉末凝集剤」を提供することができる。このような第３の水処理用無機系粉末凝集剤を、例えば、有害重金属イオンの六価Ｃｒイオン（Ｃｒ６＋）を含有する廃水に対して、硫酸第１鉄塩が［Ｆｅ２＋→Ｆｅ３＋］として還元剤として作用し、廃水中の六価Ｃｒを［Ｃｒ６＋→Ｃｒ３＋］に還元させて、凝集沈降物中に捕捉させることができる。本発明においては、第１及び第２の水処理用無機系粉末凝集剤１００重量部当たり、硫酸第１鉄塩粉末の１．５〜３重量部で、好ましくは、２〜２．８重量部を配合させたものである。通常、例えばＣｒ６＋が０．８〜１（ｐｐｍ）含有する汚濁廃水に、第３の水処理用無機系粉末凝集剤を通常の水処理添加量範囲で処理することで、Ｃｒイオンを０．０５（ｐｐｍ）以下の処理廃水として排出させることができる。<Third inorganic powder flocculant for water treatment>
Further, according to the present invention, the “third water” in which the ferrous sulfate salt powder is preliminarily blended in a one-pack shape with the first and second inorganic powder flocculants for water treatment as necessary. An inorganic powder flocculant for processing ”can be provided. Such a third inorganic powder flocculant for water treatment, for example, with respect to waste water containing hexavalent Cr ions (Cr 6+ ) of harmful heavy metal ions, ferrous sulfate [Fe 2+ → Fe 3+ ] As a reducing agent, and can reduce hexavalent Cr in the wastewater to [Cr 6+ → Cr 3+ ] and trap it in the aggregated sediment. In the present invention, 1.5 to 3 parts by weight, preferably 2 to 2.8 parts by weight of the ferrous sulfate powder per 100 parts by weight of the first and second inorganic powder flocculants for water treatment. Is blended. Usually, for example, by treating the contaminated waste water containing 0.8 to 1 (ppm) of Cr 6+ with the third water treatment inorganic powder flocculant in the normal water treatment addition amount range, the Cr ion is reduced to 0. It can be discharged as a treatment wastewater of 05 (ppm) or less.
また、このように提供でいる本発明による水処理用無機系粉末凝集剤は、各種の工業廃材を含む数種の無機系粉末配合剤をワンパックタイプにした凝集剤であることから、クロム、カドミウム等の重金属類や、ダイオキシン等の有機物の含有されていないことが重要である。一般的に、産業廃棄物をリサイクル、リユースするには、環境保全、水質規制の立場からその可溶成分に留意しなかればならない。既に上述することから明らかなように、本発明による水処理用無機系粉末凝集剤を使用しても、例えば、有害物質として、環境庁告示令として定めている溶質基準値は、以下の通りである。例えば、鉛化合物（１．０ｍｇ／ｋｇ以下）、カドミウム化合物（０．３０ｍｇ／ｋｇ以下）、全クロム化合物（１・５ｍｇ／ｋｇ以下）、全水銀（０．００５ｍｇ／ｋｇ以下）、ヒ素化合物（３．０ｍｇ／ｋｇ以下）、シアン化合物（１．０ｍｇ／ｋｇ以下）、有機リン化合物（１．５ｍｇ／ｋｇ以下）、ＰＣＢ（０．００３０ｍｇ／ｋｇ以下）、トリクロロエチレン（０．１ｍｇ／ｋｇ以下）、テトラクロロエチレン（０．１ｍｇ／ｋｇ以下）である。
以下に本発明を実施例で説明するが、本発明はこれらにいささかも限定されるものではない。Further, the inorganic powder flocculant for water treatment according to the present invention thus provided is a flocculant obtained by making several inorganic powder compounding agents including various industrial waste materials into one pack type, so that chromium, It is important that heavy metals such as cadmium and organic substances such as dioxin are not contained. Generally, in order to recycle and reuse industrial waste, it is necessary to pay attention to its soluble components from the standpoint of environmental conservation and water quality regulation. As is clear from the above, even when the inorganic powder flocculant for water treatment according to the present invention is used, for example, the solute standard value defined as the environmental agency notification order as a hazardous substance is as follows. is there. For example, lead compounds (1.0 mg / kg or less), cadmium compounds (0.30 mg / kg or less), total chromium compounds (1.5 mg / kg or less), total mercury (0.005 mg / kg or less), arsenic compounds ( 3.0 mg / kg or less), cyanide compound (1.0 mg / kg or less), organophosphorus compound (1.5 mg / kg or less), PCB (0.0030 mg / kg or less), trichlorethylene (0.1 mg / kg or less) , Tetrachlorethylene (0.1 mg / kg or less).
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
（実施例１）
無機粉末（１）として吸水量が８０ｍｌ／１００ｇの焼成ダスト５３ｄと、硅砂粉末（２）としてシリカ成分が７５重量％で、平均粒子径４５μｍで、吸水量が３８ｍｌ／１００ｇの硅砂粉末の３５．２５ｇと、半水石膏粉末（３）の１０ｇと、高分子凝集剤（４）としてポリアクリルアミド粉末の１．７５ｇとの合量１００ｇに対して、水可溶金属塩無機粉末（５）として硫酸バンド粉末の０．５ｇ、３ｇ、１０ｇ及び１５ｇのそれぞれを粉末混合させて、本発明によるワンパックタイプの粉末状の水処理凝集剤−１、水処理凝集剤−２、水処理凝集剤−３及び水処理凝集剤−４をそれぞれ調製した。なお、硫酸バンド粉末の１０ｇを配合させて水処理凝集剤−３において硫酸バンド粉末に代えてポリ塩化アルミニウム（ＰＡＣ）粉末１０ｇとしたものを水処理凝集剤−５として調製した。
＜水処理凝集試験＞
次いで、ジャーテスト試験装置を用いて、製紙会社で排出された活性汚泥法で処理された懸濁物質（ＳＳ）の濁度濃度が４４０ｍｇ／リットル（４４０ｐｐｍ）の汚泥廃水５００ｍｌを１リットルビーカーに採集し、１４０ｒｐｍの高速撹拌下に、本発明によるワンパックタイプの粉末状凝集剤を、従来の水処理方法とは異なり全くの一段法で、水処理凝集剤−１［４０００］、水処理凝集剤−２［３０００］、水処理凝集剤−３［１０００，２０００，３０００，４０００］、水処理凝集剤−４［２０００］及び水処理凝集剤−５［１０００］のそれぞれを［ｐｐｍ］内に示す添加量で添加し、１分間撹拌保持した。次いで、６０ｒｐｍの緩速撹拌下に２分間撹拌保持した後、撹拌停止・撹拌羽根を引き上げて静置２分後の上澄み液である凝集処理水の濁度ＳＳ（ｐｐｍ）を測定した結果を下記＜ｐｐｍ＞内に表示した。
なお、従来から、通常、実施されているこのような廃水処理法としては、このような廃水に対して多段法で、すなわち、例えば、無機凝集剤の硫酸バンドを添加し、次いでＮａ（ＯＨ）２でｐＨ７に中和し、次いでアニオン系高分子凝集剤とを添加させて凝集沈殿させて上澄み処理水を排出させているのが実状である。
＜凝集水処理結果＞
水処理凝集剤−１［３０００］／＜１７８＞
水処理凝集剤−２［４０００］／＜ ８０＞
水処理凝集剤−３［１０００］／＜１３５＞
水処理凝集剤−３［２０００］／＜ ３７＞
水処理凝集剤−３［３０００］／＜ ９＞
水処理凝集剤−３［４０００］／＜ ５＞
水処理凝集剤−４［２０００］／＜ ２２＞
水処理凝集剤−５［１０００］／＜１２８＞
水処理凝集剤−０［ − ］／＜４４０＞Example 1
As the inorganic powder (1), calcined dust 53d having a water absorption of 80 ml / 100 g, and as the silica sand powder (2), the silica component is 75% by weight, the average particle diameter is 45 μm, and the water absorption is 38 ml / 100 g. 25g, 100g of hemihydrate gypsum powder (3) and 100g of polyacrylamide powder 1.75g as polymer flocculant (4), sulfuric acid as water soluble metal salt inorganic powder (5) Each of 0.5 g, 3 g, 10 g, and 15 g of the band powder is powder-mixed to obtain a one-pack type powdery water treatment flocculant-1, water treatment flocculant-2, and water treatment flocculant-3 according to the present invention. And water treatment flocculant-4 were prepared. In addition, 10 g of sulfuric acid band powder was blended, and water treatment flocculant-3 was prepared as water treatment flocculant-5 in place of sulfuric acid band powder and 10 g of polyaluminum chloride (PAC) powder.
<Water treatment aggregation test>
Next, using a jar test test device, 500 ml of sludge wastewater with a turbidity concentration of 440 mg / liter (440 ppm) of suspended solids (SS) discharged by a paper company and processed by the activated sludge method is collected in a 1 liter beaker. Then, under high-speed stirring at 140 rpm, the one-pack type powder flocculant according to the present invention is completely different from the conventional water treatment method in that it is a one-step process, and water treatment flocculant-1 [4000], water treatment flocculant -2 [3000], water treatment flocculant-3 [1000, 2000, 3000, 4000], water treatment flocculant -4 [2000] and water treatment flocculant -5 [1000] are shown in [ppm]. Added in an added amount and kept stirring for 1 minute. Next, after stirring and holding for 2 minutes under slow agitation at 60 rpm, the turbidity SS (ppm) of the agglomerated treated water, which is the supernatant liquid after standing still for 2 minutes after raising the stirring and stirring blades, was measured. Displayed in <ppm>.
In addition, conventionally, as such a wastewater treatment method that has been generally performed, a multistage method is used for such wastewater, that is, for example, a sulfuric acid band of an inorganic flocculant is added, and then Na (OH) 2 is neutralized to pH 7 and then an anionic polymer flocculant is added to cause coagulation precipitation to discharge the supernatant treated water.
<Aggregated water treatment result>
Water treatment flocculant-1 [3000] / <178>
Water treatment flocculant-2 [4000] / <80>
Water treatment flocculant-3 [1000] / <135>
Water treatment flocculant-3 [2000] / <37>
Water treatment flocculant-3 [3000] / <9>
Water treatment flocculant-3 [4000] / <5>
Water treatment flocculant-4 [2000] / <22>
Water treatment flocculant-5 [1000] / <128>
Water treatment flocculant-0 [-] / <440>
（実施例２）
無機粉末（１）として焼成ダスト４０ｇと、硅砂粉末（２）として１７．５ｇと、半水石膏粉末（３）の２３ｇと、高分子凝集剤（４）としてポリアクリルアミド粉末の１．５ｇと、軽焼マグネシア粉末（６）の１８ｇとの合量１００ｇに対して、水可溶金属塩無機粉末（５）として硫酸バンド粉末の１０ｇを粉末混合させて、本発明によるワンパックタイプの粉末状の水処理凝集剤−６を調製した。
＜水処理凝集試験＞
次いで、ジャーテスト試験装置を用いて、トンネル工事で排出された廃水を予め沈殿槽で沈降させた懸濁物質（ＳＳ）の濁度濃度が９５ｍｇ／リットル（９５ｐｐｍ）の汚濁廃水５００ｍｌを１リットルビーカーに採集し、１４０ｒｐｍの高速撹拌下に、実施例１と同様に一段法で、本発明によるワンパックタイプの水処理凝集剤−６［２５０］、水処理凝集剤−６［５００］、水処理凝集剤−６［７５０］、水処理凝集剤−６［１０００］及び水処理凝集剤−６［１２５０］のそれぞれを［ｐｐｍ］内に示す添加量を添加し、１分間撹拌保持した。次いで、６０ｒｐｍの緩速撹拌下に２分間撹拌保持した後、撹拌停止・撹拌羽根を引き上げて静置２分後の上澄液である凝集処理水の濁度ＳＳ（ｐｐｍ）を測定した結果を下記＜ｐｐｍ＞内に表示した。
＜凝集水処理結果＞
水処理凝集剤−６［２５０］／＜４８＞
水処理凝集剤−６［５００］／＜２１＞
水処理凝集剤−６［７５０］／＜ ７＞
水処理凝集剤−６［１０００］／＜３＞
水処理凝集剤−６［１２５０］／＜３＞
水処理凝集剤−０［ − ］／＜９４＞(Example 2)
Baked dust 40 g as inorganic powder (1), 17.5 g as cinnabar powder (2), 23 g of hemihydrate gypsum powder (3), 1.5 g of polyacrylamide powder as polymer flocculant (4), 10 g of sulfuric acid band powder as a water-soluble metal salt inorganic powder (5) is mixed with 100 g of the total amount of light-fired magnesia powder (6) with 18 g, and the one-pack type powdery form according to the present invention is used. Water treatment flocculant-6 was prepared.
<Water treatment aggregation test>
Next, using a jar test test device, 500 ml of contaminated waste water with a turbidity concentration of 95 mg / liter (95 ppm) of suspended solids (SS) obtained by precipitating the waste water discharged in tunnel construction in advance in a settling tank is 1 liter beaker. In a single-stage method as in Example 1 under high-speed stirring at 140 rpm, the one-pack type water treatment flocculant -6 [250], water treatment flocculant-6 [500], water treatment according to the present invention is collected. Addition amounts indicated in [ppm] for each of flocculant-6 [750], water treatment flocculant-6 [1000] and water treatment flocculant-6 [1250] were added and held for 1 minute with stirring. Next, after stirring and holding for 2 minutes under slow stirring at 60 rpm, the result of measuring the turbidity SS (ppm) of the agglomerated treated water, which is the supernatant after 2 minutes of standing and lifting the stirring blade, was measured. Displayed within <ppm> below.
<Aggregated water treatment result>
Water treatment flocculant-6 [250] / <48>
Water treatment flocculant-6 [500] / <21>
Water treatment flocculant-6 [750] / <7>
Water treatment flocculant-6 [1000] / <3>
Water treatment flocculant-6 [1250] / <3>
Water treatment flocculant-0 [-] / <94>
以上から、本発明による複数の粉末状配合剤をワンパック状にした無機系粉末状凝集剤によって、各種の汚泥・汚濁廃水に対して、従来の水処理である多段法による水処理法とは全く相違して、極めて簡便、低コストな一段法による水処理法を提供することができる。 From the above, the water treatment method by the multi-stage method, which is a conventional water treatment, for various sludges and polluted wastewaters, with an inorganic powdery flocculant made of a plurality of powdered compounding agents according to the present invention in one pack form Quite differently, it is possible to provide a one-stage water treatment method that is extremely simple and low cost.
Claims (9)
シリカ成分が６５〜８０重量％で、平均粒子径１５〜１５０μｍで、吸水量が２０〜４０ｍｌ／１００ｇの範囲にある硅砂粉末（２）と、
半水石膏粉末（３）及び高分子凝集剤（４）とを含有し、
且つ無機粉末（１）、硅砂粉末（２）、半水石膏粉末（３）及び高分子凝集剤（４）との合計含量１００重量部当たり、原子価が３価以上の水可溶性金属塩無機粉末（５）が０．０５〜２０重量部の範囲で含有することを特徴とする水処理用無機系粉末凝集剤。 An inorganic powder (1) having a water absorption of 50 to 90 ml / 100 g containing silica, alumina, magnesia and calcia components;
Silica sand powder (2) having a silica component of 65 to 80% by weight, an average particle size of 15 to 150 μm, and a water absorption of 20 to 40 ml / 100 g;
Hemihydrate gypsum powder (3) and polymer flocculant (4),
Water-soluble metal salt inorganic powder having a valence of 3 or more per 100 parts by weight of the total content of inorganic powder (1), cinnabar powder (2), hemihydrate gypsum powder (3) and polymer flocculant (4) (5) The inorganic powder flocculant for water treatment characterized by containing in 0.05-20 weight part.
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