JPH0437041B2 - - Google Patents

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Publication number
JPH0437041B2
JPH0437041B2 JP56022813A JP2281381A JPH0437041B2 JP H0437041 B2 JPH0437041 B2 JP H0437041B2 JP 56022813 A JP56022813 A JP 56022813A JP 2281381 A JP2281381 A JP 2281381A JP H0437041 B2 JPH0437041 B2 JP H0437041B2
Authority
JP
Japan
Prior art keywords
hydrazine
slime
water
concentration
cooling water
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.)
Expired - Lifetime
Application number
JP56022813A
Other languages
Japanese (ja)
Other versions
JPS57136502A (en
Inventor
Tooru Hayakawa
Sunao Ikuta
Shoichiro Kajiwara
Kenji Ayabe
Bunichi Ozaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2281381A priority Critical patent/JPS57136502A/en
Publication of JPS57136502A publication Critical patent/JPS57136502A/en
Publication of JPH0437041B2 publication Critical patent/JPH0437041B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は、微生物類の増殖抑制方法に関する。
更に詳しくは、開放型循環式冷却水中のヒドラジ
ン濃度を0.1〜20ppmに保持することを特徴とす
る冷却水中の微生物類の抑制方法に関する。 近年、化学工業およびその他の諸工業の発展に
伴い多量の工業用水が必要となつている。工業用
水の水源として、工業用水道水の他に、海水、湖
沼水、河川水および地下水などが使用されてい
る。 これら工業用水中には必ず各種の微生物が生育
しており、この微生物類の中には、その存在する
水質、環境によつてはさらに増殖を続け各種の障
害を起こす原因となるものが多い。たとえば、冷
却用水として使用する場合に、水中に生息してい
る微生物が増殖し、用水設備の壁などに着生して
スライムを形成し、このスライムによる熱交換率
の低下および流水不良などの障害が発生する。 殊に、用水の循環使用において開放型冷却塔な
どを用いた開放型の場合には、系の一部で循環水
が強制ばつ気されて空気に接触し、かつ太陽光線
が照射されることにより細菌および藻類などの好
気性微生物類の繁殖が助長される。またビルや工
場などの空調、冷暖房施設における小型冷却塔を
設置した冷却水系などにおいても同様な障害が発
生している。 これらの開放型循環式冷却水の系内に生育、増
殖した微生物類に由来するスライム障害を防止す
るためには、従来、塩素もしくは塩素系有機化合
物、塩素系無機化合物、第4級アンモニウム塩、
シアン化合物などの殺菌剤及び/又は抗菌剤がそ
れぞれ用いられてきた。しかしながら、これらの
薬剤は、排水公害の公害源となり、現実に使用不
可能なものも、あるいは人畜または魚類などの生
物に対する毒性が大きく、また装置材質に対する
腐食性が大きいなどの問題があり、無公害薬剤の
開発が望まれている。 本発明者らは、このような薬剤として、従来か
らヒドラジンに着目してきた。ヒドラジンはそれ
自体従来のスライム処理剤に比し毒性が弱く、し
かも分解して無毒な水と窒素ガスになるという特
長を有する。 ヒドラジンは、特公昭53−17649に記載されて
いるように有効なスライム処理剤であることが知
られているが、この場合一般に20ppm以上の濃度
のヒドラジンを開放型循環式冷却水に添加して処
理することが好ましいとされてきており、実際に
そのような濃度で数日に1回冷却水中に衝撃的に
添加して処理する方法が採られてきている。とこ
ろが、冷却水中の微生物の栄養源の濃度が高くス
ライム障害の著しい系や、近年の循環式冷却水系
の高濃縮運転化による微生物栄養源の蓄積がスラ
イム障害をより著しくさせ、そのような系におい
てヒドラジンを衝撃的に添加しても効果が低いこ
とが明らかとなつた。 たとえば、上記のような系に100ppm程度の多
量のヒドラジンを数日に1回衝撃的に添加して
も、単に経済的に高価なものとなるに過ぎず、ま
た排水後の魚毒やPHの上昇の危険性があることな
どに留まらず、殆ど効果を発揮し得ないこともし
ばしば認められる。 本発明者らは、このようなヒドラジンによるス
ライムの防除方法の改良について鋭意検討を行つ
た結果、意外にも冷却水中のヒドラジンの濃度を
20ppm以下の低濃度に保持すべく冷却水中にヒド
ラジンを連続的に供給することが極めて有効であ
ることを見出した。 ところで、スライムコントロール剤の用水系へ
の添加方法は、一般的には上記したように、間欠
的な衝撃投与方法が採られている。これは薬剤を
連続的に投与した場合には、耐薬品性獲得現象や
交代菌の出現現象が起こり、そのため薬剤の添加
濃度を増加させたり、いくつかの薬剤を交互に添
加するなどの対応が必要となり、ついには効力を
発揮しないようになつたりすることを避けるため
である。 従来使用されてきた代表的なスライムコントロ
ール剤において、塩素系薬剤は連続的な添加でも
有効であるが、耐薬品性を生じ易い問題があり一
般には衝撃的添加方法がとられている。一方、第
4級アンモニウム塩は、たとえば10ppm以上の比
較的高濃度の場合殺菌性を示すが、数ppm程度の
低濃度では効果が極めて乏しい。このため低濃度
の連続添加では殆ど効果を示さず比較的高濃度で
衝撃的投与方法が一般にとられている。 これに反して、ヒドラジンは上記したように、
連続的に添加して冷却水中のヒドラジン濃度を低
濃度に保持した場合スライム防除に有効である。 ヒドラジンのスライム起源の微生物類に対する
殺菌・抗菌力は20ppm以下では弱いにもかかわら
ずこのような低濃度での恒常的作用がスライム防
除に有効であることは極めて驚くべきことであ
る。 本発明方法によるヒドラジンのスライムに対す
る防除効果は、長時間低濃度のヒドラジンが用水
中の微生物類に作用することによつてスライム形
成能力を消失せしめ、また一旦発生付着したスラ
イムに対しては、その粘性を破壊して分散消失さ
せてしまうことによるものと思われる。 本発明に用いられるヒドラジンは、種々の水溶
液濃度の水加ヒドラジンの他に用水中にヒドラジ
ン(N2H4)を存在させ得る各種のヒドラジン塩
類、たとえば硫酸ヒドラジン、塩酸ヒドラジンな
ど、その他の可溶性塩類が使用できるが、通常は
水加ヒラジンが使用される。 本発明の方法においてヒドラジンの添加量は冷
却水系の汚染の程度によつて異なるが、一般には
冷却水中でのヒドラジン(N2H4として)保持濃
度が0.1〜20ppmとなる量であり、好ましくは1
〜10ppmである。また、冷却水中への添加方法
は、上記濃度が恒常的に保持されるように連続し
て添加することが望ましいが、本発明の方法は一
旦発生して付着したスライムの分散除去作用をも
有するから、上記の濃度を保持できる範囲内で一
般的に注入(添加)を停止することも差し支えな
い。 以上のように、ヒドラジンが低濃度の連続作用
によつてスライムの防除に極めて有効であること
を見出したことによつて、従来の開放型循環式冷
却水系におけるスライム障害の処理方法ならびに
各種障害の処理方法を飛躍的に改良することが可
能となつた。 以下に実施例によつて本発明を更に詳しく説明
する。 実施例 1 1の工業用水を入れたビーカー内に5cm角の
木片を浸漬固定し、これに一定量のスライム濃度
となるように、現場(工場)冷却塔から採取した
ズーグレアを主とするスライムを加えて、本発明
方法のヒドラジンによるスライム付着防止効果を
試験した。試験は14日間にわたつて行い、ビーカ
ー内と同一濃度となるスライムを加えた工業用水
を連続的に供給、ブローし、ビーカー内の滞留時
間を12時間とした。ヒドラジンの添加は試験開始
時から行い、衝撃的添加する場合はビーカー内に
一括投与し、連続的に添加する場合はビーカー内
のヒドラジンを所定濃度に調整した後、その濃度
を保持すべく連続的に供給した。なお、ヒドラジ
ンは50%水加ヒドラジン(N2H4・H2O)を用
い、ビーカー内の工業用水はマグネチツクスター
ラーで500rpmにて攪拌すると共に、エアレーシ
ヨンして溶存酸素を過飽和に保持した。
The present invention relates to a method for inhibiting the proliferation of microorganisms.
More specifically, the present invention relates to a method for inhibiting microorganisms in cooling water, which is characterized by maintaining the hydrazine concentration in open circulation cooling water at 0.1 to 20 ppm. In recent years, with the development of the chemical industry and other industries, large amounts of industrial water have become necessary. In addition to industrial tap water, seawater, lake water, river water, and groundwater are used as sources of industrial water. Various types of microorganisms are always growing in these industrial waters, and depending on the water quality and environment in which they exist, many of these microorganisms can continue to proliferate and cause various problems. For example, when water is used for cooling purposes, microorganisms living in the water proliferate and grow on the walls of water facilities, forming slime, resulting in problems such as a decrease in heat exchange efficiency and poor water flow. occurs. In particular, in the case of open-type water circulation using an open-type cooling tower, etc., the circulating water is forcibly aerated in a part of the system and comes into contact with the air, and is exposed to sunlight. The growth of aerobic microorganisms such as bacteria and algae is encouraged. Similar problems are also occurring in air conditioning systems in buildings and factories, and cooling water systems installed with small cooling towers in heating and cooling facilities. In order to prevent slime damage caused by microorganisms that have grown and multiplied in these open circulation cooling water systems, chlorine or chlorine-based organic compounds, chlorine-based inorganic compounds, quaternary ammonium salts,
Bactericidal and/or antibacterial agents such as cyanide have been used, respectively. However, these chemicals are a source of wastewater pollution, some are not practical, or they have problems such as being highly toxic to living things such as humans, livestock, and fish, and being highly corrosive to equipment materials. The development of anti-pollution agents is desired. The present inventors have traditionally focused on hydrazine as such a drug. Hydrazine itself is less toxic than conventional slime treatment agents, and has the advantage of decomposing into non-toxic water and nitrogen gas. Hydrazine is known to be an effective slime treatment agent as described in Japanese Patent Publication No. 53-17649, but in this case, hydrazine in a concentration of 20 ppm or more is generally added to open circulation cooling water. It has been said that it is preferable to treat it, and in fact, a method has been adopted in which treatment is performed by shockingly adding it to cooling water at such a concentration once every few days. However, in systems where the concentration of microbial nutrients in the cooling water is high and slime damage is significant, and in recent years due to the highly concentrated operation of circulating cooling water systems, the accumulation of microbial nutrients has made the slime damage even more severe. It has become clear that the impact of adding hydrazine is less effective. For example, even if a large amount of hydrazine (approximately 100 ppm) is shockingly added once every few days to the above-mentioned system, it will simply become economically expensive, and it will also cause fish poisoning and PH after drainage. It is not only recognized that there is a risk of an increase in the rate of increase, but also that it is often ineffective. The inventors of the present invention have conducted intensive studies to improve methods for controlling slime using hydrazine, and have unexpectedly found that the concentration of hydrazine in cooling water can be reduced.
It has been found that it is extremely effective to continuously feed hydrazine into the cooling water to maintain the concentration at a low concentration of 20 ppm or less. By the way, as a method of adding a slime control agent to a water system, an intermittent impact injection method is generally adopted as described above. This is because when drugs are administered continuously, phenomena such as the acquisition of chemical resistance and the appearance of replacement bacteria occur, so countermeasures such as increasing the concentration of the drug added or adding several drugs alternately are necessary. This is to avoid it becoming necessary and eventually becoming ineffective. In typical slime control agents that have been used in the past, continuous addition of chlorine-based chemicals is effective, but there is a problem that chemical resistance tends to occur, so an impact addition method is generally used. On the other hand, quaternary ammonium salts exhibit bactericidal properties at relatively high concentrations of, for example, 10 ppm or more, but are extremely ineffective at low concentrations of several ppm. For this reason, continuous addition at low concentrations has little effect, and shock administration at relatively high concentrations is generally used. On the other hand, hydrazine, as mentioned above,
It is effective in controlling slime when it is added continuously to maintain the hydrazine concentration in the cooling water at a low concentration. Although the bactericidal and antibacterial activity of hydrazine against slime-originating microorganisms is weak below 20 ppm, it is extremely surprising that its constant action at such low concentrations is effective in controlling slime. The slime control effect of hydrazine according to the method of the present invention is that hydrazine at a low concentration for a long period of time acts on microorganisms in the water, causing them to lose their slime-forming ability. This seems to be due to the fact that the viscosity is destroyed and the dispersion disappears. The hydrazine used in the present invention includes not only hydrated hydrazine at various aqueous solution concentrations but also various hydrazine salts that can make hydrazine (N 2 H 4 ) present in the water used, such as hydrazine sulfate, hydrazine hydrochloride, and other soluble salts. can be used, but hydrazine hydrazine is usually used. In the method of the present invention, the amount of hydrazine added varies depending on the degree of contamination of the cooling water system, but is generally an amount such that the concentration of hydrazine (as N 2 H 4 ) retained in the cooling water is 0.1 to 20 ppm, and is preferably an amount. 1
~10ppm. Furthermore, as for the method of adding to the cooling water, it is desirable to add it continuously so that the above concentration is constantly maintained, but the method of the present invention also has the effect of dispersing and removing slime that has once formed and adhered. Therefore, the injection (addition) may generally be stopped within the range where the above concentration can be maintained. As described above, we have discovered that hydrazine is extremely effective in controlling slime through its continuous action at low concentrations, and we have developed a method for treating slime problems in conventional open circulation cooling water systems, as well as ways to eliminate various problems. It has become possible to dramatically improve the processing method. The present invention will be explained in more detail below with reference to Examples. Example 1 A 5 cm square piece of wood was immersed and fixed in a beaker filled with industrial water from step 1, and a slime mainly consisting of zooglare collected from a cooling tower at the site (factory) was added to it so that the slime concentration was a certain amount. In addition, the slime adhesion prevention effect of hydrazine in the method of the present invention was tested. The test was conducted over 14 days, and industrial water with slime added to the same concentration as in the beaker was continuously supplied and blown, and the residence time in the beaker was set for 12 hours. Hydrazine should be added from the start of the test; if it is to be added by shock, it should be administered all at once into a beaker; if it should be added continuously, after adjusting the hydrazine in the beaker to a predetermined concentration, it should be added continuously to maintain that concentration. supplied. The hydrazine used was 50% hydrated hydrazine (N 2 H 4 .H 2 O), and the industrial water in the beaker was stirred at 500 rpm with a magnetic stirrer and aerated to maintain dissolved oxygen at supersaturation.

【表】 実施例 2 実施例1と同様にして本発明方法によるヒドラ
ジンのスライム除去効果を試験した。なお、本実
施例においては予め7日間にわたつてスライムを
木片に付着させた後、薬剤の添加を開始し、その
後、供給水はスライムを含まない工業用水のみと
して14日間の試験を行つた。 実施結果を第2表に示す。
[Table] Example 2 The slime removal effect of hydrazine by the method of the present invention was tested in the same manner as in Example 1. In this example, after the slime had been attached to the wood piece for 7 days, the addition of the chemicals was started, and then the test was conducted for 14 days using only industrial water that did not contain slime as the supplied water. The implementation results are shown in Table 2.

【表】 実施例 3 保有水量15m3、循環水量110m3/hr、濃度倍数
1.5の化学工場の開放型循環式冷却水では、装置
から系内への有機物の混入があつて著しいスライ
ム障害が発生していた。このような系で本発明方
法によるヒドラジンの処理効果を試験した。ヒド
ラジンは50%水加ヒドラジンを使用し、各試験期
間は21日間とした。実施結果を第3表に示す。
[Table] Example 3 Retained water volume 15m 3 , Circulating water volume 110m 3 /hr, Concentration multiple
In the open circulation cooling water system of the chemical factory in 1.5, organic matter was mixed into the system from the equipment, causing a significant slime problem. In such a system, the effect of treating hydrazine according to the method of the present invention was tested. The hydrazine used was 50% hydrated hydrazine, and each test period was 21 days. The implementation results are shown in Table 3.

【表】【table】

【表】 実施例 4 保有水量120m3、循環水量600m3/hr、濃縮倍数
2.5の機械工場の開放型循環式冷却水系では、ブ
ロー水が直接魚類生息池に流入するため、一般の
スライム処理剤やヒドラジンの衝撃的添加による
処理が困難であつた。 そこで、ヒドラジンの微量濃度の連続注入によ
る処理を試みた。その結果、50%水加ヒドラジン
8〜12ppm(N2H4として2.6〜3.8ppm)を保持す
べく連続的添加することで、従来冷却水系の貯水
槽などに著しく付着していた藻類やスライムは約
2週間後にほぼすべてが分散消失し、その後発生
も認められなかつた。また魚類への影響も全く認
められなかつた。
[Table] Example 4 Retained water volume 120m 3 , Circulating water volume 600m 3 /hr, Concentration factor
In the open circulation cooling water system of the 2.5 machine shop, the blow water flows directly into the fish pond, making it difficult to treat it with general slime treatment agents or the impact addition of hydrazine. Therefore, we attempted a treatment using continuous injection of trace concentrations of hydrazine. As a result, by continuously adding 50% hydrated hydrazine at 8 to 12 ppm (2.6 to 3.8 ppm as N 2 H 4 ), the algae and slime that had previously adhered to the water tank of the cooling water system were eliminated. Almost all of the dispersion disappeared after about two weeks, and no outbreak was observed thereafter. Also, no effects on fish were observed.

Claims (1)

【特許請求の範囲】[Claims] 1 開放型循環式冷却水にヒドラジンを連続的に
供給し、冷却水中のヒドラジン濃度を0.1〜
20ppmに保持することを特徴とする微生物類の増
殖抑制方法。
1 Continuously supply hydrazine to the open circulation type cooling water to keep the hydrazine concentration in the cooling water from 0.1 to
A method for inhibiting the proliferation of microorganisms, characterized by maintaining the concentration at 20 ppm.
JP2281381A 1981-02-18 1981-02-18 Propagation control of microorganisms Granted JPS57136502A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2281381A JPS57136502A (en) 1981-02-18 1981-02-18 Propagation control of microorganisms

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2281381A JPS57136502A (en) 1981-02-18 1981-02-18 Propagation control of microorganisms

Publications (2)

Publication Number Publication Date
JPS57136502A JPS57136502A (en) 1982-08-23
JPH0437041B2 true JPH0437041B2 (en) 1992-06-18

Family

ID=12093126

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2281381A Granted JPS57136502A (en) 1981-02-18 1981-02-18 Propagation control of microorganisms

Country Status (1)

Country Link
JP (1) JPS57136502A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4882032A (en) * 1972-02-12 1973-11-02
JPS5428449A (en) * 1977-08-03 1979-03-03 Kubota Ltd Method of removing ammoniacal nitrogen of digested, separated liquid of raw sewage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4882032A (en) * 1972-02-12 1973-11-02
JPS5428449A (en) * 1977-08-03 1979-03-03 Kubota Ltd Method of removing ammoniacal nitrogen of digested, separated liquid of raw sewage

Also Published As

Publication number Publication date
JPS57136502A (en) 1982-08-23

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