JP2000308900A - Treatment of wastewater containing ammonia - Google Patents
Treatment of wastewater containing ammoniaInfo
- Publication number
- JP2000308900A JP2000308900A JP11117410A JP11741099A JP2000308900A JP 2000308900 A JP2000308900 A JP 2000308900A JP 11117410 A JP11117410 A JP 11117410A JP 11741099 A JP11741099 A JP 11741099A JP 2000308900 A JP2000308900 A JP 2000308900A
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen
- ammonia
- bacteria
- nitrite nitrogen
- treatment
- 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
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアンモニア含有排水
の処理方法に関するものである。さらに詳しくは、生物
学的手法と物理化学的手法を組み合わせ、アンモニア性
窒素を効率的に除去する方法に関する。TECHNICAL FIELD The present invention relates to a method for treating ammonia-containing wastewater. More specifically, the present invention relates to a method for efficiently removing ammonia nitrogen by combining a biological technique and a physicochemical technique.
【０００２】[0002]
【従来の技術】高濃度のアンモニアを含有する排水は、
製鉄所コークス工場、屎尿、肥料工場、半導体工場、皮
革工場などから発生する。例えば、製鉄所コークス工場
から発生するアンモニア含有排水は、安水と呼ばれ、ア
ンモニア性窒素を数百〜数千ｍｇ／ｌ程度も含有してい
る。これらの排水は、アンモニア性窒素の濃度が、都市
下水（数十ｍｇ／ｌ程度）や養殖場排水（数ｍｇ／ｌ）
と比較すると極端に高く、従来の技術では処理にさまざ
まな課題を有している。2. Description of the Related Art Wastewater containing a high concentration of ammonia is
It is generated from steelworks coke factories, human waste, fertilizer factories, semiconductor factories, leather factories, etc. For example, ammonia-containing wastewater generated from a coke plant of an ironworks is referred to as low-temperature water and contains several hundred to several thousand mg / l of ammonia nitrogen. These effluents have a concentration of ammonia nitrogen that is lower than that of city sewage (several tens of mg / l) or farm effluent (several mg / l)
This is extremely high compared to the conventional technology, and the conventional technology has various problems in processing.
【０００３】従来のアンモニア性窒素の除去方法として
は、以下のようなプロセスが広く知見されている。[0003] As a conventional method for removing ammoniacal nitrogen, the following process is widely known.
【０００４】（１）アンモニアストリッピング法 （２）ブレークポイント（不連続点）塩素注入法 （３）吸着法 （４）生物学的硝化−脱窒素法(1) Ammonia stripping method (2) Break point (discontinuous point) chlorine injection method (3) Adsorption method (4) Biological nitrification-denitrification method
【０００５】まず、（１）アンモニアストリッピング法
について説明する。これは排水のｐＨを１０．５〜１
１．５に調整し、クーリングタワーと同様の塔から水を
垂らし、空気によりアンモニアイオンをアンモニアガス
として空気中に飛散させる。First, (1) the ammonia stripping method will be described. This adjusts the pH of the wastewater to 10.5-1.
It is adjusted to 1.5, water is dropped from a tower similar to the cooling tower, and ammonia ions are scattered into the air as ammonia gas by air.
【０００６】ＮＨ4 + → ＮＨ3 ↑ ＋ Ｈ+ NH 4 + → NH 3 ＋+ H +
【０００７】ｐＨが１１．３程度で計算上は９９％除去
が可能となる（例えば、藤田賢二著、下水道工学演習、
学献社）。しかし、アンモニアガスによる二次公害、気
温の影響、ランニングコスト等に課題が多い。When the pH is about 11.3, it is possible to remove 99% from the calculation (for example, Kenji Fujita, Sewage Engineering Exercise,
Academic sponsor). However, there are many problems in terms of secondary pollution due to ammonia gas, temperature effects, running costs, and the like.
【０００８】次に、（２）ブレークポイント（不連続
点）塩素注入法について説明する。アンモニア性窒素を
含む排水に塩素を加えていくと、残留塩素量は最初は増
大するがやがて減少をはじめ、ついで再び増加する。こ
の極小点をブレークポイントと呼び、この点まで達する
まで塩素を注入する方法がブレークポイント塩素注入法
である。塩素とアンモニア性窒素は以下のように反応
し、窒素ガスとなる。Next, the (2) break point (discontinuous point) chlorine injection method will be described. As chlorine is added to wastewater containing ammoniacal nitrogen, the amount of residual chlorine initially increases, but then begins to decrease and then increases again. This minimum point is called a breakpoint, and a method of injecting chlorine until reaching this point is the breakpoint chlorine injection method. Chlorine and ammoniacal nitrogen react as follows to form nitrogen gas.
【０００９】２Ｃｌ2 ＋ ＮＨ4 + → Ｎ2 ＋ ８
Ｈ+＋ ６Ｃｌ- 2Cl 2 + NH 4 + → N 2 +8
H + + 6Cl -
【００１０】本方法の場合、アンモニア性窒素１ｍｇ／
ｌを酸化するためには、Ｃｌ2が理論上７．６ｍｇ／ｌ
必要である（例えば、藤田賢二著、下水道工学演習、学
献社）。したがって、アンモニア性窒素を大量に含有す
る排水に適用することは、ランニングコスト上ほとんど
不可能である。また、通常余剰に塩素を加えるため、残
留する塩素の処理が必要となる。In the case of the present method, ammonia nitrogen 1 mg /
In order to oxidize l, Cl 2 is theoretically 7.6 mg / l
Necessary (for example, Kenji Fujita, Seminar on Sewer Engineering, Academic Cooperation). Therefore, it is almost impossible in terms of running cost to apply the method to wastewater containing a large amount of ammonia nitrogen. Further, since chlorine is usually added in excess, it is necessary to treat residual chlorine.
【００１１】次に（３）吸着法であるが、これはゼオラ
イトのような選択性のイオン交換樹脂に吸着させ除去す
るものである。しかし、吸着量には限界があり、また、
イオン交換樹脂を再生すると再びアンモニア性窒素が発
生する。大量に含有する排水処理に適用することは、実
際上は難しい。[0011] Next, (3) the adsorption method, which is carried out by adsorbing on a selective ion exchange resin such as zeolite and removing it. However, the amount of adsorption is limited,
When the ion exchange resin is regenerated, ammonia nitrogen is generated again. It is practically difficult to apply to wastewater treatment containing a large amount.
【００１２】最後に、（４）生物学的硝化−脱窒素法に
ついて説明する。生物学的硝化−脱窒素法は、好気性独
立栄養細菌（ニトロゾモナス、ニトロバクター等の硝化
細菌）による生物学的酸化と通性嫌気性従属栄養細菌
（シュードモナス等）による生物学的還元の組み合わせ
から成っている。Finally, (4) biological nitrification-denitrification method will be described. The biological nitrification-denitrification method is based on the combination of biological oxidation by aerobic autotrophic bacteria (nitrifying bacteria such as Nitrozomonas and Nitrobactor) and biological reduction by facultative anaerobic heterotrophic bacteria (such as Pseudomonas). Made up of
【００１３】まず、硝化工程は以下の２段の反応から成
っており、関与する硝化細菌の種類は異なっている。First, the nitrification step consists of the following two steps, and the types of nitrifying bacteria involved are different.
【００１４】 ２ＮＨ4 + ＋ ３Ｏ2 → ２ＮＯ2 -＋２Ｈ2Ｏ＋４Ｈ+ （１）2NH 4 + + 3O 2 → 2NO 2 − + 2H 2 O + 4H + (1)
【００１５】 ２ＮＯ2 - ＋ Ｏ2 → ２ＮＯ3 - （２）2NO 2 − + O 2 → 2NO 3 − (2)
【００１６】（１）式に示す反応は、ニトロゾモナスを
代表種とする亜硝酸菌によってもたらされ、（２）式に
示す反応は、ニトロバクターを代表種とする硝酸菌によ
ってもたらされる。The reaction represented by the formula (1) is caused by nitrites represented by Nitrozomonas, and the reaction represented by the formula (2) is caused by nitrites represented by Nitrobacter.
【００１７】上記反応によって生成した亜硝酸性窒素並
びに硝酸性窒素は、一般に通性嫌気性従属栄養細菌によ
り、還元されて酸化窒素ガス（Ｎ2Ｏ）あるいは窒素ガ
ス（Ｎ2）となり大気中に放散される。The nitrite nitrogen and nitrate nitrogen produced by the above reaction are reduced by a facultative anaerobic heterotrophic bacterium into nitrogen oxide gas (N 2 O) or nitrogen gas (N 2 ) and are released into the atmosphere. Dissipated.
【００１８】 ２ＮＯ2 - ＋ ６Ｈ2 → Ｎ2 ＋２Ｈ2Ｏ＋２ＯＨ- （３）2NO 2 − + 6H 2 → N 2 + 2H 2 O + 2OH − (3)
【００１９】 ２ＮＯ3 - ＋１０Ｈ2 → Ｎ2 ＋４Ｈ2Ｏ＋２ＯＨ- （４）2NO 3 − + 10H 2 → N 2 + 4H 2 O + 2OH − (4)
【００２０】通性嫌気性従属栄養細菌は、水素供与体が
必要であり、有機物質が利用される。都市下水では下水
中の有機物がそのまま用いられ、有機物を含まない排水
ではメタノールがよく用いられる。A facultative anaerobic heterotrophic bacterium requires a hydrogen donor and utilizes an organic substance. In municipal sewage, organic matter in sewage is used as it is, and in wastewater containing no organic matter, methanol is often used.
【００２１】この生物学的硝化−脱窒素法は、アンモニ
ア性窒素濃度が１００ｍｇ／ｌ以下では問題が少なく、
また、最も安価で安定した処理方法である。This biological nitrification-denitrification method has few problems when the concentration of ammonia nitrogen is 100 mg / l or less.
Moreover, it is the cheapest and stable processing method.
【００２２】[0022]
【発明が解決しようとする課題】しかし、生物学的硝化
−脱窒素法は、アンモニア性窒素濃度が１００ｍｇ／ｌ
を超えると様々な課題が生じ、安定した処理が困難とな
る。However, the biological nitrification-denitrification method has an ammonia nitrogen concentration of 100 mg / l.
When the number exceeds, various problems occur, and stable processing becomes difficult.
【００２３】すなわち、アンモニア性窒素濃度が１００
ｍｇ／ｌを超えると、硝化工程において、アンモニア性
窒素の酸化が硝酸性窒素まで進行しないこと、すなわ
ち、ニトロバクターが阻害を受け、処理水中の亜硝酸性
窒素が蓄積しやすいことが知見されている。この原因と
して、遊離のアンモニウムイオンのニトロバクターへの
阻害が知られている。特に、ｐＨが高いと遊離のアンモ
ニウムイオンが発生する。That is, when the ammonia nitrogen concentration is 100
When the amount exceeds mg / l, it has been found that in the nitrification step, the oxidation of ammonia nitrogen does not proceed to nitrate nitrogen, that is, the nitrobacter is inhibited and nitrite nitrogen in the treated water tends to accumulate. I have. As a cause of this, inhibition of free ammonium ions on nitrobacter is known. In particular, when the pH is high, free ammonium ions are generated.
【００２４】この結果、以下の（１）、（２）の障害が
生ずる。As a result, the following faults (1) and (2) occur.
【００２５】（１）亜硝酸性窒素は、従属栄養細菌に対
して毒性が強く処理水質が悪化しやすい（例えば、遠矢
泰典、下水道協会誌、ＶＯＬ７，ＮＯ７４，１９７
０）。この結果、通常、脱窒素に用いられている細菌は
従属栄養細菌であるから、蓄積した亜硝酸性窒素によっ
て脱窒素反応の進行に阻害が生ずる。(1) Nitrite nitrogen is highly toxic to heterotrophic bacteria and easily deteriorates treated water quality (for example, Yasunori Toya, Journal of Japan Sewerage Association, VOL7, NO74, 197).
0). As a result, the bacteria used for denitrification are usually heterotrophic bacteria, and the accumulated nitrite nitrogen inhibits the progress of the denitrification reaction.
【００２６】（２）進行が停止すると、亜硝酸性窒素が
処理水に流出し、亜硝酸性窒素起因のＣＯＤ（化学的酸
素要求量）の増大等の問題を発生させる。(2) When the progress is stopped, nitrite nitrogen flows into the treated water, causing problems such as an increase in COD (chemical oxygen demand) caused by nitrite nitrogen.
【００２７】このようなことから、アンモニア性窒素濃
度が１００ｍｇ／ｌを超えるような場合、硝化工程が極
めて重要となる。このため、希釈したり、処理時間を長
くして負荷を下げたり、あるいは、ｐＨの厳密な管理
（７近辺）を行うことが要求される。しかし、処理の安
定化は困難でしばしば亜硝酸性窒素の蓄積が生じてい
る。From the above, when the ammonia nitrogen concentration exceeds 100 mg / l, the nitrification step becomes extremely important. For this reason, it is required to dilute, to reduce the load by prolonging the treatment time, or to perform strict management of pH (around 7). However, stabilization of the process is difficult and often results in the accumulation of nitrite nitrogen.
【００２８】[0028]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく検討を重ねた結果、以下の方法により、
高濃度のアンモニア性窒素を含有する排水を処理するこ
とに成功した。本発明の要旨とするところは、次の
（１）〜（６）である。Means for Solving the Problems The present inventors have repeatedly studied to solve the above-mentioned problems, and as a result, by the following method,
The wastewater containing high concentration of ammonia nitrogen was successfully treated. The gist of the present invention is the following (1) to (6).
【００２９】（１）アンモニア含有排水に含まれるアン
モニア性窒素を生物処理により亜硝酸性窒素に酸化した
後、独立栄養細菌を用いた生物学的脱窒素法により亜硝
酸性窒素を窒素ガスに還元して排水から除去することを
特徴とするアンモニア含有排水の処理方法。(1) After oxidizing ammonium nitrogen contained in the ammonia-containing wastewater to nitrite nitrogen by biological treatment, the nitrite nitrogen is reduced to nitrogen gas by a biological denitrification method using autotrophic bacteria. And treating the wastewater containing ammonia.
【００３０】（２）アンモニア含有排水に含まれるアン
モニア性窒素を生物処理により亜硝酸性窒素に酸化した
後、紫外線を用いた物理化学的手法を用いて硝酸性窒素
に酸化した後、従属栄養細菌または独立栄養細菌を用い
た生物学的脱窒素法により亜硝酸性窒素を窒素ガスに還
元して排水から除去することを特徴とするアンモニア含
有排水の処理方法。(2) Ammoniacal nitrogen contained in the ammonia-containing wastewater is oxidized to nitrite nitrogen by biological treatment, and then oxidized to nitrate nitrogen using a physicochemical method using ultraviolet light. Alternatively, a method for treating ammonia-containing wastewater, wherein nitrite nitrogen is reduced to nitrogen gas and removed from the wastewater by a biological denitrification method using autotrophic bacteria.
【００３１】（３）独立栄養細菌として硫黄酸化細菌を
用いることを特徴とする前記（１）または（２）のアン
モニア含有排水の処理方法。(3) The method for treating wastewater containing ammonia according to the above (1) or (2), wherein a sulfur-oxidizing bacterium is used as an autotrophic bacterium.
【００３２】（４）生物学的脱窒素法により発生する余
剰の有機物または硫黄化合物を、紫外線および／または
オゾンおよび／または過酸化水素を用いた物理化学的手
法を用いて酸化することを特徴とする前記（１）〜
（３）のいずれかのアンモニア含有排水の処理方法。(4) Excessive organic substances or sulfur compounds generated by the biological denitrification method are oxidized by a physicochemical method using ultraviolet light and / or ozone and / or hydrogen peroxide. Said (1)-
(3) The method for treating ammonia-containing wastewater according to any of (3).
【００３３】（５）紫外線を用いた物理化学的手法にお
いて、光触媒を併用した中圧紫外線ランプまたは高圧紫
外線ランプまたはブラックライトを用いることを特徴と
する前記（２）〜（４）のいずれかのアンモニア含有排
水の処理方法。(5) In the physicochemical method using ultraviolet rays, a medium-pressure ultraviolet lamp, a high-pressure ultraviolet lamp or a black light combined with a photocatalyst is used. A method for treating ammonia-containing wastewater.
【００３４】（６）海水とアンモニア含有排水を混合し
て処理を行うことを特徴とする前記（１）〜（５）のい
ずれかのアンモニア含有排水の処理方法。(6) The method for treating ammonia-containing wastewater according to any one of the above (1) to (5), wherein the treatment is carried out by mixing seawater and ammonia-containing wastewater.
【００３５】[0035]
【発明の実施の形態】発明者らは、高濃度のアンモニア
を含有する排水の生物学的硝化工程において、硝化反応
を制御することは極めて困難と考え、以下の２つの方法
を発明した。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have considered that it is extremely difficult to control the nitrification reaction in the biological nitrification step of wastewater containing a high concentration of ammonia, and have invented the following two methods.
【００３６】（１）脱窒素工程において、亜硝酸性窒素
に耐性のある独立栄養細菌を用い、亜硝酸性窒素を還元
し、窒素ガスとする。このような方法を用いると、硝化
工程において、硝酸性窒素を生成する必要が無くなり、
処理時間の短縮や維持管理が容易となる。(1) In the denitrification step, nitrite nitrogen is reduced to nitrogen gas using autotrophic bacteria resistant to nitrite nitrogen. Using such a method eliminates the need to generate nitrate nitrogen in the nitrification step,
Processing time can be shortened and maintenance is easy.
【００３７】（２）独立栄養細菌の耐性以上の亜硝酸性
窒素が蓄積する場合には、硝化工程から発生する亜硝酸
性窒素を紫外線により硝酸性窒素まで酸化した後、独立
栄養細菌または従属栄養細菌により窒素ガスまで還元す
る。(2) When nitrite nitrogen that accumulates beyond the resistance of the autotrophic bacterium accumulates, nitrite nitrogen generated from the nitrification step is oxidized to nitrate nitrogen by ultraviolet light, and then cultivated by the autotrophic bacterium or heterotrophic bacterium. Reduced to nitrogen gas by bacteria.
【００３８】まず、亜硝酸性窒素に耐性のある独立栄養
細菌を用いて、亜硝酸性窒素を還元し、窒素ガスとする
方法について説明する。First, a method of reducing nitrite nitrogen to nitrogen gas using autotrophic bacteria resistant to nitrite nitrogen will be described.
【００３９】水素細菌や硫黄酸化細菌などの独立栄養細
菌は、それぞれ水素や還元性硫黄化合物を酸化した時に
発生するエネルギーと空気中の炭酸ガスから菌体を合
成、増殖する微生物である。これらの細菌は、増殖速度
が小さいことやフロック形成能力が弱い等の理由から脱
窒素作用が知られていたが、ほとんど実際には用いられ
ていない。Autotrophic bacteria such as hydrogen bacteria and sulfur oxidizing bacteria are microorganisms that synthesize and proliferate cells from the energy generated when hydrogen and reducing sulfur compounds are oxidized, respectively, and carbon dioxide gas in the air. These bacteria have been known to have a denitrifying effect because of their low growth rate and weak floc-forming ability, but they are hardly actually used.
【００４０】発明者らは、これらの独立栄養細菌が亜硝
酸性窒素に対し、従属栄養細菌と比較し極めて強い耐性
を有していることを知見した。すなわち、亜硝酸性窒素
濃度が２０００ｍｇ／ｌ以下の範囲で脱窒素速度の低下
は見られなかった（ｐＨ：６〜８、水温２０℃の条件
下）。The inventors have found that these autotrophic bacteria have extremely strong resistance to nitrite nitrogen as compared to heterotrophic bacteria. That is, no reduction in the denitrification rate was observed when the nitrite nitrogen concentration was in the range of 2000 mg / l or less (pH: 6 to 8; water temperature: 20 ° C.).
【００４１】特に、独立栄養細菌の中でも、硫黄酸化細
菌は、自己造粒作用を有しているため、リアクターでの
高濃度化・処理の高効率化が容易であり、本方法に使用
する独立栄養細菌としては最適である。さらに、硫黄酸
化細菌がエネルギー獲得に必要なチオ硫酸等の硫黄化合
物は、余剰に残留しても、紫外線、オゾン、過酸化水素
等で容易に硫酸イオンまで酸化される。もちろん、好気
性の硫黄酸化細菌を用いて、残留する硫黄化合物を硫酸
イオンまで生物酸化してもかまわない。In particular, among the autotrophic bacteria, the sulfur-oxidizing bacteria have a self-granulating effect, so that it is easy to increase the concentration and the treatment efficiency in the reactor, and to use the independent oxidizing bacteria in the present method. It is optimal as a vegetative bacterium. Furthermore, sulfur compounds such as thiosulfuric acid necessary for sulfur-oxidizing bacteria to obtain energy are easily oxidized to sulfate ions by ultraviolet rays, ozone, hydrogen peroxide, etc., even if they remain in excess. Of course, the remaining sulfur compounds may be biologically oxidized to sulfate ions using aerobic sulfur oxidizing bacteria.
【００４２】このように、亜硝酸性窒素に耐性のある独
立栄養細菌を用いることにより、従来困難であった高濃
度のアンモニアを含有する排水安定処理が可能となる。As described above, by using an autotrophic bacterium that is resistant to nitrite nitrogen, it is possible to stably treat wastewater containing a high concentration of ammonia, which has been difficult in the past.
【００４３】次に、硝化工程から発生する亜硝酸性窒素
を、紫外線によって硝酸まで酸化した後、従属栄養細菌
あるいは独立栄養細菌により窒素ガスまで還元する方法
について説明する。発明者らは、紫外線が、残留性が無
く、しかも、優れた亜硝酸性窒素酸化力があることを知
見し、生物学的硝化−紫外線酸化−生物学的脱窒法によ
り、従来困難であった高濃度のアンモニアを含む排水の
安定処理が可能となることを見いだした。Next, a method of oxidizing nitrite nitrogen generated from the nitrification step to nitric acid by ultraviolet rays and reducing it to nitrogen gas by heterotrophic bacteria or autotrophic bacteria will be described. The present inventors have found that ultraviolet light has no residual property and has excellent nitrite nitrogen oxidizing power, and it has been conventionally difficult to carry out the biological nitrification-ultraviolet light oxidation-biological denitrification method. It has been found that stable treatment of wastewater containing a high concentration of ammonia is possible.
【００４４】亜硝酸性窒素がオゾン、過酸化水素、塩素
などによって硝酸性窒素まで酸化されることは広く知見
されている。しかし、過酸化水素や塩素などの薬剤は、
残留性があるため、後段に生物処理があると活性に悪影
響を及ぼす。オゾンは速やかに酸素となるが、後段に嫌
気性生物処理がある場合、酸素が影響を及ぼすことがあ
る。It is widely known that nitrite nitrogen is oxidized to nitrate nitrogen by ozone, hydrogen peroxide, chlorine and the like. However, drugs such as hydrogen peroxide and chlorine
Due to the persistence, the subsequent biological treatment adversely affects the activity. Ozone quickly becomes oxygen, but if there is an anaerobic biological treatment at a later stage, the oxygen may have an effect.
【００４５】また、先に述べた亜硝酸性窒素に耐性のあ
る独立栄養細菌を用いて脱窒素を行っても、亜硝酸性窒
素が２０００ｍｇ／ｌ以上蓄積すると阻害が生じ、亜硝
酸性窒素が処理水に残留することになる。In addition, even if denitrification is performed using the above-described autotrophic bacteria resistant to nitrite nitrogen, inhibition occurs when nitrite nitrogen is accumulated at 2000 mg / l or more, and nitrite nitrogen is reduced. It will remain in the treated water.
【００４６】このため、このような場合、生物学的硝化
槽の後段に、紫外線によって亜硝酸性窒素を速やかに硝
酸性窒素まで酸化する工程を組み込むことが望ましい。
この結果、亜硝酸性窒素が減少し、生物学的硝化および
生物学的脱窒に好影響を及ぼす。Therefore, in such a case, it is desirable to incorporate a step of rapidly oxidizing nitrite nitrogen to nitrate nitrogen by ultraviolet rays at a stage subsequent to the biological nitrification tank.
As a result, nitrite nitrogen is reduced and has a favorable effect on biological nitrification and biological denitrification.
【００４７】さらに、紫外線酸化を効率化するために
は、光触媒を併用した中圧紫外線ランプまたは高圧紫外
線ランプまたはブラックライトを用いることが望まし
い。発生するＯＨラジカルにより、亜硝酸性窒素酸化力
が向上する。Further, in order to increase the efficiency of ultraviolet oxidation, it is desirable to use a medium-pressure ultraviolet lamp, a high-pressure ultraviolet lamp or a black light using a photocatalyst in combination. The generated OH radicals improve the nitrite nitrogen oxidizing power.
【００４８】さらに、海水により排水を希釈すると、ア
ンモニア性窒素濃度や亜硝酸性窒素濃度が低下するばか
りでなく、さらにＯＨラジカル発生量が増大し、亜硝酸
性窒素酸化力が向上することがわかった。これは、海水
中の鉄イオンや臭素イオンの影響と推定される。Further, it is found that when the waste water is diluted with seawater, not only the concentration of ammonia nitrogen and the concentration of nitrite nitrogen are reduced, but also the amount of generated OH radicals is increased and the oxidizing power of nitrite nitrogen is improved. Was. This is presumed to be the effect of iron ions and bromine ions in seawater.
【００４９】なお、本方法で亜硝酸性窒素を硝酸性窒素
まで酸化した場合、脱窒素工程に用いる細菌は、従属栄
養細菌でも独立栄養細菌でもかまわない。When nitrite nitrogen is oxidized to nitrate nitrogen by the present method, the bacterium used in the denitrification step may be a heterotrophic bacterium or an autotrophic bacterium.
【００５０】[0050]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００５１】[0051]
【実施例１】製鉄所コークス工場安水処理への適用 本発明の方法を製鉄所コークス工場から発生する安水の
活性汚泥処理水に適用した。安水は、フェノールが主体
の排水であるが、アンモニア性窒素を１０００〜５００
０ｍｇ／ｌ程度含有している。従来は、海水で３〜５倍
程度希釈し、活性汚泥によりフェノールを中心に分解除
去していた。このような安水活性汚泥処理水は、活性汚
泥によってフェノール等の有機物は除去されているもの
の、アンモニア性窒素を３００〜１０００ｍｇ／ｌ含有
していることが多い。[Example 1] Application to the water treatment of a steel mill coke plant The method of the present invention was applied to the activated sludge treated water of a low water generated from a steel plant coke plant. The low-temperature water is effluent mainly composed of phenol.
It contains about 0 mg / l. Conventionally, it is diluted about 3 to 5 times with seawater, and phenol is mainly decomposed and removed by activated sludge. Such an activated water activated sludge treatment water contains 300 to 1000 mg / l of ammonia nitrogen in many cases, although organic substances such as phenol are removed by activated sludge.
【００５２】この安水活性汚泥処理水に本発明の方法を
適用した。この処理フローを図１に示す。The method of the present invention was applied to this treated water with activated sludge. This processing flow is shown in FIG.
【００５３】まず、硝化槽１でアンモニア性窒素を亜硝
酸性窒素まで酸化するために以下の運転条件で硝化槽１
を運転した。硝化槽１にはセラミック担体をリアクター
容積あたり７０％投入し、硝化菌を付着させた（固定床
型バイオリアクター）。硝化槽１は、硫酸および水酸化
ナトリウムによって、ｐＨを７〜８に制御するととも
に、空気および／または酸素により、ＤＯを２ｍｇ／ｌ
以上、ＯＲＰを１５０ｍＶ（銀／塩化銀基準）以上に維
持するように運転した。アンモニア性窒素容積負荷が５
ｋｇ−Ｎ／ｍ3・日の範囲で、アンモニア性窒素（８５
０ｍｇ／ｌ）は、８０％が亜硝酸性窒素に、２０％が硝
酸性窒素になった。First, in order to oxidize ammonia nitrogen to nitrite nitrogen in the nitrification tank 1, the nitrification tank 1 is operated under the following operating conditions.
Drove. The nitrification tank 1 was charged with a ceramic carrier at 70% per reactor volume to allow nitrifying bacteria to adhere (fixed bed type bioreactor). The nitrification tank 1 controls the pH to 7 to 8 with sulfuric acid and sodium hydroxide, and controls DO at 2 mg / l with air and / or oxygen.
As described above, the operation was performed so as to maintain the ORP at 150 mV or more (based on silver / silver chloride). Ammoniacal nitrogen volume load is 5
kg-N / m 3 · day, ammonia nitrogen (85
(0 mg / l), 80% became nitrite nitrogen and 20% became nitrate nitrogen.
【００５４】脱窒素槽２には自己造粒させた硫黄酸化細
菌を投入し、硫黄源としてチオ硫酸を硫黄として窒素の
３倍量添加した。硝酸性窒素と亜硝酸性窒素の容積負荷
が１０ｋｇ−Ｎ／ｍ3・日の条件で運転したところ、処
理水中の窒素濃度は１０ｍｇ／ｌ以下となった。Self-granulated sulfur oxidizing bacteria were charged into the denitrification tank 2, and thiosulfuric acid was added as a sulfur source in an amount three times as much as nitrogen as sulfur. When the operation was performed under the conditions of a volume load of nitrate nitrogen and nitrite nitrogen of 10 kg-N / m 3 · day, the nitrogen concentration in the treated water became 10 mg / l or less.
【００５５】さらに、処理水中に残留するチオ硫酸は、
紫外線酸化槽３によって硫酸イオンまで酸化した。紫外
線酸化槽３は、曝気によって溶存酸素を２ｍｇ／ｌ以上
に維持した。紫外線酸化槽３の滞留時間２０分で、チオ
硫酸は硫酸イオンまで酸化され、ＣＯＤも３０ｍｇ／ｌ
以下となった。さらに、紫外線として光触媒を併用した
中圧紫外線を用いると酸化力が向上し、滞留時間１０分
でチオ硫酸が硫酸イオンまで酸化され、難分解性有機物
の酸化も進行し、ＣＯＤも２０ｍｇ／ｌ以下となった。Further, thiosulfuric acid remaining in the treated water is:
It was oxidized to sulfate ions by the ultraviolet oxidation tank 3. The ultraviolet oxidation tank 3 maintained dissolved oxygen at 2 mg / l or more by aeration. With a residence time of 20 minutes in the ultraviolet oxidation tank 3, thiosulfuric acid is oxidized to sulfate ions, and COD is also 30 mg / l.
It was as follows. Furthermore, the use of medium-pressure ultraviolet light in combination with a photocatalyst as ultraviolet light improves oxidizing power, thiosulfuric acid is oxidized to sulfate ions in a residence time of 10 minutes, oxidation of hardly decomposable organic substances proceeds, and COD is 20 mg / l or less. It became.
【００５６】[0056]
【実施例２】屎尿処理活性汚泥処理水への適用 本発明の方法の屎尿処理への適用を検討した。従来の標
準的な脱窒素法では、収集屎尿を１０〜２０倍程度に希
釈した後、活性汚泥で処理し有機物除去（ＢＯＤ）を行
っていた。窒素除去も併せて行う場合には、循環式硝化
−脱窒素法が採用されている場合が多い（硝化液を脱窒
素槽に循環し、排水中の有機物により脱窒素を行う脱窒
素−硝化のフローとなる）。しかし、窒素除去を行う場
合、亜硝酸性窒素蓄積が生じやすく、窒素除去効率が低
下しやすい。このため、希釈倍率が大きくなり、施設の
巨大化を招いてしまう。なお、収集屎尿の水質は、ＢＯ
Ｄが１００００〜２００００ｍｇ／ｌ、ＣＯＤが５００
０〜１００００ｍｇ／ｌ、ＴＮが５０００〜１００００
ｍｇ／ｌ（大半が有機性窒素とアンモニア性窒素）程度
である。Example 2 Application to human waste treatment activated sludge treated water The application of the method of the present invention to human waste treatment was examined. In the conventional standard denitrification method, after collecting collected manure is diluted about 10 to 20 times, it is treated with activated sludge to remove organic substances (BOD). In the case where nitrogen removal is also performed, a recirculating nitrification-denitrification method is often employed (the nitrification solution is circulated to a denitrification tank and denitrification is performed using organic matter in wastewater. Flow). However, when performing nitrogen removal, nitrite nitrogen accumulation tends to occur, and the nitrogen removal efficiency tends to decrease. For this reason, the dilution ratio becomes large, and the facility becomes large. The quality of collected human waste is BO
D is 10,000-20,000 mg / l, COD is 500
0 to 10000 mg / l, TN 5000 to 10000
mg / l (mostly organic nitrogen and ammonia nitrogen).
【００５７】本発明を屎尿処理に適用した。屎尿を３倍
に希釈後、まず、活性汚泥により有機物を除去した。The present invention was applied to human waste treatment. After diluting the human waste three times, first, organic matter was removed with activated sludge.
【００５８】その後、図２の硝化槽１でアンモニア性窒
素を亜硝酸性窒素まで酸化するために以下の運転条件で
硝化槽１を運転した。硝化槽１には、浮遊性のプラスチ
ックス担体を硝化槽容積あたり２５％投入し、硝化菌を
付着させた（流動床型バイオリアクター）。硝化槽１
は、硫酸および水酸化ナトリウムによって、ｐＨを７〜
８に制御するとともに、空気および／または酸素によ
り、ＤＯを２ｍｇ／ｌ以上、ＯＲＰを１５０ｍＶ（銀／
塩化銀基準）以上に維持するように運転した。硝化槽１
のアンモニア性窒素容積負荷が５ｋｇ−Ｎ／ｍ3・日の
条件で、有機性窒素とアンモニア性窒素の合計（２５０
０ｍｇ／ｌ）は、９０％が亜硝酸性窒素に、１０％が硝
酸性窒素になった。さらに、光触媒−紫外線酸化槽５で
亜硝酸性窒素を硝酸性窒素まで酸化し、亜硝酸性窒素濃
度を２０００ｍｇ／ｌ以下とした。Thereafter, the nitrification tank 1 was operated under the following operating conditions in order to oxidize ammonia nitrogen to nitrite nitrogen in the nitrification tank 1 of FIG. Into the nitrification tank 1, a floating plastics carrier was charged at 25% per volume of the nitrification tank to allow nitrifying bacteria to adhere (a fluidized-bed bioreactor). Nitrification tank 1
Is adjusted to pH 7 to 7 with sulfuric acid and sodium hydroxide.
8 and, with air and / or oxygen, DO at 2 mg / l or more and ORP at 150 mV (silver /
It operated so that it might maintain above (silver chloride standard). Nitrification tank 1
Under the condition that the ammonia nitrogen volume load of 5 kg-N / m 3 · day is the total of organic nitrogen and ammonia nitrogen (250
(0 mg / l), 90% became nitrite nitrogen and 10% became nitrate nitrogen. Further, nitrite nitrogen was oxidized to nitrate nitrogen in the photocatalyst-ultraviolet oxidation tank 5, and the nitrite nitrogen concentration was reduced to 2000 mg / l or less.
【００５９】さらに、脱窒素槽２には自己造粒させた硫
黄酸化細菌を投入し、硫黄源としてチオ硫酸を硫黄とし
て窒素の３倍量添加した。硝酸性窒素と亜硝酸性窒素の
容積負荷が１５ｋｇ−Ｎ／ｍ3・日の条件で運転したと
ころ、処理水中の窒素濃度は１０ｍｇ／ｌ以下となっ
た。さらに、処理水中に残留するチオ硫酸は、紫外線酸
化槽３によって硫酸イオンまで酸化した。紫外線酸化槽
３は、曝気によって溶存酸素を２ｍｇ／ｌ以上に維持し
た。滞留時間３０分でチオ硫酸は硫酸イオンまで酸化さ
れ、ＣＯＤも３０ｍｇ／ｌ以下となった。Further, self-granulated sulfur-oxidizing bacteria were put into the denitrification tank 2, and thiosulfuric acid was added as a sulfur source in an amount three times as much as nitrogen as sulfur. When the operation was performed under the condition that the volume load of nitrate nitrogen and nitrite nitrogen was 15 kg-N / m 3 · day, the nitrogen concentration in the treated water became 10 mg / l or less. Further, the thiosulfuric acid remaining in the treated water was oxidized by the ultraviolet oxidation tank 3 to sulfate ions. The ultraviolet oxidation tank 3 maintained dissolved oxygen at 2 mg / l or more by aeration. In a residence time of 30 minutes, thiosulfuric acid was oxidized to sulfate ions, and COD became 30 mg / l or less.
【００６０】[0060]
【発明の効果】本発明により、アンモニア性窒素を高濃
度に含有する排水を処理する際に発生する亜硝酸性窒素
による処理効率低下を防止でき、安定した窒素除去が可
能となる。According to the present invention, it is possible to prevent a decrease in treatment efficiency due to nitrite nitrogen generated when treating wastewater containing a high concentration of ammonia nitrogen, thereby enabling stable nitrogen removal.
【図１】脱窒素工程において独立栄養細菌を用いる本発
明のアンモニア含有排水の処理方法を示す図である。FIG. 1 is a diagram showing a method for treating ammonia-containing wastewater of the present invention using autotrophic bacteria in a denitrification step.
【図２】硝化工程において、生物学的硝化工程と紫外線
酸化工程を有する本発明のアンモニア含有排水の処理方
法を示す図である。FIG. 2 is a diagram showing a method for treating ammonia-containing wastewater of the present invention, which includes a biological nitrification step and an ultraviolet oxidation step in the nitrification step.
１ 硝化槽 ２ 脱窒素槽 ３ 紫外線酸化槽 ４ チオ硫酸添加槽 ５ 光触媒−紫外線酸化槽 DESCRIPTION OF SYMBOLS 1 Nitrification tank 2 Denitrification tank 3 Ultraviolet oxidation tank 4 Thiosulfuric acid addition tank 5 Photocatalyst-Ultraviolet oxidation tank
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D037 AA11 AB02 AB12 AB13 BA18 CA07 CA11 CA12 4D040 BB02 4D050 AA13 AA16 AB07 AB35 AB42 BB02 BB09 BC04 BC09 BD08 CA17 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D037 AA11 AB02 AB12 AB13 BA18 CA07 CA11 CA12 4D040 BB02 4D050 AA13 AA16 AB07 AB35 AB42 BB02 BB09 BC04 BC09 BD08 CA17
Claims (6)
ア性窒素を生物処理により亜硝酸性窒素に酸化した後、
独立栄養細菌を用いた生物学的脱窒素法により亜硝酸性
窒素を窒素ガスに還元して排水から除去することを特徴
とするアンモニア含有排水の処理方法。1. After oxidizing ammonia nitrogen contained in ammonia-containing waste water to nitrite nitrogen by biological treatment,
A method for treating ammonia-containing wastewater, comprising reducing nitrite nitrogen to nitrogen gas and removing it from wastewater by a biological denitrification method using autotrophic bacteria.
ア性窒素を生物処理により亜硝酸性窒素に酸化した後、
紫外線を用いた物理化学的手法を用いて硝酸性窒素に酸
化した後、従属栄養細菌または独立栄養細菌を用いた生
物学的脱窒素法により硝酸性窒素を窒素ガスに還元して
排水から除去することを特徴とするアンモニア含有排水
の処理方法。2. After oxidizing ammonia nitrogen contained in the ammonia-containing waste water to nitrite nitrogen by biological treatment,
After being oxidized to nitrate nitrogen using a physicochemical method using ultraviolet light, nitrate nitrogen is reduced to nitrogen gas and removed from wastewater by biological denitrification using heterotrophic or autotrophic bacteria A method for treating ammonia-containing wastewater, comprising:
ることを特徴とする請求項１または２に記載のアンモニ
ア含有排水の処理方法。3. The method according to claim 1, wherein a sulfur-oxidizing bacterium is used as the autotrophic bacterium.
有機物または硫黄化合物を、紫外線および／またはオゾ
ンおよび／または過酸化水素を用いた物理化学的手法を
用いて酸化することを特徴とする請求項１〜３のいずれ
かに記載のアンモニア含有排水の処理方法。4. The method according to claim 1, wherein excess organic substances or sulfur compounds generated by the biological denitrification method are oxidized by a physicochemical method using ultraviolet light and / or ozone and / or hydrogen peroxide. The method for treating ammonia-containing wastewater according to claim 1.
て、光触媒を併用した中圧紫外線ランプまたは高圧紫外
線ランプまたはブラックライトを用いることを特徴とす
る請求項２〜４のいずれかに記載のアンモニア含有排水
の処理方法。5. The ammonia-containing method according to claim 2, wherein a medium-pressure ultraviolet lamp, a high-pressure ultraviolet lamp, or a black light combined with a photocatalyst is used in the physicochemical method using ultraviolet light. Wastewater treatment method.
理を行うことを特徴とする請求項１〜５のいずれかに記
載のアンモニア含有排水の処理方法。6. The method for treating ammonia-containing wastewater according to claim 1, wherein the treatment is performed by mixing seawater and ammonia-containing wastewater.
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| JP11117410A JP2000308900A (en) | 1999-04-26 | 1999-04-26 | Treatment of wastewater containing ammonia |
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|---|---|---|---|
| JP11117410A JP2000308900A (en) | 1999-04-26 | 1999-04-26 | Treatment of wastewater containing ammonia |
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| EP1695942A2 (en) | 2005-02-28 | 2006-08-30 | Sharp Kabushiki Kaisha | Wastewater treatment device and wastewater treatment method |
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| CN110467276A (en) * | 2019-09-16 | 2019-11-19 | 南京大学 | Preparation and application of a sulfur autotrophic and heterotrophic denitrification biofiller |
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| CN111924977A (en) * | 2020-07-14 | 2020-11-13 | 海南微能科技有限公司 | Method for treating nitrate nitrogen wastewater by using composite flora |
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