JP5621256B2 - Wastewater coagulation method - Google Patents
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- JP5621256B2 JP5621256B2 JP2009293188A JP2009293188A JP5621256B2 JP 5621256 B2 JP5621256 B2 JP 5621256B2 JP 2009293188 A JP2009293188 A JP 2009293188A JP 2009293188 A JP2009293188 A JP 2009293188A JP 5621256 B2 JP5621256 B2 JP 5621256B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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Description
本発明は、廃水の凝集処理方法に関し、詳しくは、有機凝結剤及び無機凝集剤、該有機凝結剤と高分子凝集剤を使用して各種廃水及び汚濁水の浄化する凝集処理方法に関する。 The present invention relates to a coagulation treatment method for wastewater, and more particularly to an coagulation treatment method for purifying various wastewaters and polluted water using the organic coagulant and inorganic coagulant, and the organic coagulant and polymer coagulant.
自動車製造工場、製鐵所、紙パルプ製造業、クリーニング、砂利産業、その他の化学工場等で発生する廃水の凝集処理としては、一般的に、硫酸バンド、ポリ塩化アルミニウム（ＰＡＣ）等アルミ系ないし鉄系の無機凝集剤を添加した後に更に高分子凝集剤を添加して凝集フロックを生成させ、次いで、凝集沈殿又は凝集浮上法で処理する方法が採用されている。そして、浄化された処理水は、河川や下水に放流されるのが一般的である。 As agglomeration treatment of wastewater generated in automobile manufacturing factories, steel mills, pulp and paper manufacturing industry, cleaning, gravel industry, other chemical factories, etc., generally aluminum-based or sulfuric acid band, polyaluminum chloride (PAC) etc. A method is employed in which after adding an iron-based inorganic flocculant, a polymer flocculant is further added to form a floc floc and then treated by a flocculent precipitation or a flocculent levitation method. The purified treated water is generally discharged into rivers and sewage.
ところで、放流水質の規制強化に伴い、処理装置の改良や廃水処理方法の改善により、水質の向上が図られており、無機凝集剤添加量の増加が不可欠となっている。ところが、無機凝集剤の使用量を増加させると、薬品コストの増加、発生汚泥量の増加並びに発生汚泥処理コストが増大することになる。また、無機凝集剤の力だけでは、廃水中の低分子ＣＯＤ成分の充分な除去が難しいため、放流される処理水の水質に不安を残す。そして、この不安を解消すべく後段に高度処理を行う場合では、当該高度処理工程に対する負荷が高くなってしまう。 By the way, with the stricter regulation of the discharged water quality, the water quality is improved by improving the treatment apparatus and the wastewater treatment method, and it is indispensable to increase the amount of inorganic flocculant added. However, when the amount of the inorganic flocculant used is increased, the chemical cost is increased, the amount of generated sludge is increased, and the generated sludge treatment cost is increased. Moreover, since it is difficult to sufficiently remove the low-molecular-weight COD component in the wastewater only by the power of the inorganic flocculant, there remains anxiety about the quality of the treated water discharged. In the case where advanced processing is performed at a later stage in order to eliminate this anxiety, the load on the advanced processing step becomes high.
上記のような状況下で処理水の水質を維持・向上しつつ、無機凝集剤使用量の低減を目的にカチオン性凝集剤の一種である有機凝結剤の適用が進められている。有機凝結剤は、分子内に多数のカチオン基を有する高分子電解質であるので、無機凝集剤と同様に被処理水中の懸濁物質の荷電を中和する目的で使用される。しかも、有機凝結剤は、無機凝集剤よりもカチオンの電荷密度が高いために、その凝結作用は無機凝集剤よりはるかに大きいという特徴を持っている。また、有機凝結剤は懸濁物質を中和するだけでなく、負に帯電しているフミン酸等の溶解物質と反応して不溶性塩を形成する作用があり色度及びＣＯＤの減少効果も期待される。 Under the circumstances as described above, application of an organic coagulant, which is a kind of cationic coagulant, has been promoted for the purpose of reducing the amount of inorganic coagulant used while maintaining and improving the quality of treated water. Since the organic coagulant is a polyelectrolyte having a large number of cationic groups in the molecule, it is used for the purpose of neutralizing the charge of the suspended substance in the water to be treated, like the inorganic coagulant. In addition, since the organic coagulant has a higher charge density of the cation than the inorganic coagulant, the coagulation action is much larger than that of the inorganic coagulant. Organic coagulants not only neutralize suspended substances, but also react with negatively charged dissolved substances such as humic acid to form insoluble salts, and are expected to reduce chromaticity and COD. Is done.
現在使用されている有機凝結剤の代表的なものとしては、アルキルアミン・エピクロルヒドリン縮合物、アルキレンジクロライドとポリアルキレンポリアミンの縮合物、ジシアンジアミド・ホルマリン縮合物、ジメチルジアリルアンモニウムクロライド重合体等低分子量、強カチオン密度の水溶性ポリマーが挙げられる。更に、新規な有機凝結剤として色々な重合体及び廃水処理方法が提案されている。 Typical organic coagulants currently used are low molecular weight, strong compounds such as alkylamine / epichlorohydrin condensate, alkylene dichloride and polyalkylene polyamine condensate, dicyandiamide / formalin condensate, and dimethyldiallylammonium chloride polymer. Examples thereof include water-soluble polymers having a cation density. Furthermore, various polymers and waste water treatment methods have been proposed as novel organic coagulants.
例えば、固有粘度０．００２〜０．５ｄｌ／ｇのアルキルアミン−エピクロロヒドリン縮合物、固有粘度０．０１〜０．５ｄｌ／ｇのポリジメチルジアリルアンモニウムハライド及び固有粘度０．０５〜１．０ｄｌ／ｇのポリジメチルアミノアルキル（メタ）アクリレートの内、何れかの荷電調整剤を添加した後に高分子凝集剤を使用して凝集処理する脱墨排水の処理方法（特許文献１）、無機凝集剤とポリメタアクリル酸エステル系のカチオン高分子凝集剤及びアニオン系高分子凝集剤を使用する処理方法（特許文献２）が提案されている。 For example, an alkylamine-epichlorohydrin condensate having an intrinsic viscosity of 0.002 to 0.5 dl / g, polydimethyldiallylammonium halide having an intrinsic viscosity of 0.01 to 0.5 dl / g, and an intrinsic viscosity of 0.05 to 1. A deinking wastewater treatment method (Patent Document 1), in which any charge control agent is added in 0 dl / g of polydimethylaminoalkyl (meth) acrylate and then agglomeration treatment is performed using a polymer flocculant (Patent Document 1), inorganic agglomeration And a treatment method using a polymethacrylate ester cationic polymer flocculant and an anionic polymer flocculant (Patent Document 2) have been proposed.
しかしながら、上記の従来技術は、カチオン密度の高い水溶性ポリマーを使用する点で共通しており、効果を発揮することもあるが、種々の廃水に対し、無機凝集剤の使用量を削減し、良好な処理水質を安定的に得るには至っていない。 However, the above prior art is common in that it uses a water-soluble polymer having a high cation density, and may have an effect, but for various wastewaters, the amount of inorganic flocculant used is reduced, It has not yet been possible to stably obtain good treated water quality.
従って、廃水の凝集処理において使用される有機凝集剤に関しては、（１）無機凝集剤の使用量をより削減できること、（２）良好な凝集フロックを形成し、固液分離性に優れること、（３）良好な処理水質（ＣＯＤ、油分、ＳＳ等）が得られること、（４）実装置における適正な反応条件の設定が容易で、安定していること、（５）処理コストがより低く出来ること等が求められている。 Therefore, regarding the organic flocculant used in the flocculation treatment of wastewater, (1) the amount of inorganic flocculant used can be further reduced, (2) good floc flocs are formed, and solid-liquid separability is excellent ( 3) Good treatment water quality (COD, oil content, SS, etc.) can be obtained, (4) Appropriate reaction conditions in the actual apparatus can be set easily and stably, and (5) Treatment costs can be further reduced. That is required.
本発明は、上記実情に鑑みなされたものであり、その目的は、無機凝集剤、有機凝結剤及び高分子凝集剤を使用した廃水処理において、無機凝集剤の使用量を削減し良好な水質を得ることが出来る廃水処理技術を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to reduce the amount of inorganic flocculant used in wastewater treatment using an inorganic flocculant, an organic flocculant, and a polymer flocculant, and to achieve good water quality. It is to provide wastewater treatment technology that can be obtained.
本発明者らは、カチオン性を有する種々の水溶性ポリマーを使用して種々検討を重ねた結果、特定の種類の有機凝結剤を使用するならば、上記の目的を容易に達成し得るとの知見を得、本発明の完成に至った。 As a result of various studies using various water-soluble polymers having a cationic property, the present inventors have found that the above object can be easily achieved if a specific type of organic coagulant is used. Knowledge was obtained and the present invention was completed.
すなわち、本発明の要旨は、廃水に無機凝集剤を添加した後、カチオン性の水溶性重合体であり、ジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩モノマー単独重合体或いはジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩モノマーとアクリルアミドモノマーとの重合体であり、ジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩：アクリルアミド＝（６０−１００）：（４０−０）モル％からなる重合体で且つ固有粘度が１．０〜２．０ｄｌ／ｇのジアルキルアミノアルキル（メタ）アクリレート系有機凝結剤を添加して一次凝集させた後、更にアニオン系又はノニオン系の高分子凝集剤を添加して二次凝集させ、次いで、固液分離することを特徴とする廃水の凝集処理方法に存する。 That is, the gist of the present invention is a cationic water-soluble polymer after adding an inorganic flocculant to wastewater, and is a dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt monomer homopolymer or dimethylaminoethyl (meta ) A polymer of an acrylate methyl chloride quaternary salt monomer and an acrylamide monomer, comprising dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt: acrylamide = (60-100): (40-0) mol% In addition, after adding a dialkylaminoalkyl (meth) acrylate organic coagulant having an intrinsic viscosity of 1.0 to 2.0 dl / g to cause primary aggregation, an anionic or nonionic polymer flocculant is further added. Thus, the present invention resides in a coagulation treatment method for wastewater, characterized in that the coagulation is secondary coagulation, followed by solid-liquid separation.
本発明の処理方法によれば、無機凝集剤の使用量を削減し、良好な凝集フロックを形成して固液分離性に優れ、良好な水質の処理水を得ることが出来る。 According to the treatment method of the present invention, it is possible to reduce the amount of the inorganic flocculant used, to form a good flocculent floc and to have excellent solid-liquid separability and to obtain a good quality water.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で対象となる廃水（汚濁水を含む）としては、製紙工業、染色工業、自動車工業、金属加工工業、製鉄工業、食品工業、砂利採取、半導体及びクリーニング業より発生する廃水等が例示される。 Examples of waste water (including polluted water) targeted by the present invention include waste water generated from the paper industry, dyeing industry, automobile industry, metal processing industry, steel industry, food industry, gravel collection, semiconductor and cleaning industry, etc. The
本発明で使用する無機凝集剤としては、ＰＡＣ（ポリ塩化アルミニウム）、硫酸バンド、塩化第二鉄、ポリ硫酸鉄等が挙げられる。 Examples of the inorganic flocculant used in the present invention include PAC (polyaluminum chloride), sulfuric acid band, ferric chloride, and polyiron sulfate.
本発明で使用する有機凝結剤は、カチオン性の水溶性ポリマーである、ジアルキルアミノアルキル（メタ）アクリレート系有機凝結剤であり、ジアルキルアミノアルキル（メタ）アクリレートモノマー単独或いはノニオン性モノマーとの共重合物である。 The organic coagulant used in the present invention is a dialkylaminoalkyl (meth) acrylate organic coagulant, which is a cationic water-soluble polymer, and is a copolymer of a dialkylaminoalkyl (meth) acrylate monomer alone or with a nonionic monomer. It is a thing.
ジアルキルアミノアルキル（メタ）アクリレートモノマーとしては、ジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩、ジメチルアミノエチル（メタ）アクリレート硫酸塩、ジメチルアミノエチル（メタ）アクリレート塩化ベンジル４級塩等が挙げられるが、これらの中ではジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩が好ましい。また、ジメチルアミノエチル（メタ）アクリレート塩化メチル４級塩を必須成分として含めば、他のジアルキルアミノアルキル（メタ）アクリレートモノマー成分を共重合させても構わない。一方、ノニオン性のモノマーとしては、アクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等が挙げられるが、これらの中ではアクリルアミドが好ましい。 Examples of the dialkylaminoalkyl (meth) acrylate monomer include dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth) acrylate sulfate, dimethylaminoethyl (meth) acrylate benzyl chloride quaternary salt, and the like. Of these, dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt is preferred. Further, if a dimethylaminoethyl (meth) acrylate methyl chloride quaternary salt is included as an essential component, other dialkylaminoalkyl (meth) acrylate monomer components may be copolymerized. On the other hand, examples of the nonionic monomer include acrylamide, methacrylamide, N, N-dimethyl (meth) acrylamide, and the like. Among these, acrylamide is preferable.
上記のカチオン性の水溶性ポリマーにおけるジアルキルアミノアルキル（メタ）アクリレートモノマーの含有量は、６０〜１００モル％、好ましくは８０〜１００モル％である。ジアルキルアミノアルキル（メタ）アクリレート塩化メチル４級塩の含有量が６０モル％未満の場合は処理水の清澄性が低下することがある。なお、カチオン性の水溶性ポリマーの重合方法としては、沈殿重合、塊状重合、分散重合、水溶液重合等が挙げられるが、特に限定されるものではない。 Content of the dialkylaminoalkyl (meth) acrylate monomer in said cationic water-soluble polymer is 60-100 mol%, Preferably it is 80-100 mol%. When the content of the dialkylaminoalkyl (meth) acrylate methyl chloride quaternary salt is less than 60 mol%, the clarity of the treated water may be lowered. Examples of the polymerization method of the cationic water-soluble polymer include precipitation polymerization, bulk polymerization, dispersion polymerization, and aqueous solution polymerization, but are not particularly limited.
上記のカチオン性の水溶性ポリマーの分子量は、１Ｎ硝酸ナトリウム水溶液中、温度３０℃で測定した固有粘度として、１．０〜３．０ｄｌ／ｇであり、好ましくは１．５〜２．５ｄｌ／ｇである。固有粘度が１．０ｄｌ／ｇ未満の場合は、凝集力が弱くなり処理水の清澄性が低下し、３．０ｄｌ／ｇ超過の場合は、反応性が悪くなり凝集フロックは粗大になるが、処理水の清澄性が低下すると共に、発生する凝集汚泥の脱水性が悪化する。 The molecular weight of the cationic water-soluble polymer is 1.0 to 3.0 dl / g, preferably 1.5 to 2.5 dl / g, as an intrinsic viscosity measured at 30 ° C. in a 1N sodium nitrate aqueous solution. g. When the intrinsic viscosity is less than 1.0 dl / g, the cohesive force becomes weak and the clarity of the treated water is lowered. When it exceeds 3.0 dl / g, the reactivity becomes poor and the aggregated floc becomes coarse. The clarity of the treated water is lowered and the dewaterability of the generated sludge is deteriorated.
本発明においては、有機凝結剤の粘性の低下や反応性の向上のために固体酸を添加することが出来る。固体酸としては、スルファミン酸、酸性亜硫酸ソーダ等が一般的に使用される。 In the present invention, a solid acid can be added in order to lower the viscosity of the organic coagulant or improve the reactivity. As the solid acid, sulfamic acid, acidic sodium sulfite and the like are generally used.
また、本発明においては、上記の有機凝結剤に他の有機凝結剤を混合して２種以上の有機凝結剤を使用することが出来る。この場合、他の有機凝結剤としては、以下の一般式（Ｉ）で表されるジアルキルアミノアルキル（メタ）アクリレート系ポリマーが好ましいが、他の組成の有機凝結剤を使用しても構わない。他の組成の有機凝結剤としては、アルキルアミン・エピクロルヒドリン縮合物、アルキレンジクロライドとポリアルキレンポリアミンの縮合物、ジシアンジアミド・ホルマリン縮合物、ジメチルジアリルアンモニウムクロライド重合体等が例示される。 In the present invention, two or more organic coagulants can be used by mixing the above organic coagulant with another organic coagulant. In this case, the other organic coagulant is preferably a dialkylaminoalkyl (meth) acrylate polymer represented by the following general formula (I), but an organic coagulant having another composition may be used. Examples of organic coagulants having other compositions include alkylamine / epichlorohydrin condensates, alkylene dichloride / polyalkylene polyamine condensates, dicyandiamide / formalin condensates, and dimethyldiallylammonium chloride polymers.
一般式（Ｉ）中、Ｒ１及びＲ２は炭素数１〜４のアルキル基であり、それぞれ同一であっても、異なってもよい。Ｒ３はＨまたはアルキル基またはベンジル基であり、（Ｘ１）−は、陰イオンである。 In the general formula (I), R 1 and R 2 is an alkyl group having 1 to 4 carbon atoms, may be the same, respectively, may be different. R 3 is H, an alkyl group, or a benzyl group, and (X 1 ) − is an anion.
本発明で使用する高分子凝集剤は、アニオン系又はカチオン系の高分子凝集剤である。
アニオン性高分子凝集剤としては、例えば、ポリアクリル酸ソーダ、ポリアクリルアミドの部分加水分解物、アクリルアミドとアクリル酸ソーダの共重合物、２−アクリルアミド−２メチルプロパンスルホン酸の重合物またはアクリルアミド等との共重合物等が挙げられる。一方、ノニオン性高分子凝集剤としては、例えば、アクリルアミドの重合物または他のノニオン性モノマーとの共重合物等が挙げられる。
The polymer flocculant used in the present invention is an anionic or cationic polymer flocculant.
Examples of the anionic polymer flocculant include polyacrylic acid soda, partially hydrolyzed polyacrylamide, a copolymer of acrylamide and sodium acrylate, a polymer of 2-acrylamide-2methylpropanesulfonic acid, acrylamide, and the like. And the like. On the other hand, examples of nonionic polymer flocculants include acrylamide polymers and copolymers with other nonionic monomers.
本発明においては、廃水に無機凝集剤を添加した後、有機凝結剤を添加して一次凝集させた後、更に高分子凝集剤を添加して二次凝集させる。すなわち、薬物の添加順序が重要であり、無機凝集剤及び有機凝結剤より先に高分子凝集剤を加えると良好な処理性能が得られない。通常、廃水に無機凝集剤を添加し、例えば３０秒〜３分程度十分に攪拌混合し、その後に有機凝結剤を添加して一次凝集させる。 In the present invention, after adding an inorganic flocculant to the waste water, an organic coagulant is added for primary aggregation, and then a polymer flocculant is added for secondary aggregation. That is, the order of drug addition is important, and if the polymer flocculant is added prior to the inorganic flocculant and organic flocculant, good processing performance cannot be obtained. Usually, an inorganic flocculant is added to the wastewater, and, for example, it is sufficiently stirred and mixed for about 30 seconds to 3 minutes, and then an organic flocculant is added to cause primary flocculation.
前記した各薬剤の添加は、それぞれ別々の槽を設置して機械攪拌下に行うのが好ましいが、一つの槽を区切って使用しても構わない。無機凝集剤と有機凝結剤は一つの槽で注入する位置をずらして添加しても構わない。混合・撹拌方法としては、機械攪拌、ライン混合等、乱流状態を作り出す方法であればよく、機械攪拌が好ましい。 The addition of each of the above-mentioned chemicals is preferably carried out with mechanical stirring under separate tanks, but one tank may be divided and used. The inorganic flocculant and the organic flocculant may be added by shifting the pouring position in one tank. The mixing / stirring method may be any method that creates a turbulent state such as mechanical stirring or line mixing, and mechanical stirring is preferable.
各薬剤の添加量は、廃水の種類により変動するが、無機凝集剤の添加量は通常５０〜_６００ｍｇ／ｌであり、有機凝結剤の添加量は通常０．５〜１０ｍｇ／ｌであり、高分子凝集剤の添加量は、通常０．１〜１０ｍｇ／ｌである。凝集生成したフロックの固液分離は、常法に従って行うことが出来る。 The amount of each agent added varies depending on the type of wastewater, but the amount of inorganic flocculant added is usually 50 to _600 mg / l, and the amount of organic coagulant added is usually 0.5 to 10 mg / l. The addition amount of the molecular flocculant is usually 0.1 to 10 mg / l. Solid-liquid separation of the flocs produced by agglomeration can be performed according to a conventional method.
以下、本発明を実施例および比較例によって更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に何ら限定されるものではない。なお、以下の諸例において採用した各測定方法は次の通りである。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example at all unless the summary is exceeded. In addition, each measuring method employ | adopted in the following examples is as follows.
（１）高分子凝集剤の固有粘度：
固有粘度は、１Ｎ硝酸ナトリウム水溶液中、温度３０℃の条件で、ウベローデ希釈型毛細管粘度計を使用し、定法に基づき測定した。（高分子学会編，「新版高分子辞典」，朝倉書店，ｐ．１０７）
(1) Intrinsic viscosity of the polymer flocculant:
Intrinsic viscosity was measured based on a conventional method using an Ubbelohde dilution type capillary viscometer in a 1N sodium nitrate aqueous solution at a temperature of 30 ° C. (Edited by the Society of Polymer Science, “New Edition Polymer Dictionary”, Asakura Shoten, p. 107)
（２）フロック径：
凝集フロックのフロック径は、目視により全体の平均を測定した。
(2) Flock diameter:
The average floc diameter of the aggregated floc was measured visually.
（３）沈降時間：
高分子凝集剤の所定量を添加し、所定時間攪拌混合した後に攪拌を停止する。そして、生成した凝集フロックが５００ｍｌのビーカーの底に沈降する迄の時間を測定した。
(3) Settling time:
A predetermined amount of the polymer flocculant is added, and after stirring for a predetermined time, stirring is stopped. And the time until the produced | generated aggregation floc settles in the bottom of a 500 ml beaker was measured.
（４）上澄液ＣＯＤ：
ＣＯＤは、ＪＩＳ Ｋ ０１０１に基づき測定した。
(4) Supernatant COD:
COD was measured based on JIS K 0101.
（５）上澄液濁度（ＳＳ）：
濁度は、ＪＩＳ Ｋ ０１０１に基づき測定した。
(5) Supernatant turbidity (SS):
Turbidity was measured based on JIS K 0101.
なお、ＣＯＤ及びＳＳは、フロック径、沈降時間を測定した後、２分間静置し、表面から５ｃｍの深さより処理水を採取して測定した。 COD and SS were measured by measuring the floc diameter and the sedimentation time, then allowing to stand for 2 minutes, and collecting treated water from a depth of 5 cm from the surface.
実施例１〜６、参考例１及び比較例１〜６：
廃水としてＡ皮革工場廃水を採取して使用した。廃水の性状はｐＨ＝１１．０、ＣＯＤ１，０００ｍｇ／ｌ、ＳＳ＝２，０００ｍｇ／ｌであった。
Examples 1 to 6, Reference Example 1 and Comparative Examples 1 to 6:
A leather factory wastewater was collected and used as wastewater. The properties of the wastewater were pH = 11.0, COD 1,000 mg / l, SS = 2,000 mg / l.
先ず、５００ｍｌのビーカーに廃水を５００ｍｌ採取し、硫酸でｐＨを７に調整した後に無機凝集剤としてＰＡＣを３００ｍｇ／ｌ添加し、１５０ｒｐｍの回転数で１分間攪拌、混合した。無機凝集剤は水で１０倍に希釈して使用した。 First, 500 ml of waste water was collected in a 500 ml beaker, pH was adjusted to 7 with sulfuric acid, 300 mg / l of PAC was added as an inorganic flocculant, and the mixture was stirred and mixed for 1 minute at a rotation speed of 150 rpm. The inorganic flocculant was diluted 10 times with water and used.
次いで、表１に示す有機凝結剤を表２に示す条件で添加し、１５０ｒｐｍの回転数で１分間攪拌、混合した。有機凝結剤は、水に溶解して、０．１〜０．３質量％の水溶液として使用した。 Subsequently, the organic coagulant shown in Table 1 was added under the conditions shown in Table 2, and the mixture was stirred and mixed for 1 minute at a rotation speed of 150 rpm. The organic coagulant was dissolved in water and used as a 0.1 to 0.3% by mass aqueous solution.
次いで、表１に示す高分子凝集剤を表２に示す条件で添加し、１００ｒｐｍの回転数で２分間攪拌し凝集フロックを形成させた。高分子凝集剤は、水に溶解して、０．１〜０．３質量％の水溶液として使用した。凝集性能試験の結果を表２に示す。 Next, the polymer flocculant shown in Table 1 was added under the conditions shown in Table 2, and stirred for 2 minutes at a rotational speed of 100 rpm to form an agglomerated floc. The polymer flocculant was dissolved in water and used as a 0.1 to 0.3 mass% aqueous solution. The results of the aggregation performance test are shown in Table 2.
比較例７〜９：
実施例１において、有機凝結剤の添加を省略した以外は、実施例１と同様の試験条件で凝集性能試験を実施した。結果を表２に示す。但し、比較例８及び９においては、無機凝集剤の添加量を多くした。
Comparative Examples 7-9:
In Example 1, the aggregation performance test was performed under the same test conditions as in Example 1 except that the addition of the organic coagulant was omitted. The results are shown in Table 2. However, in Comparative Examples 8 and 9, the amount of inorganic flocculant added was increased.
実施例８及び９：
廃水としＮ製紙工場の総合廃水を採取して使用した。廃水の性状はｐＨ＝７．４、ＣＯＤ＝４５０ｍｇ／ｌ、ＳＳ＝３００ｍｇ／ｌであった。
Examples 8 and 9:
The waste water collected from the N paper mill was used. The properties of the wastewater were pH = 7.4, COD = 450 mg / l, SS = 300 mg / l.
先ず、５００ｍｌのビーカーに廃水を５００ｍｌ採取し、無機凝集剤として硫酸バンドを１００ｍｇ／ｌ添加し、１５０ｒｐｍの回転数で１分間攪拌、混合した。無機凝集剤は水で１０倍に希釈して使用した。 First, 500 ml of waste water was collected in a 500 ml beaker, 100 mg / l of a sulfuric acid band was added as an inorganic flocculant, and the mixture was stirred and mixed at a rotation speed of 150 rpm for 1 minute. The inorganic flocculant was diluted 10 times with water and used.
次いで、表１に示す有機凝結剤を表３に示す条件で添加し、１５０ｒｐｍの回転数で２分間攪拌し凝集フロックを形成させた。有機凝結剤は、水に溶解して、０．１〜０．３質量％の水溶液として使用した。 Subsequently, the organic coagulant shown in Table 1 was added under the conditions shown in Table 3, and the mixture was stirred at 150 rpm for 2 minutes to form an aggregated floc. The organic coagulant was dissolved in water and used as a 0.1 to 0.3% by mass aqueous solution.
次いで、表１に示す高分子凝集剤を表３に示す条件で添加し、１００ｒｐｍの回転数で２分間攪拌し凝集フロックを形成させた。高分子凝集剤は、水に溶解して、０．１〜０．３質量％の水溶液として使用した。 Subsequently, the polymer flocculant shown in Table 1 was added under the conditions shown in Table 3, and the mixture was stirred for 2 minutes at a rotation speed of 100 rpm to form an aggregate floc. The polymer flocculant was dissolved in water and used as a 0.1 to 0.3 mass% aqueous solution.
その後、前記と同様に凝集性能試験を行った。結果を表３に示す。 Thereafter, the coagulation performance test was conducted in the same manner as described above. The results are shown in Table 3.
比較例１０〜１２：
実施例８及び９と同じ廃水を使用し、表３に示す条件を採用し、前記と同様に凝集性能試験を行った。結果を表３に示す。
Comparative Examples 10-12:
The same waste water as in Examples 8 and 9 was used, the conditions shown in Table 3 were adopted, and the coagulation performance test was performed in the same manner as described above. The results are shown in Table 3.
比較例１３及び１４：
実施例８及び９と同じ廃水を使用し、有機凝結剤を使用せず、表３に示す条件で無機凝集剤と高分子凝集剤を使用し、前記と同様に凝集性能試験を行った。結果を表３に示す。
Comparative Examples 13 and 14:
The same waste water as in Examples 8 and 9 was used, an organic coagulant was not used, an inorganic coagulant and a polymer coagulant were used under the conditions shown in Table 3, and the coagulation performance test was performed in the same manner as described above. The results are shown in Table 3.
表２及び表３から次のことが分かる。 The following can be understood from Tables 2 and 3.
本発明によれば、実施例１〜９に示すように、ＰＡＣ添加量３００ｍｇ／ｌまたはバンドの添加量１００ｍｇ／ｌで良好な凝集性能を示し、良好な水質の処理水が得られた。本発明の好ましい態様の有機凝結剤を使用した実施例２、３、４及び７は、より良好な凝集性能、処理水質を示した。 According to the present invention, as shown in Examples 1 to 9, good flocculation performance was exhibited at a PAC addition amount of 300 mg / l or a band addition amount of 100 mg / l, and treated water with good water quality was obtained. Examples 2, 3, 4 and 7 using the organic coagulant of the preferred embodiment of the present invention showed better agglomeration performance and treated water quality.
比較例１及び２並びに１０は、有機凝結剤の組成が本発明で規定する範囲より低いため、フロック径は大きく問題なかったが、沈降性、処理水のＳＳ、ＣＯＤが劣る結果であった。 In Comparative Examples 1 and 2 and 10, since the composition of the organic coagulant was lower than the range specified in the present invention, the floc diameter was not a big problem, but the sedimentation property, SS and COD of the treated water were inferior.
比較例３及び１１は、有機凝結剤の固有粘度が本発明で規定する範囲より低いため、フロックが小さく沈降性が劣った。 In Comparative Examples 3 and 11, since the intrinsic viscosity of the organic coagulant was lower than the range specified in the present invention, the floc was small and the sedimentation property was poor.
比較例４及び５並びに１２は、有機凝結剤の固有粘度が本発明で規定する範囲より高いため、フロックは大きく沈降性は良好であったが、処理水のＳＳ、ＣＯＤが劣る結果であった。 In Comparative Examples 4 and 5 and 12, since the intrinsic viscosity of the organic coagulant was higher than the range specified in the present invention, the floc was large and the sedimentation property was good, but the SS and COD of the treated water were inferior. .
比較例６は、有機凝結剤として一般的に使用されているジメチルジアリルアンモニウムクロライド重合体であるＫ１を使用したため、実施例よりフロックが小さく沈降性が劣り、処理水の水質が劣る結果であった。 In Comparative Example 6, K1, which is a dimethyldiallylammonium chloride polymer generally used as an organic coagulant, was used, so the floc was smaller and the sedimentation property was inferior and the water quality of the treated water was inferior. .
比較例７〜９及び１３〜１４は、無機凝集剤と高分子凝集剤の組み合わせで実施した結果である。そのため、比較例７に示す通り、有機凝結剤を使用した際のＰＡＣ添加量である３００ｍｇ／ｌでは凝集しなかった。一方、比較例９に示す通り、ＰＡＣが１，０００ｍｇ／ｌ以上の添加量で同程度のフロックが生成したが沈降速度及び処理水のＳＳ、ＣＯＤは実施例より劣った。同様に、比較例１３に示す通り、有機凝結剤を使用した際のバンド添加量である１００ｍｇ／ｌでは凝集しなかった。一方、比較例１４に示す通り、バンドが４００ｍｇ／ｌ以上と実施例よりも４倍以上添加することにより同程度のフロックが生成したが沈降速度及び処理水のＣＯＤは実施例より劣った。 Comparative Examples 7 to 9 and 13 to 14 are results obtained by combining an inorganic flocculant and a polymer flocculant. Therefore, as shown in Comparative Example 7, no aggregation occurred at the PAC addition amount of 300 mg / l when the organic coagulant was used. On the other hand, as shown in Comparative Example 9, the same level of floc was produced with an addition amount of PAC of 1,000 mg / l or more, but the sedimentation rate and SS and COD of the treated water were inferior to those of the Examples. Similarly, as shown in Comparative Example 13, no aggregation occurred at the band addition amount of 100 mg / l when the organic coagulant was used. On the other hand, as shown in Comparative Example 14, when the band was added at 400 mg / l or more, which was 4 times or more than the Example, the same level of floc was generated, but the sedimentation rate and COD of the treated water were inferior to those of the Example.
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |