JP4221422B2 - Bulking inhibitor and wastewater treatment method - Google Patents
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- JP4221422B2 JP4221422B2 JP2006161923A JP2006161923A JP4221422B2 JP 4221422 B2 JP4221422 B2 JP 4221422B2 JP 2006161923 A JP2006161923 A JP 2006161923A JP 2006161923 A JP2006161923 A JP 2006161923A JP 4221422 B2 JP4221422 B2 JP 4221422B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は活性汚泥のバルキング防止剤およびこのバルキング防止剤を用いた廃水処理方法に関する。 The present invention relates to an activated sludge bulking inhibitor and a wastewater treatment method using the bulking inhibitor.
下水、し尿および各種有機性産業廃棄物の廃水は、通常活性汚泥法によって処理されている。活性汚泥法は、細菌類や原生動物などの微生物を利用して廃水を処理する生物学的処理方法の一つであるが、従来からつぎのような問題が生じていた。すなわち、活性汚泥処理されている間、流入廃水の流量の変動、流入廃水中の有機物の変動量に伴い活性汚泥中の微生物相も変化する。これらの変化が急激なときは、汚泥が膨化し、沈降が悪くなり、汚泥が水面近くまで上昇し、汚泥の溢流量が増えて処理能力が低下して、場合によっては処理不能となる現象が生じていた。この現象が生じると、汚泥が白っぽく非常に軽く沈降し難いものとなり、ＢＯＤ除去率も極端に低下してしまう。このような現象は、いわゆるバルキング現象といわれ、活性汚泥法における廃水浄化効率や処理能力を低下させる最も大きな原因の一つとされている。 Wastewater from sewage, human waste and various organic industrial wastes is usually treated by the activated sludge method. The activated sludge method is one of biological treatment methods for treating wastewater using microorganisms such as bacteria and protozoa. However, the following problems have conventionally occurred. That is, during the activated sludge treatment, the microflora in the activated sludge also changes with the fluctuation of the flow rate of the influent wastewater and the fluctuation amount of the organic matter in the influent wastewater. When these changes are abrupt, the sludge expands, the sedimentation worsens, the sludge rises to near the water surface, the sludge overflow rate increases, the processing capacity decreases, and in some cases the treatment becomes impossible. It was happening. When this phenomenon occurs, the sludge becomes whitish and becomes very light and difficult to settle, and the BOD removal rate is extremely lowered. Such a phenomenon is called a so-called bulking phenomenon, and is considered to be one of the biggest causes of reducing the wastewater purification efficiency and treatment capacity in the activated sludge method.
たとえば、活性汚泥が正常に廃水処理機能を果たしているか否かの一つの指標として、ＳＶＩ (Sludge Volume Index 、汚泥指標）がある。このＳＶＩは、1gの活性汚泥が 30 分間の沈降により占める容積で表される。正常な機能を発揮する活性汚泥のＳＶＩは 50 〜150 、特に 100以下であるが、バルキングを起こした活性汚泥のそれは 300〜1000にもなることがある。また、このようなバルキングを起こした活性汚泥は、その機能を回復するのが容易でなく、最悪の場合には汚泥の入れ替えの必要が生じ、工場などでは入れ替えの場合汚泥の馴養がすむまで廃水処理を中止しなければならず、工場の生産計画に重大な影響を与えることとなる。また、下水処理場においては、通常１日の水量変動が大きく、午前と午後の水量が変動する時間帯に汚泥の流出が発生して著しく水質を悪化させ処理不能となる。 For example, there is SVI (Sludge Volume Index) as one index of whether activated sludge normally performs the wastewater treatment function. This SVI is expressed as the volume occupied by 1 g of activated sludge by sedimentation for 30 minutes. The SVI of activated sludge that performs normal functions is 50 to 150, especially 100 or less, but that of activated sludge that has caused bulking can be 300 to 1000. In addition, activated sludge that has caused such bulking is not easy to recover its function, and in the worst case, it is necessary to replace the sludge. Processing must be discontinued and will have a significant impact on the factory production plan. In addition, in a sewage treatment plant, fluctuations in the amount of water in a day are usually large, and sludge spills out in the time zone when the amount of water in the morning and afternoon fluctuates, causing water quality to deteriorate significantly and making it impossible to treat.
従来、活性汚泥のバルキング発生を防止する方法として、特定の構造を有するジチオカルバミン酸塩の 1種または 2種以上を水に溶解して活性汚泥に添加する方法（特許文献１）、廃水中にバリン、ロイシン、イソロイシン、Ｌグルタミン酸フェニルアラニン、チロシン等のアミノ酸の 1種または 2種以上を有効成分として含んでいる組成物を活性汚泥に添加する方法（特許文献２）等が提案されている。また、二級アミン、二官能性エポキシ化合物および多官能性アミンとの反応により得られ、 25 ℃、 37 重量％水溶液濃度で測定した溶液粘度が少なくとも 800cSt である陽イオンポリマーを活性汚泥に添加する方法（特許文献３）等が提案されている。しかし、これらの方法は、いずれも長期にわたるバルキング防止には不十分であった。 Conventionally, as a method of preventing the occurrence of bulking of activated sludge, a method of dissolving one or more dithiocarbamates having a specific structure in water and adding it to activated sludge (Patent Document 1), valine in wastewater A method of adding a composition containing one or more amino acids such as leucine, isoleucine, phenylalanine L-glutamate, and tyrosine as an active ingredient to activated sludge (Patent Document 2) has been proposed. Also added to the activated sludge is a cationic polymer obtained by reaction with secondary amines, difunctional epoxy compounds and polyfunctional amines and having a solution viscosity of at least 800 cSt measured at 25 ° C and 37 wt% aqueous solution concentration. A method (Patent Document 3) and the like have been proposed. However, none of these methods is sufficient for long-term bulking prevention.
近年、本発明者等によって、四級化アンモニウム塩をポリマーの主鎖に有する一連のバルキング防止剤（特許文献４、特許文献５、特許文献６）が持続性のあるバルキング防止剤として提案されている。 In recent years, a series of anti-bulking agents having a quaternized ammonium salt in the polymer main chain (Patent Document 4, Patent Document 5, and Patent Document 6) have been proposed by the present inventors as durable anti-bulking agents. Yes.
しかしながら、四級化アンモニウム塩をポリマーの主鎖に有するバルキング防止剤は、水溶性陽イオンポリマーの分子量が小さくなると持続性や即効性の点で必ずしも充分でなくなる。また、極限粘度が高くなるとバルキング発生菌に対する作用が減少してＳＶＩを低下させる効果が少なくなる。また、嫌気および好気運転との組合わせの時のみ有効である。これはタイプ０２１Ｎ糸状性細菌によるバルキングには効果があるが、それ以外の場合は効果が殆どみられないためである。このように、夏季や冬季など季節により異なる場合のあるバルキング発生等に対して短時間でＳＶＩを低下させ、かつその効果を持続させるバルキング防止剤は見出だされていないという問題がある。
本発明は、このような問題に対処するためになされたもので、発生原因を問わず処理操作が容易で短時間でＳＶＩを低下させ、かつその効果を持続させるバルキング防止剤およびこのバルキング防止剤を用いた廃水処理方法を提供することを目的とする。 The present invention has been made in order to cope with such a problem, and is a bulking inhibitor that can be easily treated regardless of the cause of its occurrence, reduces SVI in a short time, and maintains its effect, and the bulking inhibitor. An object of the present invention is to provide a wastewater treatment method using slag.
請求項１の活性汚泥のバルキング防止剤は、一般式Ｒ2−Ｙで表される化合物と、少なくとも陽イオン性基を含む化合物との混合物である活性汚泥のバルキング防止剤であって、上記Ｒ2は、少なくとも分子内に不飽和結合を有する炭化水素およびその誘導体の前記不飽和結合残基であり、上記Ｙはバルキング発生菌に作用する−ＯＳＯ3Ｍ基で、該Ｍが水素または金属元素であり、上記陽イオン性基を含む化合物がジメチルアミンとエピクロルヒドリンとの反応生成物であることを特徴とする。
ここで、バルキング発生菌とは、活性汚泥による廃水処理過程においてバルキング現象を引き起こす細菌類をいい、特に糸状性細菌類をいう。また、バルキング発生菌に作用するとは、バルキング発生菌を攻撃し、破壊する作用をいう。
The activated sludge bulking inhibitor according to claim 1 is an activated sludge bulking inhibitor which is a mixture of a compound represented by the general formula R 2 -Y and a compound containing at least a cationic group. 2 is the unsaturated bond residue of a hydrocarbon having at least an unsaturated bond in the molecule and derivatives thereof, Y is an -OSO 3 M group acting on bulking bacteria, and M is hydrogen or a metal element der is, wherein the compound containing the cationic group is a reaction product of dimethylamine and epichlorohydrin.
Here, the bulking bacteria refer to bacteria that cause a bulking phenomenon in the wastewater treatment process with activated sludge, and particularly filamentous bacteria. Moreover, acting on a bulking-producing bacterium means an action of attacking and destroying the bulking-producing bacterium.
請求項２の活性汚泥のバルキング防止剤は、上記分子内に不飽和結合を有する炭化水素が不飽和脂肪酸類または該不飽和脂肪酸類に対応する不飽和高級アルコール類であることを特徴とする。 The bulking inhibitor for activated sludge according to claim 2 is characterized in that the hydrocarbon having an unsaturated bond in the molecule is an unsaturated fatty acid or an unsaturated higher alcohol corresponding to the unsaturated fatty acid.
本発明の廃水処理方法は、廃水を活性汚泥により処理する廃水処理方法であって、活性汚泥の乾燥固形分 100重量部に対して請求項１または請求項２記載のバルキング防止剤を0.01〜 25重量部添加することを特徴とする。 The wastewater treatment method of the present invention is a wastewater treatment method for treating wastewater with activated sludge, wherein 0.01 to 25 of the bulking inhibitor according to claim 1 or claim 2 is applied to 100 parts by weight of the dry solid content of the activated sludge. It is characterized by adding parts by weight.
本発明のバルキング防止剤は、バルキング現象に対する長年の研究結果得られたものである。すなわち、活性汚泥のバルキング現象は、バルキング発生菌、たとえば、Sphaertilus（スフエロチルス属）、Thiothrix（チオスリックス属）、Aspergillus（アスペルギルス属）、Penicillum（ペニシリウム属）、放線菌、タイプ０８０３、タイプ１７０１、タイプ０２１Ｎ、タイプ０９６１等の一般に有鞘糸状性細菌、有鞘硫黄含有糸状性細菌等の糸状性細菌や糸状菌の異常繁殖に起因するのがほとんどであるが、特に冬季には活性汚泥中に粘性に富むゼリー状の物質が発生し、これが原因で汚泥が沈降しにくくなりバルキング現象を示すこともある。この場合、塩化亜鉛などの金属塩類や陽イオン性ポリアクリルアミド系高分子凝集剤を廃水に添加するのが効果的であるといわれているが、本発明者の研究の結果、この方法は、ばっ気槽等において、活性汚泥が気泡を包含しやすく、気泡を包含した活性汚泥は、廃水を処理する能力が極端に低下し、バルキング発生防止に顕著な効果のないことがわかった。また、微細な無機質粒子を質量付加剤として添加する方法も知られているが、この場合は少なくとも汚泥に対して 5重量％以上添加する必要があり、汚泥の真体積ならびに沈降体積の増加に伴う沈降不良も発生し、その効果は少ない。さらに再度余剰汚泥として引き抜かなければならないので、その処分費が大幅に上昇し不利である。また、バルキング発生に寄与する糸状性細菌や糸状菌を強い殺菌力を有する薬剤で処理すると一時的に糸状細菌類も破壊されるが、同時に活性汚泥も解体されるため、再び糸状細菌類が発生しやすくなり、バルキング防止に対してほとんど持続的効果のないことがわかった。さらに、バルキングの発生が頻繁になる傾向が認められることが多い。 The bulking inhibitor of the present invention is the result of many years of research on the bulking phenomenon. That is, the bulking phenomenon of activated sludge is caused by bulking bacteria such as Sphaertilus, Thiothrix, Aspergillus, Penicillum, Actinomycetes, Type 0803, Type 1701, Type 021N. Generally, it is caused by abnormal growth of filamentous bacteria such as sheathed filamentous bacteria, sheathed sulfur-containing filamentous bacteria, and filamentous fungi, such as type 0961. A rich jelly-like substance is generated, and this may cause sludge to become difficult to settle and may show a bulking phenomenon. In this case, it is said that it is effective to add a metal salt such as zinc chloride or a cationic polyacrylamide polymer flocculant to the wastewater. In an air tank or the like, it was found that the activated sludge easily contains bubbles, and the activated sludge containing bubbles has an extremely low ability to treat wastewater, and has no significant effect on preventing bulking. In addition, a method of adding fine inorganic particles as a mass adding agent is also known, but in this case, it is necessary to add at least 5% by weight with respect to the sludge, which accompanies an increase in the true volume and settling volume of the sludge. Inferior sedimentation occurs and the effect is small. Furthermore, since it has to be extracted again as surplus sludge, its disposal cost increases significantly, which is disadvantageous. In addition, when filamentous bacteria and filamentous fungi that contribute to the occurrence of bulking are treated with chemicals with strong bactericidal activity, filamentous bacteria are also temporarily destroyed, but at the same time activated sludge is dismantled, so filamentous bacteria are generated again. It has been found that it has little lasting effect on bulking prevention. In addition, there is often a tendency for bulking to occur.
本発明はこのような知見に基づきなされたものある。すなわち、本発明のバルキング防止剤は上述のように、一般式Ｒ2−Ｙで表される化合物と、少なくとも陽イオン性基を含む化合物との混合物である活性汚泥のバルキング防止剤とすることにより、廃水の種類やその状態にかかわらず活性汚泥の活性を維持したまま、糸状性細菌類を主に殺菌できることを見出だしたことによりなされたものである。 The present invention has been made based on such findings. That is, as described above, the bulking inhibitor of the present invention is a bulking inhibitor for activated sludge which is a mixture of a compound represented by the general formula R 2 —Y and a compound containing at least a cationic group. It was made by finding that filamentous bacteria can be mainly sterilized while maintaining the activity of activated sludge regardless of the type and state of wastewater.
本発明のバルキング防止剤は、分子内に不飽和結合を有する炭化水素等およびバルキング発生菌に作用する基からなる化合物と、陽イオン性基を含む化合物との混合物であるので、活性汚泥の活性を維持しつつ糸状性細菌類を主に殺菌することができる。そのため、バルキング防止剤を単に添加するだけで、短時間のうちに、活性汚泥のＳＶＩの上昇を抑えることができる。また、この効果を長時間維持することができる。以上の結果、ばっ気槽内の活性汚泥の膨化はおこらず、沈降体積を小さくし、活性汚泥濃度を高く保ち、ＢＯＤの除去効果を著しく高くすることができる。 Since the bulking inhibitor of the present invention is a mixture of a hydrocarbon compound having an unsaturated bond in the molecule and a group that acts on bulking bacteria and a compound containing a cationic group, the activity of activated sludge It is possible to mainly sterilize filamentous bacteria while maintaining the above. Therefore, the increase in SVI of activated sludge can be suppressed in a short time by simply adding a bulking inhibitor. Moreover, this effect can be maintained for a long time. As a result, the activated sludge in the aeration tank does not expand, the sedimentation volume can be reduced, the activated sludge concentration can be kept high, and the BOD removal effect can be significantly increased.
本発明の廃水処理方法は上述のバルキング防止剤を用いるので、沈降槽においても活性汚泥の沈隆分離が極めて容易になる．しかも、沈降したものの体積（沈隆体積）が著しく小さくできるため、余剰活性汚泥が生成しにくく、余剰活性汚泥の除去、焼却処理を頻繁に行う必要がなく、廃水処理方法として極めて優れている。 Since the wastewater treatment method of the present invention uses the above-mentioned bulking inhibitor, it is very easy to separate activated sludge in a sedimentation tank. Moreover, since the volume (swelling volume) of the sedimented material can be remarkably reduced, it is difficult to generate surplus activated sludge, and it is not necessary to frequently remove surplus activated sludge and incinerate, which is an excellent wastewater treatment method.
Ｙはバルキング発生菌に作用する基であり、特にバルキング発生菌を攻撃することのできる基をいう。たとえば、糸状性細菌などのバルキング発生菌を殺菌できる−ＯＳＯ3 Ｍ基や、グアニジン残基、カルボキシル基、エステル残基、ニトロ基、ニトロソ基、ハロゲン基、芳香族基などを挙げることができる。本発明にあっては、特に−ＯＳＯ3 Ｍの一般式を有する基であることが好ましい。Ｍは水素または金属元素を表す。金属元素としてはアルカリ金属が好ましく、たとえばＮａ、Ｋ、Ｌｉを例示することができる。好ましいＭとしては、生成した塩の水溶解性が高く、工業的に安価であるＮａ、Ｋを挙げることができる。このような−ＯＳＯ3 Ｍ基を有することにより、糸状性細菌類を主に殺菌できる。 Y is a group that acts on bulking bacteria, and particularly a group that can attack the bulking bacteria. For example, mention may be made of or -OSO 3 M group which can sterilize the bulking occurrence bacteria such as filamentous bacteria, guanidine residue, a carboxyl group, an ester residue, a nitro group, a nitroso group, a halogen group, and an aromatic group. In the present invention, a group having a general formula of —OSO 3 M is particularly preferable. M represents hydrogen or a metal element. The metal element is preferably an alkali metal, and examples thereof include Na, K, and Li. Preferable M includes Na and K, which are high in water solubility of the generated salt and are industrially inexpensive. By having such a -OSO 3 M group, mainly sterilized filamentous bacteria.
本発明のバルキング防止剤は、一般式Ｒ2 −Ｙで表される化合物と、少なくとも陽イオン性基を含む化合物との混合物である。一般式Ｒ2 は、少なくとも分子内に不飽和結合を有する炭化水素およびその誘導体より反応に関与する不飽和結合を除いた部分である。不飽和結合部分と、ペルオキソ二硫酸カリ（ K2 S2 O8 ）などのペルオキソ二硫酸塩や硫酸とが反応することにより、分子内にＹとなる−ＯＳＯ3 Ｍ基を導入することができる。Ｒ2 の出発原料としては、不飽和脂肪酸類や不飽和基を有する脂肪族炭化水素類を挙げることができる。不飽和脂肪酸類としては、ミリストレイン酸、パルミトレイン酸、オレイン酸、エライジン酸、シスバクセン酸、バクセン酸、エルカ酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエ酸、いわし油、ドコサヘキサエン酸などを挙げることができる。また、不飽和基を有する脂肪族炭化水素類としては、たとえば不飽和脂肪酸類に対応する不飽和高級アルコール類を挙げることができる。 The bulking inhibitor of the present invention is a mixture of a compound represented by the general formula R 2 —Y and a compound containing at least a cationic group. The general formula R 2 is a portion obtained by removing unsaturated bonds involved in the reaction from hydrocarbons having at least an unsaturated bond in the molecule and derivatives thereof. By reacting the unsaturated bond portion with peroxodisulfate such as potassium peroxodisulfate (K 2 S 2 O 8 ) or sulfuric acid, an —OSO 3 M group that becomes Y can be introduced into the molecule. . Examples of the starting material for R 2 include unsaturated fatty acids and aliphatic hydrocarbons having an unsaturated group. Examples of unsaturated fatty acids include myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, cisbaccenoic acid, vaccenic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, sardine oil, docosahexaenoic acid, etc. Can do. Examples of the aliphatic hydrocarbon having an unsaturated group include unsaturated higher alcohols corresponding to unsaturated fatty acids.
Ｙはバルキング発生菌に作用する基であり、特にバルキング発生菌を攻撃することのできる基をいい、上述と同様、−ＯＳＯ3 Ｍの一般式を有する基であることが好ましい。Ｙは、Ｒ2 の不飽和基と、硫酸ないしはペルオキソ二硫酸カリ（ K2 S2 O8 ）などのペルオキソ二硫酸塩とを反応させることにより、分子内に−ＯＳＯ3 Ｍ基などを導入することができる。具体的には、ペルオキソ二硫酸カリ（ K2 S2 O8 ）などのペルオキソ二硫酸塩を、不飽和基を有するモノマー 1モルに対してモル数で0.01〜1.5 モル添加して 50 〜 80 ℃に温度を上昇させて 2〜8 時間反応させることにより得られる。 Y is a group that acts on a bulking-producing bacterium, particularly a group capable of attacking the bulking-producing bacterium, and is preferably a group having the general formula of -OSO 3 M as described above. Y introduces an -OSO 3 M group or the like into the molecule by reacting an unsaturated group of R 2 with a peroxodisulfate such as sulfuric acid or potassium peroxodisulfate (K 2 S 2 O 8 ). be able to. Specifically, peroxodisulfate such as potassium peroxodisulfate (K 2 S 2 O 8 ) is added in an amount of 0.01 to 1.5 moles per mole of the monomer having an unsaturated group, and 50 to 80 ° C. It is obtained by reacting for 2 to 8 hours at an elevated temperature.
Ｒ2 −Ｙで表される化合物と混合される少なくとも陽イオン性基を含む化合物としては、陽イオン性基を主鎖あるいは側鎖に含む重合性化合物を挙げることができる。陽イオン性基としては、四級化窒素を有する基が好ましく、たとえばジメチルアミンとエピクロルヒドリンとの重合体や、四級化窒素を側鎖に有する重合体を挙げることができる。このような重合体の分子量は、活性汚泥の活性を阻害することのない分子量であることが好ましい。分子量が小さいと陽イオン性基の殺菌性が発現され、活性汚泥も破壊される場合がある。具体的には陽イオン性基を含む化合物の極限粘度は、0.001 〜0.6dl/g であることが好ましい。 Examples of the compound containing at least a cationic group mixed with the compound represented by R 2 —Y include polymerizable compounds containing a cationic group in the main chain or side chain. The cationic group is preferably a group having quaternized nitrogen, and examples thereof include a polymer of dimethylamine and epichlorohydrin and a polymer having quaternized nitrogen in the side chain. The molecular weight of such a polymer is preferably a molecular weight that does not inhibit the activity of the activated sludge. If the molecular weight is small, the bactericidal property of the cationic group is expressed, and the activated sludge may be destroyed. Specifically, the intrinsic viscosity of the compound containing a cationic group is preferably 0.001 to 0.6 dl / g.
このようにして得られた本発明のバルキング防止剤はそれぞれ合成反応時の溶媒を除去して固体として用いることも、また、水または親水性溶液として用いることもできる。特に水溶液として用いることが廃水処理のバルキング防止剤として好適である。 The bulking inhibitor of the present invention thus obtained can be used as a solid after removing the solvent during the synthesis reaction, or can be used as water or a hydrophilic solution. In particular, it is suitable as a bulking inhibitor for wastewater treatment to be used as an aqueous solution.
本発明の廃水処理方法は、上述のバルキング防止剤を使用することを特徴とする。その添加量は活性汚泥の乾燥固形分 100重量部に対して 0.01 〜 25 重量部、より好ましくは 0.1〜 10 重量部である。添加量がこの範囲であると、バルキング現象の発生を抑えることができるとともに、廃水に溶解して系外に流去されるなく持続的にバルキング抑制効果を維持することができる。 The wastewater treatment method of the present invention is characterized by using the above-described bulking inhibitor. The added amount is 0.01 to 25 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the dry solid content of the activated sludge. When the addition amount is within this range, the occurrence of the bulking phenomenon can be suppressed, and the bulking suppression effect can be maintained continuously without being dissolved in the waste water and flowing out of the system.
バルキング防止剤の添加方法は、（イ）流入廃水に混和、混合し、これを曝気槽に送る方法、（ロ）曝気槽や沈降槽の活性汚泥の発泡およびスカム化が起っている槽に直接添加する方法、（ハ）返送汚泥に添加する方法のいずれかの方法またはこれらを 2種以上組合せた方法で行うことができる。本発明のバルキング防止剤を添加すると、 6ケ月以上はＳＶＩの上昇を抑えることが可能となる。なお、ＳＶＩが上昇する徴候が認められたら、その時点で、本発明のバルキング防止剤を 0.01 〜 25 重量部の範囲で添加するのがよい。さらに本発明のバルキング防止剤は活性汚泥菌に対して殆ど悪影響がないために、連続添加を行い、常に活性汚泥中に存在させて廃水処理を正常に保ちながらバルキング発生の予防剤としても使用することができる。 Anti-bulking agents can be added by (a) mixing and mixing with the influent wastewater and sending it to the aeration tank. (B) active sludge foaming and scumming in the aeration tank and sedimentation tank. Either directly added, (c) added to returned sludge, or a combination of two or more of these methods can be used. When the bulking inhibitor of the present invention is added, the increase in SVI can be suppressed for 6 months or more. In addition, when the sign that SVI rises is recognized, it is preferable to add the bulking inhibitor of the present invention in the range of 0.01 to 25 parts by weight. Furthermore, since the bulking inhibitor of the present invention has almost no adverse effect on the activated sludge bacteria, it is continuously added, and is always present in the activated sludge to be used as a bulking prevention agent while maintaining wastewater treatment normally. be able to.
実施例１
攪拌器、還流冷却器、ジャケット型冷却器、温度計等を備えた密閉型反応容器に、オレイン酸 282g およびベンゼンスルホン酸ナトリウム 200g を仕込み、反応容器内を窒素雰囲気に保ちながら、濃硫酸 120g を仕込み、 15 ℃で 5時間反応させた後、水酸化カリウムで中和して、溶液１を得た。一方、ジメチルアミンの 50 重量％水溶液 100g を攪拌器、還流冷却器、温度計等を備えた密閉型反応容器に仕込み、反応容器内を窒素雰囲気に保ちながら、102gのエピクロルヒドリンを 30 〜80℃に維持しながら徐々に添加して、溶液２を得た。溶液１と溶液２とを重量比で 1：1 の割合で混合してバルキング防止剤を得た。
Example 1
A sealed reaction vessel equipped with a stirrer, reflux condenser, jacket-type cooler, thermometer, etc. was charged with 282 g of oleic acid and 200 g of sodium benzenesulfonate, and 120 g of concentrated sulfuric acid was added while maintaining a nitrogen atmosphere in the reaction vessel. After charging and reacting at 15 ° C. for 5 hours, the solution was neutralized with potassium hydroxide to obtain Solution 1. On the other hand, 100 g of a 50% by weight aqueous solution of dimethylamine was charged into a closed reaction vessel equipped with a stirrer, reflux condenser, thermometer, etc., and 102 g of epichlorohydrin was maintained at 30 to 80 ° C. while keeping the reaction vessel in a nitrogen atmosphere. While maintaining, the solution was gradually added to obtain a solution 2. Solution 1 and solution 2 were mixed at a weight ratio of 1: 1 to obtain a bulking inhibitor.
実施例２
オレイン酸に代えてリノール酸を、ベンゼンスルホン酸ナトリウムに代えてパラトルエンスルホン酸を、それぞれ使用する以外は、実施例１と同一の条件方法でバルキング防止剤を得た。
Example 2
A bulking inhibitor was obtained by the same method as in Example 1 except that linoleic acid was used instead of oleic acid, and paratoluenesulfonic acid was used instead of sodium benzenesulfonate.
実施例３
ＣＯＤが 380ppm の廃水原水を、容量 370 m3 のばっ気槽 4室に、1 基あたり80m3 ／時間の速度で送り、活性汚泥濃度 3500ppm（廃水に対する乾燥固形分を意味する）とし、さらにばっ気槽での原水をＣＯＤ：窒素元素：燐元素の比を 100: 5: 1、 pH を 7にそれそれ調節した後、各ばっ気槽に空気を 800 m3 ／時間の速度で吹き込んだ。この処理後、容量 500 m3 の沈降槽に送り、汚泥を白然沈降させ、上澄液と活性汚泥の濃縮液相とを分離し、上澄液は流出水として河川に流した。活性汚泥の濃縮液は、返送汚泥として 80m3 ／時間の速度でばっ気槽に返送し、活性汚泥の濃縮液のうち 1 m3 ／時間を余剰活性汚泥として、これに凝集剤を添加して汚泥を凝集させ、遠心脱水機で脱水して含水率が 90 重量％の脱水ケーキを得た。この廃水処理操作を長期間継続したところ、ばっ気槽の活性汚泥のＳＶＩが 320に達した。
Example 3
Waste water with a COD of 380 ppm is sent to 4 aeration tanks with a capacity of 370 m 3 at a rate of 80 m 3 / hour per unit, with an activated sludge concentration of 3500 ppm (meaning dry solid content of waste water), and further The raw water in the air tank was adjusted to a ratio of COD: nitrogen element: phosphorus element to 100: 5: 1 and pH to 7, respectively, and then air was blown into each aeration tank at a rate of 800 m 3 / hour. After this treatment, it was sent to a sedimentation tank with a capacity of 500 m 3 to settle the sludge, separating the supernatant and the concentrated liquid phase of activated sludge, and flowing the supernatant into the river as effluent. The activated sludge concentrate is returned to the aeration tank as a return sludge at a rate of 80 m 3 / hour. 1 m 3 / hour of the activated sludge concentrate is used as surplus activated sludge, and a flocculant is added to the sludge. And a dehydrated cake having a water content of 90% by weight was obtained. When this wastewater treatment operation was continued for a long period of time, the SVI of activated sludge in the aeration tank reached 320.
上記ばっ気槽から、乾燥後の固形分濃度が 3500ppm、ＳＶＩが 320の活性汚泥をビーカーに採取した。このビーカー中の活性汚泥に対して、実施例１で得られたバルキング防止剤を重合体固形分の乾燥重量として 50 〜 400ppm の範囲で添加量を変えて添加し、活性性汚泥のＳＶＩの低下状況を観察した。バルキング防止剤を、採取した活性汚泥に対し上の範囲で添加すると、ＳＶＩは130まで低下した。
そこで上記廃水処理場の汚泥を、実際の廃水処理場を想定したばっ気槽容量が 3 m3 、沈降槽容量が 1 m3 の活性汚泥の小型模型に入れ、ＣＯＤが 380ppm の廃水原水をばっ気槽においてＣＯＤ：窒素：燐元素の比が 100： 5： 1になるように連続的に添加し、ばっ気槽の溶存酸素濃度を 1〜2 ppm に調節し、さらに汚泥返送率を 50 ％として連続連転した。この活性汚泥の活性模型で、ばっ気槽容積に対してバルキング防止剤を重合体固形分の乾燥重量として 150ppmとなるように水道水で 100倍に希釈しながら 24 時間連続添加した。バルキング防止剤の添加終了後、ばっ気槽内の活性汚泥のＳＶＩは 120まで低下し、添加終了から 3日後には、ＳＶＩが 80 まで低下して、沈降槽内での上澄液と活性汚泥の濃縮液との分離性が向上した。さらにバルキング防止剤を添加した後、 1カ月間を経過しても糸状性細菌の急激な増加が抑制され、沈降槽内の活性汚泥の沈降界面の水準は上昇しなかった。また、処理水のＢＯＤについては変化がなく良好な状態であった。
From the aeration tank, activated sludge having a solid concentration after drying of 3500 ppm and an SVI of 320 was collected in a beaker. With respect to the activated sludge in this beaker, the bulking inhibitor obtained in Example 1 was added by changing the addition amount in the range of 50 to 400 ppm as the dry weight of the polymer solids, and the SVI of the activated sludge was lowered. The situation was observed. When the bulking inhibitor was added to the collected activated sludge in the above range, the SVI decreased to 130.
Therefore, the sludge from the above wastewater treatment plant is put into a small model of activated sludge with an aeration tank capacity of 3 m 3 and a sedimentation tank capacity of 1 m 3 assuming an actual wastewater treatment plant, and raw water with a COD of 380 ppm is discharged. Continuously add COD: nitrogen: phosphorus element ratio to 100: 5: 1 in the tank, adjust the dissolved oxygen concentration in the aeration tank to 1-2 ppm, and further reduce the sludge return rate to 50%. As a continuous revolving. In this activated sludge model, the bulking inhibitor was continuously added to the aeration tank volume while being diluted 100-fold with tap water so that the dry weight of polymer solids was 150 ppm. After the addition of the bulking inhibitor, the SVI of the activated sludge in the aeration tank drops to 120. Three days after the addition, the SVI drops to 80, and the supernatant and activated sludge in the settling tank Separation from the concentrate was improved. Furthermore, after adding a bulking inhibitor, the rapid increase of filamentous bacteria was suppressed even after 1 month, and the level of the sedimentation interface of activated sludge in the sedimentation tank did not rise. Further, the BOD of the treated water was in a good state with no change.
実施例４
実施例３におけるばっ気槽から、乾燥後の固形分濃度が 3500ppm、ＳＶＩが 320の活性汚泥をビーカーに採取した。このビーカー中の活性汚泥に対して、実施例２で得られたバルキング防止剤を重合体固形分の乾燥重量として 50 〜 400ppm の範囲で添加量を代えてばっ気槽から採取した汚泥に添加し、活性性汚泥のＳＶＩの低下状況を観察した。バルキング防止剤を、採取した活性汚泥に対し上の範囲で添加すると、ＳＶＩは 160まで低下した。そこで、上記の廃水処理場の汚泥を実施例３と同様の活性汚泥処理の小型模型に入れ、さらに実施例３に記載したばっ気槽の溶存酸素量、廃水原水添加量および汚泥返送率と同様の条件で連続運転した。この活性汚泥の小型模型で、汚泥に対してバルキング防止剤を重合体固形分の乾燥重量として 150ppm となるように水道水で 100倍に希釈しながら 24 時間連続添加した。バルキング防止剤の添加終了後、ばっ気槽内の活性汚泥のＳＶＩは 150まで低下し、添加終了から 3日後には、ＳＶＩが 110まで低下して、沈降槽内での上澄液と活性汚泥の濃縮液との分離性が向上した。さらにバルキング防止剤を添加した後、 1カ月間を経過しても糸状性細菌の急激な増加が抑制され、沈降槽内の活性汚泥の沈降界面の水準は上昇しなかった。また、処理水のＢＯＤについては変化がなく良好な状態であった。
Example 4
From the aeration tank in Example 3, activated sludge having a solid concentration after drying of 3500 ppm and an SVI of 320 was collected in a beaker. To the activated sludge in the beaker, the bulking agent obtained in Example 2 was added to the sludge collected from the aeration tank by changing the addition amount in the range of 50 to 400 ppm as the dry weight of the polymer solids. The state of SVI decrease in activated sludge was observed. When the bulking inhibitor was added in the above range to the collected activated sludge, the SVI decreased to 160. Therefore, the sludge from the above-mentioned wastewater treatment plant is put into a small model for activated sludge treatment similar to that in Example 3, and the dissolved oxygen amount, the amount of raw water added to the aeration tank and the sludge return rate described in Example 3 are the same. Continuous operation was performed under the conditions of In this small model of activated sludge, a bulking inhibitor was continuously added to sludge for 24 hours while diluting 100 times with tap water so that the dry weight of polymer solids was 150 ppm. After the addition of the bulking inhibitor, the SVI of the activated sludge in the aeration tank drops to 150. Three days after the addition, the SVI drops to 110, and the supernatant and activated sludge in the settling tank Separation from the concentrate was improved. Furthermore, after adding a bulking inhibitor, the rapid increase of filamentous bacteria was suppressed even after 1 month, and the level of the sedimentation interface of activated sludge in the sedimentation tank did not rise. Further, the BOD of the treated water was in a good state with no change.
比較例１
実施例３で用いたバルキング防止剤に代えて、市販されている陽イオン性ポリアクリルアミド系凝集剤（たとえばダイアクリアー（三菱化学社製、商品名）、ハイモロック（株式会社ハイモ製、商品名）、サンフロック（三洋化成工業社製、商品名）、ダイヤフロック（ダイヤフロック社製、商品名）、クリフロック（栗田工業社製、商品名）の水溶液を用い、実施例３と同様にそれぞれの添加量を変えて活性汚泥のＳＶＩの低下状況を観察した。上の市販の処埋液の場合、全てにおいてほぼ同様の挙動を示し、ばっ気槽から採取した活性汚泥に対して処理液中の固形分の乾燥重量が 20 ppm 前後において共に良好な沈降フロックを形成しはじめ、処理液中の固形分の乾燥重量が 60 ppm となるようにして添加した後では、活性汚泥のＳＶＩは 130前後になった。しかしながら、このメスシリンダーの中にエアストンを入れて 30 分間ばっ気したところ、沈降していた汚泥が気泡を巻き込んで全部浮上してしまい、沈降分離不能となった。また、実施例３の廃水処理場において、糸状性細菌の多量発生によってばっ気槽内の活性汚泥のＳＶＩが 300まで上昇し、沈降槽で汚泥層と上澄液との分離が困難になった時点で、陽イオン性メタクリル酸エステル系凝集剤（分子量 Mw 約 500万）を 0.5重量％濃度に調整し、重合体固形分の乾燥重量が 60 kgに相当する量を 24 時間連続添加したところ、処理液の添加終了後では、ばっ気槽内の活性汚泥のＳＶＩは 120まで低下したが、最終沈殿槽に凝集したフロックに気泡が付着して汚泥が多量に浮上し、処理水とともに流出し処理不能となった。また、添加終了後から 3日後には再びＳＶＩが 300を越え、沈降槽内での上澄液と活性汚泥の濃縮液との分離が困難になった。
Comparative Example 1
Instead of the bulking inhibitor used in Example 3, a commercially available cationic polyacrylamide-based flocculant (for example, Diaclear (trade name, manufactured by Mitsubishi Chemical Corporation), Hymo Lock (trade name, manufactured by Hymo Corporation), Using an aqueous solution of Sanflock (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name), Diafloc (manufactured by Diafrock Co., Ltd., trade name), Cliflock (trade name, manufactured by Kurita Kogyo Co., Ltd.) The amount of SVI in activated sludge was observed by changing the amount, and all of the above commercially available treatment liquids showed almost the same behavior, and the solids in the treatment liquid were compared with the activated sludge collected from the aeration tank. After the addition of the solids in the treatment liquid to a dry weight of 60 ppm, the activated sludge has an SVI of 130. However, when airstone was put into the graduated cylinder and aerated for 30 minutes, the sludge that had settled entrained bubbles and all floated, making it impossible to separate. In the wastewater treatment plant of No. 3, the SVI of the activated sludge in the aeration tank rises to 300 due to the large generation of filamentous bacteria, and it becomes difficult to separate the sludge layer from the supernatant in the sedimentation tank. The amount of ionic methacrylate ester flocculant (molecular weight Mw approx. 5 million) was adjusted to 0.5% by weight, and the amount corresponding to 60 kg dry weight of polymer solids was added continuously for 24 hours. After completion, the SVI of the activated sludge in the aeration tank decreased to 120, but air bubbles adhered to the floc aggregated in the final sedimentation tank, and a large amount of sludge floated, and the sludge flowed out together with the treated water, making it impossible to treat. Also added Beyond the SVI 300 again after 3 days After the completion, it became difficult to separate the concentrate supernatant and activated sludge in sedimentation tank.
比較例２
実施例３で用いたバルキング防止剤に代えて、以下の方法で調整したバルキング防止剤を用い、活性汚泥のＳＶＩの低下状況を観察した。比較試料の調製：エピクロルヒドリンに等モルの 50 ％ジメチルアミンを冷却下で温度を 60 ℃に保持しつつ 5時間かけて連続的に添加した。添加終了後、 12 時間、温度を 40 ℃に保持して熟成した。得られた混合反応組成物を分取用ＧＰＣを用いて、濃度 2mol/l KBr 水溶液により温度 25 ℃で測定した極限粘度が0.40 となる重合体を分取して比較試料とした。
Comparative Example 2
In place of the bulking inhibitor used in Example 3, a bulking inhibitor prepared by the following method was used, and the SVI decrease state of the activated sludge was observed. Preparation of comparative sample: equimolar 50% dimethylamine was continuously added to epichlorohydrin over 5 hours while maintaining the temperature at 60 ° C under cooling. After completion of the addition, the mixture was aged while maintaining the temperature at 40 ° C. for 12 hours. A polymer having an intrinsic viscosity of 0.40 measured at a temperature of 25 ° C. with a 2 mol / l KBr aqueous solution was fractionated from the obtained mixed reaction composition using a preparative GPC to prepare a comparative sample.
実施例３に記載の活性汚泥を、実施例３で記載した活性汚泥の小型模型に入れ、実施例３と同じ条件で連続連転した。この活性汚泥の小型模型で、汚泥に対して上述の比較試料のバルキング防止剤を重合体固形分の乾燥重量として 100ppmとなるように水道水で 100倍に希釈しながら 24 時間連続添加した。比較試料のバルキング防止剤の添加から 11 時間後には、ばっ気槽内の活性汚泥のＳＶＩは 140まで低下した。この時の汚泥を顕微鏡で観察すると、汚泥が糸状性細菌を包含し、大きなフロックを形成していた。しかしながら、添加から 3日後には再びＳＶＩが 300を越え、沈降槽内での上澄液と活性汚泥の濃縮液との分離が困難となった。この時の汚泥を顕微鏡で観察すると、大きな汚泥フロックは比較試料のバルキング防止剤を添加する以前の大きさに戻り、長い糸状性細菌が多量に観察された。 The activated sludge described in Example 3 was put into the small model of activated sludge described in Example 3 and continuously rotated under the same conditions as in Example 3. In this small model of activated sludge, the above-mentioned comparative sample bulking inhibitor was continuously added to sludge for 24 hours while diluting 100 times with tap water so that the dry weight of the polymer solids was 100 ppm. 11 hours after the addition of the bulking inhibitor of the comparative sample, the SVI of the activated sludge in the aeration tank decreased to 140. When the sludge at this time was observed with a microscope, the sludge contained filamentous bacteria and formed a large floc. However, after 3 days from the addition, the SVI again exceeded 300, making it difficult to separate the supernatant from the activated sludge in the sedimentation tank. When the sludge at this time was observed with a microscope, the large sludge floc returned to the size before the addition of the bulking inhibitor of the comparative sample, and a large amount of long filamentous bacteria were observed.
Claims (3)
前記Ｒ2は、少なくとも分子内に不飽和結合を有する炭化水素およびその誘導体の前記不飽和結合残基であり、前記Ｙはバルキング発生菌に作用する−ＯＳＯ3Ｍ基で、該Ｍが水素または金属元素であり、前記陽イオン性基を含む化合物がジメチルアミンとエピクロルヒドリンとの反応生成物であることを特徴とする活性汚泥のバルキング防止剤。 A compound represented by the general formula R 2 -Y, a bulking inhibitor activated sludge is a mixture of a compound containing at least a cationic group,
R 2 is an unsaturated bond residue of at least a hydrocarbon having an unsaturated bond in the molecule and derivatives thereof, Y is an —OSO 3 M group acting on bulking bacteria, and M is hydrogen or metal element der is, bulking agents of activated sludge, wherein the compound containing the cationic group is a reaction product of dimethylamine and epichlorohydrin.
A wastewater treatment method for treating wastewater with activated sludge, characterized in that 0.01 to 25 parts by weight of the bulking inhibitor according to claim 1 or 2 is added to 100 parts by weight of dry solid content of activated sludge. Wastewater treatment method.
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