JP4835536B2 - Removal of organic substances and nitrogen from liquid to be treated - Google Patents

Removal of organic substances and nitrogen from liquid to be treated Download PDF

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JP4835536B2
JP4835536B2 JP2007206671A JP2007206671A JP4835536B2 JP 4835536 B2 JP4835536 B2 JP 4835536B2 JP 2007206671 A JP2007206671 A JP 2007206671A JP 2007206671 A JP2007206671 A JP 2007206671A JP 4835536 B2 JP4835536 B2 JP 4835536B2
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立夫 角野
和一 井坂
創 生田
祐子 向井
豊一 横田
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Hitachi Plant Technologies Ltd
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本発明は、一の嫌気性処理槽内において行われる被処理液の有機物と窒素の除去方法、該方法に用いられ得る微生物を収容したグラニュール、馴養用溶液及びグラニュールや担体を用いた有機物と窒素の除去装置に関する。   The present invention relates to a method for removing organic matter and nitrogen in a liquid to be treated performed in one anaerobic treatment tank, granule containing microorganisms that can be used in the method, organic solution using a conditioned solution, granule and carrier. And nitrogen removal device.

ビール工場排水等の有機性排水には、ＢＯＤ（生物化学的酸素消費量）成分である糖類、有機酸等の有機物とともに、アンモニア態窒素も豊富に含まれている。排水中のアンモニア態窒素は、河川等の富栄養化の原因となるため、環境保護の点から、排水中の有機物とアンモニア態窒素は効率よく除去されることが好ましい。特に近年の総量規制の強化に伴い、排水中の窒素含有量を低減する必要が高まっている。このため、コストを抑えながらも効率的に有機物と窒素の両方を除去する方法の開発が待たれている。   Organic wastewater such as beer factory wastewater contains abundant ammonia nitrogen as well as organic substances such as saccharides and organic acids, which are BOD (biochemical oxygen consumption) components. Since ammonia nitrogen in the wastewater causes eutrophication of rivers and the like, it is preferable that organic matter and ammonia nitrogen in the wastewater are efficiently removed from the viewpoint of environmental protection. In particular, with the recent tightening of total amount regulations, there is an increasing need to reduce the nitrogen content in wastewater. For this reason, development of the method of removing both organic substance and nitrogen efficiently while waiting for cost is awaited.

有機性排水を浄化する場合、一般的には、メタン発酵等の嫌気性処理により有機物の大部分を除去した後に、アンモニア態窒素を硝化・脱窒工程によって窒素ガスまで分解して窒素を除去する。具体的には、好気条件下における硝化工程において、独立栄養性細菌であるアンモニア酸化細菌と亜硝酸酸化細菌によって、アンモニア態窒素が酸化され、亜硝酸態窒素や硝酸態窒素が生成される。その後、嫌気性条件下における脱窒工程において、従属栄養性脱窒菌によって、亜硝酸態窒素及び硝酸態窒素から窒素ガスが生成される。   When purifying organic wastewater, in general, after removing most of organic matter by anaerobic treatment such as methane fermentation, nitrogen is removed by decomposing ammonia nitrogen into nitrogen gas through nitrification and denitrification processes. . Specifically, in the nitrification step under aerobic conditions, ammonia nitrogen is oxidized by ammonia oxidizing bacteria and nitrite oxidizing bacteria, which are autotrophic bacteria, and nitrite nitrogen and nitrate nitrogen are generated. Thereafter, in the denitrification step under anaerobic conditions, nitrogen gas is generated from nitrite nitrogen and nitrate nitrogen by heterotrophic denitrifying bacteria.

近年、独立栄養性脱窒微生物群を利用した新しい排水の窒素処理方法（嫌気アンモニア酸化、アナモックス（ＡＮＡＭＭＯＸ）法等と呼ばれる）が実用化されつつある。該独立栄養性脱窒微生物群を利用した排水の窒素処理方法として、例えば、（１）アンモニアおよび亜硝酸性窒素を含有する排液を脱窒槽の下部から脱窒槽内へ供給する排液の供給工程と、脱窒槽内においてアンモニアを電子供与体とし、かつ亜硝酸を電子受容体として脱窒反応を行う独立栄養性脱窒微生物のグラニュールと前記排液を接触させて生物学的に脱窒処理する生物学的処理工程と、処理液を脱窒槽の上部から排出する排出工程とを有する排液の脱窒方法が開示されている（例えば、引用文献１参照。）。つまり、独立栄養性脱窒微生物は、嫌気条件下で、アンモニア態窒素を電子供与体とし、亜硝酸態窒素を電子受容体として脱窒反応を行うことができるため、大量の曝気が必要な硝化工程と、電子供与体として有機物の添加が必要な脱窒工程により構成される従来法と比較して、コストを大幅に削減し得ることが期待される。
特開２００２−３４６５９３号公報 In recent years, new wastewater nitrogen treatment methods (referred to as anaerobic ammonia oxidation, anammox methods, etc.) using autotrophic denitrifying microorganisms have been put into practical use. As a nitrogen treatment method of waste water using the autotrophic denitrifying microorganism group, for example, (1) Supply of waste liquid that supplies waste liquid containing ammonia and nitrite nitrogen from the lower part of the denitrification tank to the denitrification tank A biological denitrification process by contacting the effluent with a granule of an autotrophic denitrifying microorganism that performs denitrification using ammonia as an electron donor and nitrous acid as an electron acceptor in a denitrification tank. A waste liquid denitrification method having a biological treatment process to be processed and a discharge process for discharging the treatment liquid from the upper part of the denitrification tank is disclosed (for example, refer to Citation 1). In other words, autotrophic denitrifying microorganisms can perform a denitrification reaction using ammonia nitrogen as an electron donor and nitrite nitrogen as an electron acceptor under anaerobic conditions. It is expected that the cost can be greatly reduced as compared with a conventional method constituted by a process and a denitrification process that requires addition of an organic substance as an electron donor.
JP 2002-346593 A

しかしながら、該独立栄養性脱窒微生物を用いて排水処理を行うには、さまざまな問題点がある。例えば、該脱窒微生物は、独立栄養性微生物であり、多量の有機物の存在下では他の微生物に対して優位に増殖できない。具体的には、該脱窒微生物による脱窒反応を達成するためには、排水中のＢＯＤが５０ｍｇ／Ｌ以下となる程度に有機物を除去して、脱窒微生物が優先的に増殖できるようにすることが必要である。その他、該脱窒微生物は、酸素に対する感受性が高く、排水中の微量の酸素によって阻害されるため、脱窒活性が低下するという問題もある。
したがって、従来は、該脱窒微生物による脱窒反応は、高度に嫌気的な環境下で、メタン発酵等の嫌気性処理により有機物を除去した後に活性汚泥を絞って得られる脱離液や、無機排水等に対して行われており、メタン発酵槽内で、メタン発酵と同時に該脱窒反応を行うことは非常に困難であった。このため、ある排水に対して、メタン発酵による有機物除去処理と、該脱窒微生物による脱窒処理を行う場合には、まず、メタン発酵槽においてメタン発酵を行った後、メタン発酵槽等から濾過等により脱離液を調製し、該脱離液を、脱窒処理用槽へ移送して脱窒処理を行わなくてはならず、除去工程が多く煩雑であり、大掛かりな除去装置が必要であった。 However, there are various problems in performing wastewater treatment using the autotrophic denitrifying microorganism. For example, the denitrifying microorganism is an autotrophic microorganism and cannot proliferate predominantly over other microorganisms in the presence of a large amount of organic matter. Specifically, in order to achieve the denitrification reaction by the denitrifying microorganism, the organic matter is removed so that the BOD in the wastewater is 50 mg / L or less so that the denitrifying microorganism can proliferate preferentially. It is necessary to. In addition, since the denitrifying microorganism is highly sensitive to oxygen and is inhibited by a small amount of oxygen in the waste water, there is a problem that the denitrifying activity is lowered.
Therefore, conventionally, the denitrification reaction by the denitrifying microorganism has been carried out in a highly anaerobic environment by removing the organic matter by anaerobic treatment such as methane fermentation and then squeezing the activated sludge, It has been carried out on wastewater and so on, and it has been very difficult to carry out the denitrification reaction simultaneously with methane fermentation in a methane fermentation tank. For this reason, when organic matter removal treatment by methane fermentation and denitrification treatment by the denitrifying microorganism are performed on a certain wastewater, first, methane fermentation is performed in the methane fermentation tank, and then filtered from the methane fermentation tank or the like. It is necessary to prepare a desorbing solution, etc., and transfer the desorbing solution to a denitrification treatment tank to perform a denitrification treatment, which requires many removal steps and a large removal device. there were.

本発明は、メタン発酵等の嫌気性処理と、独立栄養性脱窒微生物を用いた脱窒処理とを、一の嫌気性処理槽内において行うことができる、被処理液の有機物と窒素の除去方法、該方法に用いられ得る微生物を収容したグラニュール、馴養用溶液及びグラニュールや担体を用いた有機物と窒素の除去装置を提供することを目的とする。   The present invention is capable of performing anaerobic treatment such as methane fermentation and denitrification treatment using an autotrophic denitrifying microorganism in one anaerobic treatment tank, and removing organic substances and nitrogen from the liquid to be treated. It is an object of the present invention to provide a method, a granule containing microorganisms that can be used in the method, an acclimatization solution, and an organic substance and nitrogen removing apparatus using the granule and carrier.

本発明者らは、上記課題を解決すべく鋭意研究した結果、一の嫌気性処理槽内に、嫌気性処理用微生物を収容する第１層と、独立栄養性脱窒微生物を収容した第２層を設け、被処理液を、最初に第１層に接触させて、該被処理液中の有機物を除去した後に、該第２層に接触させることにより、該第２層において、独立栄養性脱窒微生物による脱窒反応を良好に進行させ得ることを見出し、本発明を完成させた。   As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have a first layer containing anaerobic microorganisms and a second layer containing autotrophic denitrifying microorganisms in one anaerobic treatment tank. An autotrophic layer is provided in the second layer by providing a layer and bringing the liquid to be treated into contact with the first layer by first removing organic substances in the liquid to be treated and then contacting the second layer. The present inventors have found that the denitrification reaction by the denitrifying microorganism can proceed well, and completed the present invention.

すなわち、本発明の第１の態様は、嫌気性処理槽を用いて、有機物と窒素を含有する被処理液から有機物と窒素を除去する方法において、前記嫌気性処理槽が、嫌気性処理用微生物を収容した第１層と、独立栄養性脱窒微生物を収容した第２層を有し、（ａ） 前記被処理液を、嫌気性処理用微生物を収容した第１層に接触させ、嫌気性処理により有機物を分解する工程と、（ｂ） 前記第１層に接触させた後の被処理液を、独立栄養性脱窒微生物を収容した第２層に接触させ、脱窒を行う工程とを有し、前記工程（ａ）〜（ｂ）を１回以上行い、前記嫌気性処理槽内の酸化還元電位を、−３８０〜−２８０ｍＶに制御することを特徴とする、被処理液の有機物と窒素の除去方法である。 That is, the first aspect of the present invention is a method for removing organic matter and nitrogen from a liquid to be treated containing an organic matter and nitrogen using an anaerobic treatment bath, wherein the anaerobic treatment vessel is an anaerobic treatment microorganism. And a second layer containing autotrophic denitrifying microorganisms, and (a) bringing the liquid to be treated into contact with the first layer containing anaerobic microorganisms, anaerobic A step of decomposing an organic substance by treatment, and (b) a step of bringing the liquid to be treated after being brought into contact with the first layer into contact with a second layer containing autotrophic denitrifying microorganisms and performing denitrification. We have, have the step (a) ~ row at least once (b), the redox potential of the anaerobic treatment tank, and controlling the -380~-280mV, organic liquid to be treated And nitrogen removal method .

本発明の第１の態様及び第２の態様である被処理液の有機物と窒素の除去方法により、メタン発酵等の嫌気性処理と独立栄養性脱窒微生物を用いた脱窒処理とを、一の嫌気性処理槽内において行うことができる。このため、嫌気性処理と脱窒処理とを別個の反応槽にて行う従来法に比べて、除去装置のコンパクト化及び処理工程の簡略化が図られ、有機物及び窒素の除去に要するコストの低減も期待することができる。また、独立栄養性脱窒微生物を用いた脱窒処理を行うことができる排水種が拡大し、屎尿排水等の一般的な有機性排水の脱窒が可能となる。
また、本発明の第３の態様であるグラニュール、並びに本発明の第５の態様及び本発明の第６の態様である有機物と窒素の除去装置を用いることにより、排水等被処理液の有機物及び窒素の除去を、より簡便かつ低コストで行うことが可能となる。
さらに、本発明の第４の態様である馴養用溶液を用いることにより、本発明の第２の態様で用いられるグラニュールや担体を、簡便かつ効率よく作製することができる。 According to the first aspect and the second aspect of the present invention, the organic matter and nitrogen removal method of the liquid to be treated includes an anaerobic treatment such as methane fermentation and a denitrification treatment using an autotrophic denitrification microorganism. In an anaerobic treatment tank. For this reason, compared with the conventional method in which anaerobic treatment and denitrification treatment are performed in separate reaction vessels, the removal apparatus can be made compact and the treatment process can be simplified, and the cost required for removing organic substances and nitrogen can be reduced. Can also expect. In addition, the number of drainage species that can be denitrified using autotrophic denitrifying microorganisms is expanded, and denitrification of general organic wastewater such as manure wastewater becomes possible.
Further, by using the granule according to the third aspect of the present invention, and the organic matter and nitrogen removing apparatus according to the fifth aspect of the present invention and the sixth aspect of the present invention, the organic matter of the liquid to be treated such as waste water. In addition, nitrogen can be removed more easily and at low cost.
Furthermore, by using the acclimatization solution according to the fourth aspect of the present invention, the granules and carriers used in the second aspect of the present invention can be easily and efficiently produced.

まず、本発明の第１の態様について説明する。
本発明における被処理液は、有機物と窒素を含有する液であれば、特に限定されるものではない。また、該被処理液に含まれる窒素の形態は特に限定されるものではないが、有機態窒素、アンモニア態窒素、硝酸態窒素や亜硝酸態窒素であることが好ましい。有機態窒素は嫌気性処理により、独立栄養性脱窒微生物による脱窒処理に供されるアンモニア態窒素や亜硝酸態窒素に分解され得る。該被処理液として、例えば、ビール工場等の食品工場の産業排水や生活排水等の排水や、河川、湖沼、海水等の自然水等がある。 First, the first aspect of the present invention will be described.
The to-be-processed liquid in this invention will not be specifically limited if it is a liquid containing organic substance and nitrogen. Further, the form of nitrogen contained in the liquid to be treated is not particularly limited, but organic nitrogen, ammonia nitrogen, nitrate nitrogen, and nitrite nitrogen are preferable. Organic nitrogen can be decomposed by anaerobic treatment into ammonia nitrogen and nitrite nitrogen that are subjected to denitrification treatment by autotrophic denitrifying microorganisms. Examples of the liquid to be treated include wastewater such as industrial wastewater and domestic wastewater from food factories such as beer factories, natural water such as rivers, lakes, and seawater.

本発明において、嫌気性処理とは、嫌気性微生物により有機物を分解する処理であって、通常排水等に含有されている有機物を除去するために用いられる処理であれば、特に限定されるものではないが、メタン発酵であることが好ましい。メタン発酵は、有機物の分解処理と同時に、エネルギーとして利用可能なメタンを生成することができ、かつ、余剰汚泥が少ないためである。
本発明において、嫌気性処理槽とは、嫌気性処理を行うための反応槽であり、通常、排水等の嫌気性処理に用いられる反応槽であれば、特に限定されるものではないが、メタン発酵槽であることが好ましい。 In the present invention, the anaerobic treatment is a treatment for decomposing organic matter by anaerobic microorganisms, and is not particularly limited as long as it is a treatment used for removing organic matter usually contained in waste water or the like. Although not, methane fermentation is preferred. This is because methane fermentation can produce methane that can be used as energy at the same time as the decomposition of organic matter, and there is little excess sludge.
In the present invention, the anaerobic treatment tank is a reaction tank for performing anaerobic treatment, and is not particularly limited as long as it is a reaction tank used for anaerobic treatment such as waste water. A fermenter is preferred.

本発明における嫌気性処理用微生物は、有機物を分解し得る嫌気性微生物であれば、特に限定されるものではなく、任意のものを用いることができる。例えば、メタン発酵処理に用いられている微生物（メタン発酵微生物）や、従属栄養性脱窒菌であることが好ましい。該メタン発酵微生物は、メタン発酵処理において用いられる微生物であれば特に限定されるものではなく、通常用いられているメタン発酵汚泥中に存在する微生物であってもよい。該微生物として、例えば、有機物の加水分解・酸生成反応を担う酸生成菌、酸生成反応の結果生じる中間代謝脂肪酸を酢酸と水素に分解する水素生成酢酸化菌、酢酸をメタンガスに転換する酢酸資化性メタン菌や水素をメタンガスに転換する水素資化性メタン菌、メタンを酸化するメタン酸化菌等がある。
本発明の嫌気性処理用微生物として、予め単離・精製された微生物を用いてもよく、有機物を含む排水等を嫌気的に分解させたものから採取した微生物を用いてもよい。その他、既存のメタン発酵槽や脱窒槽等より採取した汚泥や、嫌気性処理用微生物群が存在する環境より採取した汚泥等を用いてもよい。通常、これらの汚泥中には、嫌気性処理に関与する様々な微生物が存在しているためである。 The anaerobic treatment microorganism in the present invention is not particularly limited as long as it is an anaerobic microorganism capable of decomposing organic matter, and any microorganism can be used. For example, a microorganism (methane fermentation microorganism) used for methane fermentation treatment or a heterotrophic denitrifying bacterium is preferable. The methane fermentation microorganism is not particularly limited as long as it is a microorganism used in methane fermentation treatment, and may be a microorganism present in methane fermentation sludge that is usually used. Examples of the microorganism include acid-producing bacteria responsible for hydrolysis and acid-generating reactions of organic substances, hydrogen-producing acetic acid bacteria that decompose intermediate metabolic fatty acids resulting from the acid-producing reaction into acetic acid and hydrogen, and acetic acid resources that convert acetic acid into methane gas. There are hydrous methane bacteria, hydrogen-utilizing methane bacteria that convert hydrogen into methane gas, methane-oxidizing bacteria that oxidize methane, and the like.
As the anaerobic treatment microorganism of the present invention, a microorganism isolated and purified in advance may be used, or a microorganism collected from an anaerobically decomposed wastewater containing organic matter may be used. In addition, sludge collected from an existing methane fermentation tank, denitrification tank, or the like, or sludge collected from an environment where anaerobic microorganisms exist may be used. This is because these sludges usually contain various microorganisms that are involved in anaerobic treatment.

本発明における独立栄養性脱窒微生物は、嫌気条件下で、アンモニア態窒素を電子供与体とし、亜硝酸態窒素を電子受容体とした脱窒反応（アナモックス反応）を行うことができる微生物であれば、特に限定されるものではなく、任意のものを用いることができる。該独立栄養性脱窒微生物として、例えば、アナモックス菌群がある。
本発明の独立栄養性脱窒微生物として、予め単離・精製された微生物を用いてもよく、アンモニア態窒素と亜硝酸態窒素を含む排水等を嫌気的に分解させたものから採取した微生物を用いてもよい。その他、既存のアナモックス反応槽等より採取した汚泥や、独立栄養性脱窒微生物群が存在する環境より採取した汚泥等を用いてもよい。 The autotrophic denitrifying microorganism in the present invention may be a microorganism capable of performing a denitrification reaction (anammox reaction) using ammonia nitrogen as an electron donor and nitrite nitrogen as an electron acceptor under anaerobic conditions. If it is not specifically limited, arbitrary things can be used. Examples of the autotrophic denitrifying microorganism include the anammox bacteria group.
As the autotrophic denitrifying microorganism of the present invention, a microorganism isolated and purified in advance may be used. A microorganism collected from anaerobically decomposed wastewater containing ammonia nitrogen and nitrite nitrogen is used. It may be used. In addition, sludge collected from an existing Anammox reaction tank or the like, or sludge collected from an environment where autotrophic denitrifying microorganisms exist may be used.

嫌気性処理用微生物を収容した第１層や、独立栄養性脱窒微生物を収容した第２層等の、微生物を収容した微生物層は、１種類の微生物からなる層であってもよく、複数種類の微生物からなる層であってもよい。また、これらの微生物層は、微生物を密集して存在させ得るものであれば、特に限定されるものではなく、層状、平板状、球状、筒状等のどのような形態であってもよい。このような微生物層として、例えば、微生物が自己造粒したグラニュールや、微生物を固定した担体等がある。該グラニュールとして、例えば、メタン菌や酸生成菌等の嫌気性処理用微生物が棲息する嫌気性排水処理装置より採取した顆粒状の自己造粒汚泥であるメタン発酵グラニュール等がある。また、該微生物を固定した担体としては、例えば、ポリエステル等の不織布に微生物を付着固定させたものや、非生物担体の周りに微生物膜を形成させることにより作製されたグラニュール等がある。該非生物担体は、通常グラニュール作製のための核として用いられるものであれば、特に限定されるものではなく、例えば、粒径１０〜５００μｍの活性炭やケイ砂等がある。その他、該微生物を固定した担体は、ゲル材料を用いて微生物を包括した包括担体であってもよい。該ゲル材料は、包括する微生物の種類等を考慮して適宜決定することができるが、アクリルアミド／メチレンビスアクリルアミドゲルやポリエチレングリコール（ＰＥＧ）プレポリマー等であることが好ましい。該微生物を固定した担体が包括担体である場合には、簡便に多種多様な形態の微生物層を形成することができる。   The microorganism layer containing microorganisms, such as the first layer containing anaerobic microorganisms and the second layer containing autotrophic denitrifying microorganisms, may be a layer composed of one type of microorganism, It may be a layer composed of various types of microorganisms. In addition, these microorganism layers are not particularly limited as long as microorganisms can be densely present, and may be in any form such as layered, flat, spherical, and cylindrical. Examples of such a microbial layer include granules in which microorganisms are self-granulated and carriers on which microorganisms are fixed. Examples of the granule include a methane fermentation granule that is a granular self-granulating sludge collected from an anaerobic wastewater treatment apparatus inhabited by anaerobic microorganisms such as methane bacteria and acid-producing bacteria. Examples of the carrier on which the microorganisms are fixed include those in which microorganisms are adhered and fixed on a nonwoven fabric such as polyester, and granules produced by forming a microorganism film around a non-biological carrier. The non-biological carrier is not particularly limited as long as it is normally used as a nucleus for producing granules, and examples thereof include activated carbon and silica sand having a particle diameter of 10 to 500 μm. In addition, the carrier on which the microorganisms are immobilized may be a comprehensive carrier in which microorganisms are included using a gel material. The gel material can be appropriately determined in consideration of the types of microorganisms to be included, but is preferably an acrylamide / methylenebisacrylamide gel, a polyethylene glycol (PEG) prepolymer, or the like. When the carrier on which the microorganism is immobilized is a entrapping carrier, a variety of microbial layers can be easily formed.

本発明の第１の態様である被処理液の有機物と窒素の除去方法は、嫌気性処理槽を用いて、有機物と窒素を含有する被処理液から有機物と窒素を除去する方法であり、前記嫌気性処理槽が、嫌気性処理用微生物を収容した第１層と、独立栄養性脱窒微生物を収容した第２層を有し、（ａ） 前記被処理液を、嫌気性処理用微生物を収容した第１層に接触させ、嫌気性処理により有機物を分解する工程と、（ｂ） 前記第１層に接触させた後の被処理液を、独立栄養性脱窒微生物を収容した第２層に接触させ、脱窒を行う工程とを有し、前記工程（ａ）〜（ｂ）を１回以上行うことを特徴とする。独立栄養性脱窒微生物を、嫌気性処理用微生物等の他の微生物から予め分離しておくことにより、有機物を多く含む被処理液中においても、独立栄養性脱窒微生物をより効果的に維持し増殖させることができる。   The method for removing organic matter and nitrogen in a liquid to be treated according to the first aspect of the present invention is a method for removing organic matter and nitrogen from a liquid to be treated containing an organic matter and nitrogen using an anaerobic treatment tank, The anaerobic treatment tank has a first layer containing anaerobic processing microorganisms and a second layer containing autotrophic denitrifying microorganisms, and (a) the liquid to be treated is treated with anaerobic processing microorganisms. A step of contacting the first layer accommodated and decomposing the organic matter by anaerobic treatment; and (b) a second layer containing the autotrophic denitrifying microorganisms as the liquid to be treated after contacting the first layer. And performing the denitrification, and performing the steps (a) to (b) at least once. By pre-separating autotrophic denitrifying microorganisms from other microorganisms such as anaerobic microorganisms, the autotrophic denitrifying microorganisms can be more effectively maintained even in liquids containing a large amount of organic matter. And can be grown.

本発明の有機物と窒素の除去方法においては、該嫌気性処理槽内において、有機物と窒素を含有する被処理液を、各微生物層に接触させる順番が重要であり、最初に第１層に接触させた後、第２層に接触させる。被処理液を第１層に接触させると、第１層に収容されている嫌気性処理用微生物によって、被処理液に溶存している有機物が分解除去される。その後、第２層に接触させることにより、第２層に収容されている独立栄養性脱窒微生物によって、元々該被処理液中に含まれていたアンモニア態窒素や、第１層での嫌気性処理により生成されたアンモニア態窒素、硝酸態窒素や亜硝酸態窒素等から、窒素が除去される。   In the organic matter and nitrogen removal method of the present invention, the order in which the liquid to be treated containing the organic matter and nitrogen is brought into contact with each microorganism layer in the anaerobic treatment tank is important. And then contact the second layer. When the liquid to be treated is brought into contact with the first layer, the organic matter dissolved in the liquid to be treated is decomposed and removed by the anaerobic microorganisms contained in the first layer. Thereafter, by contacting with the second layer, by the autotrophic denitrifying microorganisms contained in the second layer, ammonia nitrogen originally contained in the liquid to be treated or anaerobic in the first layer Nitrogen is removed from ammonia nitrogen, nitrate nitrogen, nitrite nitrogen, and the like produced by the treatment.

例えば、該嫌気性処理用微生物として既存のメタン発酵槽から採取した汚泥等を用いた場合には、該第１層には、通常、酢酸資化性メタン菌や従属栄養性脱窒菌が収容されており、メタン発酵や従属栄養性脱窒反応により溶存している有機物が除去される。この時、酢酸資化性メタン菌によるメタン発酵により、独立栄養微生物の炭素源となり得る炭酸イオンも生成される。また、メタン酸化菌、メタン発酵菌やアナモックス菌群の共役反応により、アンモニウムイオンの一部は亜硝酸イオンや硝酸イオンに酸化されるものと考えられる。特にメタン酸化菌が結合酸素を利用してアンモニアイオンの一部を酸化しているものと考えられる。酸化により生じた硝酸イオンは、従属栄養性脱窒菌により還元され亜硝酸イオンが生成される。なお、該エネルギー獲得反応におけるエネルギー源であるアンモニウムイオンは、元々被処理液中に豊富に含まれている場合が多い。   For example, when sludge collected from an existing methane fermenter is used as the anaerobic microorganism, the first layer usually contains acetic acid-assimilating methane bacteria and heterotrophic denitrifying bacteria. The dissolved organic matter is removed by methane fermentation and heterotrophic denitrification. At this time, carbonate ions that can serve as a carbon source for autotrophic microorganisms are also produced by methane fermentation using acetic acid-assimilating methane bacteria. Moreover, it is thought that a part of ammonium ion is oxidized to a nitrite ion or a nitrate ion by the coupling reaction of a methane oxidizing bacterium, a methane fermenting bacterium, and an anammox bacteria group. In particular, it is considered that methane-oxidizing bacteria oxidize part of ammonia ions using bound oxygen. Nitrate ions generated by oxidation are reduced by heterotrophic denitrifying bacteria to produce nitrite ions. In many cases, ammonium ions, which are energy sources in the energy acquisition reaction, are originally abundantly contained in the liquid to be treated.

つまり、被処理液を最初に第１層に接触させることにより、第２層に接触する被処理液の状態を、溶存している有機物がより少なく、かつ、炭酸イオン、亜硝酸イオン及びアンモニウムイオンがより適当に共存する状態、すなわち、独立栄養性微生物の増殖やアナモックス反応にとってより好適な状態にすることができる。このように、有機物除去を行う第１層と、窒素除去を行う第２層を保持し、被処理液を、第１層に接触させた後に第２層に接触させることにより、嫌気性処理とアナモックス反応の両方を好適に行うことができるため、一の嫌気性処理槽内で有機物と窒素を除去することが可能となる。   That is, by first bringing the liquid to be treated into contact with the first layer, the state of the liquid to be treated in contact with the second layer is less dissolved organic matter, and carbonate ions, nitrite ions, and ammonium ions. Can coexist more appropriately, that is, a more suitable state for growth of autotrophic microorganisms and anammox reaction. As described above, the first layer for removing organic substances and the second layer for removing nitrogen are held, and the liquid to be treated is brought into contact with the first layer and then brought into contact with the second layer, thereby anaerobic treatment. Since both anammox reactions can be suitably performed, it is possible to remove organic substances and nitrogen in one anaerobic treatment tank.

嫌気性処理槽の被処理液導入口付近に第１層を、被処理液導入口からより離れた場所に第２層を設置することにより、被処理液を第１層に接触させた後に第２層に接触させることができる。ここで、第１層中に収容されている嫌気性処理用微生物の量が、被処理液中の有機物量に対して過剰量である場合には、被処理液が第１層を通過する間に、ほぼ全ての有機物が分解除去され得るため、第２層でのアナモックス反応も効率よく行われる。この結果、前記工程（ａ）〜（ｂ）を１回行うことにより、被処理液から有機物と窒素を効果的に除去することができるため、短い処理時間で大量の被処理液を処理することができる。一方で、第１層中の嫌気性処理用微生物の量が、過剰量ではない場合であっても、被処理液を嫌気性処理槽に循環させる等により、前記工程（ａ）〜（ｂ）を繰り返すことによって、充分量の有機物と窒素を除去し、被処理液中のこれらの含有量を所望の濃度まで低下させることができる。なお、このように被処理液を循環させることにより、アナモックス反応の副生成物である硝酸を第１層に接触させることができ、第１層に収容されている従属栄養性脱窒菌による脱窒反応により、硝酸が還元され亜硝酸を生成し、亜硝酸は第２層のアナモックス反応で除去されるため、該硝酸も効果的に除去することができる。   By placing the first layer near the treatment liquid inlet of the anaerobic treatment tank and the second layer at a location further away from the treatment liquid inlet, the first liquid is brought into contact with the first layer. Two layers can be contacted. Here, when the amount of anaerobic microorganisms contained in the first layer is excessive with respect to the amount of organic matter in the liquid to be processed, the liquid to be processed passes through the first layer. In addition, since almost all organic substances can be decomposed and removed, the anammox reaction in the second layer is also performed efficiently. As a result, by performing the steps (a) to (b) once, organic substances and nitrogen can be effectively removed from the liquid to be processed, so that a large amount of liquid to be processed can be processed in a short processing time. Can do. On the other hand, even if the amount of the anaerobic treatment microorganism in the first layer is not an excessive amount, the steps (a) to (b) are performed by circulating the liquid to be treated to the anaerobic treatment tank. By repeating the above, a sufficient amount of organic substances and nitrogen can be removed, and the content of these in the liquid to be treated can be reduced to a desired concentration. By circulating the liquid to be treated in this way, nitric acid, which is a by-product of the anammox reaction, can be brought into contact with the first layer, and denitrification by heterotrophic denitrifying bacteria contained in the first layer. Nitric acid is reduced by the reaction to produce nitrous acid, and nitrous acid is removed by the anammox reaction of the second layer, so that the nitric acid can also be effectively removed.

本発明の有機物と窒素の除去方法においては、嫌気性処理とアナモックス反応の双方を好適に行うために、被処理液の酸化還元電位を調整することが好ましい。例えば、メタン発酵の前提となる酸生成が過剰に進行すると、被処理液の酸化還元電位が著しく低下し、メタン発酵には好適であるが、アナモックス反応には不適な条件となる。一方、酸生成がほとんど進行しない状態では、被処理液の酸化還元電位が低下せず、メタン発酵も進行しない。図１は、各酸化還元電位におけるメタン発酵活性とアナモックス活性を表した図である。ここで、メタン発酵活性とは、被処理液中の有機物の除去率（％）であり、アナモックス活性とは、被処理液中の窒素の除去率（％）である。図中、曲線ａがメタン発酵活性を、曲線ｂがアナモックス活性を、それぞれ示している。図１に示されるように、嫌気性処理とアナモックス反応の双方を好適に行うためには、被処理液の酸化還元電位、特に第１層と第２層の界面における酸化還元電位が、−３８０〜−２８０ｍＶであることが好ましく、−３５０〜−３１０ｍＶ付近であることがより好ましい。   In the organic substance and nitrogen removal method of the present invention, it is preferable to adjust the oxidation-reduction potential of the liquid to be treated in order to suitably perform both the anaerobic treatment and the anammox reaction. For example, if the acid generation that is the premise of methane fermentation proceeds excessively, the oxidation-reduction potential of the liquid to be treated is remarkably lowered, which is suitable for methane fermentation but unsuitable for anammox reaction. On the other hand, in a state where acid generation hardly proceeds, the oxidation-reduction potential of the liquid to be treated does not decrease and methane fermentation does not proceed. FIG. 1 is a diagram showing methane fermentation activity and anammox activity at each oxidation-reduction potential. Here, the methane fermentation activity is the removal rate (%) of organic substances in the liquid to be treated, and the anammox activity is the removal rate (%) of nitrogen in the liquid to be treated. In the figure, curve a shows methane fermentation activity, and curve b shows anammox activity. As shown in FIG. 1, in order to suitably perform both the anaerobic treatment and the anammox reaction, the redox potential of the liquid to be treated, particularly the redox potential at the interface between the first layer and the second layer is −380. It is preferably ˜−280 mV, more preferably around −350 to −310 mV.

嫌気性処理槽に、酸素を供給することや、有機酸、糖類、アミノ酸等を添加することにより、被処理液の酸化還元電位を調整することができる。酸素の供給は、空気等の酸素含有気体を用いた曝気処理等により行うことができる。該有機酸は、メタン菌に資化される酢酸以外の有機酸であれば、特に限定されるものではなく、任意の有機酸を用いることができるが、乳酸、プロピオン酸、酪酸等が好ましく、乳酸又はプロピオン酸であることがより好ましい。また、有機酸の添加は、有機酸液を直接添加してもよく、有機酸発酵により得られた有機酸を添加してもよい。例えば、有機酸生成菌が充填された酸生成槽において生成させた有機酸を、配管等を通して嫌気性処理槽に添加することができる。   The oxidation-reduction potential of the liquid to be treated can be adjusted by supplying oxygen to the anaerobic treatment tank or adding an organic acid, sugar, amino acid, or the like. The supply of oxygen can be performed by an aeration process using an oxygen-containing gas such as air. The organic acid is not particularly limited as long as it is an organic acid other than acetic acid assimilated to methane bacteria, and any organic acid can be used, but lactic acid, propionic acid, butyric acid and the like are preferable, More preferred is lactic acid or propionic acid. Moreover, the addition of an organic acid may add an organic acid liquid directly, and may add the organic acid obtained by organic acid fermentation. For example, the organic acid produced | generated in the acid production tank with which the organic acid production microbe was filled can be added to an anaerobic treatment tank through piping etc.

第２層におけるアナモックス活性をさらに高めるために、嫌気性処理槽において、酸素含有気体による曝気処理、酸化剤の添加、及び硫酸還元処理等を行うことが好ましい。これらの処理により、第１層において低く維持されている酸化還元電位が上昇し、アナモックス反応にとってより好適な状態にすることができる。これらの処理は、第２層や、第１層と第２層の界面において行われることがより好ましい。また、該曝気処理は、通常メタン発酵槽等で用いられる散気装置等を用いて行うことができる。但し、該曝気処理は、被処理液中の酸素濃度が、独立栄養性脱窒微生物の増殖等を阻害しない濃度に維持するよう、留意すべきである。   In order to further enhance the anammox activity in the second layer, it is preferable to perform an aeration treatment with an oxygen-containing gas, addition of an oxidizing agent, a sulfuric acid reduction treatment, and the like in an anaerobic treatment tank. By these treatments, the redox potential maintained at a low level in the first layer increases, and a more suitable state for the anammox reaction can be obtained. These treatments are more preferably performed at the second layer or at the interface between the first layer and the second layer. Moreover, this aeration process can be performed using the aeration apparatus etc. which are normally used with a methane fermentation tank etc. However, in the aeration treatment, care should be taken so that the oxygen concentration in the liquid to be treated is maintained at a concentration that does not inhibit the growth of autotrophic denitrifying microorganisms.

図２は、本発明の第５の態様である有機物と窒素の除去装置、すなわち、一の嫌気性処理槽内に、嫌気性処理用微生物を収容した第１層と、独立栄養性脱窒微生物を収容した第２層とを少なくとも備えることを特徴とする、有機物と窒素を含有する被処理液から有機物と窒素を除去するための装置の一態様の概略図である。被処理液導入口４と処理液出口５を有する嫌気性処理槽１の内部に、被処理液導入口４付近に第１層であるメタン発酵グラニュール２を、嫌気性処理槽１上部にある処理液出口５付近に第２層である不織布に付着固定した固定化アナモックス菌群３を、それぞれ設置する。これにより、被処理液導入口４から導入された被処理液は、最初にメタン発酵グラニュール２と接触し、メタン発酵により有機物が分解除去された後、固定化アナモックス菌群３と接触し、窒素が除去され、その後処理液出口５から流出する。該除去装置に循環ポンプ６を備えることにより、被処理液を循環させることができる。   FIG. 2 shows an organic matter and nitrogen removal apparatus according to the fifth aspect of the present invention, that is, a first layer containing an anaerobic treatment microorganism in one anaerobic treatment tank, and an autotrophic denitrifying microorganism. It is the schematic of the one aspect | mode of the apparatus for removing organic substance and nitrogen from the to-be-processed liquid containing organic substance and nitrogen characterized by including the 2nd layer which accommodated. Inside the anaerobic treatment tank 1 having the treatment liquid inlet 4 and the treatment liquid outlet 5, the methane fermentation granule 2, which is the first layer, is located in the upper part of the anaerobic treatment tank 1 near the treatment liquid introduction port 4. The immobilized anammox bacteria group 3 adhered and fixed to the nonwoven fabric as the second layer is installed near the treatment liquid outlet 5. Thereby, the to-be-processed liquid introduced from the to-be-processed liquid inlet 4 first contacts the methane fermentation granule 2, and after the organic matter is decomposed and removed by methane fermentation, it contacts the immobilized anammox bacteria group 3. Nitrogen is removed and then flows out from the processing solution outlet 5. By providing the removal device with the circulation pump 6, the liquid to be treated can be circulated.

本発明の第５の態様である有機物と窒素の除去装置は、さらに、酸化還元電位を計測するためのＯＲＰセンサー７と、散気装置８を備えてもよい。嫌気性処理槽１内の被処理液の酸化還元電位をＯＲＰセンサー７でモニターし、有機酸発酵により酸化還元電位が−３８０ｍＶ以下、好ましくは−３５０ｍＶ以下になった時点で、嫌気性処理槽１内の被処理液に、散気装置８を介して空気等の酸素含有気体を混入させることにより、酸化還元電位を上昇させることができる。このように、被処理液の酸化還元電位を調整することにより、メタン発酵とアナモックス反応の双方を、安定して行うことができる。なお、ＯＲＰセンサー７や散気装置８は、固定化アナモックス菌群３付近、又はメタン発酵グラニュール２と固定化アナモックス菌群３の界面に設置することが好ましい。図１に示すように、酸化還元電位の低下により、メタン発酵活性はほとんど影響を受けないが、アナモックス活性は急激に低下するため、アナモックス菌群３が存在する領域の酸化還元電位を速やかに上昇させる必要があるためである。   The organic matter and nitrogen removing apparatus according to the fifth aspect of the present invention may further include an ORP sensor 7 for measuring the oxidation-reduction potential and an air diffuser 8. The oxidation-reduction potential of the liquid to be treated in the anaerobic treatment tank 1 is monitored by the ORP sensor 7, and when the oxidation-reduction potential becomes −380 mV or less, preferably −350 mV or less by organic acid fermentation, the anaerobic treatment tank 1 The oxidation-reduction potential can be increased by mixing an oxygen-containing gas such as air into the liquid to be treated via the air diffuser 8. Thus, by adjusting the oxidation-reduction potential of the liquid to be treated, both methane fermentation and anammox reaction can be performed stably. The ORP sensor 7 and the air diffuser 8 are preferably installed near the immobilized anammox bacteria group 3 or at the interface between the methane fermentation granule 2 and the immobilized anammox bacteria group 3. As shown in FIG. 1, the methane fermentation activity is hardly affected by the reduction of the oxidation-reduction potential, but the anammox activity is rapidly reduced, so that the oxidation-reduction potential in the region where the anammox group 3 is present is rapidly increased. It is necessary to make it.

次に、本発明の第２の態様について説明する。なお、被処理液、嫌気性処理槽、嫌気性処理用微生物、独立栄養性脱窒微生物は、前述した第１の態様と同じである。
本発明の第２の態様の被処理液の有機物と窒素の除去方法は、前記嫌気性処理槽には、微生物を収容したグラニュール又は担体が充填されており、前記グラニュール又は担体の表層部に、嫌気性処理用微生物が局在し、内層部に、独立栄養性脱窒微生物が局在しており、前記被処理液を、前記グラニュール又は担体に接触させて、有機物の分解及び脱窒を行うことを特徴とする。このようなグラニュールや担体であれば、被処理液を、表層部に局在する嫌気性処理用微生物に接触させた後に、内層部に局在する独立栄養性脱窒微生物に接触させることができるため、嫌気性処理用微生物を収容した第１層と、独立栄養性脱窒微生物を収容した第２層を有する本発明の第１の態様の場合と同様に、一の嫌気性処理槽において嫌気性処理とアナモックス反応の両方を好適に行うことができるためである。なお、該グラニュール又は担体に収容されている嫌気性処理用微生物と独立栄養性脱窒微生物は、それぞれ、１種類の微生物であってもよく、複数種類の微生物であってもよい。また、嫌気性処理とアナモックス反応の双方を好適に行うために、本発明の第１の態様の除去方法と同様に、被処理液の酸化還元電位を調整することが好ましい。 Next, the second aspect of the present invention will be described. The liquid to be treated, the anaerobic treatment tank, the anaerobic treatment microorganism, and the autotrophic denitrification microorganism are the same as those in the first aspect described above.
In the method for removing organic substances and nitrogen from the liquid to be treated according to the second aspect of the present invention, the anaerobic treatment tank is filled with granules or carriers containing microorganisms, and the surface layer of the granules or carriers. In addition, anaerobic microorganisms are localized, autotrophic denitrifying microorganisms are localized in the inner layer, and the treatment liquid is brought into contact with the granules or the carrier to decompose and desorb organic matter. It is characterized by performing nitrogenation. With such a granule or carrier, the liquid to be treated can be brought into contact with an anaerobic microorganism that is localized in the surface layer, and then contacted with an autotrophic denitrifying microorganism that is localized in the inner layer. Therefore, in the same anaerobic treatment tank as in the case of the first aspect of the present invention having the first layer containing the anaerobic treatment microorganism and the second layer containing the autotrophic denitrification microorganism. This is because both the anaerobic treatment and the anammox reaction can be suitably performed. Each of the anaerobic treatment microorganism and the autotrophic denitrifying microorganism housed in the granule or carrier may be one kind of microorganism or a plurality of kinds of microorganisms. Further, in order to suitably perform both the anaerobic treatment and the anammox reaction, it is preferable to adjust the oxidation-reduction potential of the liquid to be treated, similarly to the removal method of the first aspect of the present invention.

本発明の第２の態様において用いられる微生物を収容した担体は、例えば、以下のようにして得ることができる。まず、嫌気性処理用微生物と、独立栄養性脱窒微生物を、適当なゲル材料に混合し、ゲル材料を重合させることにより、微生物を包括したゲル状の包括担体（微生物包括担体）を作製する。次に、作製した微生物包括担体を、適当な形状に成形した後、後述する馴養用溶液に接触させ、常法により馴養する。馴養するにつれて、該微生物包括担体の表層部に嫌気性処理用微生物が、内層に独立栄養性脱窒微生物が、それぞれ局在するようになる。馴養期間は、担体中において微生物の局在化が生じる期間であれば特に限定されるものではなく、用いる微生物の増殖活性等を考慮して、適宜決定することができる。
例えば、メタン発酵グラニュールをすり潰した汚泥と、アナモックス菌群とを、アクリルアミド等のゲル材料に混合し、重合させて得られた微生物包括担体を、乳酸１００ｍｇＣ／Ｌ、アンモニア態窒素２５ｍｇＮ／Ｌ、亜硝酸態窒素２５ｍｇＮ／Ｌの組成を有する馴養用溶液中で、１週間〜６ヶ月程度馴養することにより、表層部にメタン発酵菌が局在し、内層にアナモックス菌群が局在する担体を得ることができる。なお、図３は、このようにして得られた微生物を収容した担体９の断面の概略図であり、メタン発酵菌９１とアナモックス菌群９２の局在を示した図である。 The carrier containing the microorganism used in the second aspect of the present invention can be obtained, for example, as follows. First, an anaerobic treatment microorganism and an autotrophic denitrifying microorganism are mixed in an appropriate gel material, and the gel material is polymerized to prepare a gel-like inclusion carrier (microorganism inclusion carrier) containing microorganisms. . Next, after the produced microorganism-encapsulated carrier is formed into an appropriate shape, it is brought into contact with an acclimatization solution described later and acclimatized by a conventional method. As acclimatized, anaerobic microorganisms are localized in the surface layer of the microorganism-encapsulating carrier, and autotrophic denitrifying microorganisms are localized in the inner layer. The acclimatization period is not particularly limited as long as microorganisms are localized in the carrier, and can be appropriately determined in consideration of the growth activity of the microorganisms used.
For example, a microbial inclusion carrier obtained by mixing sludge obtained by grinding methane fermentation granules and anammox bacteria group into a gel material such as acrylamide and polymerizing the mixture is 100 mg C / L lactic acid, 25 mg N / L ammonia nitrogen, In the acclimatization solution having a composition of nitrite nitrogen of 25 mgN / L, by acclimating for about 1 week to 6 months, a carrier in which methane-fermenting bacteria are localized in the surface layer and anammox bacteria group is localized in the inner layer Obtainable. FIG. 3 is a schematic view of the cross section of the carrier 9 containing the microorganisms thus obtained, and shows the localization of the methane fermentation bacteria 91 and the anammox bacteria group 92.

本発明の第２の態様において用いられる微生物を収容したグラニュール、すなわち、本発明の第３の態様であるグラニュールは、メタン発酵槽等の嫌気性処理槽から採取したグラニュール汚泥を、後述する馴養用溶液に接触させ、常法により馴養することにより得ることができる。既存の嫌気性処理槽中の活性汚泥には、微量のアナモックス菌群が含まれている場合があり、アナモックス菌群の増殖及びアナモックス反応に好適な馴養用溶液に接触させて馴養することにより、アナモックス菌群を増殖させ、内層に充分量のアナモックス菌群９２が局在するグラニュール１０を形成することができる。馴養期間は、グラニュール汚泥採取時に内部に存在するアナモックス菌群量に依存するが、１週間〜６ヶ月程度の馴養により、目的のグラニュール１０を得ることができる。なお、図４は、このようにして得られた本発明の第３の態様の一態様である微生物を収容したグラニュール１０の断面の概略図であり、メタン発酵菌９１とアナモックス菌群９２の局在を示した図である。   The granule containing the microorganism used in the second aspect of the present invention, that is, the granule which is the third aspect of the present invention, is granule sludge collected from an anaerobic treatment tank such as a methane fermentation tank. It can obtain by making it contact with the solution for acclimatization, and acclimatizing by a conventional method. The activated sludge in the existing anaerobic treatment tank may contain a small amount of anammox bacteria group, and by acclimatizing it by contacting with a habituation solution suitable for the growth and anammox reaction of the anammox bacteria group, The anammox bacteria group can be grown to form granules 10 in which a sufficient amount of the anammox bacteria group 92 is localized in the inner layer. The acclimatization period depends on the amount of anammox bacteria existing inside the granule sludge, but the target granule 10 can be obtained by acclimatization for about 1 week to 6 months. FIG. 4 is a schematic view of a cross-section of the granule 10 containing the microorganism according to one aspect of the third aspect of the present invention obtained in this manner. The methane-fermenting bacteria 91 and the anammox bacteria group 92 are shown in FIG. It is the figure which showed localization.

本発明の第４の態様である馴養用溶液は、本発明の第３の態様であるグラニュールや第２の態様で用いられる担体を作製するために好適に用いられる馴養用溶液である。表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在するグラニュールや担体を作製するために用いられる馴養用溶液は、アンモニア態窒素と亜硝酸態窒素を有する溶液であれば、特に限定されるものではないが、乳酸等の有機酸を有することが好ましい。特に、乳酸又はプロピオン酸、アンモニア態窒素、及び亜硝酸態窒素を含む、本発明の第４の態様である馴養用溶液であることがより好ましい。該馴養用溶液の、乳酸、アンモニア態窒素、亜硝酸態窒の、それぞれの組成比は、馴養する微生物の種類や量等を考慮して、適宜決定することができるが、乳酸２０〜５００ｍｇＣ／Ｌ、アンモニア態窒素５〜１２５ｍｇＮ／Ｌ、亜硝酸態窒素５〜１２５ｍｇＮ／Ｌの組成を有する馴養用溶液であることが好ましい。さらに、該馴養用溶液の溶存酸素は、０．５ｍｇ／Ｌ以下であることが好ましい。なお、「ｍｇＣ／Ｌ」は、炭素濃度を意味する。このような組成を有する馴養用溶液を用いることにより、調整操作を要することなく、馴養用溶液中の酸化還元電位を、メタン菌等の嫌気性処理用微生物及びアナモックス菌群の両者に好適な数値範囲に維持することができるためである。   The acclimatization solution that is the fourth aspect of the present invention is an acclimatization solution that is suitably used for preparing the granule that is the third aspect of the present invention and the carrier used in the second aspect. The acclimatization solution used to produce granules and carriers in which the anaerobic microorganisms are localized in the surface layer and the autotrophic denitrifying microorganisms are localized in the inner layer is composed of ammonia nitrogen and nitrite nitrogen. Although it will not specifically limit if it is a solution which has, It is preferable to have organic acids, such as lactic acid. In particular, the acclimatization solution according to the fourth aspect of the present invention containing lactic acid or propionic acid, ammonia nitrogen, and nitrite nitrogen is more preferable. The composition ratios of lactic acid, ammonia nitrogen, and nitrite nitrogen in the acclimatization solution can be appropriately determined in consideration of the type and amount of microorganisms to be acclimatized, but lactic acid 20-500 mgC / It is preferable that the solution is a habituation solution having a composition of L, ammonia nitrogen 5 to 125 mg N / L, and nitrite nitrogen 5 to 125 mg N / L. Furthermore, it is preferable that the dissolved oxygen of the acclimatization solution is 0.5 mg / L or less. “MgC / L” means carbon concentration. By using the acclimatization solution having such a composition, the oxidation-reduction potential in the acclimatization solution is a numerical value suitable for both anaerobic microorganisms such as methane bacteria and the anammox bacteria group without requiring an adjustment operation. This is because the range can be maintained.

本発明の第３の態様であるグラニュールや第２の態様で用いられる担体の形状や大きさは、各微生物による嫌気性処理やアナモックス反応が阻害されない形状や大きさであれば、特に限定されるものではない。例えば、平均粒径は０．５〜４０ｍｍであることが好ましく、１〜２ｍｍであることがより好ましい。充分な比表面積を有するため、嫌気性処理を効率的に行うことができる上に、内層に充分量のアナモックス菌群を収容することができるためである。   The shape and size of the granules used in the third aspect of the present invention and the carrier used in the second aspect are particularly limited as long as the shape and size do not inhibit the anaerobic treatment and anammox reaction by each microorganism. It is not something. For example, the average particle size is preferably 0.5 to 40 mm, more preferably 1 to 2 mm. This is because it has a sufficient specific surface area, so that anaerobic treatment can be performed efficiently and a sufficient amount of anammox bacteria group can be accommodated in the inner layer.

図５は、本発明の第６の態様である有機物と窒素の除去装置、すなわち、一の嫌気性処理槽内に、微生物を収容したグラニュール又は担体が充填されており、前記グラニュール又は担体の表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在していることを特徴とする、有機物と窒素を含有する被処理液から有機物と窒素を除去するための装置の一態様の概略を示した図である。被処理液導入口４と処理液出口５を有する嫌気性処理槽１の内部に、図３に示した微生物を収容した担体９を充填する。これにより、被処理液導入口４から導入された被処理液は、最初に担体９の表層部のメタン発酵菌９１と接触し、メタン発酵により有機物が分解除去される。その後、有機物が除去された被処理液が、担体９のより内層に染み込み、アナモックス菌群９２と接触することにより、窒素が除去される。該除去装置は、本発明の第５の態様の除去装置と同様に、循環ポンプ６、酸化還元電位を計測するためのＯＲＰセンサー７、散気装置８を備えていてもよい。
このような担体又はグラニュールを、メタン発酵グラニュールに代えて、又はメタン発酵グラニュールとともに、既設のメタン発酵槽に充填して排液処理を行うことにより、大掛かりな装置等を導入することなく、簡便に、被処理液中の有機物と窒素を効果的に除去することが可能となる。 FIG. 5 shows the organic substance and nitrogen removing apparatus according to the sixth embodiment of the present invention, that is, one anaerobic treatment tank is filled with a granule or carrier containing microorganisms, and the granule or carrier. Removes organic matter and nitrogen from the liquid to be treated containing organic matter and nitrogen, characterized in that anaerobic microorganisms are localized in the surface layer of the substrate and autotrophic denitrifying microorganisms are localized in the inner layer It is the figure which showed the outline of the one aspect | mode of the apparatus for. The inside of the anaerobic treatment tank 1 having the treatment liquid inlet 4 and the treatment liquid outlet 5 is filled with the carrier 9 containing the microorganisms shown in FIG. Thereby, the to-be-processed liquid introduce | transduced from the to-be-processed liquid inlet 4 contacts the methane fermentation bacteria 91 of the surface layer part of the support | carrier 9 first, and organic substance is decomposed | disassembled and removed by methane fermentation. Thereafter, the liquid to be treated from which organic substances have been removed soaks into the inner layer of the carrier 9 and comes into contact with the anammox bacteria group 92, whereby nitrogen is removed. The removal device may include a circulation pump 6, an ORP sensor 7 for measuring the oxidation-reduction potential, and an air diffuser 8 as in the removal device of the fifth aspect of the present invention.
By replacing such a carrier or granule with the methane fermentation granule or together with the methane fermentation granule and filling an existing methane fermentation tank to perform the drainage treatment, without introducing a large-scale apparatus or the like It is possible to simply and effectively remove organic substances and nitrogen in the liquid to be treated.

また、本発明の第５の態様及び第６の態様においては、嫌気性処理槽１内の被処理液の酸化還元電位を調整するために、嫌気性処理槽１の他に、酸生成菌を充填した酸生成槽１１を備えてもよい。図６は、本発明の第５の態様である有機物と窒素の除去装置のうち、酸生成槽１１を備えた一態様の概略図を示したものであり、図７は、本発明の第６の態様である有機物と窒素の除去装置のうち、酸生成槽１１を備えた一態様の概略図を示したものである。ＯＲＦセンサー７により、嫌気性処理槽１内の酸化還元電位が−２８０ｍＶ以上、好ましくは−３１０ｍＶ以上になったことを検出した場合に、有機酸添加バルブ１３を調整して、酸発生槽１１から供給される有機酸量を増大させることにより、嫌気性処理槽１内の酸化還元電位を下降させることができる。なお、酸生成槽１１に充填される酸生成菌は、活性汚泥等の流動性を有するものであってもよく、不織布に付着固定した固定化酸生成菌１２であってもよい。   Moreover, in the 5th aspect and 6th aspect of this invention, in order to adjust the oxidation-reduction potential of the to-be-processed liquid in the anaerobic processing tank 1, in addition to the anaerobic processing tank 1, an acid producing microbe is used. You may provide the acid generation tank 11 with which it filled. FIG. 6 shows a schematic view of one aspect of the fifth aspect of the present invention, in which the organic substance and nitrogen removing apparatus includes the acid generation tank 11, and FIG. 7 shows the sixth aspect of the present invention. The schematic of the one aspect | mode provided with the acid production | generation tank 11 among the organic substance and nitrogen removal apparatuses which are this aspect is shown. When the ORF sensor 7 detects that the oxidation-reduction potential in the anaerobic treatment tank 1 is −280 mV or more, preferably −310 mV or more, the organic acid addition valve 13 is adjusted to By increasing the amount of organic acid supplied, the oxidation-reduction potential in the anaerobic treatment tank 1 can be lowered. In addition, the acid producing bacteria filled in the acid producing tank 11 may have fluidity such as activated sludge, or may be the immobilized acid producing bacteria 12 adhered and fixed to the nonwoven fabric.

本発明の第５の態様及び第６の態様において、嫌気性処理槽内に充填される嫌気性処理用微生物や独立栄養性脱窒微生物の量は、特に限定されるものではなく、用いる微生物の活性や増殖能、各微生物層の形態、被処理液中の有機物や窒素の含有量等を考慮して、適宜決定することができる。例えば、第５の態様において、第１層としてメタン発酵グラニュールを、第２層として担体に固定したアナモックス菌群をそれぞれ用いる場合には、嫌気性処理槽の５〜４０％の容量のメタン発酵グラニュールを充填することが好ましく、１０〜３０％を充填することがより好ましい。一方で、嫌気性処理槽の容量換算で１００〜５０００ｍｇ／Ｌのアナモックス菌群量を充填することが好ましく、１０００〜３０００ｍｇ／Ｌを充填することがより好ましい。また、表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在するグラニュール又は担体を用いる第６の態様の場合には、嫌気性処理槽の５〜５０％の容量の担体等を充填することが好ましく、１０〜４０％を充填することがより好ましい。   In the fifth and sixth aspects of the present invention, the amount of anaerobic treatment microorganisms and autotrophic denitrification microorganisms filled in the anaerobic treatment tank is not particularly limited, and the microorganisms to be used It can be determined as appropriate in consideration of the activity and growth ability, the form of each microorganism layer, the content of organic matter and nitrogen in the liquid to be treated, and the like. For example, in the fifth aspect, when the methane fermentation granule is used as the first layer and the anammox fungus group fixed to the carrier is used as the second layer, methane fermentation with a capacity of 5 to 40% of the anaerobic treatment tank is used. It is preferable to fill with granules, and more preferably 10 to 30%. On the other hand, it is preferable to fill an anammox bacteria group amount of 100 to 5000 mg / L in terms of the capacity of the anaerobic treatment tank, and more preferably 1000 to 3000 mg / L. Moreover, in the case of the 6th aspect using the granule or support | carrier in which the anaerobic processing microbe localizes in a surface layer part, and an autotrophic denitrification microbe localizes in an inner layer, 5-50 of an anaerobic processing tank. It is preferable to fill a carrier with a capacity of%, and more preferably 10 to 40%.

また、本発明の第５の態様及び第６の態様は、バッチ式の除去装置であってもよく、連続式の除去装置であってもよい。嫌気性処理槽内に充填される嫌気性処理用微生物や独立栄養性脱窒微生物の量が、被処理液中の有機物や窒素含量に対して充分量であれば、連続式除去装置により、短期間で大量の被処理液から有機物と窒素を除去することができる。一方、各微生物の充填量が過剰量ではない場合や、被処理液中の有機物等の含量が不明確である場合には、一定量の被処理液を嫌気性処理槽に導入し、循環させるバッチ式除去装置により、被処理液中の有機物や窒素を、所望の濃度まで充分に除去することができる。   Further, the fifth aspect and the sixth aspect of the present invention may be a batch type removal apparatus or a continuous type removal apparatus. If the amount of anaerobic treatment microorganisms and autotrophic denitrification microorganisms filled in the anaerobic treatment tank is sufficient for the organic matter and nitrogen content in the liquid to be treated, a continuous removal device can be used for a short period of time. In the meantime, organic substances and nitrogen can be removed from a large amount of liquid to be treated. On the other hand, when the filling amount of each microorganism is not excessive or when the content of organic matter in the liquid to be treated is unclear, a certain amount of liquid to be treated is introduced into the anaerobic treatment tank and circulated. The batch-type removal device can sufficiently remove organic substances and nitrogen in the liquid to be treated to a desired concentration.

次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。   EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.

（実施例１）
硝酸や亜硝酸を含有しない被処理液から、有機物と窒素を除去した。供試廃水として、総窒素量が４２０〜６８０ｍｇ／Ｌ（アンモニア態窒素量が４００〜６２０ｍｇ／Ｌ）、ＢＯＤ成分（有機物）量が１５４０〜１７００ｍｇ／Ｌである食品廃水を用いた。
１０Ｌのメタン発酵槽に、該メタン発酵槽の２０％の容量のメタン発酵グラニュールを充填し、さらに、該メタン発酵槽の４０％の容量のアナモックス菌群を付着固定した不織布（固定アナモックス菌群）を、図２に示すように設置した。該不織布には、メタン発酵槽の容量換算で１４００ｍｇ／Ｌのアナモックス菌群が付着固定されていた。また、該不織布を設置せず、メタン発酵グラニュールのみを充填したメタン発酵槽を対照とした。
このメタン発酵槽に、該供試廃水を、滞留時間が１２時間として流し処理した。酸化還元電位は、散気装置で空気を供給することにより、−３８０〜−２８０ｍＶになるように制御した。２ヶ月運転後の安定期での処理結果を表１に示す。表中、「実施例１」が、メタン発酵グラニュールと固定アナモックス菌群を充填したメタン発酵槽における処理を、「比較例１」が、メタン発酵グラニュールのみを充填したメタン発酵槽における処理を、それぞれ意味している。また、「Ｔ−Ｎ除去率」は供試廃水中の総窒素量の除去率を、「ＢＯＤ除去率」はＢＯＤ成分量の除去率を、それぞれ意味する。 Example 1
Organic substances and nitrogen were removed from the liquid to be treated that did not contain nitric acid or nitrous acid. As the test wastewater, food wastewater having a total nitrogen amount of 420 to 680 mg / L (ammonia nitrogen amount of 400 to 620 mg / L) and a BOD component (organic matter) amount of 1540 to 1700 mg / L was used.
A non-woven fabric (fixed anammox bacteria group) in which a 10 L methane fermentation tank is filled with methane fermentation granules having a capacity of 20% of the methane fermentation tank, and the anammox bacteria group having a capacity of 40% of the methane fermentation tank is adhered and fixed. ) Was installed as shown in FIG. On the nonwoven fabric, 1400 mg / L anammox bacteria group was adhered and fixed in terms of the volume of the methane fermentation tank. Moreover, the methane fermentation tank which did not install this nonwoven fabric and was filled only with the methane fermentation granule was made into the control | contrast.
The test wastewater was flowed into the methane fermentation tank for a residence time of 12 hours. The oxidation-reduction potential was controlled to be −380 to −280 mV by supplying air with an air diffuser. Table 1 shows the treatment results in the stable period after 2 months of operation. In the table, “Example 1” is a treatment in a methane fermentation tank filled with methane fermentation granules and fixed anammox bacteria group, and “Comparative Example 1” is a treatment in a methane fermentation tank filled only with methane fermentation granules. , Each mean. “TN removal rate” means the removal rate of the total nitrogen amount in the test wastewater, and “BOD removal rate” means the removal rate of the BOD component amount.

Figure 0004835536
Figure 0004835536

実施例１では、比較例１と比べて、供試廃水中の総窒素量の除去率が飛躍的に向上していた。したがって、実施例１の結果から、本発明の有機物と窒素の除去方法、すなわち、メタン発酵菌からなる第１層と、アナモックス菌群からなる第２層とを有するメタン発酵槽を用いて排水処理を行うことにより、メタン発酵槽においてアナモックス反応を良好に行うことが可能であり、従来になく効率よく排水中の窒素を除去し得ることが明らかである。
また、実施例１において、供試廃水中のＢＯＤ成分の除去率も改善されていたことから、アナモックス菌群が活性化されることによりメタン発酵菌群が活性化される可能性が示唆された。 In Example 1, compared with Comparative Example 1, the removal rate of the total nitrogen amount in the test wastewater was dramatically improved. Therefore, from the results of Example 1, the organic matter and nitrogen removal method of the present invention, that is, wastewater treatment using a methane fermenter having a first layer made of methane fermentation bacteria and a second layer made of anammox bacteria group. It is clear that the anammox reaction can be satisfactorily performed in the methane fermenter by performing the process, and nitrogen in the wastewater can be efficiently removed compared to the conventional method.
Moreover, in Example 1, since the removal rate of the BOD component in test wastewater was also improved, the possibility that the methane fermentation bacteria group might be activated by activating the anammox bacteria group was suggested. .

（実施例２）
表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在する微生物包括担体を作製した。
表２に記載の組成により、微生物を含有する微生物包括担体を得た。なお、表中記載のグラニュール汚泥は、ビール工場嫌気性処理設備より採取したグラニュール汚泥を、乳鉢にて破砕したものである。 (Example 2)
A microorganism inclusion carrier in which anaerobic microorganisms were localized in the surface layer and autotrophic denitrifying microorganisms were localized in the inner layer was prepared.
With the composition described in Table 2, a microorganism-containing carrier containing microorganisms was obtained. The granular sludge described in the table is obtained by crushing granular sludge collected from a beer factory anaerobic treatment equipment in a mortar.

Figure 0004835536
Figure 0004835536

得られた微生物包括担体を３ｍｍ角に成形し、図５に示すように、メタン発酵槽に充填率３８％となるように充填した。その後、馴養用溶液（乳酸１００ｍｇＣ／Ｌ、アンモニア態窒素２５ｍｇＮ／Ｌ、亜硝酸態窒素２５ｍｇＮ／Ｌ）を被処理液導入口４から導入し、該微生物包括担体と接触させ、２ヶ月間馴養することにより、目的の微生物包括担体を得た。   The obtained microorganism-encapsulated carrier was molded into a 3 mm square, and filled in a methane fermentation tank so as to have a filling rate of 38% as shown in FIG. Thereafter, a solution for acclimation (lactic acid 100 mgC / L, ammonia nitrogen 25 mgN / L, nitrite nitrogen 25 mgN / L) is introduced from the treatment liquid inlet 4 and brought into contact with the microorganism-containing carrier for habituation for 2 months. As a result, the target microorganism-containing carrier was obtained.

（実施例３）
表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在するグラニュールを作製した。
実施例２において、微生物包括担体に代えて、ビール工場嫌気性処理設備より採取したグラニュール汚泥を、メタン発酵槽に充填率３８％となるように充填した後、同様に、２ヶ月間馴養することにより、目的のグラニュールを得た。 (Example 3)
A granule was prepared in which anaerobic microorganisms were localized in the surface layer and autotrophic denitrifying microorganisms were localized in the inner layer.
In Example 2, instead of microbial inclusion carriers, granule sludge collected from a beer factory anaerobic treatment facility is filled in a methane fermentation tank so that the filling rate is 38%, and then similarly acclimatized for 2 months. As a result, the desired granule was obtained.

（実施例４）
硝酸や亜硝酸を含有しない被処理液から、有機物と窒素を除去した。供試廃水として、総窒素量が４２０〜６８０ｍｇ／Ｌ（アンモニア態窒素量が４００〜６２０ｍｇ／Ｌ）、ＢＯＤ成分（有機物）量が１５４０〜１７００ｍｇ／Ｌである食品廃水を用いた。
まず、表３に記載の組成により、微生物包括担体を得た。なお、表中記載のグラニュール汚泥は、実施例２と同じものである。 (Example 4)
Organic substances and nitrogen were removed from the liquid to be treated that did not contain nitric acid or nitrous acid. As the test wastewater, food wastewater having a total nitrogen amount of 420 to 680 mg / L (ammonia nitrogen amount of 400 to 620 mg / L) and a BOD component (organic matter) amount of 1540 to 1700 mg / L was used.
First, the microorganism inclusion carrier was obtained by the composition described in Table 3. The granular sludge described in the table is the same as that in Example 2.

Figure 0004835536
Figure 0004835536

得られた微生物包括担体を３ｍｍ角に成形し、メタン発酵槽に、充填率３８％となるように充填した。その後、馴養用溶液（乳酸１００ｍｇＣ／Ｌ、アンモニア態窒素２５ｍｇＮ／Ｌ、亜硝酸態窒素２５ｍｇＮ／Ｌ）を被処理液導入口４から導入し、該包括担体と接触させ、２ヶ月間馴養することにより、目的の微生物包括担体を得た。
得られた微生物包括担体を、１０Ｌのメタン発酵槽に、充填率３０％となるように充填した。このメタン発酵槽を用いて、該供試廃水を、実施例１と同様に処理した。２ヶ月運転後の安定期での処理結果を表４に示す。表中、「実施例４」が、グラニュール汚泥とアナモックス菌群を有する微生物包括担体を充填したメタン発酵槽における処理を意味しており、「比較例１」は、実施例１記載の比較例１を意味している。また、「Ｔ−Ｎ除去率」は供試廃水中の総窒素量の除去率を、「ＢＯＤ除去率」はＢＯＤ成分量の除去率を、それぞれ意味する。 The obtained microorganism-encapsulated carrier was formed into a 3 mm square and filled into a methane fermentation tank so that the filling rate was 38%. Thereafter, a solution for acclimation (lactic acid 100 mg C / L, ammonia nitrogen 25 mg N / L, nitrite nitrogen 25 mg N / L) is introduced from the treated liquid inlet 4 and brought into contact with the entrapping carrier for habituation for 2 months. Thus, the target microorganism-encapsulated carrier was obtained.
The obtained microorganism-encapsulated carrier was filled in a 10 L methane fermentation tank so that the filling rate was 30%. Using this methane fermentation tank, the test wastewater was treated in the same manner as in Example 1. Table 4 shows the results of treatment in the stable period after 2 months of operation. In the table, “Example 4” means treatment in a methane fermentation tank filled with a microbial inclusion carrier having granular sludge and anammox bacteria group, and “Comparative Example 1” is a comparative example described in Example 1. 1 means. “TN removal rate” means the removal rate of the total nitrogen amount in the test wastewater, and “BOD removal rate” means the removal rate of the BOD component amount.

Figure 0004835536
Figure 0004835536

実施例１と同様に、実施例４においても、比較例１と比べて、供試廃水中の総窒素量の除去率が飛躍的に向上していた。また、実施例１よりも若干、総窒素量の除去率とＢＯＤ成分の除去率が改善されていた。なお、実施例２で得られた微生物包括担体や、実施例３で得られたグラニュールを用いた場合であっても、同様に、供試廃水中の総窒素量の除去率が飛躍的に向上していた。
これらの結果から、表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在する微生物包括担体やグラニュールを用いた場合であっても、一の嫌気性処理槽を用いて排水処理を行うことにより、嫌気性処理とアナモックス反応を良好に行うことが可能であり、従来になく効率よく排水中の窒素を除去し得ることが明らかである。 Similar to Example 1, also in Example 4, the removal rate of the total nitrogen content in the test wastewater was dramatically improved as compared with Comparative Example 1. Further, the removal rate of the total nitrogen amount and the removal rate of the BOD component were slightly improved as compared with Example 1. Even when the microbial inclusion carrier obtained in Example 2 or the granule obtained in Example 3 is used, the removal rate of the total nitrogen amount in the test wastewater is also dramatically increased. It was improving.
From these results, even when an anaerobic treatment microorganism is localized in the surface layer and a microbial inclusion carrier or granule in which an autotrophic denitrifying microorganism is localized in the inner layer, one anaerobic treatment is performed. By performing wastewater treatment using a tank, it is clear that anaerobic treatment and anammox reaction can be carried out satisfactorily, and nitrogen in wastewater can be removed more efficiently than ever before.

（実施例５）
５００ｍＬ容の上向流型カラムの下部に、ビール工場嫌気性処理設備より採取したグラニュール汚泥を５０ｍＬ充填し、上部にアナモックス菌群を付着固定したポリエステル不織布を充填し、ジャケット水を循環させることにより３５℃に保温した排水処理装置を作製した。該排水処理装置に、１５Ｎ標識した硝酸１０ｍｇＮ、アンモニア１０ｍｇ／Ｌと、酸化還元電位を下げるための乳酸を５０、１００、２００ｍｇＣ／Ｌの各濃度で添加した馴養用溶液を、４．０ｍＬ／ｍｉｎでカラム下部より送液し、各乳酸濃度でそれぞれ約１週間ずつ運転を行った。馴養用溶液の酸化還元電位は、当初１５０ｍＶであったが、カラムに流入した乳酸が酢酸へと酸発酵することにより、いずれの濃度でも汚泥床の中央部付近で−２８０〜−３３０ｍＶとなった。また、流出水中から乳酸は検出されず、ＴＯＣ（Total Organic Carbon；全有機態炭素）除去率は７０％以上、全窒素除去率は５０％以上に維持できた。さらに、発生ガス中に著量のメタンガスが検出された。各濃度の最終の２日間に発生したガスを採取し、ＧＣ−ＭＳを用いて同位体分析（２９Ｎ２ ：３０Ｎ２）を行ったところ、アナモックス反応に由来する分子量２９の窒素（２９Ｎ２）と従属脱窒に由来する分子量３０の窒素（３０Ｎ２）の割合は馴養用溶液中の乳酸濃度にかかわらず１：４であった。
すなわち、これらの結果から、嫌気性処理設備より採取したグラニュール汚泥を、適当な馴養用溶液を用いて馴養することにより、メタン発酵とアナモックス反応を一の反応槽において行うことができるグラニュール、すなわち本発明のグラニュールが得られることが明らかである。また、適当な馴養用溶液中においては、メタン発酵中にアナモックス反応も行われており、有機物だけではなく窒素除去も行われていることが明らかになった。 (Example 5)
Fill the bottom of a 500 mL upflow column with 50 mL of granular sludge collected from an anaerobic treatment facility at a beer factory, fill the top with a polyester nonwoven fabric with anammox bacteria attached and fixed, and circulate jacket water. Thus, a wastewater treatment apparatus kept at 35 ° C. was produced. To the wastewater treatment apparatus was added a conditioned solution containing 10 N of 15 N-labeled nitric acid, 10 mg / L of ammonia, and lactic acid for lowering the redox potential at concentrations of 50, 100, and 200 mg C / L at 4.0 mL / Min was fed from the bottom of the column, and the operation was performed for about 1 week at each lactic acid concentration. The oxidation-reduction potential of the acclimatization solution was initially 150 mV, but lactic acid flowing into the column was subjected to acid fermentation to acetic acid, so that it became −280 to −330 mV near the center of the sludge bed at any concentration. . In addition, lactic acid was not detected from the effluent, and the TOC (Total Organic Carbon) removal rate was maintained at 70% or more and the total nitrogen removal rate was maintained at 50% or more. Furthermore, a significant amount of methane gas was detected in the generated gas. The gas generated in the last two days at each concentration was collected and subjected to isotope analysis ( 29 N 2 : 30 N 2 ) using GC-MS. As a result, nitrogen having a molecular weight of 29 derived from the anammox reaction ( 29 N ratio of 2) and dependent denitrification to molecular weight 30 derived nitrogen (30 N 2) regardless of the concentration of lactic acid acclimatization for solution was 1: 4.
That is, from these results, the granule sludge collected from the anaerobic treatment facility is acclimated using an appropriate acclimation solution, whereby the methane fermentation and the anammox reaction can be performed in one reaction tank, That is, it is clear that the granule of the present invention can be obtained. In addition, in an appropriate solution for habituation, it was revealed that an anammox reaction was also performed during methane fermentation, and not only organic matter but also nitrogen was removed.

（実施例６）
ビール排水を処理する嫌気性処理装置よりメタン発酵グラニュールを採取し、「Microbial analyses by fluorescence in situ hybridization of well-settled granular sludge in brewery wastewater treatment plants.」（Saiki, Y. et al.、２００２年、Journal of bioscience and bioengineering、第９３巻、ｐ６０１〜６０６）に記載の方法に従い、約５μｍの薄切片を作成した。その後、古細菌を検出するＣｙ３標識ＡＲＣ９１５プロ-ブ、アナモックス菌群が属するＰｌａｃｔｏｍｙｃｅｔａｌｅｓを検出するＣｙ３標識ＰＬ４６プローブ、アナモックス菌群を検出するＦＩＴＣ標識ＡＭＸ８２０プローブを用いて、ＦＩＳＨを行い、メタン菌、アナモックス菌群を染色した。図８はメタン発酵グラニュールの薄切片に対して行ったＦＩＳＨの結果得られた染色像であり、（ｂ）は、（ａ）の白色点線の四角で囲われた部分の拡大図である。図８（ａ）は、Ｃｙ３標識ＡＲＣ９１５プロ-ブを用いて行ったＦＩＳＨの結果であり、白色部分がメタン菌の局在を示している。図８（ｂ）は、ＦＩＴＣ標識ＡＭＸ８２０プローブを用いて行ったＦＩＳＨの結果であり、白色点線の四角で囲われた内部の白色部分がアナモックス菌群の局在を示している。該染色像から明らかであるように、用いたグラニュール汚泥には表面から１００μｍの深さの領域にメタン菌が、メタン発酵グラニュールの中心付近にごくわずかのアナモックス菌群が生息していていた。この汚泥を実施例１のカラムに充填し、亜硝酸態窒素とアンモニア態窒素を各２０ｍｇＮ／Ｌとグルコース２００ｍｇＣ／Ｌを含有する馴養用溶液を、一旦１００ｍＬ容の酸生成槽で３時間滞留させ、有機酸を生成させた後に、４．０ｍＬ／ｍｉｎでカラム下部より送液した。酸生成槽で滞留させることにより、グラニュール汚泥を充填したカラムに流入する直前の馴養用溶液には、約６０ｍｇＣの酢酸、５５ｍｇＣのプロピオン酸が含有していた。運転当初は、ＢＯＤ成分除去率は７０％、窒素除去率は１０％であったが、１０ヶ月の運転ののち測定するとＢＯＤ成分除去率は７０％に維持されたまま、窒素除去率が５０％に向上していた。
これらの結果から、嫌気性処理装置由来のグラニュールを、アナモックス菌群等の独立栄養性脱窒微生物の増殖やアナモックス活性に適した馴養用溶液に接触させて馴養することにより、グラニュール中の微生物の局在化と独立栄養性脱窒微生物の増殖が進行する結果、本発明のグラニュール、すなわち、表層部に嫌気性処理用微生物が局在し、内層に独立栄養性脱窒微生物が局在したグラニュールが得られること、及び、本発明のグラニュールは、馴養前のグラニュールに比べて窒素除去能が飛躍的に改善されていることが明らかである。 (Example 6)
Methane fermentation granules are collected from an anaerobic treatment device that treats beer wastewater, and "Microbial analyzes by fluorescence in situ hybridization of well-settled granular sludge in brewery wastewater treatment plants." (Saiki, Y. et al., 2002) According to the method described in Journal of bioscience and bioengineering, Vol. 93, p601-606), a thin section of about 5 μm was prepared. Thereafter, FISH was performed using a Cy3-labeled ARC915 probe for detecting archaea, a Cy3-labeled PL46 probe for detecting Pactomycetes to which the anammox bacteria group belongs, and a FITC-labeled AMX820 probe for detecting the anammox bacteria group. The fungal group was stained. FIG. 8 is a stained image obtained as a result of FISH performed on a thin section of a methane fermentation granule, and (b) is an enlarged view of a portion surrounded by a white dotted square in (a). FIG. 8A shows the result of FISH performed using a Cy3-labeled ARC915 probe, and the white portion indicates the localization of methane bacteria. FIG. 8B shows the result of FISH performed using the FITC-labeled AMX820 probe, and the white part inside the box surrounded by a white dotted line indicates the localization of the anammox bacteria group. As is clear from the stained image, the granule sludge used was inhabited by methane bacteria in the region of a depth of 100 μm from the surface, and very few anammox bacteria groups near the center of the methane fermentation granule. . The sludge is packed in the column of Example 1, and a habituation solution containing 20 mg N / L of nitrite nitrogen and ammonia nitrogen and 200 mg C / L of glucose is once retained in a 100 mL acid generation tank for 3 hours. After generating the organic acid, the solution was fed from the bottom of the column at 4.0 mL / min. The acclimatization solution immediately before flowing into the column filled with granular sludge by containing in the acid generation tank contained about 60 mgC acetic acid and 55 mgC propionic acid. At the beginning of operation, the BOD component removal rate was 70% and the nitrogen removal rate was 10%, but when measured after 10 months of operation, the BOD component removal rate was maintained at 70% and the nitrogen removal rate was 50%. Had improved.
From these results, the granule derived from the anaerobic treatment apparatus was brought into contact with a conditioned solution suitable for the growth and anammox activity of autotrophic denitrifying microorganisms such as the anammox bacteria group. As a result of the localization of microorganisms and the growth of autotrophic denitrifying microorganisms, the granule of the present invention, that is, the anaerobic microorganisms are localized in the surface layer, and the autotrophic denitrifying microorganisms are localized in the inner layer. It is clear that the existing granules can be obtained, and that the granule of the present invention has drastically improved nitrogen removal ability compared to the granules before acclimatization.

本発明の被処理液の有機物と窒素の除去方法、該方法に用いられ得る微生物を収容したグラニュール及び担体、並びに有機物と窒素の除去装置は、メタン発酵等の嫌気性処理と独立栄養性脱窒微生物を用いた脱窒処理を用いることにより、一の嫌気性処理槽内において行うことができるため、有機物と窒素を含む排水処理の分野で利用が可能である。   The method for removing organic matter and nitrogen from the liquid to be treated of the present invention, the granule and carrier containing microorganisms that can be used in the method, and the organic matter and nitrogen removing device are used for anaerobic treatment such as methane fermentation and autotrophic desorption. By using a denitrification treatment using a nitrogenous microorganism, it can be carried out in one anaerobic treatment tank, so that it can be used in the field of wastewater treatment containing organic matter and nitrogen.

各酸化還元電位におけるメタン発酵活性とアナモックス活性を表した図である。図中、曲線ａがメタン発酵活性を、曲線ｂがアナモックス活性を、それぞれ示している。It is a figure showing the methane fermentation activity and anammox activity in each oxidation-reduction potential. In the figure, curve a shows methane fermentation activity, and curve b shows anammox activity. 本発明の第５の態様である有機物と窒素の除去装置の一態様の概略図である。It is the schematic of one aspect | mode of the organic substance and nitrogen removal apparatus which is the 5th aspect of this invention. 本発明の第２の態様に用いられる担体の一態様の断面の概略図である。It is the schematic of the cross section of the one aspect | mode of the support | carrier used for the 2nd aspect of this invention. 本発明の第３の態様であるグラニュールの一態様の断面の概略図である。It is the schematic of the cross section of the one aspect | mode of the granule which is the 3rd aspect of this invention. 本発明の第６の態様である有機物と窒素の除去装置の一態様の概略を示した図である。It is the figure which showed the outline of the one aspect | mode of the organic substance and nitrogen removal apparatus which is the 6th aspect of this invention. 本発明の第５の態様である有機物と窒素の除去装置のうち、酸生成槽１１を備えた一態様の概略図を示したものである。The schematic of the one aspect | mode provided with the acid production | generation tank 11 among the organic substance and nitrogen removal apparatuses which are the 5th aspect of this invention is shown. 本発明の第６の態様である有機物と窒素の除去装置のうち、酸生成槽１１を備えた一態様の概略図を示したものである。The schematic of the one aspect | mode provided with the acid production tank 11 among the organic substance and nitrogen removal apparatuses which are the 6th aspect of this invention is shown. メタン発酵グラニュールの薄切片に対して行ったＦＩＳＨの結果得られた染色像であり、（ｂ）は、（ａ）の白色点線の四角で囲われた部分の拡大図である。図８（ａ）は、Ｃｙ３標識ＡＲＣ９１５プロ-ブを用いて行ったＦＩＳＨの結果であり、白色部分がメタン菌の局在を示している。図８（ｂ）は、ＦＩＴＣ標識ＡＭＸ８２０プローブを用いて行ったＦＩＳＨの結果であり、白色点線の四角で囲われた内部の白色部分がアナモックス菌群の局在を示している。It is the dyeing | staining image obtained as a result of FISH performed with respect to the thin section of the methane fermentation granule, (b) is an enlarged view of the part enclosed by the square of the white dotted line of (a). FIG. 8A shows the result of FISH performed using a Cy3-labeled ARC915 probe, and the white portion indicates the localization of methane bacteria. FIG. 8B shows the result of FISH performed using the FITC-labeled AMX820 probe, and the white part inside the box surrounded by a white dotted line indicates the localization of the anammox bacteria group.

符号の説明Explanation of symbols

１…嫌気性処理槽、２…メタン発酵グラニュール、３…固定化アナモックス菌群、４…被処理液導入口、５…処理液出口、６…循環ポンプ、７…ＯＲＰセンサー、８…散気装置、９…微生物を収容した担体、９１…メタン発酵菌、９２…アナモックス菌群、１０…微生物を収容したグラニュール、１１…酸生成槽、１２…固定化酸生成菌、１３…有機酸添加バルブ   DESCRIPTION OF SYMBOLS 1 ... Anaerobic processing tank, 2 ... Methane fermentation granule, 3 ... Immobilization anammox bacteria group, 4 ... Treatment liquid inlet, 5 ... Treatment liquid outlet, 6 ... Circulation pump, 7 ... ORP sensor, 8 ... Aeration Device: 9 ... Carrier containing microorganisms, 91 ... Methane fermentation bacteria, 92 ... Anammox bacteria group, 10 ... Granules containing microorganisms, 11 ... Acid production tank, 12 ... Immobilized acid production bacteria, 13 ... Addition of organic acid valve

Claims (3)

嫌気性消化処理槽を用いて、有機物と窒素を含有する被処理液から有機物と窒素を除去する方法において、
前記嫌気性消化処理槽が、嫌気性消化処理用微生物を収容した第１層と、独立栄養性脱窒微生物を収容した第２層を有し、
（ａ） 前記被処理液を、嫌気性消化処理用微生物を収容した第１層に接触させ、嫌気性消化処理により有機物を分解する工程と、
（ｂ） 前記第１層に接触させた後の被処理液を、独立栄養性脱窒微生物を収容した第２層に接触させ、脱窒を行う工程とを有し、
前記工程（ａ）〜（ｂ）を１回以上行い、
前記嫌気性処理槽内の酸化還元電位を、−３８０〜−２８０ｍＶに制御することを特徴とする、被処理液の有機物と窒素の除去方法。 In the method of removing organic matter and nitrogen from the treatment liquid containing organic matter and nitrogen using an anaerobic digestion treatment tank,
The anaerobic digestion tank has a first layer containing microorganisms for anaerobic digestion and a second layer containing autotrophic denitrifying microorganisms,
(A) contacting the liquid to be treated with a first layer containing anaerobic digestion microorganisms, and decomposing organic matter by anaerobic digestion;
(B) bringing the liquid to be treated after being brought into contact with the first layer into contact with the second layer containing the autotrophic denitrifying microorganisms, and performing denitrification,
The step of (a) ~ (b) have a row at least once,
A method for removing organic substances and nitrogen from a liquid to be treated, wherein an oxidation-reduction potential in the anaerobic treatment tank is controlled to -380 to -280 mV . 前記嫌気性処理槽内の酸化還元電位を、有機酸を用いて制御することを特徴とする、請求項１記載の被処理液の有機物と窒素の除去方法。 Wherein the redox potential of the anaerobic treatment tank, and controls with organic acids, the method of removing the organic matter and nitrogen in the liquid to be treated according to claim 1, wherein. 前記第１層が、メタン発酵グラニュールであり、前記第２層が、独立栄養性脱窒微生物を固定した担体であることを特徴とする、請求項１又は２記載の有機物と窒素の除去方法。 The method for removing organic matter and nitrogen according to claim 1 or 2 , wherein the first layer is a methane fermentation granule, and the second layer is a carrier on which an autotrophic denitrifying microorganism is fixed. .
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