JP2009066515A - Method, device, and agent for decoloring dye-containing wastewater - Google Patents

Method, device, and agent for decoloring dye-containing wastewater Download PDF

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JP2009066515A
JP2009066515A JP2007237443A JP2007237443A JP2009066515A JP 2009066515 A JP2009066515 A JP 2009066515A JP 2007237443 A JP2007237443 A JP 2007237443A JP 2007237443 A JP2007237443 A JP 2007237443A JP 2009066515 A JP2009066515 A JP 2009066515A
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wastewater
calcium chloride
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decoloring
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JP5117803B2 (en
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Hideyuki Yamada
英幸 山田
Kazuhisa Tsujimoto
和久 辻本
Masahiro Sakurai
理博 櫻井
Norihide Shimizu
紀英 清水
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Seiren Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a decoloring method, device and agent which can easily decolor colored wastewater containing hardly decomposable coloring-causing substances at a low cost. <P>SOLUTION: The decoloring method for dye-containing waste-water comprises the process for introducing the dye-containing wastewater into a treatment tank, and the process for adding calcium chloride and a microorganism belonging to Enterococcus genus to the introduced wastewater. The decoloring device is equipped with a means for introducing the dye-containing wastewater into the treatment tank, a means for adding calcium chloride and the microorganism belonging to Enterococcus genus to the introduced wastewater, a means for adjusting pH of the wastewater in the treatment tank, a means for controlling the wastewater in the treatment tank from a microaerophilic condition to an aerobic condition, and a means for leading out the wastewater in the treatment tank. The decoloring agent for dye-containing wastewater contains calcium chloride and the microorganism belonging to Enterococcus genus. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、廃水の脱色処理方法、脱色処理装置およびそれに使用する脱色処理剤に関する。詳しくは、染料を含有する廃水の脱色処理方法、脱色処理装置およびそれに使用する脱色処理剤に関する。   The present invention relates to a decolorization treatment method for wastewater, a decolorization treatment apparatus, and a decolorization treatment agent used therefor. In detail, it is related with the decoloring processing method of the wastewater containing dye, the decoloring processing apparatus, and the decoloring processing agent used for it.

現在、染料製造工場、繊維染色工場、紙・パルプ染色工場および食品加工場など、様々な業種の工場で染料を含む廃水(以下、着色廃水と称す)が発生している。この着色廃水は、着色原因成分として、直接染料、酸性染料、反応染料、カチオン染料、硫化染料および分散染料などの染料を含んでいる。
現在利用されているこれら各種染料においては、アゾ系の染料の割合が多く、全体の約70%を占めるといわれている。アゾ系の染料は、化学構造的に安定で分解され難い特徴があり、通常の活性汚泥法のみでは分解および脱色することが非常に困難である。そのため、着色廃水の脱色技術として、凝集沈澱法、活性炭吸着法、あるいはオゾンなどによる酸化分解処理方法を、単独または組合せて使用している。
Currently, wastewater containing dyes (hereinafter referred to as colored wastewater) is generated in factories of various industries such as dye manufacturing factories, fiber dyeing factories, paper / pulp dyeing factories, and food processing plants. This colored wastewater contains dyes such as direct dyes, acid dyes, reactive dyes, cationic dyes, sulfur dyes, and disperse dyes as coloring cause components.
In these various dyes currently used, the ratio of azo dyes is large, and it is said that it accounts for about 70% of the total. Azo dyes are characterized by a chemical structure that is stable and difficult to be decomposed, and it is very difficult to decompose and decolorize only by a normal activated sludge method. Therefore, as a decolorization technique for colored wastewater, a coagulation precipitation method, an activated carbon adsorption method, or an oxidative decomposition method using ozone or the like is used alone or in combination.

凝集沈殿法は、無機凝集剤であるアルミニウム塩類(硫酸アルミニウム、アルミン酸ナトリウムおよび塩基性塩化アルミニウムなど)、鉄塩類(硫酸第1鉄、硫酸第2鉄および塩化第2鉄など)および有機高分子凝集剤(陰イオン性ポリマー、陽イオン性ポリマーおよび非イオン性ポリマーなど)を廃水に添加し、染料などの着色原因成分を凝集させて除去する手法である。   Aggregation and precipitation methods include inorganic flocculants such as aluminum salts (such as aluminum sulfate, sodium aluminate and basic aluminum chloride), iron salts (such as ferrous sulfate, ferric sulfate and ferric chloride) and organic polymers. This is a technique in which a flocculant (an anionic polymer, a cationic polymer, a nonionic polymer, etc.) is added to waste water to coagulate and remove coloring-causing components such as dyes.

しかしながら、凝集沈澱法は、染料などの着色原因成分を含む泥状の二次廃棄物が大量に発生し、これらの廃棄物処理コストが高いという問題があった。また、この手段は水溶性が高く、凝集性の乏しい低分子の着色原因成分に対しては適用できないという問題がある。   However, the coagulation precipitation method has a problem in that a large amount of mud-like secondary waste containing a color-causing component such as a dye is generated, and the cost for treating these wastes is high. Further, this means has a problem that it cannot be applied to a low-molecular color-causing component having high water solubility and poor aggregation.

活性炭吸着法では、通常、活性炭を充填した濾過装置で脱色を行うが、濾過装置の閉塞などが起こり易いという問題があり、運転の維持管理が煩雑な場合がある。また、使用後の活性炭を再生あるいは廃棄するために莫大なコストがかかるという問題がある。   In the activated carbon adsorption method, decolorization is usually performed by a filtration device filled with activated carbon, but there is a problem that the filtration device is likely to be clogged, and operation maintenance may be complicated. In addition, there is a problem that enormous costs are required to regenerate or discard the used activated carbon.

また、オゾンによる酸化分解処理方法では、オゾン発生装置などの特殊設備の導入が必要な点や、電力消費量が多くランニングコストが高くなる点が問題であり、繊維染色工場からの廃水などの大量の着色廃水処理への適用は実現性が低いものであった。   In addition, the oxidative decomposition treatment method using ozone requires the introduction of special equipment such as an ozone generator and the problem of high power consumption and high running costs. Application to the treatment of colored wastewater was not feasible.

したがって、前記の方法の多くは、処理コストが高いこと、運転および維持管理が煩雑であることなどに問題があり、依然として安価で効果の高い脱色処理方法が求められている。   Therefore, many of the above-mentioned methods have problems such as high processing cost and complicated operation and maintenance, and there is a need for a decoloring processing method that is inexpensive and highly effective.

そこで、前記化学的および物理的処理以外の方法として、微生物を用いた着色廃水の処理方法が検討されている。微生物処理は、スケールアップ時の処理コストが小さいという利点があると考えられている。   Thus, as a method other than the chemical and physical treatments, a method for treating colored wastewater using microorganisms has been studied. Microbial treatment is believed to have the advantage of low processing costs at scale-up.

このような微生物を用いた処理方法の例として、染料を含む排水を硫酸還元細菌、硝化菌および、脱窒菌と接触させて、廃水の脱色及び脱窒を行う脱色装置に関するもの(特許文献1)、アゾ染料分解能を有するRhodopseudomonas属及び/又はRhodobacter sphaeroides種に属する微生物及びそれを用いたアゾ染料の分解に関するもの(特許文献2)、クレブシエラ(Klebsiella)属、フラボバクテリウム(Flavobacterium)属及びアエロモナス(Aeromonas)属から選ばれる1種又は2種以上の微生物を含有する染料の脱色剤及びこれを用いる脱色方法に関するもの(特許文献3)などがある。   As an example of a treatment method using such a microorganism, a decolorization apparatus for decolorizing and denitrifying wastewater by bringing wastewater containing a dye into contact with sulfate-reducing bacteria, nitrifying bacteria, and denitrifying bacteria (Patent Document 1) Microorganisms belonging to the genus Rhodopseudomonas and / or Rhodobacter sphaeroides having azo dye resolution and those relating to the degradation of azo dyes using the same (Patent Document 2), the genus Klebsiella, the genus Flavobacterium and the Aeromonas ( And a decoloring agent for dyes containing one or more microorganisms selected from the genus Aeromonas) and a decoloring method using the same (Patent Document 3).

しかし、これらの方法では、微生物の染料に対する特異性が高いために、様々な染料や着色成分を含む実際の廃水に対して汎用性が低いという問題があった。さらに、工場から排出される実際の着色廃水は、着色原因物質としての染料に加えて、生産現場で使用される製品原料、副産物、分散剤、可溶化剤、界面活性剤、均染剤、フィックス剤、サイズ剤、ソーピング剤などの加工剤を大量に含んでいる場合がある。これらの化合物は、微生物の生育を阻害することから、前述の方法では微生物の増殖を維持できず、十分な脱色効果が得られないという問題があった。   However, these methods have a problem of low versatility with respect to actual wastewater containing various dyes and coloring components because of the high specificity of microbial dyes. Furthermore, the actual colored wastewater discharged from the factory is not only the dyes that cause coloration, but also the raw materials, by-products, dispersants, solubilizers, surfactants, leveling agents, and fixants used at the production site. In some cases, a large amount of a processing agent such as an agent, a sizing agent or a soaping agent is contained. Since these compounds inhibit the growth of microorganisms, there has been a problem that the above-described method cannot maintain the growth of microorganisms and a sufficient decoloring effect cannot be obtained.

また、エンテロコッカス属の微生物を用いた廃水処理方法が特許文献4、5、6および7に記載されている。しかし、これらの方法は、生活排水の浄化を目的とするものであり、難分解性の染料に対しては十分な脱色効果が得られない場合がある。また、エンテロコッカス属の微生物を単独で使用した場合の着色廃水の脱色には、高濃度の菌を用いて長時間の処理が必要になり、そのため、処理上清中の懸濁物が多くなるという問題があった。   Patent Documents 4, 5, 6 and 7 describe wastewater treatment methods using Enterococcus microorganisms. However, these methods are intended for purification of domestic wastewater, and there are cases where a sufficient decoloring effect cannot be obtained for persistent dyes. In addition, decolorization of colored wastewater when using Enterococcus microorganisms alone requires long-term treatment with high-concentration bacteria, which increases the amount of suspension in the treated supernatant. There was a problem.

さらに、特許文献8には、シュードモナス属に属する微生物と塩化カルシウムとを着色液に添加して脱色させる方法が記載されている。しかし、この方法では、まずシュードモナス属の微生物が凝集能物質を生産するような培養条件を整える必要がある。すなわち、廃水に高濃度のグルコースや酵母エキスなどの微生物が利用可能な栄養分を添加しなければならず、結果的に廃水中の有機物濃度が高くなり、廃水処理の負荷が大きくなるという問題がある。   Furthermore, Patent Document 8 describes a method of decoloring by adding a microorganism belonging to the genus Pseudomonas and calcium chloride to a coloring solution. However, in this method, first, it is necessary to prepare a culture condition in which Pseudomonas microorganisms produce an aggregating substance. That is, nutrients that can be used by microorganisms such as high concentrations of glucose and yeast extract must be added to the wastewater, resulting in an increase in the concentration of organic matter in the wastewater and an increase in the wastewater treatment load. .

これらのことから、実際の工場廃水の処理に適した、低コストで脱色効果の高い処理方法が依然として強く望まれている。   For these reasons, there is still a strong demand for a treatment method that is suitable for treatment of actual factory wastewater and has a low decolorization effect and high cost.

特開2004−82107号公報JP 2004-82107 A 特開2002−45172号公報JP 2002-45172 A 特開2002−28691号公報JP 2002-28691 A 特開2000−51891号公報JP 2000-51891 A 特開2003−80290号公報JP 2003-80290 A 特開2003−334588号公報JP 2003-334588 A 特開2005−270735号公報JP 2005-270735 A 特開平6−277692号公報Japanese Patent Application Laid-Open No. 6-276992

本発明は、このような従来技術の問題点に鑑みなされたものであり、難分解性の着色原因物質を含む着色廃水を、低コストで簡便に脱色することが可能な脱色処理方法、脱色処理装置および脱色処理剤を提供することを目的とする。   The present invention has been made in view of such problems of the prior art, and a decolorization treatment method and a decolorization treatment capable of easily decolorizing colored wastewater containing a hardly decomposable coloring cause substance at low cost. An object is to provide an apparatus and a decoloring agent.

すなわち、本発明は、処理槽に染料を含有する廃水を導入する工程、および、導入された廃水に塩化カルシウムとエンテロコッカス属に属する微生物とを添加する工程を含む染料を含有する廃水の脱色処理方法に関する。   That is, the present invention relates to a method for decolorizing wastewater containing a dye, including a step of introducing wastewater containing a dye into a treatment tank and a step of adding calcium chloride and a microorganism belonging to the genus Enterococcus to the introduced wastewater. About.

前記処理槽内の廃水のpHが6.0〜9.0であり、塩化カルシウム濃度が0.003〜0.3重量%であることが好ましい。   It is preferable that the waste water in the treatment tank has a pH of 6.0 to 9.0 and a calcium chloride concentration of 0.003 to 0.3% by weight.

前記処理槽内の廃水の微生物濃度が、乾燥重量で1000〜10000mg/Lであることが好ましい。   It is preferable that the microbial concentration of the wastewater in the treatment tank is 1000 to 10,000 mg / L in terms of dry weight.

前記微生物が活性汚泥由来であり、前記廃水が微好気条件にあることが好ましい。   It is preferable that the microorganism is derived from activated sludge and the wastewater is in a microaerobic condition.

また、本発明は、処理槽に染料を含有する廃水を導入する手段、導入された廃水に塩化カルシウムとエンテロコッカス属に属する微生物とを添加する手段、該処理槽内の廃水のpHを調整する手段、該処理槽内の廃水を微好気条件から好気条件に制御する手段、および、該処理槽内の廃水を導出する手段を備えた脱色処理装置に関する。   Further, the present invention provides means for introducing waste water containing a dye into a treatment tank, means for adding calcium chloride and a microorganism belonging to the genus Enterococcus to the introduced waste water, means for adjusting the pH of waste water in the treatment tank The present invention also relates to a decoloring apparatus comprising means for controlling waste water in the treatment tank from a microaerobic condition to an aerobic condition, and means for deriving the waste water in the treatment tank.

さらにまた、本発明は、塩化カルシウムとエンテロコッカス属に属する微生物とを含む、染料を含有する廃水の脱色処理剤に関する。   Furthermore, this invention relates to the decoloring treatment agent of the wastewater containing a dye containing the calcium chloride and the microorganisms which belong to the genus Enterococcus.

本発明によれば、塩化カルシウムとエンテロコッカス属に属する微生物とを用いることにより、着色廃水を簡便に脱色することができ、安全、低コスト、かつ、処理上清の懸濁が少ないという実用性に優れた脱色処理方法、脱色処理装置および脱色処理剤を提供することができる。   According to the present invention, by using calcium chloride and a microorganism belonging to the genus Enterococcus, it is possible to easily decolorize colored wastewater, which is safe, low in cost, and practical in that there is little suspension of the treated supernatant. An excellent decolorization treatment method, decolorization treatment apparatus, and decolorization treatment agent can be provided.

以下、本発明の実施の形態について、図面を参照して詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

図1は、本発明の脱色処理装置の実施形態の一つであって、処理槽に染料を含有する廃水を導入する手段、導入された廃水に塩化カルシウムとエンテロコッカス属に属する微生物とを添加する手段、該処理槽内の廃水のpHを調整する手段、該処理槽内の廃水を微好気条件から好気条件に制御する手段、および、該処理槽内の廃水を導出する手段を備えた脱色処理装置を示す模式図である。   FIG. 1 shows one embodiment of a decoloring apparatus according to the present invention, which is a means for introducing waste water containing a dye into a treatment tank, and calcium chloride and microorganisms belonging to the genus Enterococcus are added to the introduced waste water. Means, means for adjusting the pH of the wastewater in the treatment tank, means for controlling the wastewater in the treatment tank from a microaerobic condition to an aerobic condition, and means for deriving the wastewater in the treatment tank It is a schematic diagram which shows a decoloring processing apparatus.

図1において、符号1は廃水導入手段としての廃水供給管、符号2は処理槽、符号3は廃水導出手段としての処理水排出管である。また、pHを調整する手段として、pHを測定する測定器4、その値に応じて酸またはアルカリの投入量を制御する制御装置5、酸およびアルカリ貯蔵槽6および酸またはアルカリ供給管7を備えており、塩化カルシウムとエンテロコッカス属に属する微生物とを添加する手段として、微生物貯蔵槽8、微生物供給管9、塩化カルシウム貯蔵槽11および塩化カルシウム供給管12、さらに、微好気条件から好気条件制御手段として撹拌手段10または空気送り込み手段(図示せず)を備えている。   In FIG. 1, reference numeral 1 denotes a waste water supply pipe as waste water introduction means, reference numeral 2 denotes a treatment tank, and reference numeral 3 denotes a treated water discharge pipe as waste water deriving means. Further, as means for adjusting pH, a measuring instrument 4 for measuring pH, a control device 5 for controlling an input amount of acid or alkali according to the value, an acid and alkali storage tank 6 and an acid or alkali supply pipe 7 are provided. As means for adding calcium chloride and microorganisms belonging to the genus Enterococcus, a microorganism storage tank 8, a microorganism supply pipe 9, a calcium chloride storage tank 11 and a calcium chloride supply pipe 12, and further from a microaerobic condition to an aerobic condition A stirring means 10 or an air feeding means (not shown) is provided as a control means.

前記処理槽2は、塩化カルシウムとエンテロコッカス属に属する微生物との添加により脱色処理できるものであれば特に限定されない。例えば、常時撹拌や間欠撹拌をおこなう完全混合型、微生物固定化担体を投入した流動床型などを利用することができる。   The treatment tank 2 is not particularly limited as long as it can be decolorized by adding calcium chloride and a microorganism belonging to the genus Enterococcus. For example, a complete mixing type in which continuous stirring or intermittent stirring is performed, or a fluidized bed type in which a microorganism-immobilized support is introduced can be used.

また、本発明の脱色処理装置は、処理槽2の後段に、微生物と処理水とを分離するための固液分離手段として、沈殿槽、脱水機および濃縮機などを備えていてもよい。   Moreover, the decoloring apparatus of this invention may be equipped with the precipitation tank, the dehydrator, the concentrator, etc. as a solid-liquid separation means for isolate | separating microorganisms and treated water in the back | latter stage of the processing tank 2. FIG.

さらに、本発明の脱色処理装置は、単独で使用するものであっても、従来の活性汚泥処理槽の前段または後段に設置して使用するものであってもよい。   Furthermore, even if the decoloring apparatus of this invention is used independently, it may be installed and used in the front | former stage or back | latter stage of the conventional activated sludge processing tank.

本発明において、処理の対象となる廃水は、直接染料、酸性染料、反応染料、カチオン染料、硫化染料および分散染料などの染料を含んだ着色廃水であり、とくに限定されない。なかでも、着色廃水中の総有機炭素量(TOC)が100〜3000mg/Lの範囲であると、高い脱色効果を得ることができるため好ましい。総有機炭素量(TOC)が100mg/Lよりも低い場合には、微生物の栄養源が乏しいため、微生物の染料分解機能が活性化しないことがある。この場合は、微生物の栄養源となる有機物を着色廃水に添加して、TOC濃度を調整すれば、本発明の方法に適用することができる。一方、総有機炭素量(TOC)が3000mg/Lよりも高い場合は、生分解され易い有機物が被処理廃水中に高濃度で存在するため、染料分解以外の分解反応が優先され、十分な脱色効果が得られないことがある。また、汚泥の増加や代謝産物の蓄積、腐敗臭の発生などの二次的な水質汚濁の問題が生じる場合がある。   In the present invention, wastewater to be treated is colored wastewater containing direct dyes, acid dyes, reactive dyes, cationic dyes, sulfur dyes, disperse dyes and the like, and is not particularly limited. Especially, since the high decoloring effect can be acquired when the total organic carbon amount (TOC) in colored wastewater is the range of 100-3000 mg / L, it is preferable. When the total organic carbon content (TOC) is lower than 100 mg / L, the microorganism's dye-decomposing function may not be activated due to a lack of nutrient sources for microorganisms. In this case, an organic substance serving as a nutrient source for microorganisms can be added to the colored wastewater to adjust the TOC concentration, and can be applied to the method of the present invention. On the other hand, when the total organic carbon content (TOC) is higher than 3000 mg / L, organic matter that is easily biodegraded is present in the wastewater to be treated at a high concentration. The effect may not be obtained. In addition, secondary water pollution problems such as increase in sludge, accumulation of metabolites, and generation of rot odor may occur.

本発明で使用される塩化カルシウムおよびエンテロコッカス属に属する微生物の添加方法は、特に限定されず、あらかじめ混合してから着色廃水に添加してもよいし、それぞれ独立に着色廃水に添加してもよい。いずれの場合にも相乗的な脱色効果を得ることができる。   The method of adding the calcium chloride and the microorganism belonging to the genus Enterococcus used in the present invention is not particularly limited, and may be added to the colored wastewater after mixing in advance, or may be added independently to the colored wastewater. . In any case, a synergistic decoloring effect can be obtained.

処理槽内の被処理着色廃水のpHは、6.0〜9.0に維持されていることが好ましい。この範囲外であると、微生物の活性が低下するため、十分な脱色効果が得られない場合がある。また、pHが9.0よりも高い廃水に塩化カルシウムを添加すると、水酸化物などの凝集体が形成される場合がある。とくに好ましくは、pH6.5〜8.5である。   The pH of the color wastewater to be treated in the treatment tank is preferably maintained at 6.0 to 9.0. If it is out of this range, the activity of the microorganisms is lowered, so that a sufficient decoloring effect may not be obtained. In addition, when calcium chloride is added to wastewater having a pH higher than 9.0, aggregates such as hydroxide may be formed. Particularly preferably, the pH is 6.5 to 8.5.

本発明は、塩化カルシウムとエンテロコッカス属に属する微生物とを併用することが特徴である。塩化カルシウムとエンテロコッカス属の微生物とによる脱色機構の詳細は、まだ十分に解明されていない部分もあるが、カルシウムが細胞外層に作用し、染料吸着能力を高めるとともに、微生物由来の各種酵素を安定化する効果があり、微生物の脱色活性を相乗的に高めるものと考えられる。   The present invention is characterized in that calcium chloride and a microorganism belonging to the genus Enterococcus are used in combination. The details of the decolorization mechanism by calcium chloride and Enterococcus microorganisms have not been fully elucidated, but calcium acts on the extracellular layer to increase the ability to adsorb dyes and stabilize various microorganism-derived enzymes. It is thought that it synergistically increases the decoloring activity of microorganisms.

塩化カルシウムは、海水など自然環境の中に広く存在し、毒性が少なく、比較的低コストの物質として知られている。   Calcium chloride is widely present in the natural environment such as seawater, and is known as a relatively low-cost substance with low toxicity.

被処理着色廃水の塩化カルシウム濃度は、0.003〜0.3重量%であることが好ましく、より好ましくは0.005〜0.2重量%、さらに好ましくは0.01〜0.2重量%である。塩化カルシウム濃度がこの範囲であると、脱色効果を相乗的に高めることができる。濃度が0.003重量%より低いと、添加効果が不十分となり、微生物処理との相乗的な脱色効果が得られにくい傾向にある。濃度が0.3重量%をこえても、それ以上の添加効果は得られない傾向にあり、また、過剰なカルシウムが処理水中に残存するため、水質の悪化につながる場合がある。塩化カルシウムの着色廃水への添加量は、廃水の種類、着色の程度および処理廃水に求められる水質などに応じて、前記の濃度範囲内において適宜調整することができる。   The calcium chloride concentration of the color wastewater to be treated is preferably 0.003 to 0.3% by weight, more preferably 0.005 to 0.2% by weight, and still more preferably 0.01 to 0.2% by weight. It is. When the calcium chloride concentration is within this range, the decoloring effect can be synergistically enhanced. When the concentration is lower than 0.003% by weight, the effect of addition becomes insufficient, and a synergistic decoloring effect with microbial treatment tends to be difficult to obtain. Even if the concentration exceeds 0.3% by weight, no further effect of addition tends to be obtained, and excessive calcium remains in the treated water, which may lead to deterioration of water quality. The amount of calcium chloride added to the colored wastewater can be appropriately adjusted within the above-mentioned concentration range according to the type of wastewater, the degree of coloring, the water quality required for the treated wastewater, and the like.

本発明で使用される微生物は、エンテロコッカス属に属するものである。エンテロコッカス属は、一般的に高塩濃度の条件下や広いpH範囲で生育が可能であるため、廃水中での生育も良好で、塩化カルシウムを併用したときの脱色効果が優れている。   The microorganism used in the present invention belongs to the genus Enterococcus. Enterococcus is generally capable of growing under conditions of high salt concentration and in a wide pH range, so that it grows well in waste water and has an excellent decolorizing effect when calcium chloride is used in combination.

さらに、エンテロコッカス属に属する微生物を用いた場合、懸濁物質が少なく透明度の高い、水質の優れた脱色処理水が得られるという利点がある。エンテロコッカス属に属する微生物は一般的に運動性を有さない球菌という特徴があり、運動性を有するシュードモナス属や、他の形状の異なる微生物と比較して、微生物の沈降性に優れている。したがって、脱色処理後の処理水と微生物との分離が容易であり、例えば静置分離後の上澄みとして透明度の高い処理水を得ることができるため、実用性が極めて高い。   Furthermore, when a microorganism belonging to the genus Enterococcus is used, there is an advantage that decolorized water with less suspended substances and high transparency and excellent water quality can be obtained. Microorganisms belonging to the genus Enterococcus are generally characterized as cocci that do not have motility, and are superior in sedimentation of microorganisms compared to the genus Pseudomonas having motility and other types of microorganisms. Therefore, separation of the treated water and the microorganisms after the decoloring treatment is easy, and for example, highly transparent treated water can be obtained as a supernatant after stationary separation, so that the practicality is extremely high.

また、乳酸菌の一種として知られており、安全性が高く廃水処理に好適に用いることができる。前記微生物は、エンテロコッカス属に属するものであれば、とくに限定されるものではない。たとえば、エンテロコッカス・フェカリス(Enterococcus faecalis)、エンテロコッカス・マロドラタス(Enterococcus malodoratus)、エンテロコッカス・アビウム(Enterococcus avium)などがあげられる。なかでも、低栄養条件下での増殖が優れる、エンテロコッカス・アビウムが好ましい。   Moreover, it is known as a kind of lactic acid bacteria, and has high safety and can be suitably used for wastewater treatment. The microorganism is not particularly limited as long as it belongs to the genus Enterococcus. Examples include Enterococcus faecalis, Enterococcus malodoratus, Enterococcus avium and the like. Of these, Enterococcus abium, which is excellent in growth under low nutrient conditions, is preferable.

本発明で使用されるエンテロコッカス属に属する微生物は、例えばエンテロコッカス・アビウム(Enterococcus avium)種として、NBRC100477、JCM 8722、ATCC 14025、DST0703、NCTC 9938等を挙げることができるが、これらに限定されるものではない。   Examples of the microorganism belonging to the genus Enterococcus used in the present invention include, but are not limited to, Enterococcus avium species, NBRC100477, JCM8722, ATCC 14025, DST0703, NCTC 9938, and the like. is not.

また、前記微生物は、処理すべき廃水への適応力が高く、かつ周辺環境への悪影響の懸念が小さいという点で、活性汚泥由来であることが好ましい。   In addition, the microorganism is preferably derived from activated sludge in that it has high adaptability to wastewater to be treated and is less susceptible to adverse effects on the surrounding environment.

この微生物は、たとえば、繊維染色工場の廃水処理施設の活性汚泥から採取される。採取した活性汚泥を適宜希釈し、反応染料(C.I.Reactive Red 3)を0.03%含むSCD寒天培地(日水製薬社製)に塗布する。25℃で24時間培養後、脱色ハローを形成したコロニーから、脱色効果の高い微生物1種を単離することによって得られる。本発明者らが、常法に従って、単離した微生物の16SrDNA上流領域(約500bp)の塩基配列を解析し、BLASTによるデータベース検索による同定を行ったところ、本菌は、エンテロコッカス属の16SrDNAの塩基配列と高い相同性があることが判明し、エンテロコッカス属に属する微生物であると同定された。   This microorganism is collected from, for example, activated sludge in a wastewater treatment facility of a fiber dyeing factory. The collected activated sludge is appropriately diluted and applied to an SCD agar medium (Nissui Pharmaceutical Co., Ltd.) containing 0.03% reactive dye (C.I. Reactive Red 3). After culturing at 25 ° C. for 24 hours, it is obtained by isolating one microorganism having a high decolorization effect from the colony that has formed a decolorization halo. The present inventors analyzed the base sequence of the 16S rDNA upstream region (about 500 bp) of the isolated microorganism according to a conventional method and identified it by BLAST database search. As a result, the present bacterium was found to be a 16S rDNA base of Enterococcus It was found to be highly homologous to the sequence and was identified as a microorganism belonging to the genus Enterococcus.

本発明において、処理槽内の処理すべき廃水中には、エンテロコッカス属に属する微生物以外の微生物、例えば活性汚泥由来の微生物等が存在していても良く、この場合、複数種の微生物による相乗的な水質浄化機能が得られる。   In the present invention, the wastewater to be treated in the treatment tank may contain microorganisms other than those belonging to the genus Enterococcus, such as microorganisms derived from activated sludge, and in this case, synergistically with a plurality of microorganisms. Water purification function.

さらに、本発明における微生物は、担体に担持させた状態で利用することができる。用いる担体は特に限定されないが、例えばセルロース、ポリエチレン、ポリプロピレン、ポリエステル、ポリスチレン、アクリル、ポリウレタン、炭素繊維、活性炭、ゼオライト、ポリビニルアルコールなどから成る繊維状構造体や多孔質体、ゲル状体などが挙げられる。   Furthermore, the microorganism in the present invention can be used in a state of being supported on a carrier. The carrier to be used is not particularly limited, and examples thereof include fibrous structures, porous bodies, and gel-like bodies made of cellulose, polyethylene, polypropylene, polyester, polystyrene, acrylic, polyurethane, carbon fiber, activated carbon, zeolite, polyvinyl alcohol, and the like. It is done.

本発明で使用されるエンテロコッカス属に属する微生物の濃度は、乾燥重量で1000〜10000mg/Lであることが好ましく、より好ましくは、1000〜9000mg/Lであり、さらに好ましくは、2000〜8000mg/Lである。微生物濃度が1000mg/Lよりも小さい場合にも、脱色効果は得られるが、処理に長時間を有する場合がある。一方、10000mg/Lよりも大きい場合には、高い脱色効果が得られるが、脱色処理後の処理水と微生物との固液分離が困難になるため、廃水処理工程が複雑になる場合がある。   The concentration of the microorganism belonging to the genus Enterococcus used in the present invention is preferably 1000 to 10,000 mg / L in dry weight, more preferably 1000 to 9000 mg / L, and still more preferably 2000 to 8000 mg / L. It is. Even when the microbial concentration is lower than 1000 mg / L, a decoloring effect can be obtained, but the treatment may take a long time. On the other hand, when it is larger than 10000 mg / L, a high decoloring effect can be obtained, but the solid-liquid separation between the treated water and the microorganisms after the decoloring process becomes difficult, and the wastewater treatment process may be complicated.

本発明で使用されるエンテロコッカス属に属する微生物と塩化カルシウムとの割合は、とくに限定されないが、エンテロコッカス属に属する微生物:塩化カルシウムが乾燥重量で、1:0.03〜1:3であると、相乗的に高い脱色効果が得られるため好ましい。   The ratio of the microorganism belonging to the genus Enterococcus and calcium chloride used in the present invention is not particularly limited, but the microorganism belonging to the genus Enterococcus: calcium chloride is in a dry weight of 1: 0.03 to 1: 3. This is preferable because a high decolorization effect can be obtained synergistically.

本発明の脱色処理剤は、エンテロコッカス属に属する微生物と塩化カルシウムとを前記の割合、すなわち、乾燥重量1:0.03〜1:3で含んでなることが好ましい。   The decolorization treatment agent of the present invention preferably comprises a microorganism belonging to the genus Enterococcus and calcium chloride in the above ratio, that is, a dry weight of 1: 0.03 to 1: 3.

その形態としては、粉体および懸濁液などがあげられる。   Examples of the form include powder and suspension.

前記脱色処理剤には、その他、各種炭素源、タンパク質、ペプトン、酵母エキス、肉エキス、アミノ酸等の炭窒素源、リン酸カリウム、塩化ナトリウム、硫酸マグネシウム、硝酸ナトリウム、硫酸アンモニウム等の各種無機塩類など、一般的に微生物の活性化に必要とされる成分が含まれていてもよい。例えば、微生物に対する活性化効果が高く、かつ安価なものとして、可溶化汚泥や酵母エキスなどの微生物由来成分、米ぬかなどの穀物残渣などが含まれていてもよい。   Examples of the decoloring agent include various carbon sources, protein, peptone, yeast extract, meat extract, carbon dioxide sources such as amino acids, various inorganic salts such as potassium phosphate, sodium chloride, magnesium sulfate, sodium nitrate, and ammonium sulfate. In general, components necessary for activating microorganisms may be included. For example, microorganism-derived components such as solubilized sludge and yeast extract, and grain residues such as rice bran may be included as those having a high activation effect on microorganisms and inexpensive.

本発明の脱色処理は、高い脱色効果が得られる点で、微好気条件から好気条件の範囲内で行うことが好ましい。   The decoloring treatment of the present invention is preferably performed within the range of slightly aerobic conditions to aerobic conditions in that a high decoloring effect can be obtained.

本発明における前記好気条件とは、酸化還元電位(ORP)が好ましくは300〜0mV、より好ましくは250〜50mVの範囲であり、曝気装置を用いるなど、積極的な通気撹拌を行う条件をいう。なお、酸化還元電位(ORP)は、一般的なORPメーター(Ag/AgCl電極)等で測定できる。   The aerobic condition in the present invention is a condition in which the redox potential (ORP) is preferably in the range of 300 to 0 mV, more preferably in the range of 250 to 50 mV, and active aeration stirring is performed, such as using an aeration apparatus. . The oxidation-reduction potential (ORP) can be measured with a general ORP meter (Ag / AgCl electrode).

また、本発明における前記微好気条件とは、酸化還元電位(ORP)が好ましくは0〜−250mV、より好ましくは−30〜−200mVの範囲をいう。このような微好気条件は、微生物を添加した着色廃水を静置または緩やかに撹拌することで制御することができる。   In the present invention, the microaerobic condition refers to a range in which the redox potential (ORP) is preferably 0 to −250 mV, more preferably −30 to −200 mV. Such microaerobic conditions can be controlled by standing or gently stirring the colored wastewater to which microorganisms have been added.

酸化還元電位(ORP)が300mVをこえると、微生物の死骸や分解物が発生しやすく、処理水の水質が悪化する場合がある。逆に酸化還元電位(ORP)が−250mVより低いと、嫌気状態に近くなるため、脱色に必要な反応が効率的に進行し難くなるとともに、腐敗臭の発生などの問題が生じる場合がある。   When the oxidation-reduction potential (ORP) exceeds 300 mV, dead bodies and decomposition products of microorganisms are likely to be generated, and the quality of treated water may be deteriorated. On the other hand, when the oxidation-reduction potential (ORP) is lower than −250 mV, it becomes close to an anaerobic state, so that the reaction necessary for decolorization does not easily proceed efficiently, and problems such as the generation of rot odor may occur.

なかでも、エアレーションポンプ等を用いた曝気が不要であるため、設備がコンパクトであり、ランニングコストを削減することができる点で、微好気条件で脱色処理を行うことが好ましい。   Especially, since aeration using an aeration pump etc. is unnecessary, it is preferable to perform a decoloring process on microaerobic conditions at the point that an installation is compact and a running cost can be reduced.

以下、実施例により本発明を詳細に説明するが、本発明は実施例によって何ら制限されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by an Example.

モデル着色廃水に対する脱色効果
<染料を含むモデル着色廃水の調製>
SCD液体培地(日水製薬社製)10ml、水90ml、反応染料(C.I.Reactive Red 3)を0.03ml添加したものを、モデル着色廃水とした。この廃水のpHは、6.8であった。
Decolorization effect on model colored wastewater <Preparation of model colored wastewater containing dye>
A model colored waste water was prepared by adding 10 ml of SCD liquid medium (manufactured by Nissui Pharmaceutical), 90 ml of water, and 0.03 ml of reactive dye (CIReactive Red 3). The pH of this wastewater was 6.8.

実施例1
前記モデル着色廃水100mlに、塩化カルシウム0.05gおよび、乾燥重量換算で0.2gのエンテロコッカス・アビウム(NBRC100477、独立行政法人 製品評価技術基盤機構から購入)を添加した。エンテロコッカス・アビウムの菌体は、あらかじめSCD液体培地で培養後、遠心分離により集菌したものを用いた。菌体の乾燥重量は、集菌した菌体の一部を用い、赤外線水分計FD−610(株式会社ケット科学研究所)を使用して105℃の乾燥条件により求めた。
調製した着色廃水を処理槽(200mlのプラスチック広口ビン)に入れて静置することにより微好気条件とし、25℃で24時間の脱色処理を行った。
Example 1
To 100 ml of the model-colored wastewater, 0.05 g of calcium chloride and 0.2 g of Enterococcus abium (NBRC 100477, purchased from National Institute of Technology and Evaluation) were added in terms of dry weight. Enterococcus abium cells were collected in advance after culturing in an SCD liquid medium and centrifuged. The dry weight of the microbial cells was determined by using a part of the collected microbial cells and using an infrared moisture meter FD-610 (Kett Science Laboratory Co., Ltd.) under drying conditions at 105 ° C.
The prepared colored wastewater was placed in a treatment tank (200 ml plastic wide-mouthed bottle) and allowed to stand to make a microaerobic condition, and a decolorization treatment was performed at 25 ° C. for 24 hours.

実施例2
前記モデル着色廃水100mlに、塩化カルシウム0.2g、および乾燥重量換算で0.2gのエンテロコッカス・アビウム(NBRC100477)を添加して、実施例1と同様に脱色処理を行った。
Example 2
Decolorization treatment was performed in the same manner as in Example 1 by adding 0.2 g of calcium chloride and 0.2 g of Enterococcus abium (NBRC100477) in terms of dry weight to 100 ml of the model colored waste water.

実施例3
前記モデル着色廃水100mlに、塩化カルシウム0.05g、および乾燥重量換算で0.6gのエンテロコッカス・アビウム(NBRC100477)を添加して、実施例1と同様に脱色処理を行った。
Example 3
Decolorization treatment was performed in the same manner as in Example 1 by adding 0.05 g of calcium chloride and 0.6 g of Enterococcus abium (NBRC100477) to 100 ml of the model colored waste water.

実施例4
前記モデル着色廃水100mlに、塩化カルシウム0.2g、および乾燥重量換算で0.6gのエンテロコッカス・アビウム(NBRC100477)を添加して、実施例1と同様に脱色処理を行った。
Example 4
Decolorization treatment was performed in the same manner as in Example 1 by adding 0.2 g of calcium chloride and 0.6 g of Enterococcus abium (NBRC100477) to 100 ml of the model colored waste water.

比較例1
塩化カルシウムおよびエンテロコッカス属に属する微生物を含まないモデル着色廃水を、処理槽(200mlのプラスチック広口ビン)に入れて25℃で24時間静置した。
Comparative Example 1
A model colored wastewater not containing microorganisms belonging to the genus Calcium chloride and Enterococcus was placed in a treatment tank (200 ml plastic wide-mouth bottle) and allowed to stand at 25 ° C. for 24 hours.

比較例2
前記モデル着色廃水100mlに、塩化カルシウム0.2gのみを添加して、実施例1と同様に脱色処理を行った。
Comparative Example 2
Only 100 g of calcium chloride was added to 100 ml of the model colored waste water, and the decolorization treatment was performed in the same manner as in Example 1.

比較例3
前記モデル着色廃水100mlに、乾燥重量換算で0.6gのエンテロコッカス・アビウム(NBRC100477)のみを添加して、実施例1と同様に脱色処理を行った。
Comparative Example 3
Only 100 g of Enterococcus abium (NBRC100477) in terms of dry weight was added to 100 ml of the model colored waste water, and the color removal treatment was performed in the same manner as in Example 1.

比較例4
前記モデル着色廃水100mlに、塩化カルシウム0.2g、および乾燥重量換算で0.6gのクレブシエラ属の微生物(NBRC13277)を添加し、実施例1と同様に脱色処理を行った。前記クレブシエラ属の微生物は、あらかじめSCD液体培地で培養後、遠心分離により集菌したものを用いた。
Comparative Example 4
To 100 ml of the model colored waste water, 0.2 g of calcium chloride and 0.6 g of Klebsiella microorganism (NBRC13277) in terms of dry weight were added, and decolorization treatment was performed in the same manner as in Example 1. As the microorganism belonging to the genus Klebsiella, a microorganism collected in advance after centrifugation in an SCD liquid medium was used.

比較例5
前記モデル着色廃水100mlに、塩化カルシウム0.2g、および乾燥重量換算で0.6gのシュードモナス属の微生物(NBRC13275)を添加し、実施例1と同様に脱色処理を行った。前記シュードモナス属の微生物は、あらかじめSCD液体培地で培養後、遠心分離により集菌したものを用いた。
Comparative Example 5
To 100 ml of the model-colored waste water, 0.2 g of calcium chloride and 0.6 g of Pseudomonas microorganisms (NBRC13275) in terms of dry weight were added, and decolorization treatment was performed in the same manner as in Example 1. The microorganism belonging to the genus Pseudomonas was previously cultured in an SCD liquid medium and then collected by centrifugation.

繊維染色工場の実廃水に対する脱色効果
<廃水サンプルの調製>
繊維染色工場から分散染料、反応染料、界面活性剤、糊剤等を含む着色廃水を採取した。本着色廃水の総有機炭素量および総窒素量をTOC計((株)島津製作所製)により測定した結果、総有機炭素量は295mg/L、総窒素量は、69mg/Lであった。前記着色廃水に硫酸を添加してpHを7.8に調整し、以下の脱色試験に用いた。
Decolorization effect on actual wastewater from textile dyeing factory <Preparation of wastewater sample>
Colored wastewater containing disperse dyes, reactive dyes, surfactants, pastes, etc. was collected from a textile dyeing factory. As a result of measuring the total organic carbon amount and the total nitrogen amount of this colored wastewater with a TOC meter (manufactured by Shimadzu Corporation), the total organic carbon amount was 295 mg / L and the total nitrogen amount was 69 mg / L. Sulfuric acid was added to the colored wastewater to adjust the pH to 7.8 and used for the following decolorization test.

実施例5
前記の繊維染色工場から採取した着色廃水100mlに、0.2gの塩化カルシウムを添加した。さらに、乾燥重量換算で0.6gの前記のエンテロコッカス・アビウム(NBRC100477、独立行政法人 製品評価技術基盤機構から購入)を添加した。続いて該廃水を、処理槽(200mlのプラスチック広口ビン)に入れて静置することにより微好気条件とし、25℃で16時間の脱色処理を行った。
Example 5
0.2 g of calcium chloride was added to 100 ml of colored waste water collected from the fiber dyeing factory. Further, 0.6 g of the above-mentioned Enterococcus abium (NBRC 100477, purchased from the National Institute of Technology and Evaluation) was added in terms of dry weight. Subsequently, the wastewater was placed in a treatment tank (200 ml plastic wide-mouthed bottle) and allowed to stand to make a microaerobic condition, and decolorization treatment was performed at 25 ° C. for 16 hours.

比較例6
前記の繊維染色工場から採取した着色廃水100mlに、塩化カルシウムおよびエンテロコッカス属に属する微生物を添加することなく、実施例5と同様に25℃で16時間の脱色処理を行った。
Comparative Example 6
Decolorization treatment was carried out at 25 ° C. for 16 hours in the same manner as in Example 5 without adding calcium chloride and microorganisms belonging to the genus Enterococcus to 100 ml of colored wastewater collected from the fiber dyeing factory.

比較例7
前記の繊維染色工場から採取した着色廃水100mlに、0.2gの塩化カルシウムのみを添加し、実施例5と同様に25℃で16時間の脱色処理を行った。
Comparative Example 7
Only 0.2 g of calcium chloride was added to 100 ml of colored waste water collected from the above-mentioned fiber dyeing factory, and decolorization treatment was performed at 25 ° C. for 16 hours in the same manner as in Example 5.

比較例8
前記の繊維染色工場から採取した着色廃水100mlに、乾燥重量換算で0.6gのエンテロコッカス・アビウムを(NBRC100477)添加し、実施例5と同様に25℃で16時間の脱色処理を行った。
Comparative Example 8
To 100 ml of colored waste water collected from the fiber dyeing factory, 0.6 g of Enterococcus abium (NBRC100477) in terms of dry weight was added, and decolorization treatment was performed at 25 ° C. for 16 hours in the same manner as in Example 5.

比較例9
前記の繊維染色工場から採取した着色廃水100mlに、0.2gの塩化カルシウムおよび、乾燥重量換算で0.6gのシュードモナス属に属する微生物(Pseudomonas aeruginosa:NBRC13275)を添加し、実施例5と同様に25℃で16時間の脱色処理を行った。
Comparative Example 9
To 100 ml of colored waste water collected from the fiber dyeing factory, 0.2 g of calcium chloride and 0.6 g of microorganisms belonging to the genus Pseudomonas (Pseudomonas aeruginosa: NBRC13275) in terms of dry weight were added. Decolorization treatment was performed at 25 ° C for 16 hours.

<脱色効果の評価>
着色廃水における着色度の指標として、着色廃水の可視光領域(350nm〜700nm)の吸光度を1nm間隔で測定し、その積算値(以下、積算吸光度と表記)を求めた。さらに、以下の式から、脱色率(%)を算出した。吸光度の測定には、各着色廃水をポアサイズ0.45μmのフィルターでろ過したものを用いた。なお、吸光度の測定および積算吸光度の算出には、UV−2450((株)島津製作所製)を用いた。
脱色率(%)=((A−A)/A)×100
:脱色処理前の着色廃水の積算吸光度
:脱色処理後の着色廃水の積算吸光度
<Evaluation of decoloring effect>
As an index of the degree of coloration in the colored wastewater, the absorbance in the visible light region (350 nm to 700 nm) of the colored wastewater was measured at 1 nm intervals, and the integrated value (hereinafter referred to as integrated absorbance) was obtained. Furthermore, the decolorization rate (%) was calculated from the following equation. For measuring the absorbance, each colored wastewater filtered through a filter having a pore size of 0.45 μm was used. Note that UV-2450 (manufactured by Shimadzu Corporation) was used for measurement of absorbance and calculation of integrated absorbance.
Decolorization rate (%) = ((A 0 −A 1 ) / A 0 ) × 100
A 0 : Integrated absorbance of colored wastewater before decolorization treatment A 1 : Integrated absorbance of colored wastewater after decolorization treatment

<脱色処理後の上清の濁度評価>
脱色処理後の廃水の上清を採取し、波長610nmにおける吸光度(上清の濁度)を測定した。吸光度が低いほど、汚濁の原因となる懸濁物質が少なく、処理後の廃水の水質がよい。
<Evaluation of turbidity of supernatant after decolorization treatment>
The supernatant of the waste water after decoloring treatment was collected, and the absorbance (turbidity of the supernatant) at a wavelength of 610 nm was measured. The lower the absorbance, the less the suspended matter that causes pollution and the better the quality of the wastewater after treatment.

モデル廃水に対する脱色効果
塩化カルシウムおよび微生物の両方を添加しない場合(比較例1)および、塩化カルシウムのみを添加した場合(比較例2)には、脱色効果が得られなかった。また、エンテロコッカス属に属する微生物のみを添加した場合(比較例3)は、脱色率は約68%であったが、実施例には及ばなかった。
Decoloring effect on model wastewater When both calcium chloride and microorganisms were not added (Comparative Example 1) and when only calcium chloride was added (Comparative Example 2), no decoloring effect was obtained. In addition, when only the microorganism belonging to the genus Enterococcus was added (Comparative Example 3), the decolorization rate was about 68%, but it did not reach the example.

また、塩化カルシウムおよび、エンテロコッカス属以外の微生物を添加した比較例4および比較例5では、70%に近い脱色率が得られたものもあるが、処理廃水の上清の濁度が非常に高く、処理水の水質が劣っていた。   Further, in Comparative Example 4 and Comparative Example 5 to which calcium chloride and microorganisms other than Enterococcus were added, there was obtained a decolorization rate close to 70%, but the turbidity of the treated wastewater supernatant was very high. The quality of the treated water was inferior.

一方、塩化カルシウムとエンテロコッカス属に属する微生物を着色廃水に添加し、静置による微好気条件で脱色処理を行った実施例1〜4では、いずれの場合にも相乗的に高い脱色効果を得ることができ、脱色率は70%以上であった。さらに、廃水の上清の濁度は、実施例ではいずれも0.7以下になっていた。   On the other hand, in Examples 1 to 4, in which calcium chloride and microorganisms belonging to the genus Enterococcus were added to colored wastewater and subjected to decolorization treatment under slightly aerobic conditions by standing, a high decoloration effect was obtained synergistically in any case. The decolorization rate was 70% or more. Furthermore, the turbidity of the supernatant of wastewater was 0.7 or less in all examples.

したがって実施例は、着色廃水に対する脱色効果が高く、且つ懸濁物質が少ない処理水を得られるものである。   Therefore, the Example has a high decoloring effect with respect to colored wastewater, and can obtain the treated water with few suspended solids.

Figure 2009066515
Figure 2009066515

繊維染色工場の実廃水に対する脱色効果
塩化カルシウムと微生物の両方を添加しない場合(比較例6)および、塩化カルシウムのみを添加した場合(比較例7)には、脱色効果が得られなかった。また、エンテロコッカス属に属する微生物のみを添加した場合(比較例8)は、脱色率は約63%であったが、実施例には及ばなかった。
Decoloring effect on actual waste water of textile dyeing factory When both calcium chloride and microorganisms were not added (Comparative Example 6) and when only calcium chloride was added (Comparative Example 7), no decoloring effect was obtained. Further, when only the microorganism belonging to the genus Enterococcus was added (Comparative Example 8), the decolorization rate was about 63%, but it did not reach the example.

また、塩化カルシウムおよび、エンテロコッカス属以外の微生物を添加した比較例9では、約70%の脱色率が得られたものの、処理廃水の上清の濁度が5.0と非常に高く、処理水の水質が劣っており実用性が低かった。   Further, in Comparative Example 9 to which calcium chloride and microorganisms other than Enterococcus were added, although a decolorization rate of about 70% was obtained, the turbidity of the supernatant of the treated wastewater was as high as 5.0, and the treated water The water quality was inferior and the practicality was low.

一方、実施例5では、塩化カルシウムとエンテロコッカス属に属する微生物を着色廃水に添加し、75%の高い脱色率を得た。さらに、このときの廃水の上清の濁度は、0.9であり、懸濁物質の少ない、水質のよい処理水を得ることができた。   On the other hand, in Example 5, a microorganism belonging to the genus Calcium chloride and Enterococcus was added to the colored wastewater to obtain a high decolorization rate of 75%. Furthermore, the turbidity of the supernatant of the wastewater at this time was 0.9, and treated water with good suspended water quality with few suspended substances could be obtained.

さらに、実施例5、比較例6、7および8の処理廃水の吸収スペクトル測定結果を図3に示した。実施例5の処理廃水では、可視光領域の吸光度が大幅に低下していることが確認され、実廃水の脱色に極めて有効性が高いことが確認された。   Furthermore, the absorption spectrum measurement result of the treated waste water of Example 5 and Comparative Examples 6, 7 and 8 is shown in FIG. In the treated wastewater of Example 5, it was confirmed that the absorbance in the visible light region was significantly reduced, and it was confirmed that the treatment wastewater was extremely effective in decolorizing the actual wastewater.

Figure 2009066515
Figure 2009066515

<エンテロコッカス属に属する微生物の単離と解析>
繊維染色工場の廃水処理施設の活性汚泥を採取して適宜希釈し、反応染料(C.I.Reactive Red 3)を0.03%含むSCD寒天培地(日水製薬社製)に塗布した。25℃で24時間培養後、脱色ハローを形成したコロニーから、脱色効果の高い微生物1種を単離した。常法に従って、単離した微生物の16SrDNA上流領域(約500bp)の塩基配列を解析し、BLASTによるデータベース検索による同定を行った。その結果、本菌は、エンテロコッカス属の16SrDNAの塩基配列と高い相同性があることが判明し、エンテロコッカス属に属する微生物であると同定された。
<Isolation and analysis of microorganisms belonging to the genus Enterococcus>
The activated sludge from the wastewater treatment facility of the textile dyeing factory was collected, diluted as appropriate, and applied to an SCD agar medium (Nissui Pharmaceutical Co., Ltd.) containing 0.03% of reactive dye (CIReactive Red 3). After culturing at 25 ° C. for 24 hours, one kind of microorganism having a high decolorization effect was isolated from the colony that formed the decolorization halo. According to a conventional method, the base sequence of the upstream region (about 500 bp) of the 16S rDNA of the isolated microorganism was analyzed and identified by database search by BLAST. As a result, this bacterium was found to be highly homologous to the base sequence of 16S rDNA belonging to the genus Enterococcus, and was identified as a microorganism belonging to the genus Enterococcus.

この活性汚泥から単離したエンテロコッカス属の微生物を用いて、実施例1〜5と同様の評価を行ったところ、モデル着色廃水および繊維染色工場の実廃水のいずれに対しても、市販のエンテロコッカス・アビウム(NBRC100477)と同様に、高い脱色効果を示すことが確認された。   Using the microorganism of the genus Enterococcus isolated from this activated sludge, the same evaluation as in Examples 1 to 5 was carried out. As a result, commercially available Enterococcus Similar to abium (NBRC100477), it was confirmed to show a high decoloring effect.

本発明の脱色処理装置の一実施形態を示す模式図である。It is a schematic diagram which shows one Embodiment of the decoloring processing apparatus of this invention. 本発明のエンテロコッカス属に属する微生物の16SrDNAの上流領域約500bpの塩基配列データを示している。The base sequence data of about 500 bp upstream region of 16S rDNA of microorganisms belonging to the genus Enterococcus of the present invention are shown. 実施例5、比較例6、7および8の処理廃水の吸収スペクトル測定結果を示すグラフである。It is a graph which shows the absorption-spectrum measurement result of Example 5 and the treatment wastewater of Comparative Examples 6, 7, and 8.

符号の説明Explanation of symbols

1 廃水供給管
2 処理槽
3 処理水排出管
4 pH測定器
5 酸またはアルカリの投入量制御装置
6 酸またはアルカリ貯蔵槽
7 酸またはアルカリ供給管
8 微生物貯留槽
9 微生物供給管
10 撹拌手段
11 塩化カルシウム貯蔵槽
12 塩化カルシウム供給管
DESCRIPTION OF SYMBOLS 1 Waste water supply pipe 2 Treatment tank 3 Treated water discharge pipe 4 pH measuring device 5 Acid or alkali input amount control device 6 Acid or alkali storage tank 7 Acid or alkali supply pipe 8 Microorganism storage tank 9 Microorganism supply pipe 10 Stirring means 11 Chlorination Calcium storage tank 12 Calcium chloride supply pipe

Claims (6)

処理槽に染料を含有する廃水を導入する工程、および、導入された廃水に塩化カルシウムとエンテロコッカス属に属する微生物とを添加する工程を含む染料を含有する廃水の脱色処理方法。 A method for decolorizing wastewater containing a dye, comprising a step of introducing wastewater containing a dye into a treatment tank, and a step of adding calcium chloride and a microorganism belonging to the genus Enterococcus to the introduced wastewater. 前記処理槽内の廃水のpHが6.0〜9.0であり、塩化カルシウム濃度が0.003〜0.3重量%である請求項1記載の脱色処理方法。 The decoloring treatment method according to claim 1, wherein the pH of the waste water in the treatment tank is 6.0 to 9.0, and the calcium chloride concentration is 0.003 to 0.3% by weight. 前記処理槽内の廃水の微生物濃度が、乾燥重量で1000〜10000mg/Lである請求項1または2記載の脱色処理方法。 The decolorization method according to claim 1 or 2, wherein the microbial concentration of the wastewater in the treatment tank is 1000 to 10000 mg / L by dry weight. 前記エンテロコッカス属に属する微生物が活性汚泥由来であり、前記廃水が微好気条件にある請求項1〜3記載の脱色処理方法。 The decolorization treatment method according to claim 1, wherein the microorganism belonging to the genus Enterococcus is derived from activated sludge, and the wastewater is in a microaerobic condition. 処理槽に染料を含有する廃水を導入する手段、導入された廃水に塩化カルシウムとエンテロコッカス属に属する微生物とを添加する手段、該処理槽内の廃水のpHを調整する手段、該処理槽内の廃水を微好気条件から好気条件に制御する手段、および、該処理槽内の廃水を導出する手段を備えた脱色処理装置。 Means for introducing waste water containing dye into the treatment tank, means for adding calcium chloride and microorganisms belonging to the genus Enterococcus to the introduced waste water, means for adjusting the pH of waste water in the treatment tank, A decoloring apparatus comprising means for controlling wastewater from a microaerobic condition to an aerobic condition and means for deriving the wastewater in the treatment tank. 塩化カルシウムとエンテロコッカス属に属する微生物とを含む、染料を含有する廃水の脱色処理剤。 A decolorizing agent for wastewater containing a dye, comprising calcium chloride and a microorganism belonging to the genus Enterococcus.
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CN115369053A (en) * 2022-04-25 2022-11-22 湖北大学 Azo dye degrading bacterium and application thereof
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CN116409909A (en) * 2023-06-09 2023-07-11 深圳永清水务有限责任公司 Device for treating waste water generated by assay or detection
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