JP2685351B2 - Prevention method of marine adherent organisms - Google Patents
Prevention method of marine adherent organismsInfo
- Publication number
- JP2685351B2 JP2685351B2 JP2307379A JP30737990A JP2685351B2 JP 2685351 B2 JP2685351 B2 JP 2685351B2 JP 2307379 A JP2307379 A JP 2307379A JP 30737990 A JP30737990 A JP 30737990A JP 2685351 B2 JP2685351 B2 JP 2685351B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- quaternary ammonium
- ammonium compound
- amount
- hydrogen peroxide
- 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
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Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、海生付着生物の付着防止方法に関し、海水
系に過酸化水素を先に添加し、次に一般式（Ｉ）で示す
第４級アンモニウム化合物を併用添加することにより、
海生付着生物特にカサネカンザシの付着を防止する方法
に関する。TECHNICAL FIELD The present invention relates to a method for preventing adherence of marine adherent organisms, wherein hydrogen peroxide is first added to a seawater system and then represented by the general formula (I). By adding together a quaternary ammonium compound,
TECHNICAL FIELD The present invention relates to a method for preventing the adhesion of marine adherent organisms, especially magnolia lanceolata.
（ロ）従来の技術 近年閉鎖系の湾内において、海生付着生物の１種であ
るカサネカンザシの付着が多くなり、海水を冷却水とす
る工場においては、熱交換器の冷却細管内に付着し孔食
腐食の原因になっている。(B) Conventional technology In recent years, in a bay with a closed system, the adhesion of maggots, which is one of the marine attached organisms, has increased, and in factories that use seawater as cooling water, they attach to holes inside the cooling tubes of heat exchangers. Causes corrosion.
従来は、電解塩素等が使用されてきたが、塩素系薬剤
は、各種の海生付着生物に対する毒性が強く、フジツボ
やムラサキイガイと共にカサネカンザシも防除されてい
た。Conventionally, electrolytic chlorine and the like have been used. However, chlorine-based chemicals are highly toxic to various marine attached organisms, and barley and blue mussels as well as maggots have been controlled.
塩素剤の注入は、ハロメタンの生成や場合によっては
ダイオキシンの生成という可能性が危惧され、両者は生
物濃縮されることから、環境汚染防止上好ましくない。The injection of a chlorine agent is feared to generate halomethane or dioxin in some cases, and both are bioconcentrated, which is not preferable from the viewpoint of preventing environmental pollution.
また、本発明で使用する過酸化水素と第４級アンモニ
ウム化合物の同時併用は、特開昭54−161592号公報に明
記されている。Further, simultaneous use of hydrogen peroxide and a quaternary ammonium compound used in the present invention is specified in JP-A-54-161592.
（ハ）発明が解決しようとする問題点 しかしながら、内湾より取水する冷却水系統では、近
年増え続けているカサネカンザシによる障害を防止する
には、過酸化水素と第４級アンモニウム化合物同時注入
や単独の高濃度の注入でも処理できず、逆に環境汚染を
引き起こす原因になり、その処理費も膨大になる。(C) Problems to be Solved by the Invention However, in the cooling water system that takes water from the inner bay, hydrogen peroxide and quaternary ammonium compound co-injection or single injection should be used in order to prevent the damage caused by the magpie stag beetle which has been increasing in recent years. Even high-concentration injection cannot be processed, which in turn causes environmental pollution, and the processing cost is enormous.
ここに海生付着生物の１種であるカサネカンザシと
は、分類上環形動物門，多毛類，カンザシゴカイ科に属
する海生付着生物であって幼生は、海中を遊泳し付着基
盤に接すると付着し、石灰質の棲管を分泌して成長して
行く。Here, one of the marine adherent organisms, Kasane kanzashi, is a marine adherent organism that belongs to the annelid phylum, polychaetes, and scorpionidae in terms of taxonomy. It secretes calcareous habitats and grows.
カサネカンザシの場合、２ケ月程度で付着層の厚みが
10cm以上に達することも珍しくない。In the case of Kasane kansaku, the thickness of the adhesion layer is about 2 months.
It is not uncommon to reach over 10 cm.
本発明は、かかる現状と認識に鑑み、ことにカサネカ
ンザシが優先的に付着する海域における海水冷却系に対
し、人畜や魚類に対する毒性が低く環境汚染の少ない有
効なカサネカンザシの付着防止方法を提供せんとするも
のである。In view of the present situation and recognition, the present invention provides an effective method for preventing adhesion of magnolia japonicum, which has low toxicity to human livestock and fish and has low environmental pollution, especially for the seawater cooling system in the sea area to which magnolia maggot preferentially adheres. To do.
（ニ）問題を解決するための手段 かくしてこの発明によれば、海水冷却水系に過酸化水
素供給化合物と第４級アンモニウム化合物とを併用して
該冷却水系内の器壁に付着する海生付着生物を防止する
にあたり、微量の過酸化水素供給化合物を添加した後、
微量の一般式（Ｉ）： 「式中,Rは炭素原子数12〜18の飽和又は不飽和の直鎖
状脂肪族炭化水素基を、R1はメチル基又は炭素原子数12
〜18の飽和又は不飽和の直鎖状脂肪族炭化水素基を、R2
はメチル基又はベンジル基を、R3はメチル基を示すか、
あるいはR1，R2，R3全部が窒素原子を介したピリジン基
又はピコリル基であってよい。但し、R1及びR2が同時に
炭素原子数12〜18の飽和又は不飽和の直鎖状脂肪族炭化
水素基及びベンジル基である場合を除く。Ｘは酸残基を
示す。」で表される第４級アンモニウム化合物の１種以
上を添加することを特徴とする海生付着生物の付着防止
方法が提供される。(D) Means for Solving the Problems Thus, according to the present invention, the marine adhesion which adheres to the vessel wall in the cooling water system by using the hydrogen peroxide supply compound and the quaternary ammonium compound in combination in the seawater cooling water system To prevent living things, after adding a trace amount of hydrogen peroxide-supplying compound,
A small amount of general formula (I): `` In the formula, R is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, and R 1 is a methyl group or 12 carbon atoms.
~ 18 saturated or unsaturated linear aliphatic hydrocarbon groups, R 2
Represents a methyl group or a benzyl group, R 3 represents a methyl group,
Alternatively, R 1 , R 2 and R 3 may all be a pyridine group or a picolyl group via a nitrogen atom. However, the case where R 1 and R 2 are simultaneously a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms and a benzyl group is excluded. X represents an acid residue. And a quaternary ammonium compound represented by the formula (1) is added.
この発明において、過酸化水素供給化合物としては水
中で過酸化水素を発生する化合物であり、過酸化水素，
過炭酸ソーダ，過酢酸等が挙げられる。In the present invention, the hydrogen peroxide supply compound is a compound which generates hydrogen peroxide in water,
Examples include sodium percarbonate and peracetic acid.
この発明において、一般式（Ｉ）で表される第４級ア
ンモニウム化合物の具体例としては、 ラウリルベンジルジメチルアンモニウムクロライド，ラ
ウリルトリメチルアンモニウムクロライド，セチルベン
ジルジメチルアンモニウムクロライド，セチルトリメチ
ルアンモニウムクロライド，ステアリルベンジルジメチ
ルアンモニウムクロライド，ステアリルトリメチルアン
モニウムクロライド，ラウリルピリジニウムクロライ
ド，ラウリルピコリニウムクロライド，セチルトリメチ
ルアンモニウムサッカライド，セチルトリメチルアンモ
ニウムブロマイド，牛脂アルキルトリメチルアンモニウ
ムブロマイド，ジラウリルジメチルアンモニウムクロラ
イド，ジセチルジメチルアンモニウムクロライド，ジス
テアリルジメチルアンモニウムクロライド等が挙げられ
る。In the present invention, specific examples of the quaternary ammonium compound represented by the general formula (I) include laurylbenzyldimethylammonium chloride, lauryltrimethylammonium chloride, cetylbenzyldimethylammonium chloride, cetyltrimethylammonium chloride and stearylbenzyldimethylammonium. Chloride, stearyltrimethylammonium chloride, laurylpyridinium chloride, laurylpicolinium chloride, cetyltrimethylammonium saccharide, cetyltrimethylammonium bromide, tallow alkyltrimethylammonium bromide, dilauryldimethylammonium chloride, dicetyldimethylammonium chloride, distearyldimethylammonium chloride Do and the like.
酸残基の具体例としては、塩酸，臭化水素酸，硝酸，
硫酸，リン酸，蟻酸，酢酸，オレイン酸，ナフテン酸，
アジピン酸，乳酸，クエン酸又はサッカリン等が挙げら
れる。Specific examples of the acid residue include hydrochloric acid, hydrobromic acid, nitric acid,
Sulfuric acid, phosphoric acid, formic acid, acetic acid, oleic acid, naphthenic acid,
Examples include adipic acid, lactic acid, citric acid, saccharin and the like.
海水冷却系への添加量は、一般に海水流量に対し、過
酸化水素供給化合物はH2O2換算で0.05〜2ppm好ましくは
0.1〜1.5ppmを、１日12〜24時間注入するのが好まし
い。そして後から添加する第４級アンモニウム化合物は
0.005〜0.1ppm好ましくは0.01〜0.08ppmを、１日８〜24
時間注入すればよい。この添加量は、海域の状況により
多少の増減はあるが、カサネカンザシの発生量の特別多
い場合には増量するのが望ましい。しかしながら、どの
ような状況においてもH2O2として2ppmと、第４級アンモ
ニウム化合物を0.1ppmまでの添加量で十分であり、それ
以上は環境汚染上もまた経済上も好ましくない。なお海
水冷却系に一般式（Ｉ）の第４級アンモニウム化合物を
添加する場合は、海水に均一分散するように適用な溶剤
（水又はアルコール，ブチルジグリコール，エチレング
リコール，プロピレングリコールモノメチルエーテル等
の有機溶剤）に溶解あるいは乳化懸濁し必要に応じ界面
活性剤を添加し適当な濃度の製剤として使用するのが好
ましい。その際の界面活性剤としては、ポリオキシエチ
レンアルキルエーテル類、ポリオキシエチレンアルキル
エステル類、ソルビタンアルキルエステル類、ポリオキ
シエチレンソルビタンアルキルエステル類、ポリオキシ
エチレンポリオキシプロピレン共重合物、アルキルベタ
イン類等が挙げられる。The addition amount of the seawater cooling system, generally to seawater flow rate, hydrogen peroxide feed compound 0.05~2ppm preferably in H 2 O 2 conversion
It is preferable to inject 0.1 to 1.5 ppm for 12 to 24 hours a day. And the quaternary ammonium compound added later is
0.005 to 0.1 ppm, preferably 0.01 to 0.08 ppm, 8 to 24 per day
You can inject it for an hour. Although the amount added may vary slightly depending on the conditions of the sea area, it is desirable to increase the amount when the amount of magnolia lanceolata is particularly large. However, in any situation, the addition amount of H 2 O 2 of 2 ppm and the quaternary ammonium compound up to 0.1 ppm is sufficient, and further addition is not preferable in terms of environmental pollution and economy. When the quaternary ammonium compound of the general formula (I) is added to the seawater cooling system, a solvent (water or alcohol, butyldiglycol, ethylene glycol, propylene glycol monomethyl ether, etc.) that is applied so as to be uniformly dispersed in seawater is used. It is preferred to dissolve or emulsify and suspend in an organic solvent) and add a surfactant if necessary to use as a preparation having an appropriate concentration. In this case, as a surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene copolymers, alkyl betaines, etc. Is mentioned.
（ホ）実施例，比較例 以下、本発明を実施例、比較例により説明するが、こ
れにより本発明は限定されるものではない。(E) Examples and Comparative Examples Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１ 内径75mm、長さ20mの塩ビパイプでテスト水路を作
り、該テスト水路の先端部と中央部にそれぞれ薬注箇所
を設けた。薬注箇所及び薬剤を表１のように組み合わ
せ、 先端部から過酸化水素を、中央部から第４級アンモニ
ウム化合物を注入した場合（実施例１〜５）、 先端部から第４級アンモニウム化合物を、中央部から
過酸化水素を注入した場合（比較例１及び２）及び 先端部から過酸化水素及び第４級アンモニウム化合物
を同時に注入した場合（比較例３及び４） について、薬剤の添加効果を比較した。Example 1 A test channel was formed with a PVC pipe having an inner diameter of 75 mm and a length of 20 m, and chemical injection points were provided at the tip and the center of the test channel. When the chemical injection points and the medicines are combined as shown in Table 1 and hydrogen peroxide is injected from the tip and the quaternary ammonium compound is injected from the center (Examples 1 to 5), the quaternary ammonium compound is introduced from the tip. , When hydrogen peroxide was injected from the central portion (Comparative Examples 1 and 2) and when hydrogen peroxide and a quaternary ammonium compound were simultaneously injected from the tip portion (Comparative Examples 3 and 4), Compared.
そして、テスト水路の後端部に試験網を入れて併用薬
剤の効果判定を行った。Then, a test net was placed at the rear end of the test water channel to determine the effect of the concomitant drug.
某製鉄所の海水導水路より、水中ポンプで海水を汲み
上げ、カサネカンザシの付着期に40日間海水を一過式に
通水（通水量約各３トン／時）し、各薬剤をケミカルポ
ンプで注入して、その時付着したカサネカンザシや他の
付着生物数を計数した。その結果は表１に示す通りであ
る。Seawater is pumped from a seawater canal of a certain steelworks with a submersible pump, and seawater is transiently passed for 40 days (the amount of water passed is about 3 tons / hour) during the period when the magnolias are attached, and each chemical is injected with a chemical pump. Then, the numbers of Hawthorn scutella and other attached organisms attached at that time were counted. The results are as shown in Table 1.
実施例２ 某製鉄所の実機導水路（海水量３万トン／時）の２箇
所（先端部と先端部より10m後のバースクリン前）に薬
注装置を取り付け、カサネカンザシの付着期に60日間試
験を行った。Example 2 A chemical injection device was attached to two points (in front of a bar scrin 10m after the tip) of a real steel canal (amount of seawater of 30,000 tons / hour) at a certain steel mill, and 60 days during the adhesion period of Kasanekanakushi The test was conducted.
即ち、導水路の先端部より35％過酸化水素水の1.5ppm
を連続的に注入し、バースクリン前にはヘキサデシルベ
ンジルジメチルアンモニウムクロライドの30％水溶液を
同じく連続的に0.1ppm注入した。That is, 1.5ppm of 35% hydrogen peroxide water from the tip of the water conduit.
Was continuously injected, and before Versculin, 0.1 ppm of a 30% aqueous solution of hexadecylbenzyldimethylammonium chloride was also continuously injected.
効果を調べるために、無添加として導水路先端部近辺
に試験網を浸漬し、両薬剤が混合されているトラベルス
クリン後のポンプピットに試験網を浸漬してその効果を
調べた。その結果は表２に示す通りである。In order to investigate the effect, a test net was immersed in the vicinity of the tip of the water conduit without addition, and the test net was immersed in a pump pit after travel screening in which both agents were mixed, and the effect was examined. The results are as shown in Table 2.
（試験結果の考察） 水路実験の結果により過酸化水素を先に添加し、その
後第４級アンモニウム化合物を添加する方法で併用する
と、少量の添加量でカサネカンザシの付着を防止できる
ことがわかる。(Discussion of Test Results) From the results of the water channel experiment, it can be seen that when hydrogen peroxide is first added and then the quaternary ammonium compound is added together, the adhesion of magnolia lanceolata can be prevented with a small addition amount.
それに比較して、過酸化水素と第４級アンモニウム化
合物の同時添加、あるいは第４級アンモニウム化合物を
過酸化水素より先に添加した場合は、カサネカンザシに
対する効果がなかった。In comparison, when hydrogen peroxide and a quaternary ammonium compound were added at the same time, or when the quaternary ammonium compound was added before hydrogen peroxide, there was no effect on the magnolia maggot.
以上の結果から、過酸化水素を先に注入し、その後第
４級アンモニウム化合物を注入する方が、少量の注入量
で処理できることから、環境汚染上もすばらしい方法と
言える。From the above results, it can be said that the method of injecting hydrogen peroxide first and then the quaternary ammonium compound after that can be treated with a small injection amount, which is excellent in terms of environmental pollution.
（ヘ）発明の効果 この発明によれば、海水冷却水系において生じる海生
付着生物による系内の障害を、極めて効率よく防止する
ことができる。 (F) Effects of the Invention According to the present invention, it is possible to extremely efficiently prevent the damage in the system due to marine attached organisms that occurs in the seawater cooling water system.
Claims (3)
４級アンモニウム化合物とを併用して該冷却水系内の器
壁に付着する海生付着生物を防止するにあたり、微量の
過酸化水素供給化合物を添加した後、微量の一般式
（Ｉ）： 「式中,Rは炭素原子数12〜18の飽和又は不飽和の直鎖状
脂肪族炭化水素基を、R1はメチル基又は炭素原子数12〜
18の飽和又は不飽和の直鎖状脂肪族炭化水素基を、R2は
メチル基又はベンジル基を、R3はメチル基を示すか、あ
るいはR1，R2，R3全部が窒素原子を介したピリジン基又
はピコリル基であってもよい。但し、R1及びR2が同時に
炭素原子数12〜18の飽和又は不飽和の直鎖状脂肪族炭化
水素基及びベンジル基である場合を除く。Ｘは酸残基を
示す。」で表される第４級アンモニウム化合物の１種以
上を添加することを特徴とする海生付着生物の付着防止
方法。1. A trace amount of hydrogen peroxide is supplied when a compound for supplying hydrogen peroxide and a quaternary ammonium compound are used in combination in a seawater cooling water system to prevent marine adherent organisms adhering to vessel walls in the cooling water system. After adding the compound, a trace amount of general formula (I): `` In the formula, R is a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms, and R 1 is a methyl group or 12 to 12 carbon atoms.
18 saturated or unsaturated linear aliphatic hydrocarbon group, R 2 is a methyl group or a benzyl group, R 3 is a methyl group, or R 1 , R 2 , R 3 are all nitrogen atoms. It may be an intervening pyridine group or a picolyl group. However, the case where R 1 and R 2 are simultaneously a saturated or unsaturated linear aliphatic hydrocarbon group having 12 to 18 carbon atoms and a benzyl group is excluded. X represents an acid residue. ] A method for preventing adhesion of marine adherent organisms, which comprises adding at least one quaternary ammonium compound represented by the formula
0.05〜2mg/lであり、一般式（Ｉ）で表される第４級ア
ンモニウム化合物の添加量が0.005〜0.1mg/lである請求
項１の付着防止方法。2. The amount of hydrogen oxide-supplying compound added is calculated as H 2 O 2 .
The anti-adhesion method according to claim 1, wherein the amount is 0.05 to 2 mg / l, and the addition amount of the quaternary ammonium compound represented by the general formula (I) is 0.005 to 0.1 mg / l.
項１の付着防止方法。3. The method of preventing adhesion according to claim 1, wherein the marine adherent organism is Magnolia solium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2307379A JP2685351B2 (en) | 1990-11-09 | 1990-11-09 | Prevention method of marine adherent organisms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2307379A JP2685351B2 (en) | 1990-11-09 | 1990-11-09 | Prevention method of marine adherent organisms |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04178310A JPH04178310A (en) | 1992-06-25 |
| JP2685351B2 true JP2685351B2 (en) | 1997-12-03 |
Family
ID=17968349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2307379A Expired - Lifetime JP2685351B2 (en) | 1990-11-09 | 1990-11-09 | Prevention method of marine adherent organisms |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2685351B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6134921B1 (en) * | 2015-09-17 | 2017-05-31 | 株式会社片山化学工業研究所 | Anticorrosion method and anticorrosive for seawater copper alloy piping |
| JP6216996B1 (en) * | 2016-05-30 | 2017-10-25 | 株式会社片山化学工業研究所 | Fault prevention method, fault prevention agent and fault prevention kit for seawater system |
| JP7340205B2 (en) | 2018-07-23 | 2023-09-07 | 株式会社片山化学工業研究所 | Method for preventing adhesion of marine organisms and slime, anti-adhesion agent, and anti-adhesion kit |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0901434D0 (en) * | 2009-01-29 | 2009-03-11 | Univ Strathclyde | Ballast water treatment system |
-
1990
- 1990-11-09 JP JP2307379A patent/JP2685351B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6134921B1 (en) * | 2015-09-17 | 2017-05-31 | 株式会社片山化学工業研究所 | Anticorrosion method and anticorrosive for seawater copper alloy piping |
| JP2017214640A (en) * | 2015-09-17 | 2017-12-07 | 株式会社片山化学工業研究所 | Anticorrosion method and anticorrosive agent for copper alloy piping of seawater system |
| JP6216996B1 (en) * | 2016-05-30 | 2017-10-25 | 株式会社片山化学工業研究所 | Fault prevention method, fault prevention agent and fault prevention kit for seawater system |
| JP7340205B2 (en) | 2018-07-23 | 2023-09-07 | 株式会社片山化学工業研究所 | Method for preventing adhesion of marine organisms and slime, anti-adhesion agent, and anti-adhesion kit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04178310A (en) | 1992-06-25 |
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