JP2005021865A - Method for treating waste water containing sulfur-containing organic compound - Google Patents

Method for treating waste water containing sulfur-containing organic compound Download PDF

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JP2005021865A
JP2005021865A JP2003270776A JP2003270776A JP2005021865A JP 2005021865 A JP2005021865 A JP 2005021865A JP 2003270776 A JP2003270776 A JP 2003270776A JP 2003270776 A JP2003270776 A JP 2003270776A JP 2005021865 A JP2005021865 A JP 2005021865A
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Kazuya Uesugi
和也 上杉
Kana Maeda
香奈 前田
Minoru Tomita
実 冨田
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Organo Corp
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Japan Organo Co Ltd
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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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Abstract

<P>PROBLEM TO BE SOLVED: To prevent the generation of a bad smell and reduce the treatment cost when the water which is to be treated and contains an organic compound containing sulfur such as dimethyl sulfoxide (DMSO) is treated by physicochemical treatment and biological treatment. <P>SOLUTION: The subject waste water treating method is carried out by using the physicochemical treatment process 4 and the biological treatment process 8 for biologically treating the water treated at the process 4. When the water 2 to be treated is treated, a part or the whole of the water 2 is sent directly to the process 8 through a bypass line 10 without sending it to the process 4. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、含硫黄有機化合物を含有する有機性排水、特にはジメチルスルホキシド（以下、ＤＭＳＯと略す）等のアルキルスルホキシドを含有する排水、例えば半導体装置や液晶装置の製造工程から排出されるアルキルスルホキシド含有排水の処理に好適な処理方法に関する。   The present invention relates to organic waste water containing sulfur-containing organic compounds, particularly waste water containing alkyl sulfoxide such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), for example, alkyl sulfoxide discharged from the manufacturing process of semiconductor devices and liquid crystal devices. The present invention relates to a treatment method suitable for treatment of contained wastewater.

ＤＭＳＯは、化学合成用溶剤、または剥離・洗浄剤などとして産業界で広く使用されており、その利用に伴い工場排水として排出されている。従来、工場から排出される有機性排水の処理方法としては、エネルギーコストが安く、有機物の無機化（完全分解）が可能な生物処理が主に用いられてきた。しかし、ＤＭＳＯはこれを分解できる細菌の種類が少ない、いわゆる難分解性物質であり、かつ分解過程で硫化ジメチル（以下、ＤＭＳと略す）、メチルメルカプタン（以下、ＭＭと略す）、硫化水素などの悪臭物質が生じることがあるため、その処理は困難であるとされてきた。   DMSO is widely used in the industry as a solvent for chemical synthesis or as a peeling / cleaning agent, and is discharged as factory effluent along with its use. Conventionally, as a method for treating organic wastewater discharged from factories, biological treatment has been mainly used, which has low energy costs and can mineralize (completely decompose) organic matter. However, DMSO is a so-called hardly degradable substance with few types of bacteria that can decompose it, and dimethyl sulfide (hereinafter abbreviated as DMS), methyl mercaptan (hereinafter abbreviated as MM), hydrogen sulfide, etc. in the degradation process. Since malodorous substances can be produced, it has been difficult to process.

ＤＭＳＯ含有排水を生物処理によって処理し、かつ悪臭を発生させない試みとしては、例えば特許第２７６９９７３号（特許文献１参照）の技術がある。この技術では、好気性生物処理槽の前段にｐＨ調整槽を設け、生物処理槽内の水のｐＨが７〜９になるようにｐＨ調整槽にアルカリ剤を添加するとともに、生物処理水をｐＨ調整槽へ循環させる。さらに、生物処理槽内の水の溶存酸素濃度が２ｍｇ／Ｌ以上になるように曝気風量を調整することにより、悪臭物質を発生させることなくＤＭＳＯ含有排水の生物処理が可能であるとしている。なお、生物処理水のｐＨ調整槽への循環は、生物処理槽への流入ＤＭＳＯ濃度を低下させることとｐＨの安定を目的としている。しかし、この処理方法をもってしても、ＤＭＳＯ分解菌が生物処理槽内に十分量蓄積するまでは、ＤＭＳＯの分解が不十分になり悪臭が発生する。また、一般にＤＭＳＯ分解菌は増殖速度が遅いため、流入水中のＤＭＳＯ濃度が変動してもそれに追随するだけの生物量がすぐには発生せず、この場合にも悪臭が発生することとなる。   As an attempt to treat DMSO-containing wastewater by biological treatment and not generate malodors, for example, there is a technique of Japanese Patent No. 2776973 (see Patent Document 1). In this technique, a pH adjustment tank is provided in front of the aerobic biological treatment tank, an alkaline agent is added to the pH adjustment tank so that the pH of the water in the biological treatment tank is 7 to 9, and the biological treatment water is adjusted to pH. Circulate to the adjustment tank. Furthermore, by adjusting the amount of aeration air so that the dissolved oxygen concentration of water in the biological treatment tank is 2 mg / L or more, biological treatment of DMSO-containing wastewater is possible without generating malodorous substances. The circulation of the biologically treated water to the pH adjusting tank aims to reduce the inflow DMSO concentration to the biologically treated tank and stabilize the pH. However, even with this treatment method, until a sufficient amount of DMSO-degrading bacteria accumulates in the biological treatment tank, DMSO is not sufficiently decomposed and a bad odor is generated. Moreover, since DMSO-degrading bacteria generally have a slow growth rate, even if the DMSO concentration in the inflowing water fluctuates, the amount of biomass that follows it does not immediately occur, and a bad odor is generated in this case as well.

一方、上記のような生物処理における処理の不安定さを解消する処理方法として、ＤＭＳＯ含有排水の物理化学的処理、あるいは物理化学的処理と生物処理との組合せが提案されている。例えば特許第２９１５２１４号（特許文献２参照）では、ＤＭＳＯ等のアルキルスルホキシド含有排水の処理方法として物理化学的処理であるフェントン処理を行ったり、フェントン処理後に生物処理を行ったりすることにより、悪臭を発生させることなく当該排水の処理が可能であることが示されている。しかし、概して有機性排水の物理化学的処理では薬品コストや電気などのエネルギーコストが生物処理に比べて高くなる上に、物理化学的処理単独ではＤＭＳＯを無機化することが困難で分解生成物が残留するという問題がある。また、特許第２９１５２１４号の技術のようにフェントン処理を用いる場合、処理に伴って大量の鉄スラッジが発生し、その処分費が処理コスト増大を招く。
特許第２７６９９７３号公報 特許第２９１５２１４号公報 On the other hand, a physicochemical treatment of DMSO-containing wastewater or a combination of physicochemical treatment and biological treatment has been proposed as a treatment method for eliminating the instability of treatment in biological treatment as described above. For example, in Japanese Patent No. 2915214 (see Patent Document 2), fouling is caused by performing fenton treatment, which is a physicochemical treatment, as a method for treating alkylsulfoxide-containing wastewater such as DMSO, or biological treatment after Fenton treatment. It is shown that the waste water can be treated without generating it. However, in general, physicochemical treatment of organic wastewater increases the cost of chemicals and energy such as electricity compared to biological treatment, and it is difficult to mineralize DMSO by physicochemical treatment alone, resulting in degradation products. There is a problem of remaining. Moreover, when using a Fenton process like the technique of the patent 2915214, a large amount of iron sludge generate | occur | produces with a process, and the disposal cost causes a process cost increase.
Japanese Patent No. 2776973 Japanese Patent No. 2915214

前述したように、ＤＭＳＯ含有排水の処理においては、生物処理では悪臭の発生を完全に防止することができず、物理化学的処理では処理コストが高く、かつＤＭＳＯの完全分解が困難であった。また、物理化学的処理と生物処理との組合せにより悪臭を発生させることなくＤＭＳＯを完全分解することは可能であるが、物理化学的処理を用いる以上、生物処理単独に比べ処理コストの増大は回避できなかった。   As described above, in the treatment of wastewater containing DMSO, the generation of malodors cannot be completely prevented by biological treatment, the treatment cost is high by physicochemical treatment, and complete decomposition of DMSO is difficult. In addition, DMSO can be completely decomposed without generating bad odor by combining physicochemical treatment and biological treatment. However, as long as physicochemical treatment is used, an increase in treatment cost is avoided compared to biological treatment alone. could not.

本発明は、前述した事情に鑑みてなされたもので、ＤＭＳＯ含有排水などの含硫黄有機化合物を含有する有機性排水の処理において、悪臭発生を防止することができ、かつ、従来の物理化学的処理あるいは物理化学的処理と生物処理との組合せよりも処理コストを安くすることができる処理方法を提供することを目的とする。   The present invention has been made in view of the above-described circumstances, and can prevent the generation of malodor in the treatment of organic wastewater containing sulfur-containing organic compounds such as DMSO-containing wastewater. It aims at providing the processing method which can make a processing cost cheaper than the combination of a process or a physicochemical process, and biological treatment.

本発明者らは、前記課題を解決するための手段として、フェントン処理と生物処理との組合せにおいて、フェントン処理への被処理水の流入割合を任意に設定することを発案した。すなわち、ＤＭＳＯを含有する有機性排水をフェントン処理した後、生物処理を行うＤＭＳＯ含有排水の処理方法において、被処理水の一部または全部を、適宜フェントン処理を介することなく生物処理に至るようにする排水処理方法が、悪臭を防止しつつ処理コストを安く抑える方法として最適であることを見出した。   As a means for solving the above-mentioned problems, the present inventors have proposed to arbitrarily set the inflow ratio of the water to be treated to the fenton treatment in the combination of the fenton treatment and the biological treatment. That is, in the DMSO-containing wastewater treatment method in which organic wastewater containing DMSO is treated with Fenton and then biologically treated, part or all of the water to be treated is appropriately subjected to biological treatment without going through Fenton treatment. It was found that the wastewater treatment method is optimal as a method for reducing the treatment cost while preventing bad odor.

本発明は、上記知見に基づいてなされたもので、含硫黄有機化合物を含有する被処理水を物理化学的に処理する物理化学的処理工程と、前記物理化学的処理工程の処理水を生物処理する生物学的処理工程とを備えた排水処理方法において、前記被処理水の処理過程で、被処理水の一部または全部を、物理化学的処理工程を介することなく生物学的処理工程に送ることを特徴とする含硫黄有機化合物含有排水の処理方法を提供する。   The present invention has been made on the basis of the above-described knowledge, and includes a physicochemical treatment step of physicochemically treating water to be treated containing a sulfur-containing organic compound, and biological treatment of the treated water of the physicochemical treatment step. In the wastewater treatment method comprising the biological treatment process, a part or all of the treated water is sent to the biological treatment process without going through the physicochemical treatment process in the treatment process of the treated water. A method for treating wastewater containing sulfur-containing organic compounds is provided.

以下、本発明につきさらに詳しく説明する。本発明において、処理対象である含硫黄有機化合物を含有する被処理水としては、例えば、半導体装置や液晶装置の製造工程から排出されるＤＭＳＯ等のアルキルスルホキシドを含有する排水が挙げられる。また、本発明において、物理化学的処理としては、例えば、（１）被処理水に第一鉄イオンおよび過酸化水素を添加する方法（フェントン処理法）、（２）被処理水にオゾンを添加する方法、（３）被処理水に過酸化水素を添加する方法、（４）被処理水にオゾンおよび過酸化水素を添加する方法、（５）被処理水に紫外線を照射する方法、（６）被処理水にオゾンを添加するとともに、紫外線を照射する方法、（７）被処理水に過酸化水素を添加するとともに、紫外線を照射する方法、（８）被処理水にオゾンおよび過酸化水素を添加するとともに、紫外線を照射する方法、（９）被処理水にオゾンおよび触媒を添加する方法等が挙げられる。これらの中で特に好ましいのはフェントン処理法である。フェントン処理法では、酸性下で第一鉄イオンが共存することによって過酸化水素が強力な酸化力を持つ水酸基ラジカルを生成し、この水酸基ラジカルがアルキルスルホキシドを酸化分解する。生物処理としては、例えば、好気性生物処理、嫌気性生物処理、好気性生物処理と嫌気性生物処理との組み合わせ（多段処理）等が挙げられる。   Hereinafter, the present invention will be described in more detail. In the present invention, the water to be treated containing the sulfur-containing organic compound to be treated includes, for example, wastewater containing alkyl sulfoxide such as DMSO discharged from the manufacturing process of semiconductor devices and liquid crystal devices. In the present invention, as the physicochemical treatment, for example, (1) a method of adding ferrous ions and hydrogen peroxide to the water to be treated (Fenton treatment method), (2) adding ozone to the water to be treated (3) a method of adding hydrogen peroxide to the water to be treated, (4) a method of adding ozone and hydrogen peroxide to the water to be treated, (5) a method of irradiating the water to be treated with ultraviolet rays, (6) ) A method of adding ozone to the water to be treated and irradiating ultraviolet rays, (7) A method of adding hydrogen peroxide to the water to be treated and irradiating ultraviolet rays, and (8) ozone and hydrogen peroxide to the water to be treated. And (9) a method of adding ozone and a catalyst to the water to be treated. Of these, the Fenton treatment method is particularly preferable. In the Fenton treatment method, hydrogen peroxide generates a hydroxyl radical having a strong oxidizing power when ferrous ions coexist in an acidic state, and this hydroxyl radical oxidizes and decomposes alkyl sulfoxide. Examples of the biological treatment include aerobic biological treatment, anaerobic biological treatment, a combination of aerobic biological treatment and anaerobic biological treatment (multistage treatment), and the like.

本発明は、含硫黄有機化合物を含有する被処理水を、物理化学的処理工程および生物学的処理工程を用いて処理するに当たり、被処理水の処理過程で、適宜被処理水の一部または全部を、物理化学的処理工程を介することなく生物学的処理工程に送るものである。この場合、本発明では、被処理水を物理化学的処理工程を介することなく生物学的処理工程に送るバイパスラインを設け、被処理水の処理過程で、被処理水の一部または全部を、上記バイパスラインを通して物理化学的処理工程を介することなく生物学的処理工程に送ることができる。   In the treatment of water to be treated containing a sulfur-containing organic compound using a physicochemical treatment process and a biological treatment process, a part of the water to be treated or The whole is sent to the biological treatment process without going through the physicochemical treatment process. In this case, in the present invention, a bypass line is provided to send the water to be treated to the biological treatment process without going through the physicochemical treatment process. It can be sent to the biological treatment process through the bypass line without going through the physicochemical treatment process.

ここで、被処理水がＤＭＳＯ含有排水であり、物理化学的処理がフェントン処理であり、生物処理が好気性生物処理であるとともに、被処理水の一部または全部をバイパスラインを通して物理化学的処理工程を介することなく生物学的処理工程に送る場合について説明する。本発明では、排水処理装置の立ち上げ時などの生物処理槽にＤＭＳＯ分解菌がほとんど存在しないときには、被処理水をほぼ１００％フェントン処理設備に通水し、下記式（１）に示す反応によりＤＭＳＯをメタンスルホン酸（以下、ＭＳＡと略す）に分解した後に、物理化学的処理水に生物処理を施す。ＭＳＡは好気性生物処理で容易に分解され、かつその分解過程で悪臭物質を発生させない。   Here, the treated water is DMSO-containing wastewater, the physicochemical treatment is Fenton treatment, the biological treatment is aerobic biological treatment, and part or all of the treated water is physicochemical treated through a bypass line. The case where it sends to a biological treatment process without going through a process is demonstrated. In the present invention, when there is almost no DMSO-degrading bacterium in the biological treatment tank at the time of starting up the wastewater treatment apparatus, the treated water is passed through almost 100% Fenton treatment facility, and the reaction shown in the following formula (1) is performed. After DMSO is decomposed into methanesulfonic acid (hereinafter abbreviated as MSA), biological treatment is performed on the physicochemically treated water. MSA is easily degraded by aerobic biological treatment and does not generate malodorous substances during the degradation process.

ＤＭＳＯ→（フェントン処理）→
ＭＳＡ→（生物処理）→ＣＯ2、ＳＯ4 2- …（１）
しかし、このままではフェントン処理の費用が継続して発生してしまうので、その後、徐々に生物処理槽でのＤＭＳＯ分解菌の蓄積を図るとともに、バイパスラインへの被処理水の流入比率を増加させ、最終的には被処理水を１００％バイパスラインへ流入させ、フェントン処理費用をゼロにすることを目標とする。ここで、被処理水中のＤＭＳＯは、下記式（２）に示す生物反応により分解されると考えられている。ＤＭＳＯ分解菌が十分量存在すれば、式（２）に示す分解が中間代謝物であるＤＭＳやＭＭを蓄積することなく進行し、結果としてこれら悪臭物質がほとんど大気中に放出されることなくＤＭＳＯの無機化が完了する。 DMSO → (Fenton treatment) →
MSA → (biological treatment) → CO 2 , SO 4 2− (1)
However, since the cost of the Fenton treatment will continue to occur as it is, the DMSO-degrading bacteria are gradually accumulated in the biological treatment tank, and the inflow ratio of the treated water to the bypass line is gradually increased. The final goal is to make the water to be treated flow into the 100% bypass line and to reduce the Fenton treatment cost to zero. Here, it is considered that DMSO in the water to be treated is decomposed by a biological reaction represented by the following formula (2). If a sufficient amount of DMSO-degrading bacteria is present, the degradation shown in formula (2) proceeds without accumulating the intermediate metabolites DMS and MM, and as a result, these malodorous substances are hardly released into the atmosphere. Is completed.

ＤＭＳＯ→（生物処理）→ＤＭＳ→（生物処理）→
ＭＭ→（生物処理）→ＣＯ2、ＳＯ4 2- …（２）
上述した処理において、バイパスラインへの被処理水の流入比率は、処理装置運転管理者が任意に設定することができ、この方法によっても運転管理者の知識や経験により安定した処理が可能となる。しかし、より好適な手段として、本発明者らは、バイパスラインへの被処理水の流入比率を予め定めた時間間隔および割合で順次増加させる方式を発案した。また、特定の濃度分析とバイパスラインへの流入制御に一定の規則性を持たせることを発案した。すなわち、ある時点で定めたバイパスラインに流入する被処理水の流量をもとに、次に当該流量を増加させる時刻およびその増加割合を予め定めておくものである。さらに、この流量制御規則とは別に、被処理水中のＤＭＳＯ濃度、生物処理水中のＤＭＳＯ濃度、および生物処理装置からの排ガス中の悪臭物質濃度のいずれか、あるいは複数を測定し、測定濃度が設定値以下であった場合にはバイパスラインに流入する被処理水の流量を増加させ、測定濃度が設定値を超える場合にはバイパスラインに流入する被処理水の流量を減じる。この際、バイパスラインに流入する被処理水の流量を増加させた場合、フェントン処理における薬品添加量を減じ、流量を減じた場合、フェントン処理における薬品添加量を増加させることを発案した。 DMSO → (Biological treatment) → DMS → (Biological treatment) →
MM → (biological treatment) → CO 2 , SO 4 2− (2)
In the processing described above, the inflow ratio of the water to be treated to the bypass line can be arbitrarily set by the processing device operation manager, and this method also enables stable processing based on the knowledge and experience of the operation manager. . However, as a more preferable means, the present inventors have devised a method of sequentially increasing the inflow ratio of the water to be treated to the bypass line at a predetermined time interval and ratio. In addition, it was proposed to have a certain regularity in specific concentration analysis and inflow control to the bypass line. That is, based on the flow rate of the water to be treated that flows into the bypass line determined at a certain time, the time for increasing the flow rate and the rate of increase are determined in advance. Furthermore, apart from this flow rate control rule, measure the DMSO concentration in the treated water, the DMSO concentration in the biologically treated water, and the malodorous substance concentration in the exhaust gas from the biological treatment device, or set the measured concentration. When it is less than the value, the flow rate of the water to be treated flowing into the bypass line is increased, and when the measured concentration exceeds the set value, the flow rate of the water to be treated flowing into the bypass line is decreased. At this time, it was proposed that when the flow rate of the water to be treated flowing into the bypass line is increased, the chemical addition amount in the Fenton treatment is decreased, and when the flow rate is decreased, the chemical addition amount in the Fenton treatment is increased.

上記一定時間ごとの流量増加制御方法、および特定の濃度分析とバイパスラインへの流入制御に一定の規則性を持たせた制御方法によれば、運転管理者の知識や経験に頼ることなく安定した処理が可能である。また、制御用タイマーを用いれば一定時間ごとの流量増加は容易に自動化することができる。さらに、オンライン型の測定装置を導入すれば、バイパスラインへの流入比率を自動制御することも可能となる。すなわち、上記のＤＭＳＯ濃度や悪臭物質濃度を測定するためには、被処理水、生物処理水および生物処理装置からの排ガスのいずれか、あるいは複数を常時または定期的に採取できるようサンプリングラインを設け、採取したサンプルをガスクロマトグラフ等の測定装置に導く。被処理水または生物処理水の場合は水中のＤＭＳＯ濃度を、排ガスの場合はガス中の悪臭物質濃度を測定し、測定値が設定値よりも大きくなった場合、バイパスラインへの自動弁等の流入調整設備の開度をあらかじめ設定した割合で絞り込むように設定すればよい。測定値が設定値以下だった場合には、逆にバイパスラインへの開度を一定の割合で大きくしてバイパスラインへの流入量を増加させればよい。フェントン処理における薬品添加量については、バイパスラインへの流入調整と逆動作になり、測定値が設定値よりも大きくなった場合には添加する薬品量を所定の割合で増加させ、測定値が設定値以下だった場合には添加する薬品量を所定の割合で減じる。   According to the control method for increasing the flow rate at regular intervals and the control method with a certain regularity in the specific concentration analysis and inflow control to the bypass line, it is stable without depending on the knowledge and experience of the operation manager. Processing is possible. Further, if a control timer is used, an increase in the flow rate at regular intervals can be easily automated. Furthermore, if an on-line type measuring device is introduced, the inflow ratio to the bypass line can be automatically controlled. In other words, in order to measure the above-mentioned DMSO concentration and malodorous substance concentration, a sampling line is provided so that any one or more of treated water, biological treated water, and exhaust gas from biological treatment equipment can be collected regularly or periodically. The collected sample is guided to a measuring device such as a gas chromatograph. In case of treated water or biologically treated water, measure the DMSO concentration in the water, and in the case of exhaust gas, measure the concentration of malodorous substances in the gas. If the measured value is larger than the set value, the automatic valve to the bypass line, etc. What is necessary is just to set so that the opening degree of inflow adjustment equipment may be narrowed down by the ratio set up beforehand. If the measured value is less than or equal to the set value, conversely, the opening to the bypass line may be increased by a certain rate to increase the amount of inflow to the bypass line. The chemical addition amount in Fenton treatment is the reverse of the inflow adjustment to the bypass line, and when the measured value is larger than the set value, the added chemical amount is increased by a predetermined ratio and the measured value is set. If the value is less than the value, the amount of chemical to be added is reduced at a predetermined rate.

以上のことからわかるように、本発明は、下記（ａ）〜（ｄ）の発明を提供する。
（ａ）物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を、予め定めた時間間隔および割合で順次増加させることを特徴とする本発明の含硫黄有機化合物含有排水の処理方法。
（ｂ）物理化学的処理前の被処理水中の含硫黄有機化合物濃度、生物学的処理後の処理水中の含硫黄有機化合物濃度、および生物学的処理工程で生じる排ガス中の含硫黄悪臭物質濃度から選ばれる１つまたは複数の濃度に応じて、被処理水の処理過程で、被処理水の一部または全部を、物理化学的処理工程を介することなく生物学的処理工程に送ることを特徴とする本発明の含硫黄有機化合物含有排水の処理方法。
（ｃ）物理化学的処理前の被処理水中の含硫黄有機化合物濃度、生物学的処理後の処理水中の含硫黄有機化合物濃度、および生物学的処理工程で生じる排ガス中の含硫黄悪臭物質濃度から選ばれる１つまたは複数の濃度の濃度を測定し、前記測定濃度が設定値以下である場合には、物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を増加させ、前記測定濃度が設定値を超える場合には、物理化学的処理工程に送る被処理水の量を増加させることを特徴とする（ｂ）の含硫黄有機化合物含有排水の処理方法。
（ｄ）物理化学的処理が被処理水に薬品を添加する処理であり、物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を増加させるときには、物理化学的処理工程における被処理水への薬品添加量を減少させ、物理化学的処理工程に送る被処理水の量を増加させるときには、物理化学的処理工程における被処理水への薬品添加量を増加させることを特徴とする（ａ）または（ｃ）の含硫黄有機化合物含有排水の処理方法。 As can be seen from the above, the present invention provides the following inventions (a) to (d).
(A) The sulfur-containing organic compound content of the present invention is characterized in that the amount of water to be treated that is sent to a biological treatment step without going through a physicochemical treatment step is sequentially increased at a predetermined time interval and ratio. Wastewater treatment method.
(B) Sulfur-containing organic compound concentration in treated water before physicochemical treatment, sulfur-containing organic compound concentration in treated water after biological treatment, and sulfur-containing malodorous substance concentration in exhaust gas generated in biological treatment process A part or all of the water to be treated is sent to the biological treatment process without passing through the physicochemical treatment process in the treatment process of the water to be treated according to one or more concentrations selected from The processing method of the sulfur-containing organic compound containing waste water of this invention.
(C) Sulfur-containing organic compound concentration in treated water before physicochemical treatment, sulfur-containing organic compound concentration in treated water after biological treatment, and sulfur-containing malodorous substance concentration in exhaust gas generated in biological treatment process When the concentration of one or a plurality of concentrations selected from the above is measured and the measured concentration is equal to or lower than a set value, the amount of water to be treated sent to the biological treatment step without going through the physicochemical treatment step When the measured concentration exceeds the set value, the amount of treated water sent to the physicochemical treatment step is increased, and the method for treating sulfur-containing organic compound-containing wastewater according to (b) is characterized.
(D) The physicochemical treatment is a treatment in which chemicals are added to the water to be treated. When the amount of water to be treated to be sent to the biological treatment step is increased without going through the physicochemical treatment step, the physicochemical treatment is performed. When reducing the amount of chemical added to the water to be treated in the process and increasing the amount of water to be treated sent to the physicochemical treatment step, increase the amount of chemical added to the water to be treated in the physicochemical treatment step. (A) or (c) a sulfur-containing organic compound-containing wastewater treatment method.

以上のように、本発明によれば、ＤＭＳＯ等の含硫黄有機化合物を含有する被処理水を物理化学的処理および生物処理によって処理するに当たり、悪臭発生を防止することができるとともに、従来の物理化学的処理あるいは物理化学的処理と生物処理との組合せよりも処理コストを安くすることができる。   As described above, according to the present invention, when the water to be treated containing a sulfur-containing organic compound such as DMSO is treated by physicochemical treatment and biological treatment, it is possible to prevent the generation of malodor and Processing costs can be reduced compared to chemical processing or a combination of physicochemical processing and biological processing.

図１に本発明の実施に用いる排水処理装置の一例を示す。図１において、２は被処理水導入ライン、４はフェントン処理槽、６は沈殿槽、８は活性汚泥槽、１０はバイパスライン、１２はバルブ、１４は沈殿槽、１６は返送汚泥ライン、１８は処理水排出ラインを示す。なお、ここでバルブ１２の開度は、０〜１００％の範囲で被処理水のバイパスライン１０への流入比率０〜１００％に正比例するものとする。   FIG. 1 shows an example of a wastewater treatment apparatus used in the practice of the present invention. In FIG. 1, 2 is a treated water introduction line, 4 is a Fenton treatment tank, 6 is a sedimentation tank, 8 is an activated sludge tank, 10 is a bypass line, 12 is a valve, 14 is a sedimentation tank, 16 is a return sludge line, 18 Indicates the treated water discharge line. In addition, the opening degree of the valve | bulb 12 shall be directly proportional to the inflow ratio 0-100% to the bypass line 10 of to-be-processed water in the range of 0-100% here.

フェントン処理槽４でのフェントン処理には、例えばＦｅＳＯ4、ＦｅＣｌ2などの二価の鉄塩を用いることができる。フェントン処理により被処理水中のＤＭＳＯを全量処理する場合、過酸化水素の添加量はＤＭＳＯに対して重量比で１〜１０倍程度とする。鉄塩の添加量は、添加した過酸化水素に対して鉄原子として０．１〜１．０倍程度添加すればよい。被処理水中にＤＭＳＯ以外に有機物や還元物質が存在する場合、上記添加比率を超えて被処理水に過酸化水素および鉄塩を添加するように、事前に最適添加比率を検討しておくことが好ましい。 For the Fenton treatment in the Fenton treatment tank 4, for example, a divalent iron salt such as FeSO 4 or FeCl 2 can be used. When the entire amount of DMSO in the water to be treated is treated by Fenton treatment, the amount of hydrogen peroxide added is about 1 to 10 times by weight with respect to DMSO. What is necessary is just to add the addition amount of an iron salt about 0.1-1.0 times as an iron atom with respect to the added hydrogen peroxide. When organic substances and reducing substances other than DMSO are present in the water to be treated, the optimum addition ratio should be examined in advance so that hydrogen peroxide and iron salt are added to the water to be treated in excess of the above addition ratio. preferable.

一定時間ごとにバイパスライン１０への被処理水の流入量を増加させる場合、装置運転直後など生物学的処理工程にＤＭＳＯ分解菌がほとんど繁殖していないと予想される時点では、バイパスライン１０への被処理水の流入量を被処理水の０／１０〜１／１０程度に設定する。流入量の増加間隔は、分解菌の増殖速度を勘案すると、１〜１０日程度がよい。流入量の増加割合は小さい方が望ましいが、被処理水の１／１０〜１／４程度が実用的である。   When the amount of treated water flowing into the bypass line 10 is increased at regular intervals, the DMSO-degrading bacteria are hardly propagated in the biological treatment process such as immediately after the operation of the apparatus. The inflow amount of the water to be treated is set to about 0/10 to 1/10 of the water to be treated. Considering the growth rate of degrading bacteria, the increase interval of the inflow amount is preferably about 1 to 10 days. A smaller increase rate of the inflow amount is desirable, but about 1/10 to 1/4 of the water to be treated is practical.

バイパスライン１０への被処理水の流入を行うに当たり、例えばバイパスラインへの流入量を被処理水の１／１０とする場合には、先に定めたフェントン処理槽４での過酸化水素および鉄塩の添加量も１／１０だけ減少させることを基本とする。ただし、被処理水中の性状によっては、被処理水のバイパスラインへの流入比率と、フェントン処理における過酸化水素および鉄塩の添加量削減比率とは必ずしも一致しないことがあるので、その場合は別途制御用アルゴリズムを工夫する必要がある。   When inflowing the water to be treated into the bypass line 10, for example, when the amount of inflow to the bypass line is 1/10, the hydrogen peroxide and iron in the Fenton treatment tank 4 defined above are used. Basically, the amount of salt added is also reduced by 1/10. However, depending on the nature of the water to be treated, the ratio of inflow of the water to be treated to the bypass line may not necessarily match the ratio of reduction in the amount of hydrogen peroxide and iron salt in the Fenton treatment. It is necessary to devise a control algorithm.

フェントン処理の処理時間は、通常、３０分〜６時間程度必要になる。この場合、反応の方式としてはバッチ処理、連続処理のいずれも採用することができる。連続処理の場合、反応槽を複数個に分けることも有効である。この際、過酸化水素や鉄塩は上流側で一度に添加してもよく、各槽に分注してもよい。   The processing time for the Fenton treatment is usually about 30 minutes to 6 hours. In this case, either batch processing or continuous processing can be employed as the reaction method. In the case of continuous processing, it is also effective to divide the reaction tank into a plurality of parts. At this time, hydrogen peroxide and iron salt may be added at once on the upstream side, or may be dispensed into each tank.

生物処理としては、その形態は問わないが、一般的には沈殿槽と汚泥返送ラインを具備する活性汚泥法や、沈殿槽を具備しない膜分離活性汚泥法、さらには固定床あるいは流動床の生物膜法等を用いる。活性汚泥の負荷設計は、被処理水にＤＭＳＯのみが含まれ、かつバイパスラインを用いてすべての被処理水を生物処理により処理すると仮定すると、０．１〜１ｋｇＤＭＳＯ／ｍ3／ｄ程度が適当である。被処理水中にＤＭＳＯ以外の有機物が含まれる場合、ＢＯＤ濃度等を加味して別途負荷設計を行う必要がある。 The biological treatment can be of any form, but in general, an activated sludge method having a sedimentation tank and a sludge return line, a membrane separation activated sludge method without a sedimentation tank, and a fixed bed or fluidized bed organism. A membrane method or the like is used. The load design of activated sludge should be about 0.1-1 kg DMSO / m 3 / d, assuming that only DMSO is contained in the treated water and all treated water is treated by biological treatment using the bypass line. It is. When organic matter other than DMSO is contained in the water to be treated, it is necessary to separately design a load in consideration of the BOD concentration and the like.

ここで、図２に一定時間ごとの流量増加と被処理水中のＤＭＳＯ濃度測定を組み合わせたバイパスライン流入量の制御例を示す。本例では、被処理水中のＤＭＳＯ濃度の測定値［Ｂ］と設定値［Ａ］および経過時間［Ｔ］によりバイパスラインへの流入量の変更割合を決定する。ここで計算値［Ａ／Ｂ］が１を超える場合、すなわち［Ａ］＞［Ｂ］の場合はバイパスラインへのバルブ開度を大きくすることを意味し、計算値［Ａ／Ｂ］が１未満の場合、すなわち［Ａ］＜［Ｂ］の場合はバルブ開度を絞り込むことを意味する。さらに上記制御とは別に、Ｔ日後にはバルブ開度ＶをＸ％増加させる。   Here, FIG. 2 shows an example of control of the inflow amount of the bypass line in which the increase in the flow rate per fixed time and the measurement of the DMSO concentration in the treated water are combined. In this example, the change rate of the inflow amount to the bypass line is determined based on the measured value [B] of DMSO concentration in the water to be treated, the set value [A], and the elapsed time [T]. If the calculated value [A / B] exceeds 1, that is, if [A]> [B], it means that the valve opening to the bypass line is increased, and the calculated value [A / B] is 1 If it is less than that, that is, if [A] <[B], it means that the valve opening is narrowed down. Further, separately from the above control, the valve opening V is increased by X% after T days.

図３に生物処理水中のＤＭＳＯ濃度測定または生物処理装置からの悪臭物質濃度測定によるバイパスライン流入量の制御例を示す。本例では、測定値［Ｂ］が設定値［Ａ］よりも大きくなった場合、バイパスラインへのバルブ開度をあらかじめ設定した割合［Ｘ1％］で絞り込んでバイパスラインへの流入量を減少させる。測定値［Ｂ］が設定値［Ａ］以下だった場合、バイパスラインへのバルブ開度をあらかじめ設定した割合［Ｘ2％］で大きくしてバイパスラインへの流入量を増加させる。バルブ開度の増減割合Ｘ1およびＸ2の設定は装置の負荷設計等によって異なるが、１０〜５０％程度が実用的である。測定値［Ｂ］と設定値「Ａ」との差によって増減割合を複数設定してもよい。処理水中のＤＭＳＯ濃度の設定値は、後段での悪臭発生防止の観点から０〜１０ｍｇ／Ｌとするのが望ましい。排ガス中の悪臭物質濃度の設定値には、悪臭防止法により規定されている敷地境界線における悪臭の規制基準などを用いることができ、例えば、排ガス中のＤＭＳ濃度の上限設定値は０．０１〜０．２ｐｐｍ、ＭＭ濃度の上限設定値は０．００２〜０．０１ｐｐｍとすることができる。設定値としては全ての悪臭物質濃度について設けることが望ましいが、生物反応で最初に発生するＤＭＳの設定値を代表値として用いてもよい。 FIG. 3 shows a control example of the inflow amount of the bypass line by measuring the DMSO concentration in the biologically treated water or measuring the malodorous substance concentration from the biological treatment device. In this example, when the measured value [B] becomes larger than the set value [A], the valve opening to the bypass line is narrowed by a preset ratio [X 1 %] to reduce the inflow amount to the bypass line. Let When the measured value [B] is less than or equal to the set value [A], the valve opening to the bypass line is increased by a preset ratio [X 2 %] to increase the inflow amount to the bypass line. Setting increase or decrease in the valve opening ratio X 1 and X 2 are different depending on the load design of the apparatus, is about 10-50% practical. A plurality of increase / decrease rates may be set according to the difference between the measured value [B] and the set value “A”. The set value of the DMSO concentration in the treated water is desirably 0 to 10 mg / L from the viewpoint of preventing the generation of malodor at the later stage. For the setting value of the malodorous substance concentration in the exhaust gas, it is possible to use the malodor control standard at the site boundary defined by the Malodor Control Law. For example, the upper limit setting value of the DMS concentration in the exhaust gas is 0.01. The upper limit set value of ˜0.2 ppm and MM concentration can be 0.002 to 0.01 ppm. Although it is desirable to provide the set values for all malodorous substance concentrations, the set values of DMS generated first in a biological reaction may be used as representative values.

上述した図２〜図３のいずれの制御例についても、制御プログラムからの出力（バイパスラインへのバルブ開度変更指令）を受けて、装置管理者がバルブ操作を行ってもよいし、自動的にバルブ開度を調整してもよい。また、フェントン処理における薬品添加量は、通常、バイパスラインへの流入増減率に反比例して増減させる。   In any of the control examples in FIGS. 2 to 3 described above, the device administrator may perform the valve operation in response to the output from the control program (the valve opening change command to the bypass line) or automatically. The valve opening may be adjusted. Moreover, the chemical addition amount in the Fenton treatment is usually increased or decreased in inverse proportion to the rate of increase / decrease in inflow to the bypass line.

図１に示したのと同様の装置であって、フェントン処理槽４の容量を０．５Ｌ、活性汚泥槽８の容量を２０Ｌとした実験装置を作製し、この装置を用いてＤＭＳＯ含有排水の処理を行った。処理条件は下記のようにした。なお、フェントン処理における鉄塩としてはＦｅＳＯ4・７ＨＯを添加した。また、過酸化水素および鉄塩の添加量はバイパスラインへの流入比率に応じて調整した。処理結果を表１に示す。
・被処理水中のＤＭＳＯ濃度：２５０ｍｇ／Ｌ
・被処理水流量：１６Ｌ／ｄ
・フェントン処理における過酸化水素添加量：（初期）１０００ｍｇ／Ｌ
・フェントン処理における鉄塩添加量：（初期）５００ｍｇＦｅ／Ｌ An apparatus similar to that shown in FIG. 1 was prepared, in which the capacity of the Fenton treatment tank 4 was set to 0.5 L, and the capacity of the activated sludge tank 8 was set to 20 L. Processed. The processing conditions were as follows. Note that FeSO 4 .7HO was added as an iron salt in the Fenton treatment. Moreover, the addition amount of hydrogen peroxide and iron salt was adjusted according to the inflow ratio to a bypass line. The processing results are shown in Table 1.
-DMSO concentration in treated water: 250 mg / L
・ Processed water flow rate: 16L / d
-Hydrogen peroxide addition amount in Fenton treatment: (initial) 1000 mg / L
-Iron salt addition amount in Fenton treatment: (initial) 500 mg Fe / L

Figure 2005021865
表１からわかるように、通水開始直後には活性汚泥槽におけるＤＭＳＯ分解菌の蓄積が十分でないため、被処理水の全量を生物処理のみで行うことは悪臭が発生するため不可能であったが、通水開始１ヶ月後には活性汚泥槽におけるＤＭＳＯ分解菌の蓄積が進み、バイパスラインへの流入比率を１００％とすることができた。これにより、本発明の有効性が確認できた。
Figure 2005021865
 As can be seen from Table 1, since the accumulation of DMSO-degrading bacteria in the activated sludge tank is not sufficient immediately after the start of water flow, it is impossible to carry out the entire amount of the water to be treated only by biological treatment because of bad odor. However, the accumulation of DMSO-degrading bacteria in the activated sludge tank progressed one month after the start of water flow, and the inflow ratio to the bypass line could be made 100%. Thereby, the effectiveness of the present invention was confirmed.

本発明の実施に用いる排水処理装置の一例を示す概略図である。It is the schematic which shows an example of the waste water treatment apparatus used for implementation of this invention. 被処理水中のＤＭＳＯ濃度測定によるバイパスライン流入量の制御例を示すフロー図である。It is a flowchart which shows the example of control of the inflow amount of a bypass line by DMSO density | concentration measurement in to-be-processed water. 生物処理水中のＤＭＳＯ濃度測定または生物処理装置からの悪臭物質濃度測定によるバイパスライン流入量の制御例を示すフロー図である。It is a flowchart which shows the example of control of the bypass line inflow by the DMSO density | concentration measurement in biologically treated water, or the malodorous substance density | concentration measurement from a biological treatment apparatus.

符号の説明Explanation of symbols

２ 被処理水導入ライン
４ フェントン処理槽
６ 沈殿槽
８ 活性汚泥槽
１０ バイパスライン
１２ バルブ
１４ 沈殿槽
１６ 返送汚泥ライン
１８ 処理水排出ライン 2 treated water introduction line 4 Fenton treatment tank 6 sedimentation tank 8 activated sludge tank 10 bypass line 12 valve 14 sedimentation tank 16 return sludge line 18 treated water discharge line

Claims (6)

含硫黄有機化合物を含有する被処理水を物理化学的に処理する物理化学的処理工程と、前記物理化学的処理工程の処理水を生物処理する生物学的処理工程とを備えた排水処理方法において、前記被処理水の処理過程で、被処理水の一部または全部を、物理化学的処理工程を介することなく生物学的処理工程に送ることを特徴とする含硫黄有機化合物含有排水の処理方法。 In a wastewater treatment method comprising: a physicochemical treatment step for physicochemically treating water to be treated containing a sulfur-containing organic compound; and a biological treatment step for biologically treating the treated water of the physicochemical treatment step A method for treating wastewater containing sulfur-containing organic compounds, wherein a part or all of the water to be treated is sent to a biological treatment step without going through a physicochemical treatment step in the treatment process of the water to be treated . 被処理水を物理化学的処理工程を介することなく生物学的処理工程に送るバイパスラインを設け、被処理水の処理過程で、被処理水の一部または全部を、前記バイパスラインを通して物理化学的処理工程を介することなく生物学的処理工程に送ることを特徴とする請求項１に記載の含硫黄有機化合物含有排水の処理方法。 A bypass line is provided to send the water to be treated to the biological treatment process without going through the physicochemical treatment process. In the process of the water to be treated, a part or all of the water to be treated is physicochemically passed through the bypass line. The method for treating wastewater containing sulfur-containing organic compounds according to claim 1, wherein the wastewater is sent to a biological treatment step without going through the treatment step. 物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を、予め定めた時間間隔および割合で順次増加させることを特徴とする請求項１または２に記載の含硫黄有機化合物含有排水の処理方法。 3. The sulfur-containing organic material according to claim 1, wherein the amount of water to be treated that is sent to the biological treatment step without going through the physicochemical treatment step is sequentially increased at a predetermined time interval and rate. Treatment method for compound-containing wastewater. 物理化学的処理前の被処理水中の含硫黄有機化合物濃度、生物学的処理後の処理水中の含硫黄有機化合物濃度、および生物学的処理工程で生じる排ガス中の含硫黄悪臭物質濃度から選ばれる１つまたは複数の濃度に応じて、被処理水の処理過程で、被処理水の一部または全部を、物理化学的処理工程を介することなく生物学的処理工程に送ることを特徴とする請求項１または２に記載の含硫黄有機化合物含有排水の処理方法。 Selected from the concentration of sulfur-containing organic compounds in the treated water before physicochemical treatment, the concentration of sulfur-containing organic compounds in the treated water after biological treatment, and the concentration of sulfur-containing malodorous substances in the exhaust gas generated in the biological treatment process A part or all of the water to be treated is sent to the biological treatment process without going through the physicochemical treatment process in the treatment process of the water to be treated according to one or a plurality of concentrations. Item 3. A method for treating wastewater containing sulfur-containing organic compounds according to item 1 or 2. 物理化学的処理前の被処理水中の含硫黄有機化合物濃度、生物学的処理後の処理水中の含硫黄有機化合物濃度、および生物学的処理工程で生じる排ガス中の含硫黄悪臭物質濃度から選ばれる１つまたは複数の濃度の濃度を測定し、前記測定濃度が設定値以下である場合には、物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を増加させ、前記測定濃度が設定値を超える場合には、物理化学的処理工程に送る被処理水の量を増加させることを特徴とする請求項１、２および４のいずれか１項に記載の含硫黄有機化合物含有排水の処理方法。 Selected from the concentration of sulfur-containing organic compounds in the treated water before physicochemical treatment, the concentration of sulfur-containing organic compounds in the treated water after biological treatment, and the concentration of sulfur-containing malodorous substances in the exhaust gas generated in the biological treatment process Measuring the concentration of one or more concentrations, and if the measured concentration is less than a set value, increasing the amount of water to be treated sent to the biological treatment step without going through the physicochemical treatment step; 5. The sulfur-containing organic material according to claim 1, wherein when the measured concentration exceeds a set value, the amount of water to be treated to be sent to the physicochemical treatment process is increased. Treatment method for compound-containing wastewater. 物理化学的処理が被処理水に薬品を添加する処理であり、物理化学的処理工程を介することなく生物学的処理工程に送る被処理水の量を増加させるときには、物理化学的処理工程における被処理水への薬品添加量を減少させ、物理化学的処理工程に送る被処理水の量を増加させるときには、物理化学的処理工程における被処理水への薬品添加量を増加させることを特徴とする請求項３または５に記載の含硫黄有機化合物含有排水の処理方法。 The physicochemical treatment is a treatment in which chemicals are added to the water to be treated. When increasing the amount of water to be treated that is sent to the biological treatment step without going through the physicochemical treatment step, the treatment in the physicochemical treatment step is performed. When the amount of chemicals added to treated water is decreased and the amount of treated water sent to the physicochemical treatment process is increased, the amount of chemical added to the treated water in the physicochemical treatment process is increased. The processing method of the sulfur-containing organic compound containing waste water of Claim 3 or 5.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006289313A (en) * 2005-04-14 2006-10-26 Matsushita Electric Ind Co Ltd Apparatus and method for treating organic waste water
JP2009034649A (en) * 2007-08-03 2009-02-19 Japan Organo Co Ltd Method and apparatus for treating water containing organic sulfur compound
CN101781068A (en) * 2010-03-31 2010-07-21 长沙环境保护职业技术学院 Method for treating crude wastewater of gallic acid
WO2016132510A1 (en) * 2015-02-19 2016-08-25 三菱重工業株式会社 Industrial effluent treatment system and treatment method
KR101778609B1 (en) * 2015-12-17 2017-09-14 주식회사 포스코 Purification apparatus for polluted water
JP2019150753A (en) * 2018-03-01 2019-09-12 住友重機械エンバイロメント株式会社 Water treatment apparatus and water treatment method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006289313A (en) * 2005-04-14 2006-10-26 Matsushita Electric Ind Co Ltd Apparatus and method for treating organic waste water
JP2009034649A (en) * 2007-08-03 2009-02-19 Japan Organo Co Ltd Method and apparatus for treating water containing organic sulfur compound
CN101781068A (en) * 2010-03-31 2010-07-21 长沙环境保护职业技术学院 Method for treating crude wastewater of gallic acid
WO2016132510A1 (en) * 2015-02-19 2016-08-25 三菱重工業株式会社 Industrial effluent treatment system and treatment method
KR101778609B1 (en) * 2015-12-17 2017-09-14 주식회사 포스코 Purification apparatus for polluted water
JP2019150753A (en) * 2018-03-01 2019-09-12 住友重機械エンバイロメント株式会社 Water treatment apparatus and water treatment method
JP7060407B2 (en) 2018-03-01 2022-04-26 住友重機械エンバイロメント株式会社 Water treatment equipment and water treatment method

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