JP2001252667A - Method and device for treating water containing nitrogen oxides - Google Patents
Method and device for treating water containing nitrogen oxidesInfo
- Publication number
- JP2001252667A JP2001252667A JP2000069054A JP2000069054A JP2001252667A JP 2001252667 A JP2001252667 A JP 2001252667A JP 2000069054 A JP2000069054 A JP 2000069054A JP 2000069054 A JP2000069054 A JP 2000069054A JP 2001252667 A JP2001252667 A JP 2001252667A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- electrode
- nitrogen
- water containing
- eluting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、上水、下水や工場
廃水、工業用水等の酸化態窒素含有水をアンモニア態窒
素に還元し、さらには窒素ガスにする処理方法および処
理装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method and a processing apparatus for reducing water containing oxidized nitrogen, such as clean water, sewage, industrial wastewater, and industrial water, to ammonia nitrogen and further converting the water to nitrogen gas.
【０００２】[0002]
【従来の技術】従来、水中の酸化態窒素、例えばＮＯ２
−ＮやＮＯ３−Ｎの処理には微生物を利用した生物処理
方法が用いられてきた。この生物処理においては、ＮＯ
２−ＮやＮＯ３−ＮをＮ２ガスに生物のもつ還元作用を
利用して処理する方法が一般的にとられてきている。 2. Description of the Related Art Conventionally, oxidized nitrogen in water, for example, NO 2
The process of -N and NO 3 -N biological treatment method using microorganisms have been used. In this biological treatment, NO
Method of processing 2 -N and NO 3 -N using a reducing action with the organism N 2 gas have been taken generally.
【０００３】また、物理・化学的な処理方法としては鉄
粉による還元の研究が行われてきている。アンモニア態
の窒素を不連続点塩素処理（ブレークポイントクロリネ
ーション法）により除去する方法や、塩素イオン存在下
で電解により不連続点塩素処理（ブレークポイントクロ
リネーション法）と同様の反応を起こさせアンモニア態
窒素を除去する方法（特開平０７−１００４６６号公
報）も知られている。さらに、膜分離法、吸着剤法、電
気透析法等が用いられている。[0003] As a physical and chemical treatment method, reduction with iron powder has been studied. Ammonia-based nitrogen is removed by discontinuous point chlorination (breakpoint chlorination method), or the same reaction as discontinuous point chlorination (breakpoint chlorination method) is caused by electrolysis in the presence of chloride ions, resulting in ammonia. There is also known a method for removing nitrogen dioxide (Japanese Patent Laid-Open No. 07-100466). Further, a membrane separation method, an adsorbent method, an electrodialysis method and the like are used.
【０００４】[0004]
【発明が解決しようとする課題】従来の生物を用いた方
法は優れた方法ではあるが、１）反応速度が小さく、特
に低水温の場合には反応速度は著しく低下する、２）高
濃度の酸化態窒素濃度の原水には適用できない、３）生
物に対する毒性物質を含む原水には適用できない、等の
問題点がある。Although the conventional method using an organism is an excellent method, 1) the reaction rate is low, and the reaction rate is remarkably reduced particularly at a low water temperature. It cannot be applied to raw water with an oxidized nitrogen concentration, and 3) it cannot be applied to raw water containing toxic substances to living organisms.
【０００５】鉄粉を用いた方法の場合には、鉄の溶解速
度が律速条件となるため、反応速度が小さいという欠点
がある。不連続点塩素処理（ブレークポイントクロリネ
ーション法）や特開平０７−１００４６６号公報に開示
の技術はアンモニア態窒素の除去は可能であるが、ＮＯ
２−ＮやＮＯ３−Ｎの除去はできない。また、生成ガス
には地球温暖化の原因物質として指摘されている亜酸化
窒素が含まれると言う問題がある。膜分離法、吸着剤
法、電気透析法等は、いずれも原水から酸化態窒素を分
離するものであり、酸化態窒素を高濃度に含む濃縮廃液
や残査、固形物が発生しその処理が必要になるという問
題点がある。The method using iron powder has the disadvantage that the reaction rate is low because the rate of dissolution of iron is the rate-determining condition. Discontinuous point chlorination (breakpoint chlorination method) and the technique disclosed in JP-A-07-100466 can remove ammonia nitrogen, but NO
Removal of 2 -N and NO 3 -N can not. Further, there is a problem that the generated gas contains nitrous oxide, which has been pointed out as a substance causing global warming. The membrane separation method, the adsorbent method, the electrodialysis method, etc. all separate oxide nitrogen from raw water, and concentrated waste liquids containing high concentrations of oxide nitrogen, residues, and solids are generated, and the treatment is performed. There is a problem that it becomes necessary.
【０００６】そこで本発明は、反応速度が大きく、高濃
度の原水にも適用でき、廃液や残査、固形物の発生しな
い水処理方法およびその装置を提供することを目的とす
る。Accordingly, an object of the present invention is to provide a water treatment method and apparatus which have a high reaction rate, can be applied to high-concentration raw water, and do not generate waste liquid, residue, or solid matter.
【０００７】[0007]
【課題を解決するための手段】上記課題を達成するため
に、本発明は、電極による電気分解を適用した水処理方
法およびその装置を提供するものであって、 （１） 酸化態窒素を含む水を電気分解処理する方法で
あって、陽極に溶出性電極を用いることを特徴とする酸
化態窒素含有水の処理方法。In order to achieve the above object, the present invention provides a water treatment method and an apparatus using electrolysis with an electrode, and (1) a method including water containing nitrogen oxides. What is claimed is: 1. A method for electrolyzing water, comprising using an eluting electrode as an anode.
【０００８】（２） 酸化態窒素を含む水を電気分解処
理する方法であって、陽極に非溶出性電極と溶出性電極
を用いることを特徴とする酸化態窒素含有水の処理方
法。(2) A method for electrolyzing water containing nitrogen oxides, wherein a non-eluting electrode and an eluting electrode are used as anodes.
【０００９】（３） 酸化態窒素を含む水を電気分解処
理する方法であって、陽極に非溶出性電極を用い、鉄イ
オンの存在下で行うことを特徴とする酸化態窒素含有水
の処理方法。(3) A method for electrolyzing water containing oxidized nitrogen, which comprises using a non-elutable electrode as an anode in the presence of iron ions. Method.
【００１０】（４） 酸化態窒素を含む水を電気分解処
理する方法であって、塩素イオンの存在下で行うことを
特徴とする（１）〜（４）に記載の酸化態窒素含有水の
処理方法。(4) A method for electrolyzing water containing oxidized nitrogen, which is carried out in the presence of chlorine ions, wherein the water containing oxidized nitrogen is subjected to electrolysis. Processing method.
【００１１】（５） 少なくとも一対の陽極と陰極を有
する電解槽を備え、前記陽極が溶出性電極であることを
特徴とする酸化態窒素含有水の処理装置。(5) An apparatus for treating water containing oxidized nitrogen, comprising an electrolytic cell having at least a pair of an anode and a cathode, wherein the anode is an eluting electrode.
【００１２】（６） 少なくとも一対の陽極と陰極を有
する電解槽を備え、前記陽極が溶出性電極と非溶出性電
極とからなることを特徴とする酸化態窒素含有水の処理
装置。(6) An apparatus for treating water containing oxidized nitrogen, comprising an electrolytic cell having at least a pair of an anode and a cathode, wherein the anode comprises an eluting electrode and a non-eluting electrode.
【００１３】（７） 少なくとも一対の陽極と陰極を有
する電解槽と、前記電解槽へ鉄イオンを供給する鉄イオ
ン供給手段を備え、前記陽極が非溶出性電極であること
を特徴とする酸化態窒素含有水の処理装置。(7) An oxidation state comprising an electrolytic cell having at least a pair of an anode and a cathode, and an iron ion supplying means for supplying iron ions to the electrolytic cell, wherein the anode is a non-eluting electrode. Equipment for treating nitrogen-containing water.
【００１４】（８） さらに前記電解槽へ塩素イオンを
供給する塩素イオン供給手段を備えていることを特徴と
する（５）〜（７）のいずれかに記載の酸化態窒素含有
水の処理装置である。(8) The apparatus for treating oxidized nitrogen-containing water according to any one of (5) to (7), further comprising a chlorine ion supply means for supplying chlorine ions to the electrolytic cell. It is.
【００１５】[0015]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明においては、まず、酸化態窒素成分を含む原水
を、電気分解処理することにより水中から酸化態窒素成
分を除去する。この電気分解に際して陽極に溶出性電極
を用いる。これにより、電極の溶出時の還元力を利用し
てＮＯ２−ＮやＮＯ３−Ｎがアンモニア態窒素に還元さ
れる。電気分解法を適用することにより、鉄粉の溶解と
は比較にならないほどの鉄の溶出反応が起こるので、反
応速度が鉄粉を用いた方法と比較して還元量が飛躍的に
増大する。陽極に溶出性電極と非溶出性電極とを用いた
場合も同様である。ここで、電気分解の電流密度は原水
の濃度などの処理条件にもよるが、０．０１〜１Ａ／ｃ
ｍ２が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, first, raw water containing an oxidized nitrogen component is electrolyzed to remove the oxidized nitrogen component from the water. In this electrolysis, an eluting electrode is used as the anode. As a result, NO 2 -N and NO 3 -N are reduced to ammonia nitrogen using the reducing power at the time of elution of the electrode. By applying the electrolysis method, an elution reaction of iron occurs that is incomparable to the dissolution of iron powder, so that the reduction rate is dramatically increased as compared with the method using iron powder. The same applies to the case where an eluting electrode and a non-eluting electrode are used for the anode. Here, the current density of the electrolysis depends on the processing conditions such as the concentration of raw water, but is 0.01 to 1 A / c.
m 2 is preferred.
【００１６】また、陽極に非溶出性電極を用い、鉄イオ
ンの存在下で電気分解を行う方法でもよい。陽極に非溶
出性電極を用いた場合には、陽極での電極の溶出に伴う
還元力が得られないが、鉄イオンを存在させることによ
り、鉄イオンを介して酸化、還元反応が起こり、ＮＯ２
−ＮやＮＯ３−Ｎがアンモニア態窒素に還元される。こ
の場合には電極材料の交換頻度を大幅に削減すること、
すなわち電極材料を半永久的に利用することが可能とな
る。Ｆｅ２＋は還元触媒として作用するが、ＮＨ４ ＋の
酸化には阻害剤として作用するので、添加量には適正な
範囲がある。このため、鉄イオンの供給は、たとえば硫
酸第一鉄を添加することにより行い、その添加量は、
０．１〜５ｍｇ／Ｌが好ましい。Further, a method may be employed in which a non-elutable electrode is used as the anode and electrolysis is performed in the presence of iron ions. When a non-eluting electrode is used for the anode, the reducing power associated with elution of the electrode at the anode cannot be obtained, but the presence of iron ions causes oxidation and reduction reactions via iron ions, resulting in NO 2
-N and NO 3 -N is reduced to ammonia nitrogen. In this case, the frequency of changing the electrode material should be significantly reduced,
That is, the electrode material can be used semi-permanently. Although Fe 2+ acts as a reduction catalyst, it acts as an inhibitor in the oxidation of NH 4 + , so the amount of addition has an appropriate range. For this reason, iron ions are supplied by, for example, adding ferrous sulfate, and the amount of addition is
0.1-5 mg / L is preferable.
【００１７】また、陽極に溶出性電極、溶出性電極と非
溶出性電極、或いは、非溶出性電極を用いた場合に塩素
イオンの存在下で電気分解を行うのがよい。これによ
り、不連続点塩素処理と同様にアンモニア態窒素の窒素
ガス化が達成される。この際の生成ガスはほとんどすべ
て窒素ガスであり、亜酸化窒素は発生しない。塩素イオ
ンの供給は、たとえば食塩（ＮＡＣｌ）を添加すること
により行い、その添加量は、被処理水の性状、濃度にも
よるが、１００〜５０００ｍｇ−Ｃｌ／Ｌが好ましい。Further, it is preferable that the electrolysis is performed in the presence of chloride ions when an eluting electrode, an eluting electrode and a non-eluting electrode, or a non-eluting electrode is used as the anode. Thereby, nitrogen gasification of ammonia nitrogen is achieved in the same manner as in the discontinuous point chlorination. Almost all generated gas at this time is nitrogen gas, and no nitrous oxide is generated. The supply of chlorine ions is performed by, for example, adding salt (NACl), and the amount of addition depends on the nature and concentration of the water to be treated, but is preferably 100 to 5000 mg-Cl / L.
【００１８】以下、図面を参照して本発明を詳細に説明
する。Hereinafter, the present invention will be described in detail with reference to the drawings.
【００１９】図１は、本発明の一例を示す廃水処理装置
の概略図である。この廃水処理装置は、被処理水４（廃
水）を入れた反応タンク１内に陽極２と陰極３とを対向
して配置する。また、必要により鉄イオン供給管（図示
せず）、塩素イオン供給管（図示せず）を配置する。そ
して、電源１から陽極２，陰極３に直流電圧を与えるこ
とにより電気分解を行う。FIG. 1 is a schematic diagram of a wastewater treatment apparatus showing an example of the present invention. In this wastewater treatment apparatus, an anode 2 and a cathode 3 are arranged opposite to each other in a reaction tank 1 containing water 4 (wastewater) to be treated. If necessary, an iron ion supply pipe (not shown) and a chlorine ion supply pipe (not shown) are provided. Then, electrolysis is performed by applying a DC voltage from the power source 1 to the anode 2 and the cathode 3.
【００２０】電極の構成および共存物質は以下の（１）
〜（３）から選択する。The structure of the electrode and the coexisting substance are as follows (1)
To (3).
【００２１】（１）陽極：溶出性電極（例：鉄電極）、
陰極：溶出性電極あるいは非溶出性電極のいずれか。こ
の場合には、溶出性電極の溶出時に発生する還元力によ
りＮＯ２−ＮやＮＯ ３−Ｎがアンモニア態窒素に還元さ
れる。さらに、この構成において、塩素イオンを添加し
た場合には、アンモニア性窒素の窒素ガス化反応が生じ
る。このことは発明者らが新たに見出したことである。
よって、この構成では、ＮＯ２−ＮやＮＯ３−Ｎがアン
モニア態窒素に還元される反応と、アンモニア性窒素の
窒素ガス化反応が同時に起こることにより、全体として
は、ＮＯ２−ＮやＮＯ３−Ｎが窒素ガス化が達成され
る。(1) anode: eluting electrode (eg, iron electrode),
Cathode: either eluting or non-eluting electrode. This
In the case of, the reducing power generated during elution of the eluting electrode
No2-N or NO 3-N is reduced to ammonia nitrogen
It is. Furthermore, in this configuration, chlorine ions are added.
In this case, a nitrogen gasification reaction of ammoniacal nitrogen occurs.
You. This is what the inventors have newly found.
Therefore, in this configuration, NO2-N or NO3-N is Ann
The reaction reduced to monic nitrogen and the formation of ammoniacal nitrogen
As a result of the simultaneous nitrogen gasification reaction,
Is NO2-N or NO3-N has achieved nitrogen gasification
You.
【００２２】（２）陽極：非溶出性電極（白金被覆電極
等）、陰極：溶出性電極あるいは非溶出性電極のいずれ
か。この構成の場合には、単に電気分解処理しただけで
はＮＯ２−ＮやＮＯ３−Ｎがアンモニア態窒素に還元さ
れる反応は起こらないが、鉄イオンを共存させることに
よりＮＯ２−ＮやＮＯ３−Ｎがアンモニア態窒素に還元
される。このことも発明者らが新たに見出したものであ
る。さらに、この構成において、鉄イオンを共存させた
上で、（１）同様に、塩素イオンを添加した場合には、
アンモニア性窒素の窒素ガス化反応が生じる。よって、
この構成では、ＮＯ２−ＮやＮＯ３−Ｎがアンモニア態
窒素に還元される反応と、アンモニア性窒素の窒素ガス
化反応が同時に起こることにより、全体としては、ＮＯ
２−ＮやＮＯ３−Ｎが窒素ガス化が達成される。(2) Anode: non-eluting electrode (such as a platinum-coated electrode); Cathode: either eluting electrode or non-eluting electrode. In the case of this configuration, the reaction of reducing NO 2 —N or NO 3 —N to ammonia nitrogen does not occur simply by electrolysis treatment. However, NO 2 —N or NO 3 3- N is reduced to ammonia nitrogen. This has also been newly found by the inventors. Further, in this configuration, when iron ions are allowed to coexist and chlorine ions are added similarly to (1),
A nitrogen gasification reaction of ammoniacal nitrogen occurs. Therefore,
In this configuration, a reaction in which NO 2 —N or NO 3 —N is reduced to ammonia nitrogen and a nitrogen gasification reaction of ammonia nitrogen occur at the same time.
2 -N and NO 3 -N nitrogen gas is achieved.
【００２３】（３）陽極：非溶出性電極（白金被覆電極
等）と溶出性電極（鉄電極）の両者、陰極：溶出性電極
あるいは非溶出性電極のいずれか。この構成の場合に
は、鉄電極の溶出時に発生する還元力と、溶出した鉄イ
オンの存在によりＮＯ２−ＮやＮＯ３−Ｎがアンモニア
態窒素に還元される。この際、塩素イオンを共存させる
ことによりアンモニア性窒素の窒素ガス化反応が生じ、
ＮＯ２−ＮやＮＯ３−Ｎがアンモニア態窒素に還元され
る反応と、アンモニア性窒素の窒素ガス化反応が同時に
起こることにより、全体としては、ＮＯ２−ＮやＮＯ３
−Ｎの窒素ガス化が達成される。このことは（１）の場
合と同様である。(3) Anode: Both a non-eluting electrode (such as a platinum-coated electrode) and an eluting electrode (iron electrode), and a cathode: either an eluting electrode or a non-eluting electrode. In this configuration, NO 2 —N and NO 3 —N are reduced to ammonia nitrogen by the reducing power generated when the iron electrode is eluted and the presence of the eluted iron ions. At this time, a nitrogen gasification reaction of ammonia nitrogen occurs by coexisting chlorine ions,
A reaction in which NO 2 —N or NO 3 —N is reduced to ammonia nitrogen and a gasification reaction of ammonia nitrogen occur simultaneously, so that NO 2 —N or NO 3 as a whole is obtained.
Nitrogen gasification of -N is achieved. This is similar to the case (1).
【００２４】本発明において、電極に通電する電流およ
び電圧は、装置構造（電極面積、電極間距離等）や、液
の電気伝導度、要求処理水質や処理時間等により変化さ
せるものであり、要望に応じて最適なものを採用する。
このことは、当業者が容易に想到できる設計事項であ
る。In the present invention, the current and voltage applied to the electrodes are varied depending on the device structure (electrode area, distance between electrodes, etc.), the electric conductivity of the liquid, the required quality of the treated water, the treatment time, and the like. The best one is adopted according to
This is a design matter that can be easily conceived by those skilled in the art.
【００２５】また、本発明によれば、鉄電極、あるいは
鉄イオンを用いた場合には溶液中のリン成分がリン酸鉄
として不溶化されるので、液側からのリンの除去および
リンの回収が可能となる。Further, according to the present invention, when an iron electrode or iron ions are used, the phosphorus component in the solution is insolubilized as iron phosphate, so that phosphorus can be removed from the liquid side and phosphorus can be recovered. It becomes possible.
【００２６】なお、鉄イオンを共存させた場合の鉄イオ
ンの挙動については現在、研究段階であるが、投入した
Ｆｅ２＋からのＦｅ３＋への酸化量以上の量の反応が生
じていると見られることもあり、鉄イオンが電子伝達の
役割をになっているか、触媒的に作用している部分もあ
るものと推測される。Although the behavior of iron ions in the presence of iron ions is currently in the research stage, it is considered that a reaction of an amount greater than the amount of oxidation of Fe 2+ into Fe 3+ is caused. It is presumed that iron ions play a role of electron transfer or that some parts act catalytically.
【００２７】[0027]
【実施例】以下、具体例および比較例を示して本発明を
さらに詳細に説明する。まず、図２に示した実験装置を
用いて実験を行った。図２に示す反応装置は、反応槽１
１内に一対の電極１２，１３を設置して電気分解処理す
る装置で、槽内の試料水（３０ｍＭ−Ｎ０．５ｌ）をサ
ンプリングし、そのｐＨをｐＨコントローラー１４で検
出し、この検出値に基づいてｐＨ調整用Ｈ２ＳＯ４を槽
内に添加する。そして、反応で生じたガスをサンプリン
グするものである。The present invention will be described in more detail with reference to specific examples and comparative examples. First, an experiment was performed using the experimental apparatus shown in FIG. The reaction apparatus shown in FIG.
A pair of electrodes 12 and 13 are installed in the apparatus 1 to perform an electrolysis treatment. A sample water (30 mM-N 0.5 l) in a tank is sampled, and its pH is detected by a pH controller 14. Then, H 2 SO 4 for pH adjustment is added into the tank. Then, the gas generated by the reaction is sampled.
【００２８】図３は、陽極に鉄電極、陽極に鉄電極を用
いた場合の実験結果、図４は陽極に鉄電極、陰極に白金
電極を用いた場合の実験結果である。いずれの場合も、
鉄粉を用いた場合の還元速度（ほぼ４〜１０ｍＭ／ｈｒ
程度の還元速度）や生物処理における還元速度（ほぼ
０．５〜２ｍＭ／ｈｒ程度の還元速度）を大幅に上回る
還元速度が得られた。FIG. 3 shows an experimental result when an iron electrode is used for the anode and an iron electrode is used for the anode. FIG. 4 shows an experimental result when an iron electrode is used for the anode and a platinum electrode is used for the cathode. In either case,
Reduction rate using iron powder (approximately 4 to 10 mM / hr)
Reduction rate) and a reduction rate in biological treatment (reduction rate of about 0.5 to 2 mM / hr).
【００２９】一方、陽極に白金電極を用いただけの場合
には、陰極の材質に関わらずＮＯ２−ＮやＮＯ３−Ｎの
還元反応は起こらなかった。しかしながら陽極に白金電
極を用いた場合においても、陰極の材質に関わらずＦｅ
２＋を共存させることによりＮＯ２−ＮやＮＯ３−Ｎの
還元反応が生じることが確認された（図５参照）。On the other hand, when only a platinum electrode was used as the anode, no reduction reaction of NO 2 -N or NO 3 -N occurred regardless of the material of the cathode. However, even when a platinum electrode is used for the anode, Fe
It was confirmed that the coexistence of 2+ causes a reduction reaction of NO 2 -N and NO 3 -N (see FIG. 5).
【００３０】また、塩素を添加して不連続点処理を行う
ことを検討したが、陽極に鉄電極を用いた場合には、Ｎ
Ｏ２−ＮやＮＯ３−Ｎのアンモニア態窒素までの還元は
起こるものの、アンモニア態窒素はＮＯ２−ＮやＮＯ３
−Ｎ量から計算される値とほぼ同じ濃度で残存し、アン
モニア態窒素の除去は達成できなかった。これに対し、
陽極に白金電極を用いた場合に、陰極の材質に関わらず
Ｆｅ２＋を共存させ、かつ、塩素を添加させることによ
りＮＯ２−ＮやＮＯ３−Ｎの還元反応とアンモニア態窒
素の除去反応が一つの反応容器内で生じることが確認さ
れた（図６参照）。この際に発生したガスの組成分析を
行った結果、アンモニア態窒素は１００％窒素ガスにな
っていることが確認された。Further, it was examined to perform a discontinuous point treatment by adding chlorine. However, when an iron electrode was used for the anode, N
Although reduction of O 2 —N or NO 3 —N to ammonia nitrogen occurs, ammonia nitrogen is NO 2 —N or NO 3
The concentration remained almost the same as the value calculated from the -N amount, and removal of ammonia nitrogen could not be achieved. In contrast,
When a platinum electrode is used as the anode, the reduction reaction of NO 2 -N or NO 3 -N and the removal reaction of ammonia nitrogen can be performed by coexisting Fe 2+ and adding chlorine regardless of the material of the cathode. It was confirmed to occur in one reaction vessel (see FIG. 6). As a result of analyzing the composition of the gas generated at this time, it was confirmed that the ammonia nitrogen was 100% nitrogen gas.
【００３１】以上のように、本発明は、適切な電極材料
を用いた電気分解と言う手法を用いたことにより、非常
に大きい反応速度を得ることができるとともに、適宜、
Ｆｅ ２＋イオンや、塩素イオンを共存させることによ
り、ＮＯ２−ＮやＮＯ３−Ｎからの最終生成物質を全く
無害な窒素ガスとすることができ、かつ、ＮＯ２−Ｎや
ＮＯ３−Ｎからのアンモニア態窒素への還元反応と、ア
ンモニア態窒素の窒素ガスへの酸化反応を同一容器内で
同時に進行させることができ、工業的価値は大きい。As described above, the present invention relates to a method for forming a suitable electrode material.
The use of a technique called electrolysis using
A large reaction rate can be obtained, and
Fe 2+Ions and chloride ions coexist
No2-N or NO3-No final product from N
Can be harmless nitrogen gas and NO2-N or
NO3-N to ammonia nitrogen, and
Oxidation reaction of ammonia nitrogen to nitrogen gas in the same vessel
It can be advanced at the same time, and the industrial value is great.
【図１】本発明の一例を示す廃水処理装置の概略図。FIG. 1 is a schematic diagram of a wastewater treatment apparatus showing an example of the present invention.
【図２】本発明の実験装置図。FIG. 2 is a diagram of an experimental apparatus of the present invention.
【図３】陽極に鉄電極、陽極に鉄電極を用いた場合の、
定電流：１．０Ａ，電圧：１５〜１０Ｖ，ｐＨ＝７にお
けるＮＨ４ ＋，ＮＯ３ −の濃度変化を示す実験結果説明
図。FIG. 3 shows a case where an iron electrode is used for the anode and an iron electrode is used for the anode.
FIG. 4 is an explanatory diagram of experimental results showing a change in concentration of NH 4 + and NO 3 − at a constant current of 1.0 A, a voltage of 15 to 10 V, and a pH of 7.
【図４】陽極に鉄電極、陰極に白金電極を用いた場合
の、定電流：１．０Ａ，電圧：４Ｖ，ｐＨ＝７における
ＮＨ４ ＋，ＮＯ３ −の濃度変化を示す実験結果説明図。FIG. 4 is an explanatory diagram of an experimental result showing a change in the concentration of NH 4 + and NO 3 − at a constant current of 1.0 A, a voltage of 4 V, and a pH of 7 when an iron electrode is used as an anode and a platinum electrode is used as a cathode. .
【図５】陽極に白金電極を用いた場合に、２ｇ／ｌ−Ｆ
ｅ２＋添加し、定電流：１．０Ａ，電圧：５〜７．５
Ｖ，ｐＨ＝３．４〜２におけるＮＨ４ ＋，ＮＯ３ −の濃
度変化を示す実験結果説明図。FIG. 5 shows that when a platinum electrode is used as an anode, 2 g / l-F
e 2+ added, constant current: 1.0 A, voltage: 5 to 7.5
FIG. 5 is an explanatory diagram of an experimental result showing a change in concentration of NH 4 + and NO 3 − at V and pH = 3.4 to 2 .
【図６】陽極に白金電極を用いた場合に、２ｇ／ｌ−Ｆ
ｅ２＋及びＣｌ−添加し、定電流：１．０Ａ，電圧：５
〜７．５Ｖ，ｐＨ＝３．４〜２におけるＮＨ４ ＋，ＮＯ
３ −，の濃度変化を示す実験結果説明図。FIG. 6 is a graph showing 2 g / l-F when a platinum electrode is used as an anode.
e2+And Cl−Addition, constant current: 1.0 A, voltage: 5
NH at ~ 7.5 V, pH = 3.4-24 +, NO
3 −FIG. 4 is an explanatory diagram of an experimental result showing a change in the density of the graph of FIG.
１・・・電源 ２・・・陽極 ３・・・陰極 ４・・・被処理水 ５・・・反応タンク DESCRIPTION OF SYMBOLS 1 ... Power supply 2 ... Anode 3 ... Cathode 4 ... Water to be treated 5 ... Reaction tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 局 俊明 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 馬場 圭 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 水野 健一郎 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 Ｆターム(参考） 4D061 DA08 DB19 DC14 EA02 EA04 EB04 EB14 EB28 EB30 ED13 ED20 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Toshiaki Inventor Bureau 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Inventor Kei Kei Baba 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Sun Inside the Honko Tube Co., Ltd. (72) Inventor Kenichiro Mizuno 1-2-1 Marunouchi, Chiyoda-ku, Tokyo F-term in the Nippon Kokan Co., Ltd. 4D061 DA08 DB19 DC14 EA02 EA04 EB04 EB14 EB28 EB30 ED20
Claims (8)
方法であって、陽極に溶出性電極を用いることを特徴と
する酸化態窒素含有水の処理方法。1. A method for electrolyzing water containing oxidized nitrogen, comprising using an eluting electrode as an anode.
方法であって、陽極に非溶出性電極と溶出性電極を用い
ることを特徴とする酸化態窒素含有水の処理方法。2. A method for electrolyzing water containing oxidized nitrogen, comprising using a non-eluting electrode and an eluting electrode as an anode.
方法であって、陽極に非溶出性電極を用い、鉄イオンの
存在下で行うことを特徴とする酸化態窒素含有水の処理
方法。3. A method for electrolyzing water containing oxidized nitrogen, which comprises using a non-elutable electrode as an anode in the presence of iron ions. .
方法であって、塩素イオンの存在下で行うことを特徴と
する請求項１〜４に記載の酸化態窒素含有水の処理方
法。4. The method for treating water containing oxidized nitrogen according to claim 1, wherein the method comprises electrolyzing water containing oxidized nitrogen in the presence of chlorine ions.
解槽を備え、前記陽極が溶出性電極であることを特徴と
する酸化態窒素含有水の処理装置。5. An apparatus for treating water containing oxidized nitrogen, comprising: an electrolytic cell having at least a pair of an anode and a cathode, wherein the anode is an eluting electrode.
解槽を備え、前記陽極が溶出性電極と非溶出性電極とか
らなることを特徴とする酸化態窒素含有水の処理装置。6. An apparatus for treating water containing oxidized nitrogen, comprising: an electrolytic cell having at least a pair of an anode and a cathode, wherein the anode comprises an eluting electrode and a non-eluting electrode.
解槽と、前記電解槽へ鉄イオンを供給する鉄イオン供給
手段とを備え、前記陽極が非溶出性電極であることを特
徴とする酸化態窒素含有水の処理装置。7. An oxidation state comprising: an electrolytic cell having at least a pair of an anode and a cathode; and an iron ion supplying means for supplying iron ions to the electrolytic cell, wherein the anode is a non-eluting electrode. Equipment for treating nitrogen-containing water.
る塩素イオン供給手段を備えていることを特徴とする請
求項５〜７のいずれかに記載の酸化態窒素含有水の処理
装置。8. The apparatus for treating oxidized nitrogen-containing water according to claim 5, further comprising a chlorine ion supply means for supplying chlorine ions to said electrolytic cell.
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|---|---|---|---|
| JP2000069054A JP2001252667A (en) | 2000-03-13 | 2000-03-13 | Method and device for treating water containing nitrogen oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000069054A JP2001252667A (en) | 2000-03-13 | 2000-03-13 | Method and device for treating water containing nitrogen oxides |
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| Publication Number | Publication Date |
|---|---|
| JP2001252667A true JP2001252667A (en) | 2001-09-18 |
Family
ID=18588014
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068340A1 (en) * | 2001-02-28 | 2002-09-06 | Sanyo Electric Co., Ltd. | Drain treating method, drain treating device and drain treating system |
| WO2002068339A1 (en) * | 2001-02-26 | 2002-09-06 | Sanyo Electric Co., Ltd. | Method and system for treating nitrogen-containing compound |
| WO2003086980A1 (en) * | 2002-04-18 | 2003-10-23 | Sanyo Electric Co., Ltd. | Method of wastewater treatment and wastewater treatment apparatus |
| US7011750B2 (en) | 2001-09-04 | 2006-03-14 | Sanyo Electric Co., Ltd. | Water treatment device |
| JP2020146647A (en) * | 2019-03-14 | 2020-09-17 | 住友金属鉱山エンジニアリング株式会社 | Treatment method of oxidized nitrogen |
-
2000
- 2000-03-13 JP JP2000069054A patent/JP2001252667A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068339A1 (en) * | 2001-02-26 | 2002-09-06 | Sanyo Electric Co., Ltd. | Method and system for treating nitrogen-containing compound |
| WO2002068340A1 (en) * | 2001-02-28 | 2002-09-06 | Sanyo Electric Co., Ltd. | Drain treating method, drain treating device and drain treating system |
| US6875362B2 (en) | 2001-02-28 | 2005-04-05 | Sanyo Electric Co., Ltd. | Waste water treating method, waste water treating apparatus, and waste water treating system |
| US7011750B2 (en) | 2001-09-04 | 2006-03-14 | Sanyo Electric Co., Ltd. | Water treatment device |
| WO2003086980A1 (en) * | 2002-04-18 | 2003-10-23 | Sanyo Electric Co., Ltd. | Method of wastewater treatment and wastewater treatment apparatus |
| US7300591B2 (en) | 2002-04-18 | 2007-11-27 | Sanyo Electronic Co., Ltd. | Wastewater treating method and wastewater treating apparatus |
| JP2020146647A (en) * | 2019-03-14 | 2020-09-17 | 住友金属鉱山エンジニアリング株式会社 | Treatment method of oxidized nitrogen |
| JP7279993B2 (en) | 2019-03-14 | 2023-05-23 | 住友金属鉱山エンジニアリング株式会社 | Method for treating nitrogen oxides |
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