JP2002346592A - Low temperature denitrification material and denitrification method using the same - Google Patents
Low temperature denitrification material and denitrification method using the sameInfo
- Publication number
- JP2002346592A JP2002346592A JP2001158894A JP2001158894A JP2002346592A JP 2002346592 A JP2002346592 A JP 2002346592A JP 2001158894 A JP2001158894 A JP 2001158894A JP 2001158894 A JP2001158894 A JP 2001158894A JP 2002346592 A JP2002346592 A JP 2002346592A
- Authority
- JP
- Japan
- Prior art keywords
- denitrification
- nitrate nitrogen
- temperature
- low
- sulfur
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Biological Treatment Of Waste Water (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、農業系廃水、工業系廃
水、一般家庭用廃水、下水処理排水等の排水、地下水、
湖沼、河川、海洋等の自然水、養魚用等の水槽水の水質
浄化に用いられる脱窒素材料及びそれを使用する硝酸性
窒素の脱窒方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to wastewater such as agricultural wastewater, industrial wastewater, general household wastewater, sewage treatment wastewater, groundwater, and the like.
The present invention relates to a denitrification material used for water purification of natural water such as lakes, rivers, oceans and the like, and aquarium water for fish culture and the like, and a method for denitrification of nitrate nitrogen using the same.
【０００２】[0002]
【従来の技術】農業系廃水、工業系廃水、一般家庭用廃
水、下水処理排水等の排水には、硝酸性窒素が含まれる
ことが多い。また、最近は、河川、湖沼、海洋等の自然
水も富栄養化などの問題が生じており、硝酸性窒素がそ
の主な原因となっていることも多い。更に、養殖用に使
用される水槽中の水や海水も同様な問題が生じやすい。
近年、廃液中の硝酸イオン濃度問題が深刻化しており、
生物学的処理法を用いた種々の処理システムが考案され
ている。この代表として、メタノールや汚泥中の有機炭
素源を水素供与体として脱窒する従属栄養性脱窒技術が
知られているが、この技術は基質当たりの脱窒率が低い
ことに加え、脱窒後は過剰な水素供与体を外部へ排出し
ないように、別途除去する必要があるため、多くの処理
設備や装置が必要となる。2. Description of the Related Art Wastewater such as agricultural wastewater, industrial wastewater, general household wastewater and sewage treatment wastewater often contains nitrate nitrogen. Also, recently, natural waters such as rivers, lakes, and oceans have caused problems such as eutrophication, and nitrate nitrogen is often the main cause. Furthermore, water and seawater in a water tank used for aquaculture tend to cause the same problem.
In recent years, the problem of nitrate ion concentration in wastewater has become serious,
Various treatment systems using biological treatment methods have been devised. As a representative example, a heterotrophic denitrification technology for denitrification using an organic carbon source in methanol or sludge as a hydrogen donor is known, but this technology has a low denitrification rate per substrate and also has a denitrification rate. Thereafter, it is necessary to separately remove the excess hydrogen donor so as not to discharge the hydrogen donor to the outside, so that many processing facilities and apparatuses are required.
【０００３】これに対し、独立栄養性硫黄酸化脱窒細菌
を用いた硝酸性窒素処理システムは、従来の従属栄養性
脱窒細菌を用いたシステムと異なり、メタノールや有機
炭素源を添加する必要がないため、供給に必要な設備
や、脱窒後の２次処理設備などが不要であり、各方面で
注目されている。特に、特開平１１−２８５３７７号公
報や特開２００１−１０４９９３号公報、特開２００１
−９３９９７号公報などの硫黄と炭酸カルシウム系成分
からなる無機質材料の溶融混合物を固体栄養とし、独立
栄養性硫黄酸化細菌を用いた方式は、ポンプ、攪拌装置
などの電源を必要としないため、メンテナンスが容易
で、脱窒処理にかかるコストの面で優れた効果を示して
いる。しかしながら、一般的に独立栄養性硫黄酸化細菌
は１５℃以下の低温での活動が鈍く、良好な脱窒性能が
得られないため、冬場の低温時の脱窒性能は低く、ヒー
ターなどで温度を確保する必要があった。[0003] On the other hand, a nitrate nitrogen treatment system using autotrophic sulfur oxidizing and denitrifying bacteria, unlike a conventional system using heterotrophic denitrifying bacteria, requires the addition of a methanol or organic carbon source. Therefore, facilities required for supply and secondary treatment facilities after denitrification are not required, and are attracting attention in various fields. In particular, JP-A-11-285377, JP-A-2001-104993,
In the method using a molten mixture of an inorganic material composed of sulfur and calcium carbonate based components such as JP-93997 as solid nutrition and using an autotrophic sulfur-oxidizing bacterium, a power source such as a pump and a stirrer is not required, so maintenance is required. , And has an excellent effect in terms of the cost of the denitrification treatment. However, in general, autotrophic sulfur-oxidizing bacteria have a low activity at low temperatures of 15 ° C or less and cannot obtain good denitrification performance. Therefore, denitrification performance at low temperatures in winter is low. It was necessary to secure.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、硝酸性窒素
を含有する被処理水が１５℃以下の低温であっても、良
好な脱窒性能が得られる脱窒材料を提供することにあ
る。また、本発明は、この脱窒材料を使用する脱窒方法
を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a denitrification material which can obtain good denitrification performance even when the water to be treated containing nitrate nitrogen is at a low temperature of 15 ° C. or less. . Another object of the present invention is to provide a denitrification method using the denitrification material.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、水
中の硝酸性窒素を処理する脱窒材料において、硫黄とカ
ルシウム系成分からなる無機質材料の溶融混合物を基質
とし、この基質に独立栄養系硫黄酸化脱窒細菌を１〜１
０℃の温度下で２日間以上培養し、定着させることを特
徴とする低温脱窒材料である。また、本発明は、基質
が、硫黄と炭酸カルシウム系成分からなる無機質材料の
溶融混合物が鉱物繊維と一体化したものである前記の低
温脱窒材料である。更に、本発明は、前記の低温脱窒材
料を、硝酸性窒素を含有する排水又は被処理水と接触さ
せることを特徴とする硝酸性窒素の脱窒方法である。That is, the present invention relates to a denitrifying material for treating nitrate nitrogen in water, wherein a molten mixture of an inorganic material composed of sulfur and a calcium-based component is used as a substrate, and the substrate is an autotrophic system. 1 to 1 sulfur oxidizing and denitrifying bacteria
A low-temperature denitrification material characterized by being cultured and fixed at a temperature of 0 ° C. for 2 days or more. Further, the present invention is the above low-temperature denitrification material, wherein the substrate is a material obtained by integrating a molten mixture of an inorganic material comprising sulfur and a calcium carbonate-based component with mineral fibers. Further, the present invention is a method for denitrifying nitrate nitrogen, which comprises contacting the low-temperature denitrification material with wastewater containing nitrate nitrogen or water to be treated.
【０００６】以下、本発明を詳細に説明する。本発明の
低温脱窒材料は、基質に独立栄養系硫黄酸化脱窒細菌を
培養、定着させたものである。基質は、硫黄と炭酸カル
シウム系成分からなる無機質材料の溶融混合物からな
り、必要により多孔質材料や無機繊維等を含有し得る。
中でも、硫黄と炭酸カルシウム系成分と鉱物繊維の溶融
混合物からなるものは、脱窒細菌の住処を増やし、良好
な生育環境を与えるため好ましい。硫黄と炭酸カルシウ
ム系成分からなる無機質材料の溶融混合物又はこれに多
孔質材料や無機繊維等を含有させた無機質材料の溶融混
合物は公知であり、例えば、上記３件の公開公報などに
記載されている。本発明で使用する基質は、上記刊行物
等で知られたものをそのまま使用することができる。Hereinafter, the present invention will be described in detail. The low-temperature denitrification material of the present invention is obtained by culturing and establishing autotrophic sulfur oxidizing and denitrifying bacteria on a substrate. The substrate is made of a molten mixture of an inorganic material composed of sulfur and a calcium carbonate-based component, and may contain a porous material, an inorganic fiber, and the like as necessary.
Among them, those composed of a molten mixture of sulfur, calcium carbonate-based components and mineral fibers are preferable because they increase the place of denitrifying bacteria and provide a favorable growth environment. A molten mixture of an inorganic material comprising sulfur and a calcium carbonate-based component or a molten mixture of an inorganic material containing a porous material, an inorganic fiber, and the like therein is known, and is described in, for example, the above three publications. I have. As the substrate used in the present invention, those known in the above publications and the like can be used as they are.
【０００７】好ましくは、石灰石粉等の炭酸カルシウム
系成分と単体硫黄とを約１：２〜２：１の割合で混合
し、これを加熱して硫黄を溶融させたのち、これを冷却
固化して一体化し、所定の粒度に粉砕することにより得
る方法である。この際、必要により無機繊維、多孔材料
等が配合される。硫黄と、炭酸カルシウム系成分及びそ
の他の添加材の割合は、これらの混合物を溶融、冷却固
化した際、所定の強度を有する一体化物が得られるかで
決められ、硫黄の割合が大きいほど強度の点では優れる
が、脱窒細菌の栄養源が片寄るので上記範囲とされる。
したがって、無機繊維、多孔材料等が配合される場合
は、炭酸カルシウム系成分の一部を無機繊維、多孔材料
等に置換するように配合することがよい。鉱物繊維を配
合する場合は、炭酸カルシウム系成分の１/１０〜１/２
の範囲がよい。また、鉱物繊維としては、ロックウー
ル、スラグウール、グラスウールなどが好ましく挙げら
れる。[0007] Preferably, a calcium carbonate component such as limestone powder and elemental sulfur are mixed at a ratio of about 1: 2 to 2: 1, and the mixture is heated to melt the sulfur and then cooled and solidified. And pulverizing to a predetermined particle size. At this time, an inorganic fiber, a porous material, and the like are added as necessary. The ratio of sulfur and calcium carbonate-based components and other additives is determined by obtaining an integrated product having a predetermined strength when these mixtures are melted and cooled and solidified. Although it is excellent in point, the nutrient source of the denitrifying bacteria is biased, so the above range is set.
Therefore, when an inorganic fiber, a porous material, or the like is blended, it is preferable to blend such that a part of the calcium carbonate-based component is replaced with the inorganic fiber, the porous material, or the like. When mineral fiber is blended, 1/10 to 1/2 of calcium carbonate component
Range is good. As mineral fibers, rock wool, slag wool, glass wool and the like are preferably mentioned.
【０００８】上記基質に定着させる独立栄養性硫黄酸化
細菌についても、一般的に自然界に存在する硫黄酸化脱
窒菌（Thiobacillus denitrificans）などでよく、上
記基質中の硫黄分及び炭酸分を栄養分の一部として生育
し、硝酸性窒素を窒素ガスにまで分解しうるものであれ
ば制限をうけない。自然界に存在するこのような独立栄
養性硫黄酸化細菌は、１５℃以下の低温では活動が大幅
に低下する。したがって、本発明で最初に使用する独立
栄養性硫黄酸化細菌は、２０℃以上では十分な脱窒能を
有するが、１０℃以下ではその１／１０以下の脱窒能と
なるものである。The autotrophic sulfur-oxidizing bacteria that colonize the substrate may be, for example, naturally occurring sulfur oxidizing and denitrifying bacteria (Thiobacillus denitrificans), and the sulfur and carbonate in the substrate may be partially converted to nutrients. No limitation is imposed as long as it can grow nitrate nitrogen into nitrogen gas. Such an autotrophic sulfur-oxidizing bacterium existing in nature has significantly reduced activity at low temperatures of 15 ° C. or lower. Therefore, the autotrophic sulfur-oxidizing bacteria used for the first time in the present invention have a sufficient denitrification ability at 20 ° C. or higher, but have a denitrification ability of 1/10 or less at 10 ° C. or lower.
【０００９】上記基質に独立栄養性硫黄酸化細菌を定着
させるには、まず自然界に存在する硫黄酸化細菌又はこ
れを含む土壌と基質を、硝酸性窒素を含む培地中で接触
させて、１〜１０℃の温度下で所定期間培養し、基質表
面及び空隙に菌を培養、繁殖させ、定着させる。培養中
は、培地中の硝酸性窒素濃度が低下した都度、硝酸性窒
素を添加し、溶存酸素の低い条件を保持する。溶存酸素
が高い場合は、硫黄酸化細菌が溶存酸素を消費し、脱窒
を行わないため、嫌気状態を保持することが好ましい。
ここで、培養方法は硝酸性窒素を含む培地であって、１
〜１０℃の温度に保持されていればよく、他の微量成分
等が存在することもできる。１〜１０℃での培養期間
は、菌の定着が行える期間であればよいが、２日間以
上、好ましくは１０日間以上、より好ましくは１ヶ月間
程度の培養期間とする。また、最初に使用する独立栄養
性硫黄酸化細菌の全部が、自然界に存在する硫黄酸化細
菌又はこれを含む土壌である場合は、硫黄酸化細菌が低
温で活性が上がるまでに時間がかかるため、２ヶ月以上
の長期間培養することが好ましい。したがって、上記の
ようにして、低温で培養された菌を含む基質又は汚泥等
がある場合は、それを一部使用することも有利である。
また、通常の脱窒材料や夏場使用した脱窒材料がある場
合は、それら自体又はそれらに新規な基質を混合して、
好ましくは０．１〜１０倍程度混合して上記条件で培
養、定着させることも有利である。In order to establish autotrophic sulfur-oxidizing bacteria on the substrate, first, a naturally occurring sulfur-oxidizing bacteria or a soil containing the same is brought into contact with a substrate in a medium containing nitrate nitrogen, for 1 to 10 days. The cells are cultured at a temperature of ° C. for a predetermined period, and the bacteria are cultured, propagated, and settled on the substrate surface and voids. During the culture, nitrate nitrogen is added each time the concentration of nitrate nitrogen in the medium decreases, and the condition of low dissolved oxygen is maintained. When the dissolved oxygen is high, the anaerobic state is preferably maintained because the sulfur-oxidizing bacteria consume the dissolved oxygen and do not perform denitrification.
Here, the culture method is a medium containing nitrate nitrogen,
It is sufficient that the temperature is maintained at a temperature of 〜１０10 ° C., and other trace components may be present. The culture period at 1 to 10 ° C. may be a period in which the colonization of the bacteria can be performed, and is set to a culture period of 2 days or more, preferably 10 days or more, more preferably about 1 month. When all of the autotrophic sulfur oxidizing bacteria used first are naturally occurring sulfur oxidizing bacteria or soil containing the same, it takes time for the activity of the sulfur oxidizing bacteria to increase at low temperatures, so that 2 It is preferable to culture for a long period of at least one month. Therefore, when there is a substrate or sludge containing bacteria cultured at a low temperature as described above, it is also advantageous to partially use it.
In addition, if there are ordinary denitrification materials or denitrification materials used in the summer, mix them with themselves or a new substrate,
It is also advantageous to mix and culture and fix the cells under the above conditions, preferably by mixing about 0.1 to 10 times.
【００１０】本発明の低温脱窒材は、１℃から１５℃の
低温においても有効に機能し、高い脱窒率を与える。更
に、１５℃から３０℃又はそれ以上の常温においても、
有効に機能し、高い脱窒率を与えるので、年間を通して
殆ど条件を変えることなく運転することが可能である。
しかし、多少の脱窒能の変化はあるので、処理量を加減
するか、多少処理能力を大きくしておくことがよい。ま
た、本発明の低温脱窒材の使用方法としては、前記刊行
物に記載されたような方法が使用できる。The low-temperature denitrification material of the present invention functions effectively even at a low temperature of 1 ° C. to 15 ° C. and gives a high denitrification rate. Furthermore, even at room temperature of 15 ° C. to 30 ° C. or higher,
It works effectively and gives a high denitrification rate, so that it can be operated with little change in conditions throughout the year.
However, since there is some change in the denitrification capacity, it is preferable to increase or decrease the processing capacity or increase the processing capacity to some extent. As a method for using the low-temperature denitrification material of the present invention, the method described in the above publication can be used.
【００１１】本発明の脱窒方法は、上記本発明の低温脱
窒材を、硝酸性窒素を含有する被処理水（以下、排水等
という）を接触させる方法である。この際の温度は１〜
３５℃程度がよく、高温の場合以外は加熱、冷却しなく
ても差し支えない。また、硝酸性窒素脱窒装置は、排水
等が低温脱窒材の間を均一に通過するものであればよ
く、円筒形や直方体などの形状が挙げられ、装置の寸
法、装置の材質や板厚などは、排水の種類や流量などに
応じて自由に設計されるものである。この硝酸性窒素脱
窒装置内に低温脱窒材を設置し、排水等を通水すること
で、硫黄酸化細菌によって亜硝酸及び硝酸からなる硝酸
性窒素がＮ2ガスまで分解されて脱窒される。低温脱窒
材使用量は、硝酸性窒素を含有する排水等の濃度により
異なるが、１日に処理する水量の１〜１／１０、好まし
くは１／３程度を装置内に充填しておくことがよい。低
温脱窒材料は、排水等の種類にもよるが１年以上交換す
ることなく連続使用することも可能である。The denitrification method of the present invention is a method in which the low-temperature denitrifying material of the present invention is brought into contact with water to be treated containing nitrate nitrogen (hereinafter referred to as waste water, etc.). The temperature at this time is 1 to
The temperature is preferably about 35 ° C., and heating and cooling are not required except at high temperatures. In addition, the nitrate nitrogen denitrification device may be any device as long as the wastewater or the like passes uniformly between the low-temperature denitrification materials, and may have a shape such as a cylindrical shape or a rectangular parallelepiped. The thickness and the like are freely designed in accordance with the type and flow rate of the drainage. By installing a low-temperature denitrification material in this nitrate nitrogen denitrification apparatus and passing water through drainage, etc., nitrate nitrogen composed of nitrous acid and nitric acid is decomposed to N 2 gas by sulfur oxidizing bacteria and denitrified. You. The amount of low-temperature denitrifier used varies depending on the concentration of wastewater containing nitrate nitrogen, but the amount of water to be treated in a day should be 1 to 1/10, preferably about 1/3, in the equipment. Is good. The low-temperature denitrification material can be used continuously without replacement for one year or more, depending on the type of drainage or the like.
【００１２】[0012]
【実施例】以下、本発明の実施例を説明する。 実施例１ 硫黄と石灰石粉を１：１（重量比）で溶融混合し、これ
を砕いて基質を得た。この基質に常法により、常温で硫
黄酸化脱窒細菌を定着させた脱窒材料を得た。この脱窒
材料と上記基質とを等量混合し、これを硝酸カリウムで
硝酸性窒素濃度２００mg/Lに調整した培地に加え、培
養、定着を行った。培地は５℃の水温で保持し、硝酸性
窒素濃度が１０mg/L以下に達した時点で硝酸カリウムを
硝酸性窒素濃度２００mg/Lとなるように添加し、１ヶ月
間培養して低温脱窒材料（１）を得た。Embodiments of the present invention will be described below. Example 1 Sulfur and limestone powder were melt-mixed at a ratio of 1: 1 (weight ratio) and crushed to obtain a substrate. A denitrification material in which sulfur oxidizing and denitrifying bacteria were fixed on the substrate at ordinary temperature by a conventional method was obtained. Equal amounts of this denitrifying material and the above-mentioned substrate were mixed, and the mixture was added to a medium adjusted to a concentration of 200 mg / L of nitrate nitrogen with potassium nitrate, followed by culturing and fixing. The culture medium was kept at a water temperature of 5 ° C., and when the nitrate nitrogen concentration reached 10 mg / L or less, potassium nitrate was added so as to have a nitrate nitrogen concentration of 200 mg / L. (1) was obtained.
【００１３】この低温脱窒材料（１）を図１に示すよう
な脱窒装置内に１．６kg装入し、硝酸カリウムで硝酸性
窒素濃度１００mg/Lに調整した人工排液を、水温５℃又
は３０℃に保持し、５L/dayで通水して低温脱窒材料
（１）の低温と高温での脱窒性能を測定した。図１は脱
窒装置1の模式図であり、脱窒装置１の底部には、底板
３が設けられ、その上に脱窒材料２が充填されている。
排水等Aは底部から流入し、脱窒材料２と接触して脱窒
され、上部から処理水Bとして流出する。図中、Hは装置
１の高さを示し４００mmであり、φは装置１の径を示
す。底板３は右側の拡大平面図に示すように５mmφの小
孔が多数設けられている。1.6 kg of this low-temperature denitrification material (1) was placed in a denitrification apparatus as shown in FIG. 1, and artificial drainage adjusted to a nitrate nitrogen concentration of 100 mg / L with potassium nitrate was subjected to a water temperature of 5 ° C. Alternatively, the temperature of the low-temperature denitrification material (1) was measured at low and high temperatures by passing water at 5 L / day while maintaining the temperature at 30 ° C. FIG. 1 is a schematic diagram of a denitrification apparatus 1. A bottom plate 3 is provided at the bottom of the denitrification apparatus 1, and a denitrification material 2 is filled thereon.
The drainage A flows in from the bottom, contacts the denitrification material 2, is denitrified, and flows out as treated water B from the top. In the figure, H indicates the height of the device 1 and is 400 mm, and φ indicates the diameter of the device 1. The bottom plate 3 is provided with many small holes of 5 mmφ as shown in the enlarged plan view on the right side.
【００１４】図３に試験開始〜１０日までの排水と処理
水の硝酸性窒素濃度測定結果を、表１に１０日間の平均
値を示す。低温脱窒材料（１）を用いることで、水温５
℃、３０℃の双方において、処理水の硝酸性窒素濃度は
平均０．４mg/Lの低濃度まで処理することが可能で、脱
窒率は９９．６％を示す結果であった。FIG. 3 shows the results of measuring the nitrate nitrogen concentration of the wastewater and treated water from the start of the test to the tenth day, and Table 1 shows the average values for the ten days. By using low-temperature denitrification material (1), water temperature 5
At both 30 ° C. and 30 ° C., it was possible to treat the treated water to a low nitrate nitrogen concentration of 0.4 mg / L on average, and the denitrification rate was 99.6%.
【００１５】実施例２ 硫黄と石灰石粉とロックウールを１：１：０．２で溶融
混合した以外は、実施例１と同様にして基質を得て、実
施例１と同様にして低温脱窒材料（２）を得た。この低
温脱窒材料（２）について、実施例１と同様にして脱窒
性能を測定した。図４に試験開始〜１０日までの排水と
処理水の硝酸性窒素濃度測定結果を、表１に１０日間の
平均値を示す。低温脱窒材料（２）を用いることで、水
温５℃、３０℃の双方において、処理水の硝酸性窒素濃
度は平均０．３mg/Lの低濃度まで処理することが可能
で、脱窒率は９９．７％を示す結果であった。Example 2 A substrate was obtained in the same manner as in Example 1, except that sulfur, limestone powder and rock wool were melt-mixed at a ratio of 1: 1: 0.2. Material (2) was obtained. The denitrification performance of this low-temperature denitrification material (2) was measured in the same manner as in Example 1. FIG. 4 shows the results of measurement of the concentration of nitrate nitrogen in the wastewater and treated water from the start of the test to the tenth day, and Table 1 shows the average values for the ten days. By using the low-temperature denitrification material (2), the nitrate nitrogen concentration in the treated water can be reduced to an average of as low as 0.3 mg / L at both the water temperature of 5 ° C and 30 ° C. Was 99.7%.
【００１６】実施例３ 実施例１の低温脱窒材料（１）を、図２に示すような脱
窒装置内に１．６kg装入し、硝酸カリウムで硝酸性窒素
濃度１００mg/Lに調整した人工排液を、５L/dayで通水
して低温脱窒材料（１）の外気温度での脱窒性能を測定
した。図２は脱窒装置４の模式図であり、脱窒装置４は
複数の室に分割されており、各室には脱窒材料５が充填
されている。排水等Aは左側上部から流入し、各室の脱
窒材料５と接触して脱窒され、右側上部から処理水Bと
して流出する。図中、H1及びH2は装置４の全体高さと水
面高さを示し、それぞれ１００mm及び８０mmであり、L
は装置４の幅を示し、３００mmである。図５に硝酸性窒
素処理結果を、表１に平均値を示す。外気の温度変化に
影響されず、脱窒率は９６％以上を保持する良好な結果
が得られた。Example 3 1.6 kg of the low-temperature denitrification material (1) of Example 1 was charged into a denitrification apparatus as shown in FIG. 2 and adjusted to a nitrate nitrogen concentration of 100 mg / L with potassium nitrate. The discharged liquid was passed at 5 L / day, and the denitrification performance of the low-temperature denitrification material (1) at the outside air temperature was measured. FIG. 2 is a schematic diagram of the denitrification apparatus 4. The denitrification apparatus 4 is divided into a plurality of chambers, each of which is filled with a denitrification material 5. Drainage A flows in from the upper left side, contacts the denitrification material 5 in each room, is denitrified, and flows out as treated water B from the upper right side. In the figure, H1 and H2 indicate the overall height and the water surface height of the device 4, which are 100 mm and 80 mm, respectively,
Indicates the width of the device 4 and is 300 mm. FIG. 5 shows the results of the nitrate nitrogen treatment, and Table 1 shows the average values. A favorable result was obtained without being affected by the temperature change of the outside air, and the denitrification rate was maintained at 96% or more.
【００１７】比較例１ 実施例１において、培地を２０℃の水温で保持した他は
同様にして、脱窒材料（３）を得た。これを、実施例１
と同様にして、脱窒材料３の低温と高温での脱窒性能を
測定した。図５に試験開始〜１７日までの排水と処理水
の硝酸性窒素濃度測定結果を、表１に１０日間の平均値
を示す。比較脱窒材料３を用いると、３０℃場合は、処
理水の硝酸性窒素濃度は平均０．４mg/Lの低濃度まで処
理することが可能で、脱窒率は９９．６％を示す結果で
あったが、水温５℃の場合は、処理水の硝酸性窒素濃度
は平均６３.９mg/Lまでしか処理することができず、脱
窒率は４１.４％を示す結果であった。Comparative Example 1 A denitrifying material (3) was obtained in the same manner as in Example 1, except that the medium was maintained at a water temperature of 20 ° C. This is referred to as Example 1
In the same manner as in the above, the denitrification performance of the denitrification material 3 at low and high temperatures was measured. FIG. 5 shows the results of measurement of the concentration of nitrate nitrogen in the wastewater and treated water from the start of the test to the 17th day, and Table 1 shows the average values for 10 days. When the comparative denitrification material 3 is used, at 30 ° C., it is possible to treat the nitrate nitrogen concentration of the treated water to a low concentration of 0.4 mg / L on average, and the denitrification rate is 99.6%. However, when the water temperature was 5 ° C., the nitrate nitrogen concentration of the treated water could only be treated up to an average of 63.9 mg / L, and the denitrification rate was 41.4%.
【００１８】比較例２ 比較例１の脱窒材料（３）を使用して、実施例３と同様
な条件で外気温度での脱窒性能を測定した。図６に硝酸
性窒素処理結果を、表１に平均値を示す。外気の温度変
化に大きく影響され、脱窒率は２３〜７０％まで変動
し、安定した処理ができない結果であった。各実施例及
び比較例の条件、結果をまとめて表１に示す。Comparative Example 2 Using the denitrifying material (3) of Comparative Example 1, the denitrifying performance at the outside air temperature was measured under the same conditions as in Example 3. FIG. 6 shows the results of the nitrate nitrogen treatment, and Table 1 shows the average values. The denitrification rate fluctuated greatly from 23 to 70%, largely affected by the temperature change of the outside air, and as a result, stable treatment was not possible. Table 1 summarizes the conditions and results of each of the examples and comparative examples.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】以上に示したように、本発明の硫黄と炭
酸カルシウム系成分又はこれらと鉱物繊維からなる無機
質材料の溶融混合物を基質とし、独立栄養系硫黄酸化脱
窒細菌を１℃〜１０℃の温度下で２日以上培養し定着さ
せた低温脱窒材料を用いることで、冬場などの低温時で
も、高い脱窒性能を発揮する硝酸性窒素の脱窒処理を行
うことが出来る。As described above, the autotrophic sulfur oxidizing and denitrifying bacterium is treated at a temperature of 1 ° C. to 10 ° C. by using the sulfur-calcium carbonate-based component of the present invention or a molten mixture of these and an inorganic material comprising mineral fibers as a substrate. By using a low-temperature denitrification material that has been cultured and fixed at a temperature of 2 ° C. for 2 days or more, it is possible to perform a denitrification treatment of nitrate nitrogen that exhibits high denitrification performance even at a low temperature such as in winter.
【図１】硝酸性窒素脱窒装置の模式図FIG. 1 is a schematic view of a nitrate nitrogen denitrification apparatus.
【図２】他の硝酸性窒素脱窒装置の模式図FIG. 2 is a schematic diagram of another nitrate nitrogen denitrification apparatus.
【図３】低温脱窒材料（１）を用いた硝酸性窒素処理結
果を示すグラフFIG. 3 is a graph showing the results of nitrate nitrogen treatment using a low-temperature denitrification material (1).
【図４】低温脱窒材料（２）を用いた硝酸性窒素処理結
果を示すグラフFIG. 4 is a graph showing the results of nitrate nitrogen treatment using a low-temperature denitrification material (2).
【図５】他の硝酸性窒素脱窒装置を用いた硝酸性窒素処
理結果を示すグラフFIG. 5 is a graph showing the results of nitrate nitrogen treatment using another nitrate nitrogen denitrifier.
【図６】脱窒材料（３）硝酸性窒素処理結果を示すグラ
フFIG. 6 is a graph showing the results of nitric nitrogen treatment of a denitrifying material (3).
１：脱窒装置 ２：脱窒材料 ３：底板（φ5mmの穴） ４：他の脱窒装置 ５：脱窒材料 1: Denitrification equipment 2: Denitrification material 3: Bottom plate (φ5mm hole) 4: Other denitrification equipment 5: Denitrification material
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１２Ｎ 1/00 Ｃ１２Ｎ 1/00 Ｎ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C12N 1/00 C12N 1/00 N
Claims (3)
おいて、硫黄とカルシウム系成分からなる無機質材料の
溶融混合物を基質とし、この基質に独立栄養系硫黄酸化
脱窒細菌を１〜１０℃の温度下で２日間以上培養し、定
着させることを特徴とする低温脱窒材料。1. A denitrifying material for treating nitrate nitrogen in water, wherein a molten mixture of an inorganic material composed of sulfur and a calcium-based component is used as a substrate, and the autotrophic sulfur oxidizing and denitrifying bacterium is used as a substrate at 1 to 10 ° C. A low-temperature denitrifying material, which is cultured and fixed at a temperature of 2 days or more.
らなる無機質材料の溶融混合物が鉱物繊維と一体化した
ものである請求項１記載の低温脱窒材料。2. The low-temperature denitrification material according to claim 1, wherein the substrate is formed by integrating a molten mixture of an inorganic material comprising sulfur and a calcium carbonate component with mineral fibers.
硝酸性窒素を含有する排水又は被処理水と接触させるこ
とを特徴とする硝酸性窒素の脱窒方法。3. The low-temperature denitrification material according to claim 1 or 2,
A method for denitrifying nitrate nitrogen, which is brought into contact with wastewater containing nitrate nitrogen or water to be treated.
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| JP2004322023A (en) * | 2003-04-28 | 2004-11-18 | Nippon Steel Chem Co Ltd | Nitrate nitrogen treatment material and nitrate nitrogen treatment method |
| JP2008029324A (en) * | 2006-06-29 | 2008-02-14 | Iris Ohyama Inc | Aquarium purifier, aquarium purification method and aquarium purification and treatment system |
| JP2013063036A (en) * | 2011-09-16 | 2013-04-11 | Clion Co Ltd | Method for raising aquatic animals, and method for removing nitrate-nitrogen |
| CN105060635A (en) * | 2015-08-07 | 2015-11-18 | 柴建中 | BBR urban sewage low temperature nitrogen removal treatment method |
| JP2017000987A (en) * | 2015-06-12 | 2017-01-05 | 新日鐵住金株式会社 | Biological nitrogen removal method and nitrogen-containing waste water treatment apparatus |
| WO2022138981A1 (en) * | 2020-12-25 | 2022-06-30 | 株式会社クボタ | Method for treating organic wastewater |
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| CN105060635A (en) * | 2015-08-07 | 2015-11-18 | 柴建中 | BBR urban sewage low temperature nitrogen removal treatment method |
| WO2022138981A1 (en) * | 2020-12-25 | 2022-06-30 | 株式会社クボタ | Method for treating organic wastewater |
| JP2022102884A (en) * | 2020-12-25 | 2022-07-07 | 株式会社クボタ | Method of treating organic wastewater |
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