JP2006167574A - Waste water treatment apparatus and biological treatment method of waste water - Google Patents

Waste water treatment apparatus and biological treatment method of waste water Download PDF

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JP2006167574A
JP2006167574A JP2004362600A JP2004362600A JP2006167574A JP 2006167574 A JP2006167574 A JP 2006167574A JP 2004362600 A JP2004362600 A JP 2004362600A JP 2004362600 A JP2004362600 A JP 2004362600A JP 2006167574 A JP2006167574 A JP 2006167574A
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JP4865211B2 (en
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Kana Maeda
香奈 前田
Akira Era
彰 恵良
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Organo Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a waste water treatment apparatus and biological treatment method of waste water allowing pH adjustment of the waste water at a low cost while supplying inorganic carbon source sufficient for activity of nitrification bacteria, and further reducing generation of calcium scale. <P>SOLUTION: This waste water treatment apparatus S nitrifies inorganic waste water containing ammonia nitrogen by biological treatment, and is provided with a biological treatment tank 2 mixing inorganic waste water with autotrophic bacteria; a pH detector 8 detecting pH of the inorganic waste water supplied in the biological treatment tank 2; a sodium hydroxide supply part 11 supplying sodium hydroxide for adjusting pH in the biological treatment tank 2 to the biological treatment tank 2; a sodium bicarbonate supply part 12 supplying sodium bicarbonate in the biological treatment tank 2; and a supply amount control part controlling the supply amounts of sodium hydroxide and sodium bicarbonate based on the detection result by the pH detector 8. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、アンモニア性窒素を含む無機廃水を生物処理によって硝化する廃水処理装置及び廃水処理方法に係り、特に、窒素及びカルシウムを含む無機廃水を微生物を用いて硝化処理する廃水処理装置及び廃水処理方法に関する。本発明は、例えば生活廃水の廃水処理のほか、半導体製造工程によって排出される産業廃水の廃水処理に適用可能である。   The present invention relates to a wastewater treatment apparatus and a wastewater treatment method for nitrifying inorganic wastewater containing ammonia nitrogen by biological treatment, and in particular, a wastewater treatment apparatus and wastewater treatment for nitrifying inorganic wastewater containing nitrogen and calcium using microorganisms. Regarding the method. The present invention is applicable to, for example, wastewater treatment of industrial wastewater discharged by a semiconductor manufacturing process in addition to wastewater treatment of domestic wastewater.

従来より、ＩＣなどの半導体の製造工程などでは、フッ酸、アンモニア、硝酸などが使用される。このため、その廃液として、フッ素（フッ酸）、窒素（アンモニア、硝酸）を含む廃水が排出される。例えば、エッチング処理等の工程においてこれらの化学物質を含む薬品が用いられ、半導体基板を超純水等で洗浄した際の洗浄廃液としてこれらの化学物質を含む廃水が排出される。 また、ＬＣＤ（液晶ディスプレイ）製造工程も基本的に半導体製造工程と同様の工程を有しており、同様の廃水が排出される。さらに、石炭火力発電所、ガラス表面加工工場等においても、フッ素、窒素を含む廃水が排出される。   Conventionally, hydrofluoric acid, ammonia, nitric acid, and the like are used in manufacturing processes of semiconductors such as ICs. For this reason, waste water containing fluorine (hydrofluoric acid) and nitrogen (ammonia, nitric acid) is discharged as the waste liquid. For example, chemicals containing these chemical substances are used in processes such as etching, and waste water containing these chemical substances is discharged as a cleaning waste liquid when the semiconductor substrate is cleaned with ultrapure water or the like. Also, the LCD (liquid crystal display) manufacturing process basically has the same process as the semiconductor manufacturing process, and the same waste water is discharged. Furthermore, wastewater containing fluorine and nitrogen is also discharged at coal-fired power plants, glass surface processing plants, and the like.

廃水中のフッ素は物理化学的に、すなわちカルシウムを添加することによりフッ化カルシウムとして除去されるのが一般的である。上述の廃水についても、水酸化カルシウム等を添加してフッ化カルシウムを析出させることによりフッ素を除去している。なお、フッ化カルシウムは細かい微粒子になりやすい。そのため、これを除去するためにアルミニウム系などの無機凝集剤やアクリル系高分子凝集剤を添加してフロックを形成させることにより、廃水中のフッ化カルシウムを沈殿除去している。   Fluorine in waste water is generally removed physicochemically, that is, as calcium fluoride by adding calcium. Also for the above-mentioned wastewater, fluorine is removed by adding calcium hydroxide or the like to precipitate calcium fluoride. Calcium fluoride tends to be fine particles. Therefore, in order to remove this, calcium fluoride in waste water is precipitated and removed by adding an inorganic flocculant such as aluminum or an acrylic polymer flocculant to form floc.

カルシウムによるフッ素除去は、２Ｆ−＋Ｃａ２ ＋→ＣａＦ２という反応で表され、この場合の溶解度積Ｋspは３．４５×１０−１１である。したがって、廃水中のフッ素を充分に除去するためには、相当量のカルシウムイオンが残留する条件とする必要がある。一般に、フッ素除去処理水中のフッ素濃度の目標濃度は１０ｍｇ／Ｌ以下程度とされ、この場合には処理水中の残留カルシウム濃度を１００〜１０００ｍｇ／Ｌ程度にする必要がある。 Fluorine removal by calcium is expressed by a reaction of 2F − + Ca 2 + → CaF 2 , and the solubility product Ksp in this case is 3.45 × 10 −11 . Therefore, in order to sufficiently remove the fluorine in the wastewater, it is necessary to make the condition that a considerable amount of calcium ions remain. Generally, the target concentration of the fluorine concentration in the fluorine removal treated water is about 10 mg / L or less, and in this case, the residual calcium concentration in the treated water needs to be about 100 to 1000 mg / L.

なお、廃水中にケイ素やリン酸等が存在する場合には、それらがフッ化カルシウムの析出に悪影響を与えてしまう。したがって、そのような場合にはより多量のカルシウムの添加や無機凝集剤や高分子凝集剤による凝集処理が必要となる場合がある。   In addition, when silicon, phosphoric acid, etc. exist in wastewater, they will have a bad influence on precipitation of calcium fluoride. Therefore, in such a case, it may be necessary to add a larger amount of calcium or agglomeration treatment with an inorganic flocculant or a polymer flocculant.

一方、窒素除去としては、一般的に生物学的脱窒が採用される。この生物学的脱窒は、通性嫌気性細菌である脱窒菌の無酸素状態における硝酸呼吸を利用して窒素を除去するものである。この生物学的脱窒においては、まず廃水を硝化処理して廃水中のアンモニア性窒素を亜硝酸性窒素又は硝酸性窒素とし、その後メタノール等の水素供与体を添加して無酸素状態とすることによって脱窒処理を行う。上述したようなフッ素除去と窒素除去を組み合わせることにより、廃水中のフッ素や窒素が除去される。フッ素を多量に含む廃水は細菌を用いた生物処理に対して悪影響を与えるので、生物学的脱窒処理は廃水中のフッ素を除去した後に行われる。したがって、生物学的脱窒処理の対象となる廃水はカルシウムを多量に含む。   On the other hand, biological denitrification is generally adopted as nitrogen removal. This biological denitrification is to remove nitrogen by utilizing nitrate respiration in the anoxic state of denitrifying bacteria which are facultative anaerobic bacteria. In this biological denitrification, the wastewater is first nitrified to make ammonia nitrogen in the wastewater nitrite nitrogen or nitrate nitrogen, and then a hydrogen donor such as methanol is added to make it oxygen-free. To perform denitrification. By combining fluorine removal and nitrogen removal as described above, fluorine and nitrogen in the wastewater are removed. Since wastewater containing a large amount of fluorine has an adverse effect on biological treatment using bacteria, biological denitrification treatment is performed after removing fluorine in wastewater. Therefore, the wastewater that is the target of biological denitrification treatment contains a large amount of calcium.

例えば、従来の好気性独立栄養性細菌の作用により廃水中のアンモニア性窒素を亜硝酸性窒素又は硝酸性窒素へと変換する生物処理方法においては、その変換に伴って廃水のｐＨが低下する。この好気性独立栄養性細菌（硝化細菌）の生育状態は以下の化学反応式で表すことができる。   For example, in a biological treatment method in which ammonia nitrogen in wastewater is converted into nitrite nitrogen or nitrate nitrogen by the action of conventional aerobic autotrophic bacteria, the pH of the wastewater decreases with the conversion. The growth state of the aerobic autotrophic bacterium (nitrifying bacterium) can be expressed by the following chemical reaction formula.

ＮＨ４ ＋＋０．１０３ＣＯ２＋１．８６Ｏ２→０．０１８２Ｃ２Ｈ５ＮＯ２＋０．００２４５Ｃ５Ｈ７ＮＯ２＋０．９７９ＮＯ３ −＋１．９８Ｈ＋＋０．９３８Ｈ２Ｏ NH 4 + + 0.103CO 2 + 1.86O 2 → 0.0182C 2 H 5 NO 2 + 0.00245C 5 H 7 NO 2 + 0.979NO 3 - + 1.98H + + 0.938H 2 O

すなわち、硝化細菌の増殖に必要な無機炭素と処理すべきアンモニア性窒素との重量比は、０．０８８ｇ−Ｃ／ｇ−Ｎと表すことができる。   That is, the weight ratio of inorganic carbon necessary for the growth of nitrifying bacteria and ammoniacal nitrogen to be treated can be expressed as 0.088 g-C / g-N.

一般に、活性汚泥法のような低負荷処理（例えば０．１〜０．３ｋｇ−Ｎ／ｍ３／ｄａｙ）の場合は、曝気による廃水への炭酸ガスの溶け込みにより上記の無機炭素量を確保することが可能である。しかし、生物固定担体を処理系内に投入して、その細菌を処理系内に留める生物膜法（例えば、固定床方式や流動床方式）では高負荷処理（例えば０．５〜１．０ｋｇ−Ｎ／ｍ３／ｄａｙ）が行われるため、硝化細菌の増殖に必要な無機炭素が不足しがちとなる。そのため、無機炭素を補充するために、重炭酸塩を廃水中に添加する場合がある。この重炭酸塩はアルカリ剤としても機能させることが可能である。 In general, in the case of low load treatment such as the activated sludge method (for example, 0.1 to 0.3 kg-N / m 3 / day), the above-mentioned inorganic carbon amount is ensured by dissolving carbon dioxide gas into wastewater by aeration. It is possible. However, in a biofilm method (for example, a fixed bed method or a fluidized bed method) in which a biological fixed carrier is introduced into a treatment system and the bacteria are retained in the treatment system, a high load treatment (for example, 0.5 to 1.0 kg- N / m 3 / day), the inorganic carbon necessary for the growth of nitrifying bacteria tends to be insufficient. Therefore, bicarbonate may be added to the wastewater to replenish inorganic carbon. This bicarbonate can also function as an alkaline agent.

なお、硝化細菌を利用した従来の廃水処理方法として、例えば特許文献１〜４に開示されたものがある。
特開昭５４−３３３６５号公報 特開昭６１−１１８１９８号公報 特開平５−１２３６９６号公報 特開２００３−３３７８８号公報 In addition, as a conventional wastewater treatment method using nitrifying bacteria, for example, there are those disclosed in Patent Documents 1 to 4.
JP 54-33365 A JP 61-118198 A JP-A-5-123696 JP 2003-33788 A

重炭酸塩のアルカリ剤としての機能を利用し、例えば重炭酸ナトリウムのみを用いて廃水を中和する場合、処理すべきアンモニア性窒素１ｇに対して重炭酸ナトリウムは約９．６ｇ／ｇ−Ｎ（約１．４ｇ−Ｃ／ｇ−Ｎ）が必要となる。しかしながら、重炭酸ナトリウムは高価であるためアルカリ剤として重炭酸ナトリウムのみを用いると廃水処理コストが高くなってしまうという問題がある。さらに、重炭酸ナトリウムはスラリー状態での取扱いとなってしまうため、廃水中に添加するには複雑な注入設備が必要となってしまう。   When neutralizing wastewater using, for example, sodium bicarbonate alone, the function of bicarbonate as an alkaline agent, sodium bicarbonate is about 9.6 g / g-N for 1 g of ammoniacal nitrogen to be treated. (About 1.4 g-C / g-N) is required. However, since sodium bicarbonate is expensive, there is a problem that wastewater treatment costs increase if only sodium bicarbonate is used as an alkaline agent. Furthermore, since sodium bicarbonate is handled in a slurry state, a complicated injection facility is required to add it to waste water.

また、上述したように生物学的脱窒処理の対象となる廃水はカルシウムを多量に含むが、このような場合に廃水中に多量の重炭酸ナトリウムを添加すると廃水を貯留している槽内又は廃水が通る管内に炭酸カルシウムのスケールが発生してしまうという問題もある。スケールの発生は、廃水処理装置内のデッドスペースの増加、廃水配管の閉塞等の問題を生じさせ得る。流動床方式の場合は、さらに流動床の流動悪化も招いてしまう。   In addition, as described above, the wastewater to be subjected to biological denitrification treatment contains a large amount of calcium. In such a case, if a large amount of sodium bicarbonate is added to the wastewater, There is also a problem that a scale of calcium carbonate is generated in the pipe through which the wastewater passes. Generation | occurrence | production of a scale can cause problems, such as an increase in the dead space in a wastewater treatment apparatus, and the blockage | conclusion of wastewater piping. In the case of the fluidized bed method, the fluidized bed is further deteriorated.

一方、水酸化ナトリウムは重炭酸ナトリウムに比較して安価な上に、アルカリ剤として用いた場合には処理すべきアンモニア窒素１ｇに対して約５．７ｇの量で済むという利点もある。   On the other hand, sodium hydroxide has an advantage that it is less expensive than sodium bicarbonate, and when used as an alkali agent, it requires only about 5.7 g per 1 g of ammonia nitrogen to be treated.

本発明は上記の事情に鑑みて為されたもので、硝化細菌が活動するのに充分な無機炭素源を供給しつつ低コストに廃水のｐＨ調整を行うことができ、さらにカルシウムスケールの発生を低減することのできる廃水処理装置及び廃水の生物処理方法を提供することを例示的な課題とする。   The present invention has been made in view of the above circumstances, and it is possible to adjust the pH of wastewater at a low cost while supplying a sufficient inorganic carbon source for nitrifying bacteria to operate, and further to generate calcium scale. It is an exemplary problem to provide a wastewater treatment apparatus and a biological treatment method for wastewater that can be reduced.

上記の課題を解決するために、本発明の例示的側面としての廃水処理装置は、アンモニア性窒素を含む無機性廃水を生物処理によって硝化する廃水処理装置であって、無機性廃水と独立栄養性細菌とが混合される生物処理槽と、生物処理槽内に供給された無機性廃水のｐＨを検出するｐＨ検出器と、生物処理槽内のｐＨを調整するｐＨ調整剤を生物処理槽に供給する第１の供給部と、生物処理槽内に無機炭素源を供給する第２の供給部と、ｐＨ検出器の検出結果に基づいてｐＨ調整剤の供給量と無機炭素源の供給量とを制御する供給量制御部とを有することを特徴とする。   In order to solve the above-mentioned problems, a wastewater treatment apparatus as an exemplary aspect of the present invention is a wastewater treatment apparatus that nitrifies inorganic wastewater containing ammoniacal nitrogen by biological treatment. A biological treatment tank in which bacteria are mixed, a pH detector for detecting the pH of inorganic wastewater supplied in the biological treatment tank, and a pH adjuster for adjusting the pH in the biological treatment tank are supplied to the biological treatment tank. A first supply unit that performs the second supply unit that supplies the inorganic carbon source into the biological treatment tank, and a supply amount of the pH adjuster and a supply amount of the inorganic carbon source based on a detection result of the pH detector. And a supply amount control unit for controlling.

供給量制御部によってｐＨ調整剤の供給量と無機炭素源の供給量とを制御することにより、ｐＨ調整剤及び無機炭素源の性質やコストに応じてそれぞれの使用量を調整することができる。例えば、ｐＨ調整剤が比較的安価な水酸化ナトリウムであり、無機炭素源が水酸化ナトリウムに比較して高価でかつｐＨ調整機能をも有する重炭酸塩又は炭酸塩である場合、高価な重炭酸塩又は炭酸塩の供給量を必要最小限に制御することが可能である。廃水のｐＨが検出されているので水酸化ナトリウムの供給量も容易に制御可能である。   By controlling the supply amount of the pH adjusting agent and the supply amount of the inorganic carbon source by the supply amount control unit, the respective usage amounts can be adjusted according to the properties and costs of the pH adjusting agent and the inorganic carbon source. For example, when the pH adjuster is relatively inexpensive sodium hydroxide and the inorganic carbon source is bicarbonate or carbonate that is more expensive than sodium hydroxide and also has a pH adjusting function, expensive bicarbonate It is possible to control the supply amount of the salt or carbonate to the minimum necessary. Since the pH of the wastewater is detected, the amount of sodium hydroxide supplied can be easily controlled.

最小限の重炭酸塩又は炭酸塩を供給しつつ廃水が中和されるように水酸化ナトリウムを供給することにより、低コストで充分な廃水処理能力を得ることができる。しかも重炭酸塩又は炭酸塩を最小限とすることによってカルシウムスケールの発生も防止することができる。このカルシウムスケール発生の防止効果は、廃水中のカルシウム含有率が高い場合、例えば廃水が１００ｍｇ／ｌ以上のカルシウムを含有している場合には、より顕著に得られる。   By supplying sodium hydroxide so that the wastewater is neutralized while supplying a minimum amount of bicarbonate or carbonate, a sufficient wastewater treatment capacity can be obtained at low cost. Moreover, generation of calcium scale can be prevented by minimizing bicarbonate or carbonate. This effect of preventing the generation of calcium scale is more prominent when the calcium content in the wastewater is high, for example, when the wastewater contains 100 mg / l or more of calcium.

この廃水処理装置は、特に廃水中のＣ／ＮＨ４−Ｎ重量比が例えば０．１未満と小さく、無機炭素不足による処理能力の低下が懸念される場合に好適である。そのような廃水として、例えば半導体製造工程によって排出される産業廃水が考えられる。また、この廃水処理装置は、高負荷処理が行われ無機炭素不足が懸念される固定床方式や流動床方式の生物膜法処理に適している。 This wastewater treatment apparatus is particularly suitable when the C / NH 4 -N weight ratio in the wastewater is as small as, for example, less than 0.1 and there is a concern about a reduction in treatment capacity due to insufficient inorganic carbon. As such waste water, for example, industrial waste water discharged by a semiconductor manufacturing process can be considered. In addition, this wastewater treatment apparatus is suitable for a fixed-bed or fluidized-bed biofilm method treatment in which high-load treatment is performed and inorganic carbon shortage is a concern.

本発明の他の例示的側面としての廃水の生物処理方法は、アンモニア性窒素を含む無機性廃水を生物処理槽内へ供給する工程と、供給された無機性廃水のｐＨを検出する工程と、生物処理槽内のｐＨを調整するｐＨ調整剤を生物処理槽に供給する工程と、生物処理槽内へ無機性廃水のｐＨを調整するとともに独立栄養性細菌の炭素源として機能する重炭酸塩又は炭酸塩を供給する工程と、ｐＨの検出結果に基づいてｐＨ調整剤の供給量と重炭酸塩又は炭酸塩の供給量とを制御する工程とを有することを特徴とする。   The biological treatment method of wastewater as another exemplary aspect of the present invention includes a step of supplying inorganic wastewater containing ammonia nitrogen into a biological treatment tank, a step of detecting the pH of the supplied inorganic wastewater, A step of supplying a pH adjusting agent for adjusting the pH in the biological treatment tank to the biological treatment tank, and adjusting the pH of the inorganic wastewater into the biological treatment tank and functioning as a carbon source of autotrophic bacteria or The method includes a step of supplying carbonate, and a step of controlling a supply amount of a pH adjusting agent and a supply amount of bicarbonate or carbonate based on a detection result of pH.

ｐＨ調整剤の供給量と重炭酸塩又は炭酸塩の供給量とを制御する工程を有しているので、ｐＨ調整剤や重炭酸塩又は炭酸塩の性質やコストに応じてそれぞれの使用量を調整することができる。例えば、ｐＨ調整剤として比較的安価な水酸化ナトリウムを用い、重炭酸塩又は炭酸塩として水酸化ナトリウムに比較して高価でかつｐＨ調整機能をも有する重炭酸ナトリウムを用いる場合、高価な重炭酸ナトリウムの供給量を必要最小限に制御することが可能である。廃水のｐＨが検出されているので水酸化ナトリウムの供給量も容易に制御可能である。もちろん重炭酸塩又は炭酸塩としては、重炭酸ナトリウムの他に、炭酸ナトリウム、炭酸カルシウム等も使用可能である。   Since it has a step of controlling the supply amount of the pH adjuster and the supply amount of bicarbonate or carbonate, the amount of each used according to the nature and cost of the pH adjuster, bicarbonate or carbonate Can be adjusted. For example, when using relatively inexpensive sodium hydroxide as a pH adjusting agent and using sodium bicarbonate as a bicarbonate or carbonate, which is more expensive than sodium hydroxide and also has a pH adjusting function, expensive bicarbonate It is possible to control the supply amount of sodium to the minimum necessary. Since the pH of the wastewater is detected, the amount of sodium hydroxide supplied can be easily controlled. Of course, as the bicarbonate or carbonate, sodium carbonate, calcium carbonate and the like can be used in addition to sodium bicarbonate.

最小限の重炭酸ナトリウムを供給しつつ廃水が中和されるように水酸化ナトリウムを供給することにより、低コストで充分な廃水処理能力を得ることができる。しかも重炭酸ナトリウムの供給量を最小限とすることによって廃水中に多量のカルシウムが含まれている場合であってもカルシウムスケールの発生を防止することができる。   By supplying sodium hydroxide so that the wastewater is neutralized while supplying a minimum amount of sodium bicarbonate, sufficient wastewater treatment capacity can be obtained at low cost. Moreover, the generation of calcium scale can be prevented even when a large amount of calcium is contained in the wastewater by minimizing the supply amount of sodium bicarbonate.

なお、制御をより容易にするために、重炭酸塩又は炭酸塩の供給量は生物処理槽への無機性廃水の供給量（流入量）に応じて一定とし、ｐＨ調整剤の供給量のみを無機性廃水のｐＨ検出結果に基づいて制御するようにしてももちろんかまわない。   In order to make the control easier, the supply amount of bicarbonate or carbonate is constant according to the supply amount (inflow amount) of inorganic wastewater to the biological treatment tank, and only the supply amount of the pH adjusting agent is set. Of course, it may be controlled based on the pH detection result of the inorganic wastewater.

独立栄養性細菌による廃水処理能力が充分発揮できるよう無機炭素源を供給するためには、その制御工程において、無機性廃水に含まれるアンモニア性窒素１ｋｇあたりの重炭酸塩又は炭酸塩の供給量を炭素量として０．１ｋｇ以上となるように制御することが好ましい。無機性廃水に含まれるアンモニア性窒素１ｋｇあたりの重炭酸塩又は炭酸塩の供給量を炭素量として０．５ｋｇ以上となるように制御するとさらに望ましい。   In order to supply the inorganic carbon source so that the wastewater treatment capacity by the autotrophic bacteria can be fully exhibited, in the control process, the supply amount of bicarbonate or carbonate per kg of ammoniacal nitrogen contained in the inorganic wastewater is set. It is preferable to control the carbon amount to be 0.1 kg or more. It is further desirable to control the amount of bicarbonate or carbonate supplied per kg of ammoniacal nitrogen contained in the inorganic wastewater to be 0.5 kg or more as the amount of carbon.

また、その制御工程において、ｐＨの検出結果が６．５以上８．５以下となるようにｐＨ調整剤の供給量と重炭酸塩又は炭酸塩の供給量とを制御することが望ましい。ｐＨが中性に保たれることにより、独立栄養性細菌の処理能力が充分に発揮できるからである。   In the control step, it is desirable to control the supply amount of the pH adjusting agent and the supply amount of bicarbonate or carbonate so that the detection result of pH is 6.5 or more and 8.5 or less. This is because the processing ability of autotrophic bacteria can be sufficiently exhibited by maintaining the pH neutral.

本発明の更なる目的又はその他の特徴は、以下添付図面を参照して説明される好ましい実施例によって明らかにされるであろう。   Further objects and other features of the present invention will become apparent from the preferred embodiments described below with reference to the accompanying drawings.

本発明によれば、独立栄養性細菌（硝化細菌）が活動するのに充分な無機炭素源を供給しつつ低コストに廃水のｐＨ調整を行うことができ、さらにカルシウムスケールの発生を低減することができる。   According to the present invention, it is possible to adjust the pH of wastewater at a low cost while supplying an inorganic carbon source sufficient for the activity of autotrophic bacteria (nitrifying bacteria), and to further reduce the occurrence of calcium scale. Can do.

［実施の形態］
以下、本発明の実施の形態について図面を用いて説明する。図１は、本発明の実施の形態に係る廃水処理装置Ｓの概略構成を示すブロック図である。この廃水処理装置Ｓは、廃水中に含まれるアンモニア性窒素を独立栄養性細菌を用いて硝化する、いわゆる生物処理を行うものである。廃水処理装置Ｓは、給水管１、生物処理槽２、排水管３、水酸化ナトリウム用タンク４、重炭酸ナトリウム用タンク５、水酸化ナトリウム供給ポンプ６、重炭酸ナトリウム供給ポンプ７、ｐＨ検出器８を有して大略構成される。この廃水処理装置Ｓは、給水管１から生物処理槽２内へと供給された無機性廃水が独立栄養性細菌と混合され、活性汚泥法又は生物膜法による無機性廃水の硝化処理が行われて排水管３から排水されるようになっている。排水管３から排水された処理後の廃水は、図示しない後段の嫌気槽（脱窒槽）へと送られるようになっている。 [Embodiment]
Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a block diagram showing a schematic configuration of a wastewater treatment apparatus S according to an embodiment of the present invention. This wastewater treatment apparatus S performs so-called biological treatment in which ammoniacal nitrogen contained in wastewater is nitrified using autotrophic bacteria. The waste water treatment apparatus S includes a water supply pipe 1, a biological treatment tank 2, a drain pipe 3, a sodium hydroxide tank 4, a sodium bicarbonate tank 5, a sodium hydroxide supply pump 6, a sodium bicarbonate supply pump 7, and a pH detector. 8 is generally configured. In this wastewater treatment apparatus S, inorganic wastewater supplied from the water supply pipe 1 into the biological treatment tank 2 is mixed with autotrophic bacteria, and nitrification treatment of inorganic wastewater by the activated sludge method or the biofilm method is performed. The drainage pipe 3 drains the water. The treated wastewater drained from the drainage pipe 3 is sent to an anaerobic tank (denitrification tank) at a later stage (not shown).

水酸化ナトリウム用タンク４内にはｐＨ調整剤としての水酸化ナトリウムが貯留され、重炭酸ナトリウム用タンク５内には無機炭素源としての重炭酸ナトリウムが貯留されている。   Sodium hydroxide as a pH adjusting agent is stored in the sodium hydroxide tank 4, and sodium bicarbonate as an inorganic carbon source is stored in the sodium bicarbonate tank 5.

水酸化ナトリウム用タンク４及び水酸化ナトリウム供給ポンプ６は第１の供給部としての水酸化ナトリウム供給部１１を構成し、ｐＨ検出器８の検出結果に基づいて生物処理槽２内に水酸化ナトリウムを供給する。水酸化ナトリウムの供給量は図示しない供給量制御部によって制御される。   The sodium hydroxide tank 4 and the sodium hydroxide supply pump 6 constitute a sodium hydroxide supply unit 11 as a first supply unit, and sodium hydroxide is introduced into the biological treatment tank 2 based on the detection result of the pH detector 8. Supply. The supply amount of sodium hydroxide is controlled by a supply amount control unit (not shown).

重炭酸ナトリウム用タンク５及び重炭酸ナトリウム供給ポンプ７は第２の供給部としての重炭酸ナトリウム供給部１２を構成し、ｐＨ検出器８の検出結果に基づいて生物処理槽２に重炭酸ナトリウムを供給する。重炭酸ナトリウムの供給量は図示しない供給量制御部によって制御される。   The sodium bicarbonate tank 5 and the sodium bicarbonate supply pump 7 constitute a sodium bicarbonate supply unit 12 as a second supply unit, and sodium bicarbonate is supplied to the biological treatment tank 2 based on the detection result of the pH detector 8. Supply. The supply amount of sodium bicarbonate is controlled by a supply amount control unit (not shown).

ｐＨ検出器８は、生物槽内の無機性廃水のｐＨを常に検出している。その検出結果は供給量制御部へと送られるようになっている。   The pH detector 8 always detects the pH of the inorganic wastewater in the biological tank. The detection result is sent to the supply amount control unit.

次にこの廃水処理装置Ｓの動作について説明する。供給管１を通って無機性廃水が生物処理槽２内へと供給される。この無機性廃水の供給量（流量）は図示しない制御手段によって制御されているが詳細については省略する。   Next, the operation of the waste water treatment apparatus S will be described. Inorganic wastewater is supplied into the biological treatment tank 2 through the supply pipe 1. The supply amount (flow rate) of the inorganic waste water is controlled by a control means (not shown), but the details are omitted.

生物処理槽２内へと流入した無機性廃水のｐＨをｐＨ検出器８が検出する。その検出結果は図示しない供給量制御部へと送られる。供給量制御部は、送られてきた検出結果に基づいて水酸化ナトリウム供給部１１及び重炭酸ナトリウム供給部１２を制御する。その制御に基づいて、水酸化ナトリウム供給部１１及び重炭酸ナトリウム供給部１２はそれぞれ水酸化ナトリウム及び重炭酸ナトリウムを生物処理槽２内へ供給する。   The pH detector 8 detects the pH of the inorganic wastewater that has flowed into the biological treatment tank 2. The detection result is sent to a supply amount control unit (not shown). The supply amount control unit controls the sodium hydroxide supply unit 11 and the sodium bicarbonate supply unit 12 based on the sent detection result. Based on the control, the sodium hydroxide supply unit 11 and the sodium bicarbonate supply unit 12 supply sodium hydroxide and sodium bicarbonate into the biological treatment tank 2, respectively.

重炭酸ナトリウムの供給量は、独立栄養性細菌が硝化能力を充分発揮するように、かつ廃水処理装置Ｓ内へのスケーリングが極力発生しないように調整される。また、水酸化ナトリウムの供給量は、ｐＨ検出器８の検出結果に基づいて重炭酸ナトリウムによる無機性廃水のアルカリ化の程度が考慮されて調整される。生物処理槽２内で処理された硝化後の廃水は処理水として排出管３から排出される。   The supply amount of sodium bicarbonate is adjusted so that the autotrophic bacteria can sufficiently exhibit the nitrification ability and that scaling into the wastewater treatment apparatus S is not generated as much as possible. The supply amount of sodium hydroxide is adjusted based on the detection result of the pH detector 8 in consideration of the degree of alkalinization of the inorganic wastewater with sodium bicarbonate. Waste water after nitrification treated in the biological treatment tank 2 is discharged from the discharge pipe 3 as treated water.

水酸化ナトリウム供給部１１による水酸化ナトリウムの供給量と重炭酸ナトリウム供給部１２による重炭酸ナトリウムの供給量とを一定の比率に設定し、例えばｐＨ検出器８の検出結果が７．０以下になると両供給部１１，１２を稼働させ、検出結果が７．５以上になると両供給部１１，１２を停止させるように制御してもよい。   The amount of sodium hydroxide supplied by the sodium hydroxide supply unit 11 and the amount of sodium bicarbonate supplied by the sodium bicarbonate supply unit 12 are set to a constant ratio. For example, the detection result of the pH detector 8 is 7.0 or less. Then, both supply units 11 and 12 may be operated, and when the detection result becomes 7.5 or more, both supply units 11 and 12 may be controlled to stop.

また、処理前の無機性廃水のアンモニア性窒素濃度を常に検出し、その検出結果及び無機性廃水の供給量から単位時間当たりの重炭酸ナトリウムの必要供給量を演算し、その必要量に基づいて重炭酸ナトリウムの供給量を自動制御してもよい。この場合において、処理前の無機性廃水のアンモニア性窒素濃度やその供給量が想定範囲を下回った場合に重炭酸ナトリウムの供給量を０としてもかまわない。   In addition, the ammonia nitrogen concentration in the inorganic wastewater before treatment is always detected, and the required amount of sodium bicarbonate per unit time is calculated from the detection result and the amount of inorganic wastewater supplied. The amount of sodium bicarbonate supplied may be automatically controlled. In this case, the supply amount of sodium bicarbonate may be set to 0 when the concentration of ammoniacal nitrogen in the inorganic wastewater before treatment and the supply amount thereof are below the assumed range.

以上、本発明の好ましい実施の形態を説明したが、本発明はこれらに限定されるものではなく、その要旨の範囲内で様々な変形や変更が可能である。   As mentioned above, although preferable embodiment of this invention was described, this invention is not limited to these, A various deformation | transformation and change are possible within the range of the summary.

本願発明の発明者らが、重炭酸ナトリウムと水酸化ナトリウムとを併用した場合の硝化能力について流動床方式担体（充填率２０％）を用いて鋭意検討した結果、以下の検討結果を得た。なお、通水に使用した無機性廃水の組成を表１に示す。希釈には水道水を使用し、通水流量は、容積負荷が１．０ｋｇ−Ｎ／ｍ３／ｄａｙとなるように調整した。 The inventors of the present invention diligently studied the nitrification ability when sodium bicarbonate and sodium hydroxide were used in combination using a fluidized bed type carrier (packing rate: 20%), and the following results were obtained. Table 1 shows the composition of the inorganic wastewater used for water flow. Tap water was used for dilution, and the water flow rate was adjusted so that the volumetric load was 1.0 kg-N / m 3 / day.

Figure 2006167574
本実施例によって得られた結果を表２及び図２に示す。
Figure 2006167574
 The results obtained by this example are shown in Table 2 and FIG.

Figure 2006167574
Figure 2006167574

本発明の実施の形態に係る廃水処理装置の概略構成を示すブロック図である。It is a block diagram which shows schematic structure of the waste water treatment apparatus which concerns on embodiment of this invention. 本発明の実施例の結果を示すグラフである。It is a graph which shows the result of the Example of this invention.

符号の説明Explanation of symbols

Ｓ：廃水処理装置
１：給水管
２：生物処理槽
３：排水管
４：水酸化ナトリウム用タンク
５：重炭酸ナトリウム用タンク
６：水酸化ナトリウム供給ポンプ
７：重炭酸ナトリウム供給ポンプ
８：ｐＨ検出器
１１：水酸化ナトリウム供給部（第１の供給部）
１２：重炭酸ナトリウム供給部（第２の供給部） S: Wastewater treatment device 1: Water supply pipe 2: Biological treatment tank 3: Drainage pipe 4: Sodium hydroxide tank 5: Sodium bicarbonate tank 6: Sodium hydroxide supply pump 7: Sodium bicarbonate supply pump 8: pH detection Device 11: Sodium hydroxide supply unit (first supply unit)
12: Sodium bicarbonate supply unit (second supply unit)

Claims (6)

アンモニア性窒素を含む無機性廃水を生物処理によって硝化する廃水処理装置であって、
前記無機性廃水と独立栄養性細菌とが混合される生物処理槽と、
該生物処理槽内に供給された前記無機性廃水のｐＨを検出するｐＨ検出器と、
該生物処理槽内のｐＨを調整するｐＨ調整剤を該生物処理槽に供給する第１の供給部と、
該生物処理槽内に無機炭素源を供給する第２の供給部と、
前記ｐＨ検出器の検出結果に基づいて前記ｐＨ調整剤の供給量と前記無機炭素源の供給量とを制御する供給量制御部とを有することを特徴とする廃水処理装置。 A wastewater treatment apparatus for nitrifying inorganic wastewater containing ammonia nitrogen by biological treatment,
A biological treatment tank in which the inorganic wastewater and autotrophic bacteria are mixed;
A pH detector for detecting the pH of the inorganic wastewater supplied into the biological treatment tank;
A first supply unit for supplying a pH adjusting agent for adjusting the pH in the biological treatment tank to the biological treatment tank;
A second supply unit for supplying an inorganic carbon source into the biological treatment tank;
A wastewater treatment apparatus comprising: a supply amount control unit that controls a supply amount of the pH adjusting agent and a supply amount of the inorganic carbon source based on a detection result of the pH detector. 前記ｐＨ調整剤が水酸化ナトリウムであり、かつ前記無機炭素源が重炭酸塩又は炭酸塩であることを特徴とする請求項１に記載の廃水処理装置。   The wastewater treatment apparatus according to claim 1, wherein the pH adjuster is sodium hydroxide, and the inorganic carbon source is bicarbonate or carbonate. 前記無機性廃水が１００ｍｇ／ｌ以上のカルシウムを含有することを特徴とする請求項１に記載の廃水処理装置。   The wastewater treatment apparatus according to claim 1, wherein the inorganic wastewater contains 100 mg / l or more calcium. アンモニア性窒素を含む無機性廃水を生物処理槽内へ供給する工程と、
該供給された無機性廃水のｐＨを検出する工程と、
前記生物処理槽内のｐＨを調整するｐＨ調整剤を前記生物処理槽に供給する工程と、
前記生物処理槽内へ前記無機性廃水のｐＨを調整するとともに独立栄養性細菌の炭素源として機能する重炭酸塩又は炭酸塩を供給する工程と、
前記ｐＨの検出結果に基づいて前記ｐＨ調整剤の供給量と前記重炭酸塩又は炭酸塩の供給量とを制御する工程とを有することを特徴とする廃水の生物処理方法。 Supplying inorganic wastewater containing ammonia nitrogen into the biological treatment tank;
Detecting the pH of the supplied inorganic wastewater;
Supplying a pH adjusting agent for adjusting the pH in the biological treatment tank to the biological treatment tank;
Adjusting the pH of the inorganic wastewater into the biological treatment tank and supplying bicarbonate or carbonate that functions as a carbon source for autotrophic bacteria;
A biological treatment method of wastewater, comprising a step of controlling a supply amount of the pH adjusting agent and a supply amount of the bicarbonate or carbonate based on a detection result of the pH. 前記制御工程において、前記無機性廃水に含まれる前記アンモニア性窒素１ｋｇあたりの前記重炭酸塩又は炭酸塩の供給量を炭素量として０．１ｋｇ以上となるように制御することを特徴する請求項４に記載の廃水の生物処理方法。   5. In the control step, the supply amount of the bicarbonate or carbonate per kg of the ammoniacal nitrogen contained in the inorganic waste water is controlled to be 0.1 kg or more as a carbon amount. A biological treatment method for wastewater as described in 1. 前記制御工程において、前記ｐＨの検出結果が６．５以上８．５以下となるように前記ｐＨ調整剤の供給量と前記重炭酸塩又は炭酸塩の供給量とを制御することを特徴とする請求項４に記載の廃水の生物処理方法。
In the control step, the supply amount of the pH adjusting agent and the supply amount of the bicarbonate or carbonate are controlled so that the detection result of the pH is 6.5 or more and 8.5 or less. A biological treatment method for wastewater according to claim 4.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010137152A (en) * 2008-12-10 2010-06-24 Hitachi Plant Technologies Ltd Method and apparatus for treating wastewater
JP2011183247A (en) * 2010-03-04 2011-09-22 Kobelco Eco-Solutions Co Ltd Water treatment apparatus and water treatment method
KR101204607B1 (en) 2011-07-14 2012-11-23 서울시립대학교 산학협력단 Nitrogen ammonia concentration detecting method
WO2013015128A1 (en) * 2011-07-22 2013-01-31 栗田工業株式会社 Biological treatment method and treatment device for amine-containing waste water
KR101249601B1 (en) 2011-07-14 2013-04-01 서울시립대학교 산학협력단 nitrogen ammonia concentration measuring agent and the kit using thereof
WO2024262073A1 (en) * 2023-06-20 2024-12-26 オルガノ株式会社 Water treatment apparatus and water treatment method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53128146A (en) * 1977-04-15 1978-11-08 Japan Gasoline Improvement of method of treating drainage utilizing biological nitrification
JPS56111097A (en) * 1980-02-07 1981-09-02 Hitachi Plant Eng & Constr Co Ltd Treatment of waste water
JP2001276851A (en) * 2000-03-29 2001-10-09 Japan Organo Co Ltd Drain treatment equipment
JP2002086190A (en) * 2000-09-12 2002-03-26 Japan Organo Co Ltd Waste water treating device
WO2004074191A1 (en) * 2003-02-21 2004-09-02 Kurita Water Industries Ltd. Method for treating water containing ammonia nitrogen
JP2004255269A (en) * 2003-02-25 2004-09-16 Kurita Water Ind Ltd Denitrification method and denitrification device
JP2006167549A (en) * 2004-12-14 2006-06-29 Kurita Water Ind Ltd Nitrogen compound and inorganic ion-containing wastewater treatment apparatus and treatment method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53128146A (en) * 1977-04-15 1978-11-08 Japan Gasoline Improvement of method of treating drainage utilizing biological nitrification
JPS56111097A (en) * 1980-02-07 1981-09-02 Hitachi Plant Eng & Constr Co Ltd Treatment of waste water
JP2001276851A (en) * 2000-03-29 2001-10-09 Japan Organo Co Ltd Drain treatment equipment
JP2002086190A (en) * 2000-09-12 2002-03-26 Japan Organo Co Ltd Waste water treating device
WO2004074191A1 (en) * 2003-02-21 2004-09-02 Kurita Water Industries Ltd. Method for treating water containing ammonia nitrogen
JP2004255269A (en) * 2003-02-25 2004-09-16 Kurita Water Ind Ltd Denitrification method and denitrification device
JP2006167549A (en) * 2004-12-14 2006-06-29 Kurita Water Ind Ltd Nitrogen compound and inorganic ion-containing wastewater treatment apparatus and treatment method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010137152A (en) * 2008-12-10 2010-06-24 Hitachi Plant Technologies Ltd Method and apparatus for treating wastewater
JP2011183247A (en) * 2010-03-04 2011-09-22 Kobelco Eco-Solutions Co Ltd Water treatment apparatus and water treatment method
KR101204607B1 (en) 2011-07-14 2012-11-23 서울시립대학교 산학협력단 Nitrogen ammonia concentration detecting method
KR101249601B1 (en) 2011-07-14 2013-04-01 서울시립대학교 산학협력단 nitrogen ammonia concentration measuring agent and the kit using thereof
WO2013015128A1 (en) * 2011-07-22 2013-01-31 栗田工業株式会社 Biological treatment method and treatment device for amine-containing waste water
JP2013022536A (en) * 2011-07-22 2013-02-04 Kurita Water Ind Ltd Biological treatment method for amine-containing wastewater and treatment equipment
WO2024262073A1 (en) * 2023-06-20 2024-12-26 オルガノ株式会社 Water treatment apparatus and water treatment method

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