JP6179630B1 - Biological treatment method and biological treatment apparatus - Google Patents
Biological treatment method and biological treatment apparatus Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
【課題】半導体・液晶製造プロセスから排出されるアミン類及び/又は4級アンモニウム塩類含有排水等の有機系排水を効率的に生物処理し、有機態窒素を高度に除去して高水質の処理水を得る。【解決手段】有機系排水を生物処理槽に導入して生物処理する方法において、該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度の測定値と、アンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度のうちの少なくとも一つの測定値とを指標として、生物処理条件を調整する生物処理方法。【選択図】なし[PROBLEMS] To efficiently biologically treat organic wastewater such as wastewater containing amines and / or quaternary ammonium salts discharged from a semiconductor / liquid crystal manufacturing process, and to remove organic nitrogen to a high degree, thereby treating water with high quality. Get. In a method for biological treatment by introducing organic wastewater into a biological treatment tank, the measured values of amine and quaternary ammonium ion concentrations in the liquid in the biological treatment tank or the effluent of the biological treatment tank, and the ammonium ion concentration , A biological treatment method for adjusting biological treatment conditions using at least one measurement value of nitrate ion concentration and nitrite ion concentration as an index. [Selection figure] None
Description
本発明は生物処理方法及び生物処理装置に係り、特に半導体・液晶製造プロセスの有機系排水回収処理システムにおける省コスト自動制御もしくは運転管理手法として有用な生物処理方法及び生物処理装置に関する。 The present invention relates to a biological treatment method and a biological treatment apparatus, and more particularly to a biological treatment method and a biological treatment apparatus that are useful as a cost-saving automatic control or operation management technique in an organic wastewater recovery treatment system of a semiconductor / liquid crystal manufacturing process.
半導体・液晶製造プロセスからは、超純水回収系有機系排水として、エタノールアミン等の各種のアミンを主体とし、N−メチルホルムアミド、テトラメチルアンモニウムヒドロキシド(TMAH)等のアルカリ成分を含む有機系排水が排出される。この有機系排水の生物処理法としては、活性汚泥法(AS)、膜分離活性汚泥法(MBR)、流動床式生物処理法(MBBR)、担体添加活性汚泥法(IFAS)等が適用される。 From the semiconductor / liquid crystal manufacturing process, as an ultrapure water recovery system organic wastewater, an organic system mainly composed of various amines such as ethanolamine and containing alkali components such as N-methylformamide and tetramethylammonium hydroxide (TMAH) Waste water is discharged. As an organic wastewater biological treatment method, an activated sludge method (AS), a membrane separation activated sludge method (MBR), a fluidized bed biological treatment method (MBBR), a support addition activated sludge method (IFAS), or the like is applied. .
生物処理槽では、アミン、その他の有機物の酸化分解、この酸化分解で生成したアンモニアを酸化して硝酸とする硝化が起き、この硝酸の生成で生物処理槽内のpHは低下する。このため、生物処理槽では、アルカリを添加してpH中性に維持する必要がある。生物処理槽の流出液は必要に応じて沈殿槽等で固液分離した後、無機凝集剤による凝集処理後、逆浸透(RO)膜分離処理され、透過水が回収再利用される。 In the biological treatment tank, amine and other organic substances are oxidatively decomposed, and nitrification occurs by oxidizing ammonia generated by this oxidative decomposition into nitric acid. The production of this nitric acid lowers the pH in the biological treatment tank. For this reason, in a biological treatment tank, it is necessary to add alkali and maintain it at pH neutrality. The effluent from the biological treatment tank is subjected to solid-liquid separation in a precipitation tank or the like, if necessary, and then subjected to a reverse osmosis (RO) membrane separation process after an aggregation process using an inorganic flocculant, and the permeate is recovered and reused.
上記の排水処理では以下の問題がある。 The above wastewater treatment has the following problems.
(1) 生物処理槽では硝化に伴うアルカリ度の低下を補い、生物処理効率を良好に維持するためには、pHを例えば7前後に維持するためのアルカリ剤の添加が必要となる。このアルカリ剤添加は、アルカリ剤自体のコストがかかることはもとより、回収水中のイオン濃度を増加させるため、RO膜分離処理のイオン負荷増大、RO膜濃縮水の塩類負荷の増大、ひいてはRO膜濃縮水を廃棄処分している場合には処分費用の増大をもたらす。 (1) In the biological treatment tank, in order to compensate for the decrease in alkalinity associated with nitrification and to maintain the biological treatment efficiency satisfactorily, it is necessary to add an alkaline agent to maintain the pH around 7, for example. The addition of the alkali agent not only increases the cost of the alkali agent itself, but also increases the ion concentration in the recovered water. Therefore, the ion load of the RO membrane separation treatment increases, the salt load of the RO membrane concentrated water increases, and the RO membrane concentration. When water is disposed of, disposal costs increase.
(2) 上記のアルカリ剤添加を過剰に行った場合、生物処理水のアルカリ度が上昇するが、後段の凝集処理における最適pHが5〜6の範囲にあるために、酸剤でpHを低下するか、酸性の無機凝集剤の過剰添加が必要となる。この酸剤添加は、酸剤自体のコストがかかることはもとより、回収水中のイオン濃度を増加させるため、RO膜分離処理のイオン負荷増大、RO膜濃縮水の塩類負荷の増大、ひいてはRO膜濃縮水を廃棄処分している場合には処分費用の増大をもたらす。また、無機凝集剤の過剰添加は、汚泥量の増大、ひいては余剰汚泥の廃棄処分費の増大をもたらす。 (2) When the above alkali agent is added excessively, the alkalinity of biologically treated water increases, but the pH is lowered with an acid agent because the optimum pH in the subsequent agglomeration treatment is in the range of 5-6. Or, an excessive addition of an acidic inorganic flocculant is required. In addition to the cost of the acid agent itself, the addition of the acid agent increases the ion concentration in the recovered water. Therefore, the ion load of the RO membrane separation treatment increases, the salt load of the RO membrane concentrated water increases, and consequently the RO membrane concentration. When water is disposed of, disposal costs increase. Further, excessive addition of the inorganic flocculant increases the amount of sludge, and consequently increases the disposal cost of excess sludge.
上記の課題を解決するための方策として、以下の(I),(II)が考えられる。
(I) 生物処理槽において、窒素処理(脱窒)の機能を導入することで、硝化に伴うアルカリ度低下を抑制し、アルカリ剤の添加量を可能な限り抑制する。この目的での運転管理を行うために、生物処理槽内液のアンモニウムイオン濃度と、硝酸イオンもしくは亜硝酸イオン(以下、これらをまとめて「(亜)硝酸イオン」と称す場合がある。)濃度を継続的にモニタリングし、適正な脱窒処理条件の調整を行う。
(II) 生物処理水のアルカリ度を低下するために、生物処理におけるpH制御の目標値を可能な限り低く設定する。
The following (I) and (II) are conceivable as measures for solving the above problems.
(I) In the biological treatment tank, by introducing the function of nitrogen treatment (denitrification), the decrease in alkalinity accompanying nitrification is suppressed, and the amount of alkali agent added is suppressed as much as possible. In order to perform operation management for this purpose, the concentration of ammonium ions and the concentration of nitrate ions or nitrite ions in the biological treatment tank (hereinafter, these may be collectively referred to as “(nitrite) nitrate ions”). Are continuously monitored and appropriate denitrification conditions are adjusted.
(II) In order to reduce the alkalinity of biologically treated water, the target value of pH control in biological treatment is set as low as possible.
硝化・脱窒処理における亜硝酸イオン濃度を監視するものとしては、特許文献1に提案がなされている。また、亜硝酸イオン濃度に基づいて処理条件を調整するものとして、特許文献2に提案がなされている。更に、アンモニウムイオン濃度等に基づいて処理条件を調整するものとして、特許文献3,4に提案がなされている。 Patent Document 1 proposes a method for monitoring the nitrite ion concentration in the nitrification / denitrification treatment. Further, Patent Document 2 has proposed that the processing conditions are adjusted based on the nitrite ion concentration. Further, Patent Documents 3 and 4 have proposed that the processing conditions are adjusted based on the ammonium ion concentration and the like.
しかしながら、上記(I),(II)では以下の課題がある。 However, the above (I) and (II) have the following problems.
前述の通り、半導体・液晶製造プロセスから排出される有機系排水は、アミン類や4級アンモニウム塩類を主体とする有機態窒素を含むため、上記(I)のアンモニウムイオン濃度と(亜)硝酸イオン濃度のみの監視では、有機態窒素の分解が不良が原因で硝化が進行していない場合にもアンモニウムイオン濃度が低下するため、硝化が十分に進行していないにも関わらず硝化が進行していると誤判断するケースが発生するなど、適正な窒素処理の管理・調整を行うことが困難である。 As described above, the organic wastewater discharged from the semiconductor / liquid crystal manufacturing process contains organic nitrogen mainly composed of amines and quaternary ammonium salts. In the case of monitoring only the concentration, the ammonium ion concentration decreases even when nitrification is not progressing due to poor decomposition of organic nitrogen, so that nitrification proceeds even though nitrification has not progressed sufficiently. It is difficult to properly manage and adjust the nitrogen treatment.
上記(II)では、pH制御目標値の低下により処理水アルカリ度を低下させることができるが、窒素処理の前提となる硝化反応は比較的高いpH(例えば7.0以上)で良好に進行することから、硝化反応を阻害しないようにどの程度までpHを下げるかの判断が困難であり、現場での対応が難しい。 In the above (II), the alkalinity of the treated water can be lowered by lowering the pH control target value, but the nitrification reaction that is the premise of the nitrogen treatment proceeds well at a relatively high pH (for example, 7.0 or higher). For this reason, it is difficult to determine how much the pH is lowered so as not to inhibit the nitrification reaction, and it is difficult to respond on site.
本発明は上記従来の問題点を解決し、半導体・液晶製造プロセスから排出されるアミン及び4級アンモニウム塩類含有排水等の有機系排水を効率的に生物処理し、有機態窒素を高度に除去して高水質の処理水を得る生物処理方法及び生物処理装置を提供することを課題とする。 The present invention solves the above-mentioned conventional problems, efficiently biologically treats organic wastewater such as amine and quaternary ammonium salt-containing wastewater discharged from the semiconductor / liquid crystal manufacturing process, and highly removes organic nitrogen. It is an object of the present invention to provide a biological treatment method and a biological treatment apparatus that obtain treated water of high quality.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、従来のアンモニウムイオン及び(亜)硝酸イオン濃度に基づく運転管理に加えて、更に生物処理プロセス内のアミン及び4級アンモニウムイオン濃度を分析し、系内のアミン及び4級アンモニウムイオンの蓄積状況をオンラインもしくは手分析で確認することにより、適正な自動制御もしくは運転管理を行うことができることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventor further added amine and quaternary ammonium ion concentrations in the biological treatment process in addition to the conventional operation management based on ammonium ion and (nitrite) nitrate ion concentrations. It was found that appropriate automatic control or operation management can be performed by checking the accumulation status of amines and quaternary ammonium ions in the system online or by manual analysis.
本発明は以下を要旨とする。 The gist of the present invention is as follows.
[1] 有機系排水を生物処理槽に導入して生物処理する方法において、該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度の測定値と、アンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度のうちの少なくとも一つの測定値とを指標として、生物処理条件を調整することを特徴とする生物処理方法。 [1] In a method for biological treatment by introducing organic wastewater into a biological treatment tank, measured values of amine and quaternary ammonium ion concentrations in the liquid in the biological treatment tank or the effluent of the biological treatment tank, ammonium ion concentration, A biological treatment method comprising adjusting biological treatment conditions using at least one measured value of nitrate ion concentration and nitrite ion concentration as an index.
[2] [1]において、前記生物処理槽が硝化槽もしくは硝化・脱窒槽であり、硝化槽の場合、生物処理条件として硝化条件及び/又はpH制御目標値を調整し、硝化・脱窒槽の場合、生物処理条件として硝化条件、脱窒条件、及びpH制御目標値のいずれかを調整することを特徴とする生物処理方法。 [2] In [1], the biological treatment tank is a nitrification tank or a nitrification / denitrification tank, and in the case of a nitrification tank, the nitrification conditions and / or pH control target values are adjusted as biological treatment conditions, In this case, the biological treatment method is characterized by adjusting any one of a nitrification condition, a denitrification condition, and a pH control target value as the biological treatment condition.
[3] [1]又は[2]において、前記生物処理が活性汚泥法、膜分離活性汚泥法、流動床式生物処理法、担体添加活性汚泥法のいずれかで処理することを特徴とする生物処理方法。 [3] The organism according to [1] or [2], wherein the biological treatment is performed by any one of an activated sludge method, a membrane separation activated sludge method, a fluidized bed biological treatment method, and a support addition activated sludge method. Processing method.
[4] [1]ないし[3]のいずれかにおいて、前記有機系排水が、半導体・液晶製造プロセスから排出されるアミン類及び/又は4級アンモニウム塩類含有排水であることを特徴とする生物処理方法。 [4] The biological treatment according to any one of [1] to [3], wherein the organic wastewater is wastewater containing amines and / or quaternary ammonium salts discharged from a semiconductor / liquid crystal manufacturing process. Method.
[5] [2]ないし[4]のいずれかにおいて、前記硝化条件の調整として、前記硝化槽内液の溶存酸素濃度の増減、もしくはpHの増減、もしくは硝化時間の増減を行うことを特徴とする生物処理方法。 [5] In any one of [2] to [4], as the adjustment of the nitrification conditions, the dissolved oxygen concentration in the nitrification tank is increased or decreased, the pH is increased or decreased, or the nitrification time is increased or decreased. Biological treatment method.
[6] [2]ないし[5]のいずれかにおいて、前記脱窒条件の調整として、前記硝化槽内液の溶存酸素濃度の増減、もしくはpHの増減、硝化時間の増減を行うことを特徴とする生物処理方法。 [6] In any one of [2] to [5], as the adjustment of the denitrification condition, the dissolved oxygen concentration in the nitrification tank is increased or decreased, the pH is increased or decreased, and the nitrification time is increased or decreased. Biological treatment method.
[7] [2]ないし[6]のいずれかにおいて、前記アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が予め設定された基準値以下である場合に、前記pH制御目標値を下げることを特徴とする生物処理方法。 [7] In any one of [2] to [6], when the total of the measured value of the amine and quaternary ammonium ion concentration and the measured value of the ammonium ion concentration is equal to or lower than a preset reference value, the pH A biological treatment method characterized by lowering a control target value.
[8] 有機系排水の生物処理装置において、該有機系排水が導入される生物処理槽と、該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度を測定する第1の測定手段と、該生物処理槽内液又は該生物処理槽流出液のアンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度のうちの少なくとも一つを測定する第2の測定手段と、該第1の測定手段の測定値と第2の測定手段の測定値に基づいて、該生物処理槽の生物処理条件を調整する制御手段とを有することを特徴とする生物処理装置。 [8] In the biological wastewater treatment apparatus, the concentration of amine and quaternary ammonium ions in the biological treatment tank into which the organic wastewater is introduced, and the liquid in the biological treatment tank or the effluent of the biological treatment tank are measured. A first measuring means, a second measuring means for measuring at least one of ammonium ion concentration, nitrate ion concentration, and nitrite ion concentration in the liquid in the biological treatment tank or the effluent from the biological treatment tank, A biological treatment apparatus comprising control means for adjusting biological treatment conditions of the biological treatment tank based on the measurement value of the first measurement means and the measurement value of the second measurement means.
[9] [8]において、前記生物処理槽が硝化槽もしくは硝化・脱窒槽であり、前記制御手段は、硝化槽の場合、生物処理条件として硝化条件及び/又はpH制御目標値を調整し、硝化・脱窒槽の場合、生物処理条件として硝化条件、脱窒条件、及びpH制御目標値のいずれかを調整する手段であることを特徴とする生物処理装置。 [9] In [8], the biological treatment tank is a nitrification tank or a nitrification / denitrification tank, and the control means adjusts a nitrification condition and / or a pH control target value as a biological treatment condition in the case of a nitrification tank, In the case of a nitrification / denitrification tank, the biological treatment apparatus is a means for adjusting any one of nitrification conditions, denitrification conditions, and pH control target values as biological treatment conditions.
[10] [8]又は[9]において、前記生物処理が活性汚泥処理、膜分離活性汚泥処理、流動床式生物処理、担体添加活性汚泥処理のいずれかを行うものであることを特徴とする生物処理装置。 [10] In the above [8] or [9], the biological treatment is any one of activated sludge treatment, membrane separation activated sludge treatment, fluidized bed biological treatment, and carrier-added activated sludge treatment. Biological treatment equipment.
[11] [8]ないし[10]のいずれかにおいて、前記有機系排水が半導体・液晶製造プロセスから排出されるアミン類及び/又は4級アンモニウム塩類含有排水であることを特徴とする生物処理装置。 [11] The biological treatment apparatus according to any one of [8] to [10], wherein the organic wastewater is wastewater containing amines and / or quaternary ammonium salts discharged from a semiconductor / liquid crystal manufacturing process. .
[12] [9]ないし[11]のいずれかにおいて、前記制御手段は、前記硝化条件の調整として、前記硝化槽内液の溶存酸素濃度の増減、もしくはpHの増減、もしくは硝化時間の増減を行う手段であることを特徴とする生物処理装置。 [12] In any one of [9] to [11], the control means adjusts the nitrification conditions by increasing / decreasing the dissolved oxygen concentration in the nitrification tank, increasing / decreasing pH, or increasing / decreasing the nitrification time. A biological treatment apparatus characterized by being a means for performing.
[13] [9]ないし[12]のいずれかにおいて、前記制御手段は、前記脱窒条件の調整として、前記硝化槽内液の溶存酸素濃度の増減、もしくはpHの増減、硝化時間の増減を行う手段であることを特徴とする生物処理装置。 [13] In any one of [9] to [12], the control means adjusts the denitrification condition by increasing / decreasing dissolved oxygen concentration in the nitrification tank solution, increasing / decreasing pH, and increasing / decreasing nitrification time. A biological treatment apparatus characterized by being a means for performing.
[14] [9]ないし[13]のいずれかにおいて、前記制御手段は、前記第1の測定手段で測定されたアミン及び4級アンモニウムイオン濃度と前記第2の測定手段で測定されたアンモニウムイオン濃度の測定値の合計が予め設定された基準値以下である場合に、前記pH制御目標値を下げる手段であることを特徴とする生物処理装置。 [14] In any one of [9] to [13], the control means includes the amine and quaternary ammonium ion concentrations measured by the first measuring means and the ammonium ions measured by the second measuring means. A biological treatment apparatus, which is means for lowering the pH control target value when the total concentration measurement value is less than or equal to a preset reference value.
本発明によれば、以下のような作用効果のもとに、有機態窒素を効率的に処理することが可能となる。
(1)半導体・液晶製造プロセスで利用されているアミン類及び4級アンモニウム塩類の分解状況を監視して制御に反映することで、窒素処理の前提となるアミン類及び4級アンモニウム塩類の分解を維持しながら窒素処理効率を最大化することができる。この結果、生物処理で添加されるアルカリ剤の添加量を最小化し、ランニングコストを低減できる。
(2)目標の窒素処理効率を維持しつつpH制御の目標値を低下することで、処理水のアルカリ度を低下させ、後段の凝集プロセスでの酸添加量・無機凝集剤添加量を最小化し、ランニングコストを低減できる。
According to the present invention, organic nitrogen can be efficiently treated based on the following effects.
(1) Decomposition of amines and quaternary ammonium salts, which are preconditions for nitrogen treatment, by monitoring and reflecting the decomposition status of amines and quaternary ammonium salts used in semiconductor / liquid crystal manufacturing processes Nitrogen treatment efficiency can be maximized while maintaining. As a result, the amount of alkaline agent added in biological treatment can be minimized and the running cost can be reduced.
(2) By reducing the pH control target value while maintaining the target nitrogen treatment efficiency, the alkalinity of the treated water is lowered, and the acid addition amount and inorganic flocculant addition amount in the subsequent agglomeration process are minimized. , Running costs can be reduced.
以下に、本発明の生物処理方法及び生物処理装置の実施の形態を詳細に説明する。
なお、本発明において、「アミン」とは、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエタノールアミンといったNR1R2R3で表されるものであり、「4級アンモニウム塩」とは、テトラメチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシドなどのN+R1R2R3・X−で表されるものであり、これらアミンや4級アンモニウムイオンは、アンモニウムイオン濃度の測定では測定できない。
Embodiments of the biological treatment method and biological treatment apparatus of the present invention are described in detail below.
In the present invention, “amine” means NR 1 R 2 R 3 such as monomethylamine, dimethylamine, trimethylamine, monoethanolamine, and “quaternary ammonium salt” means tetramethylammonium salt. It is represented by N + R 1 R 2 R 3 · X − such as tetraalkylammonium hydroxide such as hydroxide, and these amines and quaternary ammonium ions cannot be measured by measuring the ammonium ion concentration.
本発明で処理対象とする有機系排水としては、好ましくは半導体・液晶製造プロセスから排出されるアミン類及び/又は4級アンモニウム塩類含有排水、即ち、半導体・液晶製造プロセスにおける超純水回収系の有機系排水が挙げられる。このような超純水回収系有機系排水は、他の排水との混合の有無、或いは他の排水の混合量によっても異なるが、通常、次のような水質である。
<超純水回収系有機系排水水質>
pH:8〜11
TOC:10〜200mg/L
TOC成分:モノメチルアミン(MMA)、ジメチルアミン(DMA)、トリメチルアミン(TMA)、モノエタノールアミン(MEA)等のアミン類、N−メチルホルムアミド等のアミド類、テトラメチルアンモニウムヒドロキシド(TMAH)等のテトラアルキルアンモニウムヒドロキシドなどの4級アンモニウム塩類
TOC成分中のアミン類及び4級アンモニウム塩類の割合:10〜100%
The organic wastewater to be treated in the present invention is preferably an amine and / or quaternary ammonium salt-containing wastewater discharged from the semiconductor / liquid crystal manufacturing process, that is, an ultrapure water recovery system in the semiconductor / liquid crystal manufacturing process. Organic drainage can be mentioned. Such ultrapure water recovery system organic wastewater usually has the following water quality, although it varies depending on whether it is mixed with other wastewater or the amount of other wastewater mixed.
<Ultrapure water recovery system organic wastewater quality>
pH: 8-11
TOC: 10 to 200 mg / L
TOC component: amines such as monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), monoethanolamine (MEA), amides such as N-methylformamide, tetramethylammonium hydroxide (TMAH), etc. Quaternary ammonium salts such as tetraalkylammonium hydroxide Ratio of amines and quaternary ammonium salts in TOC component: 10 to 100%
本発明においては、このような有機系排水を生物処理槽に導入して生物処理するに当たり、生物処理槽内液又は生物処理槽流出液のアミン及び4級アンモニウムイオン濃度を測定すると共に、アンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度のうちの少なくとも一つを測定し、これらの測定値を指標として、生物処理条件を調整することを特徴とする。
なお、処理する有機系排水に、生物処理に必要な栄養塩や金属塩が含まれていない場合には、必要な金属塩や栄養塩を添加して生物処理に供給することが好ましい。
In the present invention, when such organic wastewater is introduced into a biological treatment tank for biological treatment, the amine and quaternary ammonium ion concentrations in the biological treatment tank liquid or the biological treatment tank effluent are measured, and ammonium ions are measured. It is characterized in that at least one of the concentration, the nitrate ion concentration, and the nitrite ion concentration is measured, and the biological treatment conditions are adjusted using these measured values as an index.
When the organic wastewater to be treated does not contain nutrient salts and metal salts necessary for biological treatment, it is preferable to add necessary metal salts and nutrient salts and supply them to biological treatment.
ここで、アミン濃度、4級アンモニウムイオン濃度、アンモニウムイオン濃度、(亜)硝酸イオン濃度は、後掲の実施例のように、イオンクロマトグラフィー分析により測定することができるが、その他LC−MS分析などによっても精度良く分析可能である。
なお、アンモニウムイオン濃度は、一般的なインドフェノール法により、亜硝酸イオン濃度はナフチルエチレンジアミン比色法により、硝酸イオン濃度はカドミカラムによる亜硝酸への還元と組み合わせたナフチルエチレンジアミン比色法(カドミカラム法)などの一般分析でも測定可能である。しかし、本発明では、アミンと4級アンモニウムイオン濃度の測定も行う必要があるため、これらを個々に分析可能なイオンクロマトグラフィー分析が最も簡易な分析手法となる。
Here, the amine concentration, the quaternary ammonium ion concentration, the ammonium ion concentration, and the (nitrite) nitrate ion concentration can be measured by ion chromatography analysis as in the examples described later, but other LC-MS analysis. Etc. can be analyzed with high accuracy.
The ammonium ion concentration is based on the general indophenol method, the nitrite ion concentration is based on the naphthylethylenediamine colorimetric method, and the nitrate ion concentration is combined with reduction to nitrous acid using a cadmium column (cadmium column method). It can be measured by general analysis. However, in the present invention, since it is necessary to measure the amine and quaternary ammonium ion concentrations, ion chromatography analysis capable of analyzing them individually is the simplest analysis technique.
生物処理槽の構成としては特に制限はなく、本発明は、一般的な硝化(脱窒)プロセスへの適用が可能である。本発明は特に生物硝化および好ましくは脱窒素も同時に行う場合に好適であるが、好気的な反応槽で窒素成分の硝化を行う場合であってもよく、硝化槽とその後段の脱窒槽を有する構成でもよく、前段に脱窒槽、後段に硝化槽を配置し硝化槽の槽内液を脱窒槽に戻す循環配管を備える2槽式で連続的に処理するものであってもよく、1槽の生物処理槽で硝化を行った後、脱窒を行うものであってもよい。 The configuration of the biological treatment tank is not particularly limited, and the present invention can be applied to a general nitrification (denitrification) process. The present invention is particularly suitable when biological nitrification and preferably denitrification are simultaneously performed, but it may be performed when nitrification of nitrogen components is performed in an aerobic reaction tank, and a nitrification tank and a subsequent denitrification tank are provided. It may be configured to have a denitrification tank in the front stage, a nitrification tank in the rear stage, and a continuous treatment in a two-tank system equipped with a circulation pipe for returning the liquid in the nitrification tank to the denitrification tank, or one tank After performing nitrification in the biological treatment tank, denitrification may be performed.
本発明において、生物処理槽内液又は生物処理槽流出液(以下「対象液」と称す場合がある。)のアミン及び4級アンモニウムイオン濃度の測定値と、アンモニウムイオン濃度、硝酸イオン濃度及び亜硝酸イオン濃度のうちの少なくとも一つの測定値とに基づく生物処理条件の調整は、例えば次のように実施される。 In the present invention, the measured values of amine and quaternary ammonium ion concentrations of the solution in the biological treatment tank or the biological treatment tank effluent (hereinafter sometimes referred to as “target liquid”), ammonium ion concentration, nitrate ion concentration and The biological treatment conditions are adjusted based on at least one measurement value of the nitrate ion concentration, for example, as follows.
(1) 対象液のアミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が予め設定された基準値を超える場合→硝化を改善する運転調整を行う。
(2) 対象液の硝酸イオン濃度の測定値と亜硝酸イオン濃度の測定値の合計が予め設定された基準値を超える場合→脱窒を改善する運転調整を行う。
脱窒処理では硝化反応の進行が必要前提条件となるため、上記(1)の条件が満たされる場合には、(1)の対応を優先し、(2)の対応は行わない。(1)の条件が満たされない場合のみ、(2)の対応を行う。
(1) When the sum of the measured value of amine and quaternary ammonium ion concentration and the measured value of ammonium ion concentration in the target liquid exceeds a preset reference value → Perform operation adjustment to improve nitrification.
(2) When the total of the measured value of the nitrate ion concentration and the measured value of the nitrite ion concentration of the target liquid exceeds a preset reference value → Perform operation adjustment to improve denitrification.
In the denitrification process, the progress of the nitrification reaction is a necessary precondition. Therefore, when the condition (1) is satisfied, the action (1) is given priority and the action (2) is not performed. Only when the condition of (1) is not satisfied, the countermeasure of (2) is performed.
硝化を改善する運転調整は以下の(1−1)→(1−2)→(1−3)の優先順位で行う。
(1−1) 硝化を行う工程での曝気強度を上げて溶存酸素濃度を上昇させる。
(1−2) 硝化工程の時間に対する、脱窒工程の時間の比を調整できる場合は、同比を小さくする(硝化工程の時間を長くする)。
(1−3) pH制御目標値を上げる。
Operation adjustment to improve nitrification is performed in the following order of priority (1-1) → (1-2) → (1-3).
(1-1) Increase the aeration intensity in the nitrification step to increase the dissolved oxygen concentration.
(1-2) When the ratio of the denitrification process time to the nitrification process time can be adjusted, the ratio is reduced (the nitrification process time is increased).
(1-3) Increase the pH control target value.
脱窒を改善する運転調整は、以下の(2−1)→(2−2)の優先順位で行う。
(2−1) 硝化工程での曝気強度を下げて溶存酸素濃度を低下させる。
(2−2) 硝化工程の時間に対する、脱窒素工程の時間の比を調整できる場合は、同比を大きくする(脱窒工程の時間を長くする)。
Operation adjustment to improve denitrification is performed in the following order of priority (2-1) → (2-2).
(2-1) Lower the aeration intensity in the nitrification step to lower the dissolved oxygen concentration.
(2-2) When the ratio of the time of the denitrification process to the time of the nitrification process can be adjusted, the ratio is increased (the time of the denitrification process is increased).
また、アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が予め設定された基準値以下で推移している場合には、pH制御目標を下げることが好ましい。 Moreover, when the sum of the measured value of amine and quaternary ammonium ion concentration and the measured value of ammonium ion concentration is below a preset reference value, it is preferable to lower the pH control target.
このような生物処理条件の調整を行うことで、硝化・脱窒を円滑に進行させた上で、更にpH制御目標値を下げて、後段の凝集処理における酸剤の添加量や無機凝集剤の添加量を低減して効率的な処理を行える。 By adjusting the biological treatment conditions as described above, the nitrification and denitrification proceeded smoothly, and the pH control target value was further lowered to reduce the amount of acid agent added and the amount of inorganic flocculant in the subsequent flocculation treatment. Efficient processing can be performed by reducing the addition amount.
以下に実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
[実施例1]
下記水質の有機系排水を本発明に従って硝化・脱窒処理した。
[Example 1]
The following water quality organic wastewater was nitrified and denitrified according to the present invention.
<有機系排水水質>
pH:9.5
NH4−N濃度:0.5mg−N/L
TMAH濃度:15mg/L
TMA濃度:0mg/L
DMA濃度:2mg/L
MMA濃度:3mg/L
アルカリ度:7mg as CaCO3/L
Na濃度:3mg/L
<Organic wastewater quality>
pH: 9.5
NH 4 -N concentration: 0.5 mg-N / L
TMAH concentration: 15 mg / L
TMA concentration: 0 mg / L
DMA concentration: 2 mg / L
MMA concentration: 3 mg / L
Alkalinity: 7 mg as CaCO 3 / L
Na concentration: 3 mg / L
生物処理槽としては、流動床式硝化脱窒槽(担体充填率40%)を用い、間欠曝気を行って、曝気と曝気停止を繰り返すことで硝化工程と脱窒工程を行った。 As the biological treatment tank, a fluidized bed type nitrification denitrification tank (carrier filling rate 40%) was used, intermittent aeration was performed, and the nitrification process and the denitrification process were performed by repeating aeration and aeration stop.
硝化工程終了時(曝気終了時)に、槽内液のアミン及び4級アンモニウムイオン濃度として、TMAH、TMA、DMA、MMAの合計濃度と、アンモニウムイオン(NH4−N)濃度、硝酸イオン(NO3−N)濃度、亜硝酸イオン(NO2−N)濃度をイオンクロマトグラフィーで定期的に分析し、以下の基準値に基づいて、生物処理条件を自動制御により調整した。 At the end of the nitrification process (at the end of aeration), the total concentration of TMAH, TMA, DMA, MMA, ammonium ion (NH 4 -N) concentration, nitrate ion (NO The 3- N) concentration and the nitrite ion (NO 2 -N) concentration were periodically analyzed by ion chromatography, and the biological treatment conditions were adjusted by automatic control based on the following reference values.
<基準値>
アミンと及び4級アンモニウムイオン濃度とNH3−N濃度の合計の上限値:0.5mg−N/L
NO3−N濃度とNO2−N濃度の合計の上限値:3mg−N/L
pH制御目標値:上限7.0〜下限6.0
pH制御目標値の1日の最大調整幅:0.1/1日当たり
<Reference value>
Upper limit of total of amine, quaternary ammonium ion concentration and NH 3 -N concentration: 0.5 mg-N / L
Upper limit of the total of NO 3 -N concentration and NO 2 -N concentration: 3 mg-N / L
pH control target value: upper limit 7.0 to lower limit 6.0
Maximum adjustment range of pH control target value per day: per 0.1 / 1 day
硝化を改善する運転調整は以下の優先順位で行った。
(1) 硝化工程での曝気強度増により溶存酸素濃度を上げる。
硝化工程での溶存酸素濃度制御目標を3.0〜6.0mg/Lの範囲で調整
溶存酸素濃度制御目標の1日の最大調整幅:0.5mg/L/1日当たり
(2) 硝化工程の時間に対する、脱窒工程の時間の比を小さくする。
脱窒工程の時間/硝化工程の時間は、0.1〜0.9の範囲で調整
Operation adjustment to improve nitrification was performed in the following order of priority.
(1) Increase the dissolved oxygen concentration by increasing the aeration intensity in the nitrification process.
Adjust the dissolved oxygen concentration control target in the nitrification process in the range of 3.0-6.0 mg / L Maximum adjustment range of the dissolved oxygen concentration control target per day: 0.5 mg / L / day (2) Decrease the ratio of time of denitrification process to time.
Denitrification process time / nitrification process time is adjusted within the range of 0.1-0.9.
脱窒を改善する運転調整は、以下の優先順位で行った。
(3) 硝化工程での曝気強度減により溶存酸素濃度を下げる。
(4) 硝化工程の時間に対する、脱窒工程の時間の比を大きくする。
Operation adjustment to improve denitrification was performed in the following order of priority.
(3) Lower the dissolved oxygen concentration by reducing the aeration intensity in the nitrification process.
(4) Increase the ratio of the denitrification process time to the nitrification process time.
その結果、得られた処理水の水質は表1に示す通りであり、良好な水質の処理水を安定に得ることができた。このため、この処理水に無機凝集剤としてポリ硫酸第2鉄溶液を添加して凝集処理した後、RO膜分離処理する際に必要な無機凝集剤添加量は110mg/Lであり、以下の比較例1,2よりも大幅に添加量を低減することができた。 As a result, the quality of the obtained treated water was as shown in Table 1, and treated water with good water quality could be stably obtained. For this reason, after adding a polyferric sulfate solution as an inorganic flocculant to the treated water and aggregating, the amount of inorganic flocculant added when performing RO membrane separation treatment is 110 mg / L. The amount added could be greatly reduced as compared with Examples 1 and 2.
[比較例1]
実施例1において、間欠曝気を行わず、連続曝気を行ってDOを3〜4.0mg/Lの範囲に維持し、硝化工程のみを行い、さらに、硝化の安定のためpH設定を7と、実施例1の6.5よりも高い条件で処理を行ったところ、4級アンモニウム塩であるTMAHは実施例1と同様に良好に分解し、TMAH分解の中間代謝物として発生するDMA等のアミンの残留は認められなかった。処理水のTOC濃度は実施例1と同レベルの3mg−C/Lで維持できており、pH設定の意図どおり、硝化は良好に進行しNH4−Nの残留もみられなかったが、脱窒工程がないためNO3−N+NO2−Nの残留濃度は高く、pH調整のために必要なNaOHの添加量が多くなり、その結果、Na濃度が上昇した。
また、pH設定の上昇に伴い処理水のアルカリ度が高くなり、後段の無機凝集剤の必要添加量が増加する傾向がみられた。
[Comparative Example 1]
In Example 1, intermittent aeration is not performed, continuous aeration is performed to maintain DO in the range of 3 to 4.0 mg / L, only the nitrification step is performed, and the pH setting is set to 7 for nitrification stability. When treated under conditions higher than 6.5 in Example 1, TMAH, which is a quaternary ammonium salt, decomposes satisfactorily in the same manner as in Example 1, and amines such as DMA generated as intermediate metabolites of TMAH decomposition No residue was observed. The TOC concentration of the treated water was maintained at 3 mg-C / L, which was the same level as in Example 1, and nitrification proceeded well and no NH 4 -N residue was observed as intended by the pH setting. Since there was no process, the residual concentration of NO 3 —N + NO 2 —N was high, and the amount of NaOH required for pH adjustment was increased, resulting in an increase in Na concentration.
Moreover, the alkalinity of the treated water became higher as the pH setting increased, and the required amount of the inorganic flocculant in the latter stage tended to increase.
[比較例2]
実施例1において、TMAHおよびアミン類の濃度による管理を行わなかったこと以外は同様に処理を行ったところ、NH4−Nの残留がなく、NO3−N+NO2−Nの残留が認められたため、ランニングコスト、処理水のアルカリ度低減の観点からpHの制御目標を6.5とし、積極的な脱窒素反応を進行させる曝気制御、すなわち脱窒工程時間/硝化工程時間比を0.4まで上げたところ、TMAH分解が悪化し、処理水TOC濃度も7mg−C/Lまで増加した。
本比較例2の場合、処理の要件である排水中の窒素成分の完全硝化ができず、また付随して有機アルカリ成分であるTMAHの残留により処理水TOC濃度の上昇があり、アルカリ度も実施例1よりも高くなる結果を招いた。この結果、後段の無機凝集剤の必要添加量が増加する傾向がみられた。
[Comparative Example 2]
In Example 1, the same treatment was performed except that the control by the concentrations of TMAH and amines was not performed, but no NH 4 -N remained and NO 3 -N + NO 2 -N remained. From the viewpoint of reducing the running cost and alkalinity of treated water, the pH control target is set to 6.5, and aeration control that promotes a positive denitrification reaction, that is, the denitrification process time / nitrification process time ratio is up to 0.4. As a result, TMAH decomposition deteriorated, and the TOC concentration of treated water increased to 7 mg-C / L.
In the case of this comparative example 2, the nitrogen component in the waste water, which is a requirement for treatment, cannot be completely nitrified, and the TMAH, which is an organic alkali component, is accompanied by an increase in the TOC concentration of the treated water and the alkalinity is also implemented The result was higher than Example 1. As a result, there was a tendency that the required addition amount of the latter inorganic flocculant increased.
表1より、本発明によれば、アミン及び4級アンモニウム塩類の分解をも良好に維持しつつ、処理水(亜)硝酸イオン濃度を有意に低下することができ、その結果、pH調整に必要なアルカリ剤の添加濃度を低減できると共に、アミン及び4級アンモニウム塩類の分解が維持されている範囲でpHの制御目標を下げる運転ができ、処理水アルカリ度を低下することができるため、後段の凝集プロセスでの酸剤および無機凝集剤の添加量を最小化できることが確認できた。 From Table 1, according to the present invention, it is possible to significantly reduce the concentration of treated water (nitrous) nitrate ions while maintaining good decomposition of amines and quaternary ammonium salts, and as a result, necessary for pH adjustment. In addition to reducing the concentration of the alkaline agent added, it is possible to operate to lower the pH control target within a range in which the decomposition of the amine and the quaternary ammonium salt is maintained, and to reduce the alkalinity of the treated water. It was confirmed that the addition amount of the acid agent and the inorganic flocculant in the aggregation process can be minimized.
なお、上記実施例では、生物処理として流動床式生物処理法を採用した例を示したが、活性汚泥法(AS)、膜分離活性汚泥法(MBR)、担体添加活性汚泥法(IFAS)等においても同様の課題があり、本運転管理手段で対応可能である。 In addition, although the example which employ | adopted the fluid bed type biological treatment method as a biological treatment was shown in the said Example, activated sludge method (AS), membrane separation activated sludge method (MBR), support | carrier addition activated sludge method (IFAS), etc. There is a similar problem, and this operation management means can cope with it.
Claims (12)
該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度の測定値に基づいて、
アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が基準値を超える場合に硝化を改善する該生物処理槽の運転調整を行い、硝酸イオン濃度の測定値と亜硝酸イオンの測定値の合計が基準値を超える場合は脱窒を改善する該生物処理槽の運転調整を行うことを特徴とする生物処理方法。 In a method for biological treatment by introducing an organic wastewater containing amines and / or quaternary ammonium salt into a biological treatment tank,
Measurements and A Nmo ion concentration of amine and quaternary ammonium ion concentration in the organism treatment tank solution or organism processing tank effluent, based on measurements of the nitrate ion concentration, and nitrous acid ion concentration,
Adjust the operation of the biological treatment tank to improve nitrification when the total of the measured values of amine and quaternary ammonium ions and the measured value of ammonium ion exceeds the reference value, and the measured value of nitrate ion concentration and nitrite ion A biological treatment method comprising adjusting the operation of the biological treatment tank to improve denitrification when the total of the measured values exceeds a reference value .
以下の(1−1)→(1−2)→(1−3)→(2−1)→(2−2)の優先順位で該生物処理槽の運転調整を行うことを特徴とする生物処理方法。
(1−1) 硝化工程での曝気強度を上げて溶存酸素濃度を上昇させる。
(1−2) 硝化工程の時間に対する、脱窒工程の時間の比を調整できる場合は、同比を小さくする(硝化工程の時間を長くする)。
(1−3) pH制御目標値を上げる。
(2−1) 硝化工程での曝気強度を下げて溶存酸素濃度を低下させる。
(2−2) 硝化工程の時間に対する、脱窒素工程の時間の比を調整できる場合は、同比を大きくする(脱窒工程の時間を長くする)。 In a method for biological treatment by introducing an organic wastewater containing amines and / or quaternary ammonium salt into a biological treatment tank,
A biological organism characterized in that operation adjustment of the biological treatment tank is performed in the following order of priority (1-1) → (1-2) → (1-3) → (2-1) → (2-2) Processing method.
(1-1) Raising the aeration intensity in the nitrification step to increase the dissolved oxygen concentration.
(1-2) When the ratio of the denitrification process time to the nitrification process time can be adjusted, the ratio is reduced (the nitrification process time is increased).
(1-3) Increase the pH control target value.
(2-1) The aeration intensity in the nitrification step is lowered to lower the dissolved oxygen concentration.
(2-2) When the ratio of the time of the denitrification process to the time of the nitrification process can be adjusted, the ratio is increased (the time of the denitrification process is increased).
該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度の測定値に基づいて、
アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が基準値を超える場合に以下の(1−1)→(1−2)→(1−3)の優先順位で硝化を改善する該生物処理槽の運転調整を行った後、硝酸イオン濃度の測定値と亜硝酸イオンの測定値の合計が基準値を超える場合は以下の(2−1)→(2−2)の優先順位で該生物処理槽の脱窒を改善する運転調整を行うことを特徴とする生物処理方法。
(1−1) 硝化工程での曝気強度を上げて溶存酸素濃度を上昇させる。
(1−2) 硝化工程の時間に対する、脱窒工程の時間の比を調整できる場合は、同比を小さくする(硝化工程の時間を長くする)。
(1−3) pH制御目標値を上げる。
(2−1) 硝化工程での曝気強度を下げて溶存酸素濃度を低下させる。
(2−2) 硝化工程の時間に対する、脱窒素工程の時間の比を調整できる場合は、同比を大きくする(脱窒工程の時間を長くする)。 In a method for biological treatment by introducing an organic wastewater containing amines and / or quaternary ammonium salt into a biological treatment tank,
Measurements and A Nmo ion concentration of amine and quaternary ammonium ion concentration in the organism treatment tank solution or organism processing tank effluent, based on measurements of the nitrate ion concentration, and nitrous acid ion concentration,
When the total of the measured value of amine and quaternary ammonium ion concentration and the measured value of ammonium ion concentration exceeds the standard value, nitrification is performed in the following order of priority (1-1) → (1-2) → (1-3) If the total of the measured value of nitrate ion concentration and the measured value of nitrite ion exceeds the reference value after adjusting the operation of the biological treatment tank to improve the following (2-1) → (2-2) The biological treatment method is characterized by performing operation adjustment for improving denitrification of the biological treatment tank in the order of priority .
(1-1) Raising the aeration intensity in the nitrification step to increase the dissolved oxygen concentration.
(1-2) When the ratio of the denitrification process time to the nitrification process time can be adjusted, the ratio is reduced (the nitrification process time is increased).
(1-3) Increase the pH control target value.
(2-1) The aeration intensity in the nitrification step is lowered to lower the dissolved oxygen concentration.
(2-2) When the ratio of the time of the denitrification process to the time of the nitrification process can be adjusted, the ratio is increased (the time of the denitrification process is increased).
該有機系排水が導入される生物処理槽と、
該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度を測定する第1の測定手段と、
該生物処理槽内液又は該生物処理槽流出液のアンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度を測定する第2の測定手段と、
該第1の測定手段の測定値と第2の測定手段の測定値に基づいて、
アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が基準値を超える場合に該生物処理槽の硝化を改善する運転調整を行い、硝酸イオン濃度の測定値と亜硝酸イオンの測定値の合計が基準値を超える場合は脱窒を改善する該生物処理槽の運転調整を行う制御手段と
を有することを特徴とする生物処理装置。 In biological treatment equipment for organic wastewater containing amines and / or quaternary ammonium salts ,
A biological treatment tank into which the organic wastewater is introduced;
First measuring means for measuring the concentration of amine and quaternary ammonium ions in the biological treatment tank internal fluid or the biological treatment tank effluent;
Ammonium ion concentration of organism treatment tank solution or organism processing tank effluent, a second measuring means for measuring the concentration of nitrate ions, and nitrite ions concentration,
Based on the measured value of the first measuring means and the measured value of the second measuring means,
When the sum of the measured values of amine and quaternary ammonium ions and the measured value of ammonium ions exceeds the standard value, operation adjustment is performed to improve nitrification of the biological treatment tank, and the measured value of nitrate ion concentration and nitrite ion And a control means for adjusting the operation of the biological treatment tank to improve denitrification when the total of the measured values exceeds a reference value .
該有機系排水が導入される生物処理槽と、
以下の(1−1)→(1−2)→(1−3)→(2−1)→(2−2)の優先順位で該生物処理槽の運転調整を行う制御手段と
を有することを特徴とする生物処理装置。
(1−1) 硝化工程での曝気強度を上げて溶存酸素濃度を上昇させる。
(1−2) 硝化工程の時間に対する、脱窒工程の時間の比を調整できる場合は、同比を小さくする(硝化工程の時間を長くする)。
(1−3) pH制御目標値を上げる。
(2−1) 硝化工程での曝気強度を下げて溶存酸素濃度を低下させる。
(2−2) 硝化工程の時間に対する、脱窒素工程の時間の比を調整できる場合は、同比を大きくする(脱窒工程の時間を長くする)。 In biological treatment equipment for organic wastewater containing amines and / or quaternary ammonium salts ,
A biological treatment tank into which the organic wastewater is introduced;
(1) → (1-2) → (1-3) → (2-1) → (2-2) control means for adjusting the operation of the biological treatment tank in the priority order A biological treatment apparatus characterized by.
(1-1) Raising the aeration intensity in the nitrification step to increase the dissolved oxygen concentration.
(1-2) When the ratio of the denitrification process time to the nitrification process time can be adjusted, the ratio is reduced (the nitrification process time is increased).
(1-3) Increase the pH control target value.
(2-1) The aeration intensity in the nitrification step is lowered to lower the dissolved oxygen concentration.
(2-2) When the ratio of the time of the denitrification process to the time of the nitrification process can be adjusted, the ratio is increased (the time of the denitrification process is increased).
該有機系排水が導入される生物処理槽と、
該生物処理槽内液又は該生物処理槽流出液のアミン及び4級アンモニウムイオン濃度を測定する第1の測定手段と、
該生物処理槽内液又は該生物処理槽流出液のアンモニウムイオン濃度、硝酸イオン濃度、及び亜硝酸イオン濃度を測定する第2の測定手段と、
該第1の測定手段の測定値と第2の測定手段の測定値に基づいて、
アミン及び4級アンモニウムイオン濃度の測定値とアンモニウムイオン濃度の測定値の合計が基準値を超える場合に以下の(1−1)→(1−2)→(1−3)の優先順位で該生物処理槽の硝化を改善する運転調整を行った後、硝酸イオン濃度の測定値と亜硝酸イオンの測定値の合計が基準値を超える場合は以下の(2−1)→(2−2)の優先順位で該生物処理槽の脱窒を改善する運転調整を行う制御手段と
を有することを特徴とする生物処理装置。
(1−1) 硝化工程での曝気強度を上げて溶存酸素濃度を上昇させる。
(1−2) 硝化工程の時間に対する、脱窒工程の時間の比を調整できる場合は、同比を小さくする(硝化工程の時間を長くする)。
(1−3) pH制御目標値を上げる。
(2−1) 硝化工程での曝気強度を下げて溶存酸素濃度を低下させる。
(2−2) 硝化工程の時間に対する、脱窒素工程の時間の比を調整できる場合は、同比を大きくする(脱窒工程の時間を長くする)。 In biological treatment equipment for organic wastewater containing amines and / or quaternary ammonium salts ,
A biological treatment tank into which the organic wastewater is introduced;
First measuring means for measuring the concentration of amine and quaternary ammonium ions in the biological treatment tank internal fluid or the biological treatment tank effluent;
Ammonium ion concentration of organism treatment tank solution or organism processing tank effluent, a second measuring means for measuring the concentration of nitrate ions, and nitrite ions concentration,
Based on the measured value of the first measuring means and the measured value of the second measuring means,
When the total of the measured value of amine and quaternary ammonium ion concentration and the measured value of ammonium ion concentration exceeds the reference value, the following order of priority (1-1) → (1-2) → (1-3) After the operation adjustment to improve nitrification of the biological treatment tank, if the total of the measured value of nitrate ion concentration and the measured value of nitrite ion exceeds the reference value, the following (2-1) → (2-2) And a control means for adjusting the operation to improve denitrification of the biological treatment tank in the order of priority .
(1-1) Raising the aeration intensity in the nitrification step to increase the dissolved oxygen concentration.
(1-2) When the ratio of the denitrification process time to the nitrification process time can be adjusted, the ratio is reduced (the nitrification process time is increased).
(1-3) Increase the pH control target value.
(2-1) The aeration intensity in the nitrification step is lowered to lower the dissolved oxygen concentration.
(2-2) When the ratio of the time of the denitrification process to the time of the nitrification process can be adjusted, the ratio is increased (the time of the denitrification process is increased).
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