JP7228148B2 - Method for preventing adhesion of marine organisms and anti-adhesion agent for marine organisms - Google Patents

Method for preventing adhesion of marine organisms and anti-adhesion agent for marine organisms Download PDF

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JP7228148B2
JP7228148B2 JP2022143725A JP2022143725A JP7228148B2 JP 7228148 B2 JP7228148 B2 JP 7228148B2 JP 2022143725 A JP2022143725 A JP 2022143725A JP 2022143725 A JP2022143725 A JP 2022143725A JP 7228148 B2 JP7228148 B2 JP 7228148B2
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seawater
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洸太 藤戸
弘宜 錦織
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Katayama Chemical Works Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/16Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P15/00Biocides for specific purposes not provided for in groups A01P1/00 - A01P13/00
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/50Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81Aquaculture, e.g. of fish

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  • Environmental & Geological Engineering (AREA)
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Description

本発明は、海生生物の付着防止方法及び海生生物の付着防止剤に関する。 TECHNICAL FIELD The present invention relates to a method for preventing adhesion of marine organisms and an anti-adhesion agent for marine organisms.

例えば、冷却水として海水を使用する発電所、製鉄所、石油化学プラントなどは、波浪などを避けるために、内海や湾内に面した所に多く建設されている。内海や湾内において海水を取水すると、海水中に生息するムラサキイガイ、フジツボ、コケムシ、ヒドロ虫などの海生生物やスライム等が、海水取水路、配管や導水路、熱交換器や復水器細管などの通水路に付着し、様々な障害を引き起こす。例えば、付着した海生生物等は、成長して熱交換器チューブ等の導水路を閉塞させて海水の通水を阻害し、また乱流を生じさせ、エロージョン腐食等の障害を引き起こす。また、付着した海生生物等が水圧や流速等によりはぎ取られることによっても、熱交換器のチューブやストレーナーの閉塞を引き起こし、海水の通水を阻害し、熱交換器本来の機能の低下を引き起こす。
また、種々の工場では、海水は冷却水としてだけではなく、例えば、希釈水や洗浄水としても用いられており、海水が流通する海水利用設備の内表面に海水中に生息する海生生物やスライム等が付着することで、海水の流通が阻害されることが問題になっている。
なお、上記海生生物等の通常の付着繁殖期は、4~10月頃と言われているが、海水温が高くなったり、外来種の流入等により冬季でも繁殖して、上述のような障害を引き起こす。
For example, many power plants, ironworks, petrochemical plants, etc. that use seawater as cooling water are built in places facing inland seas and bays in order to avoid waves. When seawater is taken in inland seas and bays, marine organisms such as mussels, barnacles, bryozoans, and hydroids living in the seawater, as well as slimes, etc. It adheres to water passages and causes various obstacles. For example, adhering marine organisms grow to clog water conduits such as heat exchanger tubes, impeding the flow of seawater and causing turbulence, causing problems such as erosion corrosion. In addition, if attached marine organisms are stripped off due to water pressure, flow velocity, etc., the tubes and strainers of the heat exchanger will be clogged, inhibiting the passage of seawater, and reducing the original function of the heat exchanger. cause.
In addition, in various factories, seawater is used not only as cooling water but also, for example, as dilution water and washing water. There is a problem that the flow of seawater is obstructed by the adhesion of slime or the like.
The normal attached breeding season for the above marine organisms is said to be from April to October. cause.

上記の海水中に生息する海生生物は、自然界において付着基盤を争奪しながら共生しており、ムラサキイガイやフジツボはその繁殖力が強く、上記のような付着の問題を起こし易い。そして、ムラサキイガイやフジツボの付着を抑制すると、これらに代わって別の海生生物が繁殖する。その代表的な海生生物がヒドロ虫類であり、中でもクダウミヒドラ類、オベリア類の付着障害が問題になっている。 The marine organisms inhabiting the seawater described above coexist in the natural world while competing for attachment substrates, and mussels and barnacles have a strong reproductive power and are likely to cause the above attachment problems. Then, when the attachment of mussels and barnacles is suppressed, other marine organisms reproduce in their place. The representative marine organisms are hydrozoans, and among them, attachment failures of the Hydra and Obelia species have become a problem.

上記海生生物種の着生(付着)を防止するために、従来から次亜塩素酸ナトリウム、電解塩素もしくは塩素ガスなどの塩素発生剤(「塩素剤」ともいう)、過酸化水素もしくは過酸化水素発生剤(「過酸化水素剤」ともいう)の添加が行われている(特許文献1及び特許文献2)。 Conventionally, sodium hypochlorite, chlorine generating agents such as electrolytic chlorine or chlorine gas (also referred to as "chlorine agents"), hydrogen peroxide or peroxides have been used to prevent the formation (adherence) of the above marine species. A hydrogen generating agent (also referred to as a “hydrogen peroxide agent”) has been added (Patent Documents 1 and 2).

例えば、特許文献2には、過酸化水素または過酸化水素発生剤を使用することを特徴とする海水動物の付着抑制方法が開示されており、易分解性を有し、残留毒性や蓄積毒性の問題が起らないより安全な海水動物の付着抑制方法を研究した結果、過酸化水素が極めて有効であることが開示されている。また、過酸化水素発生剤として、過酢酸等の有機過酸又はこれらの塩等が開示されている。 For example, Patent Document 2 discloses a method for suppressing adhesion of seawater animals, which is characterized by using hydrogen peroxide or a hydrogen peroxide generating agent, which is easily decomposable and has residual toxicity and accumulated toxicity. As a result of research into a safer method for suppressing adhesion of seawater animals without causing problems, it is disclosed that hydrogen peroxide is extremely effective. Further, organic peracids such as peracetic acid and salts thereof are disclosed as hydrogen peroxide generators.

また、例えば、特許文献3には、過酢酸を含有することを特徴とする水中有害生物付着阻止剤に関する技術が開示されている。過酢酸は、少量で短時間に殺菌作用を発揮し、生物分解性に優れ、安全性に優れていることが知られている([請求項1]等、[0014]段落等)。また、例えば、特許文献4には、製紙パルプ工業の白水循環系における微生物抑制剤として過酢酸を用いることが開示されており、特に、Flavobacterium、Alkaligenes、Serratia、Paecilomyces、Geotrichum、Cephalosporium、Rhodotorula及びCandida等のスライムを構成する菌に対し、強力な殺菌効果が認められることが開示されている。
一方、特許文献5の記載から、過酢酸を含有する薬剤に含まれる酢酸は、水系の微生物に利用されることが開示されており([0010]等)、一般的に、冷却水系中の酢酸量が増加すると、微生物量が増加することが知られている。
Further, for example, Patent Literature 3 discloses a technique relating to an aquatic pest adhesion inhibitor characterized by containing peracetic acid. It is known that peracetic acid exerts a bactericidal action in a small amount in a short period of time, is excellent in biodegradability, and is excellent in safety ([Claim 1] etc., [0014] paragraph etc.). Also, for example, U.S. Pat. No. 6,200,000 discloses the use of peracetic acid as a microbial inhibitor in the white water circulation system of the pulp and paper industry, particularly Flavobacterium, Alkaligenes, Serratia, Paecilomyces, Geotrichum, Cephalosporium, Rhodotorula and Candida. It is disclosed that a strong bactericidal effect is observed against bacteria that constitute slime such as.
On the other hand, from the description of Patent Document 5, it is disclosed that the acetic acid contained in the peracetic acid-containing drug is used by microorganisms in the water system ([0010] etc.). It is known that increasing the amount increases the microbial load.

特開平11-037666号公報JP-A-11-037666 特公昭61-002439号公報Japanese Patent Publication No. 61-002439 特開平06-227907号公報JP-A-06-227907 特開昭63-122604号公報JP-A-63-122604 特開2007-198869号公報JP 2007-198869 A

発電所海水設備の汚損対策ハンドブック(P133~P136)、火力原子力発電技術協会 編、恒星社厚生閣、2014年10月20日Handbook for Countermeasures against Fouling of Power Plant Seawater Facilities (P133-P136), edited by The Thermal and Nuclear Power Engineering Society, Kouseisha Kouseikaku, October 20, 2014

海生生物等の付着防止において、トリハロメタンや有機塩素化合物類の生成といった環境への影響を考慮して、塩素剤や臭素剤等のハロゲン系薬剤の使用を避ける動きがあり、ハロゲン系薬剤を使用することなく、優れた海生生物の付着防止効果を発揮し得る海生生物等の付着防止方法の開発が望まれている。 In order to prevent the adhesion of marine organisms, there is a movement to avoid using halogen-based agents such as chlorine agents and bromine agents in consideration of the environmental impact of the generation of trihalomethanes and organic chlorine compounds, and the use of halogen-based agents. There is a demand for the development of a method for preventing adhesion of marine organisms and the like, which can exhibit an excellent effect of preventing adhesion of marine organisms.

このような方法として、例えば上述の特許文献2に記載のように、水中で容易に水と酸素に分解する過酸化水素を使用した海水動物の付着抑制方法が挙げられる。しかしながら、過酸化水素及び過酸化水素発生剤の、海生生物に対する付着防止効果は海生生物の種類に対して選択性があるため、過酸化水素の通常の使用方法では、ヒドロ虫類のような酸化剤や殺菌剤などの影響を受けにくい海生生物の付着を防止することは困難である。
一方、効果的にヒドロ虫類の付着を防止するための薬品としては、ハロゲン系薬剤が従来から採用されているが、上述の通り環境上の観点から好ましくない。
As such a method, for example, as described in the above-mentioned Patent Document 2, there is a method for suppressing adherence of marine animals using hydrogen peroxide, which is easily decomposed into water and oxygen in water. However, since the antifouling effect of hydrogen peroxide and hydrogen peroxide generators on marine organisms is selective for the type of marine organisms, the normal use of hydrogen peroxide is limited to hydrozoans. It is difficult to prevent adhesion of marine organisms, which are not easily affected by strong oxidants and disinfectants.
On the other hand, as a chemical for effectively preventing adhesion of hydrozoans, a halogen-based chemical has conventionally been used, but as described above, it is not preferable from an environmental point of view.

また、上述の特許文献2に記載の海水動物の付着抑制方法では、過酸化水素の発生剤として、過酢酸等の有機過酸又はこれらの塩等が開示されている。しかしながら、非特許文献1に記載の通り、低濃度の過酢酸は酢酸と過酸化水素とに分解しやすい事から、海水が流通する系における海洋性生物の付着防止に関して、低濃度の過酢酸を添加することは、過酸化水素の添加と同等と考えられていたため、低濃度の過酢酸を添加する必然性はないとされていた。 In addition, in the method for suppressing adhesion of marine animals described in the above-mentioned Patent Document 2, organic peracids such as peracetic acid or salts thereof are disclosed as hydrogen peroxide generators. However, as described in Non-Patent Document 1, low-concentration peracetic acid is easily decomposed into acetic acid and hydrogen peroxide. The addition was considered equivalent to the addition of hydrogen peroxide, so it was considered unnecessary to add low-concentration peracetic acid.

また、過酢酸は殺菌剤として広く知られており、例えば、上述の特許文献3に記載のように過酢酸を使用する水中有害生物付着阻止剤及び付着阻止方法のように、過酢酸を使用する海生生物等の付着防止方法が挙げられる。しかしながら、特許文献3に記載の方法は、0.16%以上(すなわち、1600ppm以上)の高濃度の過酢酸溶液を、海苔網や海洋構造物に対して浸漬、または噴霧することによって藻類や貝類の付着を防止するものであり、海水が流通する系における海洋性生物の付着防止に関して、低濃度の過酢酸(例えば、10ppm以下)を添加することの効果は示されていない。 In addition, peracetic acid is widely known as a disinfectant, for example, peracetic acid is used as in the water pest adhesion inhibitor and adhesion prevention method using peracetic acid as described in the above-mentioned Patent Document 3. A method for preventing adhesion of marine organisms and the like can be mentioned. However, in the method described in Patent Document 3, a high concentration peracetic acid solution of 0.16% or more (i.e., 1600 ppm or more) is immersed in or sprayed on seaweed nets and marine structures to produce algae and shellfish. However, the effect of adding low-concentration peracetic acid (for example, 10 ppm or less) has not been shown for preventing the adhesion of marine organisms in a system in which seawater flows.

本発明は、ハロゲン系薬剤を使用することなく、海水が流通する海水利用設備への優れた海生生物の付着防止効果を発揮し得る海生生物の付着防止方法、及び、海生生物の付着防止剤を提供することを課題とする。
また、本発明は、ハロゲン系薬剤を使用することなく、海水が流通する海水利用設備への優れたヒドロ虫類の付着防止効果を発揮し得る海生生物の付着防止方法、及び、ヒドロ虫類の付着防止剤を提供することを課題とする。
The present invention provides a method for preventing adhesion of marine organisms and a method for preventing adhesion of marine organisms, which can exhibit an excellent effect of preventing adhesion of marine organisms to seawater utilization equipment through which seawater flows, without using a halogen-based chemical. An object of the present invention is to provide an inhibitor.
In addition, the present invention provides a method for preventing adhesion of marine organisms, which can exhibit an excellent effect of preventing adhesion of hydrozoans to seawater utilization equipment in which seawater flows, without using a halogen-based chemical, and hydrozoa. An object of the present invention is to provide an anti-adhesion agent.

本発明の発明者は、過酢酸は、ヒドロ虫のような酸化剤や殺菌剤などの影響を受けにくい海生生物に対する付着防止効果が優れていることを見出し、本発明を完成するに到った。 The inventors of the present invention have found that peracetic acid has an excellent effect of preventing adhesion of marine organisms such as hydroids, which are not easily affected by oxidizing agents and disinfectants, and have completed the present invention. rice field.

すなわち本発明は、海水が流通する海水利用設備への海生生物の付着防止方法であって、過酢酸を含有する薬剤を、上記海水の過酢酸濃度が0.1~10mg/Lになるように、上記海水に添加することを特徴とする海生生物の付着防止方法である。
本発明の方法において、過酢酸を含有する薬剤はさらに酢酸を含有し、1日当たり添加される上記酢酸の積算濃度が70mg/L以下であることが好ましい。
本発明の方法において、海水の酢酸濃度が10mg/L未満になるように過酢酸を含有する薬剤を上記海水に添加することが好ましい。
本発明の方法において、過酢酸を含有する薬剤の薬剤添加時間が、1日当たり0.5~24時間であることが好ましい。
That is, the present invention provides a method for preventing adhesion of marine organisms to seawater utilization equipment through which seawater flows, wherein a chemical containing peracetic acid is added so that the peracetic acid concentration of the seawater is 0.1 to 10 mg / L. and a method for preventing adhesion of marine organisms, characterized by adding to the seawater.
In the method of the present invention, the agent containing peracetic acid preferably further contains acetic acid, and the cumulative concentration of acetic acid added per day is 70 mg/L or less.
In the method of the present invention, it is preferable to add an agent containing peracetic acid to the seawater so that the acetic acid concentration in the seawater is less than 10 mg/L.
In the method of the present invention, the drug addition time of the peracetic acid-containing drug is preferably 0.5 to 24 hours per day.

また、本発明は、過酢酸を含有し、上記過酢酸の濃度が1質量%以上であり、海水利用設備を流通する海水へ添加されることを特徴とする海生生物の付着防止剤でもある。
本発明の付着防止剤は、さらに酢酸を含有し、上記酢酸の濃度が過酢酸濃度の25倍以下であることが好ましい。
本発明の付着防止剤は、さらに、過酸化水素を含有し、上記過酸化水素の濃度が1質量%以上であることが好ましい。
本発明の付着防止剤は、本発明の海水が流通する海水利用設備への海生生物の付着防止方法に使用されることが好ましい。
In addition, the present invention is also an antifouling agent for marine organisms, which contains peracetic acid, has a peracetic acid concentration of 1% by mass or more, and is added to seawater flowing through a seawater utilization facility. .
The antiadhesion agent of the present invention further contains acetic acid, and the concentration of acetic acid is preferably 25 times or less the concentration of peracetic acid.
The antiadhesion agent of the present invention preferably further contains hydrogen peroxide, and the concentration of hydrogen peroxide is 1% by mass or more.
The antifouling agent of the present invention is preferably used in the method of preventing adherence of marine organisms to seawater utilization facilities through which seawater flows according to the present invention.

本発明によれば、ハロゲン系薬剤を使用することなく、海水が流通する海水利用設備への優れた海生生物の付着防止効果を発揮し得る海生生物の付着防止方法、及び、海生生物の付着防止剤を提供することができる。
さらに、本発明によれば、ハロゲン系薬剤を使用することなく、海水が流通する海水利用設備への優れたヒドロ虫類の付着防止効果を発揮し得る海生生物の付着防止方法、及び、ヒドロ虫類の付着防止剤を提供することができる。
ADVANTAGE OF THE INVENTION According to the present invention, a method for preventing adhesion of marine organisms and a method for preventing adhesion of marine organisms, which can exhibit an excellent effect of preventing adhesion of marine organisms to seawater utilization equipment through which seawater flows, without using a halogen-based chemical. can provide an anti-adhesion agent.
Furthermore, according to the present invention, there is provided a method for preventing adherence of marine organisms, which can exhibit an excellent effect of preventing adherence of hydrozoans to seawater utilization equipment in which seawater flows, without using a halogen-based chemical, and a method for preventing adherence of hydrozoa. An anti-fouling agent for insects can be provided.

本発明の発明者らは、過酢酸は、ヒドロ虫のような酸化剤や殺菌剤などの影響を受けにくい海生生物に対する付着防止効果が優れていることを見出し、本発明を完成するに到った。 The inventors of the present invention have found that peracetic acid has an excellent anti-adhesion effect against marine organisms such as hydroids, which are less susceptible to oxidants and disinfectants, and have completed the present invention. was

本発明は、海水が流通する海水利用設備への海生生物の付着防止方法であって、過酢酸を含有する薬剤を、上記海水の過酢酸濃度が0.1~10mg/Lになるように、上記海水に添加することを特徴とする海生生物の付着防止方法である。
本発明の発明者らは、環境への影響を考慮して、ハロゲン系薬剤を使用することなく、ヒドロ虫類等の海生生物が海水利用設備に付着することを防止する方法及び付着防止剤を検討するために、モデル水路による実験を重ねた。その結果、本発明者らは、過酢酸を含有する薬剤を海水に添加することでヒドロ虫類のような海生生物の海水が流通する海水利用設備への付着を効果的に防止できることを見出した。上述の通り、高濃度での過酢酸の殺菌作用は知られており、例えば、特許文献3では、1600ppm以上の高濃度の過酢酸溶液を藻類や貝類の付着防止に使用している。しかしながら、例えば、10ppm以下のような低濃度での過酢酸は、過酸化水素の発生源として使用できることが知られていたのみである。また、非特許文献1によると、低濃度での過酢酸は、過酸化水素の発生源としても使用の必然性がないとされていた。そのため、低濃度の過酢酸は、現実に海生生物の付着防止の用途には使用されていなかった。
このような状況において、本発明者らは、低濃度の過酢酸(0.1mg/L以上10mg/L未満)のヒドロ虫類のような海生生物に対する優れた付着防止効果を見出した。
The present invention provides a method for preventing adhesion of marine organisms to seawater utilization equipment through which seawater flows, wherein a chemical containing peracetic acid is added so that the peracetic acid concentration of the seawater is 0.1 to 10 mg / L. and a method for preventing adhesion of marine organisms, characterized by adding to the seawater.
In consideration of the environmental impact, the inventors of the present invention have developed a method and an anti-adhesion agent for preventing marine organisms such as hydrozoans from adhering to seawater utilization equipment without using halogen-based chemicals. In order to examine the As a result, the present inventors found that adding a peracetic acid-containing agent to seawater effectively prevents marine organisms such as hydrozoans from adhering to seawater utilization facilities through which seawater flows. rice field. As described above, the bactericidal action of high-concentration peracetic acid is known. For example, in Patent Document 3, a high-concentration peracetic acid solution of 1600 ppm or more is used to prevent adhesion of algae and shellfish. However, it was only known that peracetic acid at low concentrations, eg, 10 ppm or less, could be used as a source of hydrogen peroxide. In addition, according to Non-Patent Document 1, it has been said that there is no necessity to use peracetic acid at a low concentration as a source of generation of hydrogen peroxide. Therefore, low-concentration peracetic acid has not actually been used for the purpose of preventing adhesion of marine organisms.
Under these circumstances, the present inventors have found that low concentrations of peracetic acid (0.1 mg/L or more and less than 10 mg/L) have excellent antifouling effects on marine organisms such as hydrozoans.

なお、本発明において、海水が流通する海水利用設備は、冷却水として海水を使用する発電所、製鐵所、石油化学プラント等の工場における海水冷却水系であってもよく、また、種々の工場において、海水を希釈水、洗浄水等として用いる場合の海水が流通する系であってもよく、特に限定されるものではない。上記海水利用設備としては、海水が流通する流路を形成する設備であれば特に限定されず、例えば、海水取水路、配管、導水路、熱交換器、復水器、排水路等が挙げられる。 In the present invention, the seawater utilization facility through which seawater flows may be a seawater cooling water system in factories such as power plants, steelworks, and petrochemical plants that use seawater as cooling water. , the system may be a system in which seawater flows when using seawater as dilution water, washing water, or the like, and is not particularly limited. The seawater utilization equipment is not particularly limited as long as it forms a flow path through which seawater flows, and examples thereof include seawater intake channels, pipes, water conduits, heat exchangers, condensers, and drainage channels. .

本発明の方法において、海水の過酢酸濃度が0.15mg/L以上になるように過酢酸を含有する薬剤を海水に添加することが好ましく、0.2mg/L以上になるように上記薬剤を海水に添加することがより好ましい。また、本発明の方法において、海水の過酢酸濃度が6mg/L以下になるように過酢酸を含有する薬剤を海水に添加することが好ましく、4mg/L以下になるように過酢酸を含有する薬剤を海水に添加することがより好ましく、2mg/L以下になるように上記薬剤を海水に添加することがさらに好ましい。
また、本発明の方法において、上述の海水の過酢酸濃度の下限と上限とは適宜組み合わせて数値範囲を決定することができる。
なお、本発明の方法において、過酢酸を含有する薬剤の添加濃度は、海水の過酢酸濃度が、上記範囲となるように適宜調節されることが好ましい。
In the method of the present invention, it is preferable to add an agent containing peracetic acid to seawater so that the concentration of peracetic acid in seawater is 0.15 mg/L or more, and the agent is added so that the concentration of peracetic acid in seawater is 0.2 mg/L or more. Adding to seawater is more preferable. In the method of the present invention, it is preferable to add a peracetic acid-containing agent to seawater so that the peracetic acid concentration in seawater is 6 mg/L or less, and peracetic acid is added to seawater so that the peracetic acid concentration is 4 mg/L or less. It is more preferable to add the chemical to seawater, and it is even more preferable to add the chemical to seawater so that the concentration becomes 2 mg/L or less.
Further, in the method of the present invention, the upper and lower limits of the peracetic acid concentration in seawater can be appropriately combined to determine the numerical range.
In the method of the present invention, the concentration of the agent containing peracetic acid is preferably adjusted appropriately so that the concentration of peracetic acid in seawater falls within the above range.

[過酢酸を含有する薬剤]
本発明の方法において、過酢酸を含有する薬剤は、過酢酸を含有していればよく、工業用として市販されている過酢酸溶液や、オンサイト(本発明の方法が使用される場所)で合成した過酢酸溶液を用いることができ、特に限定されるものではない。例えば、過酢酸を含有する薬剤は、水溶液中で過酸化水素と酢酸との平衡反応によって製造されたものであってよく、このような平衡反応により製造された過酢酸溶液を、過酢酸を含有する薬剤として用いることが好ましい。平衡反応により製造された過酢酸溶液は、過酸化水素と、過酢酸と、酢酸とを含有する。過酢酸溶液中の過酢酸濃度、酢酸濃度及び過酸化水素濃度(すなわち、過酢酸を含有する薬剤中の過酢酸濃度、酢酸濃度、過酸化水素濃度)は、公知の測定方法(例えば滴定法)によって測定する事ができる。
なお、過酢酸を含有する薬剤を合成する場合に用いられる酢酸は、酢酸又はその塩であってよく、工業用に市販されている酢酸溶液を用いてもよい。
また、過酢酸を含有する薬剤を合成する場合に用いられる過酸化水素は、工業用に市販されている過酸化水素、過酸化水素発生源(過酢酸を除く)を用いてもよい。
[Drug containing peracetic acid]
In the method of the present invention, the agent containing peracetic acid may contain peracetic acid. A synthesized peracetic acid solution can be used, and is not particularly limited. For example, the agent containing peracetic acid may have been produced by the equilibrium reaction of hydrogen peroxide and acetic acid in an aqueous solution, and the peracetic acid solution produced by such equilibrium reaction is converted to It is preferable to use it as a drug to The peracetic acid solution produced by the equilibrium reaction contains hydrogen peroxide, peracetic acid and acetic acid. The peracetic acid concentration, acetic acid concentration, and hydrogen peroxide concentration in the peracetic acid solution (that is, the peracetic acid concentration, acetic acid concentration, and hydrogen peroxide concentration in the drug containing peracetic acid) can be measured by a known measurement method (e.g., titration method). can be measured by
The acetic acid used in synthesizing a drug containing peracetic acid may be acetic acid or a salt thereof, and an acetic acid solution commercially available for industrial use may be used.
In addition, as the hydrogen peroxide used when synthesizing a drug containing peracetic acid, commercially available hydrogen peroxide and hydrogen peroxide generating sources (excluding peracetic acid) may be used.

本発明の海生生物の付着防止方法において、上記過酢酸を含有する薬剤はさらに酢酸を含有し、1日当たり添加される酢酸の積算濃度は70mg/L以下であることが好ましい。海水において、過酢酸はスライムを抑制する効果を有するが、酢酸は微生物に消費されスライムの増加を引き起こす。後述の実施例からも確認される通り、海水に対し、1日当たり添加される酢酸の積算濃度が70mg/Lを超えると、酢酸によるスライム増加作用が高まり、過酢酸によるスライム抑制効果が得られなくなる可能性を生じる。そのため、1日当たり添加される酢酸の積算濃度が70mg/L以下となるように過酢酸と酢酸とを含有する薬剤を海水に添加することで、酢酸によるスライムの増加を引き起こすことなく、過酢酸によるヒドロ虫類のような海生生物及びスライムの海水利用設備への付着防止効果が得られ、結果としてヒドロ虫類のような海生生物及びスライムの海水が流通する海水利用設備への付着を抑制することができる。本発明の方法において、上記過酢酸を含有する薬剤がさらに酢酸を含有する場合、海水に1日当たり添加される酢酸の積算濃度は50mg/L以下であることが好ましい。 In the method for preventing adhesion of marine organisms of the present invention, the peracetic acid-containing agent preferably further contains acetic acid, and the cumulative concentration of acetic acid added per day is preferably 70 mg/L or less. In seawater, peracetic acid has the effect of suppressing slime, but acetic acid is consumed by microorganisms and causes an increase in slime. As will be confirmed from the examples described later, when the cumulative concentration of acetic acid added per day to seawater exceeds 70 mg/L, the slime-increasing action of acetic acid increases, and the slime-suppressing effect of peracetic acid cannot be obtained. create possibilities. Therefore, by adding a drug containing peracetic acid and acetic acid to seawater so that the cumulative concentration of acetic acid added per day is 70 mg / L or less, slime due to peracetic acid is not increased. The effect of preventing adhesion of marine organisms such as hydrozoans and slime to seawater utilization equipment is obtained, and as a result, adhesion of marine organisms such as hydrozoans and slime to seawater utilization equipment in which seawater is circulated is suppressed. can do. In the method of the present invention, when the peracetic acid-containing agent further contains acetic acid, the cumulative concentration of acetic acid added to seawater per day is preferably 50 mg/L or less.

本発明の海生生物の付着防止方法において、過酢酸を含有する薬剤は、さらに酢酸を含有し、海水の酢酸濃度が10mg/L未満になるように上記過酢酸を含有する薬剤を海水に添加することが好ましい。海水中の酢酸濃度が上昇すると、海水中の微生物が酢酸を消費し、海水中のスライムの増加を引き起こす。海水の酢酸濃度が10mg/L未満となるように過酢酸と酢酸とを含有する薬剤を海水に添加することで、酢酸によるスライムの増加を引き起こすことなく、過酢酸によるヒドロ虫類のような海生生物の海水が流通する海水利用設備への付着防止効果が得られるためである。
本発明の方法において、過酢酸と酢酸とを含有する薬剤は、海水の酢酸濃度が6mg/L以下となるように海水に添加されることが好ましく、5mg/L以下となるように海水に添加されることがより好ましく、3mg/L以下となるように海水に添加されることがさらに好ましい。上述の海水における酢酸濃度の好適な上限と下限は適宜組み合わせることができる。
In the method for preventing adhesion of marine organisms of the present invention, the agent containing peracetic acid further contains acetic acid, and the agent containing peracetic acid is added to seawater so that the concentration of acetic acid in seawater is less than 10 mg/L. preferably. When the acetic acid concentration in seawater rises, microorganisms in the seawater consume acetic acid, causing an increase in slime in the seawater. By adding peracetic acid and an agent containing acetic acid to seawater so that the acetic acid concentration in the seawater is less than 10 mg/L, seawater such as peracetic acid hydrozoa can be eliminated without causing an increase in acetic acid slime. This is because it is possible to obtain the effect of preventing living organisms from adhering to seawater utilization facilities through which seawater flows.
In the method of the present invention, the agent containing peracetic acid and acetic acid is preferably added to seawater so that the acetic acid concentration in seawater is 6 mg/L or less, and added to seawater so that the concentration is 5 mg/L or less. More preferably, it is added to seawater so that the concentration becomes 3 mg/L or less. The preferred upper and lower limits of the acetic acid concentration in seawater described above can be combined as appropriate.

本発明の方法において、過酢酸を含有する薬剤の海水への添加方法は特に限定されないが、一又は複数の実施形態において、配管に接続された配管からポンプ等により送液することにより行うことが挙げられる。添加においては、海水や淡水で薬剤を適宜希釈してもよい。 In the method of the present invention, the method of adding the peracetic acid-containing agent to seawater is not particularly limited, but in one or more embodiments, it can be carried out by sending the solution from a pipe connected to the pipe with a pump or the like. mentioned. In addition, the drug may be appropriately diluted with seawater or fresh water.

本発明の方法において、過酢酸を含有する薬剤は、さらに過酸化水素を含有することが好ましい。過酸化水素は、フジツボなどの海生生物に対する付着防止効果が知られており、過酢酸によるヒドロ虫類等の海生生物に対する付着防止効果を阻害することなく、フジツボ等の海生生物に対する付着防止効果を得ることができる。本発明の方法に用いられる上記薬剤が、過酸化水素と酢酸との平衡反応によって製造されたものである場合、用いられる過酸化水素は特に限定されず、過酸化水素及び過酸化水素発生剤の少なくとも一方であればよい。過酸化水素としては、限定されない一又は複数の実施形態において、過酸化水素水溶液の形態があげられる。過酸化水素発生剤としては、水等の液中で過酸化水素を発生するものが挙げられ、一又は複数の実施形態において、過炭酸ナトリウム、過炭酸カリウム等の可溶性過炭酸塩、過ホウ酸ナトリウムや過ホウ酸カリウム等の可溶性過ホウ酸塩等の各種の可溶性ペルオキシ酸塩、尿素/過酸化水素付加物、メタケイ酸塩/過酸化水素付加物、過酸化ナトリウム等が挙げられる。ただし、本発明の方法において、過酸化水素発生源に過酢酸は含まない。 In the method of the present invention, the agent containing peracetic acid preferably further contains hydrogen peroxide. Hydrogen peroxide is known to be effective in preventing adhesion to marine organisms such as barnacles. A preventive effect can be obtained. When the above-mentioned agent used in the method of the present invention is produced by an equilibrium reaction between hydrogen peroxide and acetic acid, the hydrogen peroxide used is not particularly limited. At least one of them is sufficient. Hydrogen peroxide, in one or more non-limiting embodiments, may be in the form of an aqueous hydrogen peroxide solution. Examples of hydrogen peroxide generating agents include those that generate hydrogen peroxide in liquids such as water. In one or more embodiments, soluble percarbonates such as sodium percarbonate and potassium percarbonate, perboric acid Examples include various soluble peroxyacid salts such as soluble perborate salts such as sodium and potassium perborate, urea/hydrogen peroxide adducts, metasilicate/hydrogen peroxide adducts, and sodium peroxide. However, in the method of the present invention, the hydrogen peroxide generating source does not contain peracetic acid.

本発明の方法では、海水の過酸化水素濃度が0.1mg/L以上になるように過酢酸、酢酸及び過酸化水素を含有する薬剤を海水に添加することが好ましい。上述の通り、過酸化水素は、フジツボ類の海水利用設備への付着防止効果に優れており、海水中の過酸化水素濃度が0.1mg/L以上となるように、より好ましくは0.15mg/L以上となるように、上記薬剤を海水に添加することにより、フジツボ類の海水が流通する海水利用設備への付着を充分効果的に防止するためである。また、過酸化水素は海水が流通する海水利用設備へのフジツボ類の付着防止作用に加え、スライムの付着防止作用も有しているためである。海水の過酸化水素濃度は、海水の過酢酸濃度に対し、5倍以下となるように添加されることが好ましく、2倍以下となるように添加されることがより好ましい。また、海水の過酸化水素の濃度が2.0mg/Lを超えると、過酸化水素の添加量が増大し、過酸化水素の添加量に応じた海生生物及びスライムの海水が流通する海水利用設備への付着防止効果が期待できず、経済的な面から好ましくない。よって、本発明の方法では、海水の過酸化水素濃度が0.1~2.0mg/Lとなるように過酢酸、酢酸及び過酸化水素を含有する薬剤を海水に添加することが好ましい。 In the method of the present invention, peracetic acid, an agent containing acetic acid and hydrogen peroxide is preferably added to seawater so that the concentration of hydrogen peroxide in seawater is 0.1 mg/L or more. As described above, hydrogen peroxide has an excellent effect of preventing barnacles from adhering to seawater utilization equipment, and is more preferably 0.15mg so that the hydrogen peroxide concentration in seawater is 0.1 mg / L or more. This is because the adhesion of barnacles to seawater utilization facilities through which seawater flows can be prevented sufficiently and effectively by adding the above chemical to the seawater so that the concentration becomes 1/L or more. In addition, hydrogen peroxide has an effect of preventing adhesion of barnacles to seawater utilization facilities through which seawater flows, and also an effect of preventing adhesion of slime. The concentration of hydrogen peroxide in seawater is preferably 5 times or less, more preferably 2 times or less, that of peracetic acid in seawater. In addition, when the concentration of hydrogen peroxide in seawater exceeds 2.0 mg/L, the amount of hydrogen peroxide added increases, and the use of seawater in which marine organisms and slime seawater according to the amount of hydrogen peroxide circulates. The effect of preventing adhesion to equipment cannot be expected, and it is not preferable from an economic point of view. Therefore, in the method of the present invention, it is preferable to add peracetic acid, an agent containing acetic acid and hydrogen peroxide to seawater so that the concentration of hydrogen peroxide in seawater is 0.1 to 2.0 mg/L.

また、本発明は、過酢酸を含有し、上記過酢酸の濃度が1質量%以上であり、海水利用設備を流通する海水へ添加されることを特徴とする海生生物の付着防止剤でもある。
本発明の海生生物の付着防止剤は、上述の通り水溶液中で過酸化水素と酢酸との平衡反応によって製造されたものであることが好ましい。また、本発明の付着防止剤(100質量%)に対し過酢酸の濃度が1質量%以上であればよいが、3質量%以上であることが好ましく、5質量%以上であることがより好ましく、10質量%以上であることがさらに好ましい。また、本発明の付着防止剤は、該薬剤(100質量%)に対し、過酢酸の濃度が40質量%以下であることが好ましい。
本発明の付着防止剤において、付着防止剤に対する過酢酸の濃度の上記下限及び上記上限は適宜組み合わせることができる。
また、本発明の付着防止剤が添加される海水利用設備を流通する海水とは、海水利用設備の内部を流通している海水のみではなく、海水利用設備に導入される海水も含まれる。
In addition, the present invention is also an antifouling agent for marine organisms, which contains peracetic acid, has a peracetic acid concentration of 1% by mass or more, and is added to seawater flowing through a seawater utilization facility. .
The antifouling agent for marine organisms of the present invention is preferably produced by the equilibrium reaction of hydrogen peroxide and acetic acid in an aqueous solution as described above. Further, the concentration of peracetic acid may be 1% by mass or more with respect to the adhesion preventing agent (100% by mass) of the present invention, preferably 3% by mass or more, more preferably 5% by mass or more. , more preferably 10% by mass or more. In addition, the anti-adhesion agent of the present invention preferably has a peracetic acid concentration of 40% by mass or less with respect to the agent (100% by mass).
In the antiadhesion agent of the present invention, the above lower limit and the above upper limit of the concentration of peracetic acid with respect to the antiadhesion agent can be appropriately combined.
In addition, the seawater flowing through the seawater utilization equipment to which the anti-adhesion agent of the present invention is added includes not only seawater flowing through the seawater utilization equipment but also seawater introduced into the seawater utilization equipment.

また、本発明の付着防止剤は、さらに酢酸を含有し、上記酢酸の濃度が過酢酸濃度の25倍以下であることが好ましい。海水において、酢酸は微生物に消費されスライム増加を引き起こすため、本発明の付着防止剤における酢酸の含有量の上限は、過酢酸濃度の25倍以下であることが好ましい。本発明の付着防止剤における酢酸の濃度は、過酢酸濃度の20倍以下であることがより好ましく、過酢酸濃度の10倍以下であることがさらに好ましく、過酢酸濃度の5倍以下であることがよりさらに好ましく、過酢酸濃度の2倍以下であることが特に好ましい。
また、本発明の付着防止剤は、上記酢酸の濃度が過酢酸濃度の0.5倍以上であることが好ましい。
Moreover, it is preferable that the anti-adhesion agent of the present invention further contains acetic acid, and the concentration of the acetic acid is 25 times or less the concentration of peracetic acid. In seawater, acetic acid is consumed by microorganisms and causes an increase in slime. Therefore, the upper limit of the content of acetic acid in the antifouling agent of the present invention is preferably 25 times or less the concentration of peracetic acid. The concentration of acetic acid in the antiadhesion agent of the present invention is preferably 20 times or less the peracetic acid concentration, more preferably 10 times or less the peracetic acid concentration, and 5 times or less the peracetic acid concentration. is more preferable, and it is particularly preferable that the concentration is not more than twice the concentration of peracetic acid.
Further, in the antiadhesion agent of the present invention, the concentration of acetic acid is preferably 0.5 times or more the concentration of peracetic acid.

また、本発明の付着防止剤は、さらに過酸化水素を含有し、上記過酸化水素の濃度が1質量%以上であることが好ましい。上述の通り、海水が流通する海水利用設備において、過酸化水素はフジツボ類及びスライムの付着防止作用を有しているためである。本発明の付着防止剤に対する過酸化水素の濃度は、2.5質量%以上であることがより好ましく、5質量%以上であることがさらに好ましく、10質量%以上であることがよりさらに好ましい。また、本発明の付着防止剤に対する過酸化水素の濃度は、45質量%以下であることが好ましい。
また、本発明の付着防止剤がさらに過酸化水素を含有する場合、付着防止剤における過酸化水素の濃度は過酢酸濃度の5倍以下であることが好ましく、2倍以下であることがより好ましい。
Moreover, it is preferable that the anti-adhesion agent of the present invention further contains hydrogen peroxide, and the concentration of the hydrogen peroxide is 1% by mass or more. This is because, as described above, hydrogen peroxide has an effect of preventing adhesion of barnacles and slimes in seawater utilization facilities in which seawater flows. The concentration of hydrogen peroxide in the antiadhesion agent of the present invention is preferably 2.5% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Also, the concentration of hydrogen peroxide in the antiadhesion agent of the present invention is preferably 45% by mass or less.
When the antiadhesion agent of the present invention further contains hydrogen peroxide, the concentration of hydrogen peroxide in the antiadhesion agent is preferably 5 times or less, more preferably 2 times or less, the concentration of peracetic acid. .

本発明の海生生物の付着防止方法は、薬剤添加時間が1日当たり0.5~24時間であることが好ましい。添加は、連続添加でもよく、間欠添加でもよく特に限定されない。
また、本発明の海生生物の付着防止方法は、過酢酸を含有する薬剤の海水に対する過酢酸濃度に応じて添加時間を調整してもよく、過酢酸を含有する薬剤の添加時間に応じて過酢酸を含有する薬剤の海水に対する過酢酸濃度を調整してもよい。例えば、海水の過酢酸濃度が0.1mg/L以上2mg/L未満となるよう過酢酸を含有する薬剤が海水に添加される場合、該薬剤の添加時間は、6時間~24時間であることが好ましく、18時間~24時間であることがより好ましい。また、海水の過酢酸濃度が2mg/L以上となるよう過酢酸を含有する薬剤が海水に添加される場合、該薬剤の添加時間は、0.5時間~18時間であることが好ましく、0.5時間~12時間であることがより好ましく、0.5時間~6時間であることがさらに好ましい。
In the method for preventing adhesion of marine organisms of the present invention, it is preferable that the chemical addition time is 0.5 to 24 hours per day. The addition may be continuous addition or intermittent addition, and is not particularly limited.
Further, in the method for preventing adhesion of marine organisms of the present invention, the addition time may be adjusted according to the peracetic acid concentration of the peracetic acid-containing agent in seawater. The peracetic acid concentration of the peracetic acid-containing agent relative to seawater may be adjusted. For example, when a chemical containing peracetic acid is added to seawater so that the peracetic acid concentration in seawater is 0.1 mg/L or more and less than 2 mg/L, the addition time of the chemical is 6 hours to 24 hours. is preferred, and 18 to 24 hours is more preferred. In addition, when a peracetic acid-containing chemical is added to seawater so that the peracetic acid concentration in seawater is 2 mg/L or more, the addition time of the chemical is preferably 0.5 to 18 hours. It is more preferably from 0.5 hours to 12 hours, and even more preferably from 0.5 hours to 6 hours.

本発明の方法及び付着防止剤が用いられる海生生物は、ヒドロ虫類(クダウミヒドラ類、オベリア類)であることが好ましい。また、本発明の方法及び付着防止剤が用いられる対象は海生生物及びスライムであることがより好ましく、ヒドロ虫類及びスライムを含む海生生物等であることがさらに好ましく、ヒドロ虫類、フジツボ類及びスライムを含む海生生物等であることがよりさらに好ましい。 Preferably, the marine organisms for which the methods and antifouling agents of the present invention are used are hydrozoans (Rhododendron hydras, Obelias). Further, the object for which the method and antifouling agent of the present invention are used is more preferably marine organisms and slimes, more preferably marine organisms including hydrozoans and slimes, hydrozoans, barnacles, etc. Even more preferred are marine organisms, including worms and slimes.

本発明における薬剤(過酢酸を含有する薬剤)の添加場所は、取水路、熱交換器または復水器に付帯する配管中や導水路、熱交換器の入口または復水器の入口のいずれであってもよく、取水路、熱交換器の入り口及び復水器の入口の少なくとも一箇所が好ましい。 In the present invention, the agent (agent containing peracetic acid) is added at any of the intake channel, the pipe attached to the heat exchanger or the condenser, the water conduit, the inlet of the heat exchanger, or the inlet of the condenser. It may be present, and is preferably at least one of the intake channel, the inlet of the heat exchanger and the inlet of the condenser.

本発明の付着防止方法において、海水利用設備における過酢酸濃度、酢酸濃度及び/又は過酸化水素濃度の測定場所は特に限定されず、本発明における薬剤の添加場所より下流の海水の水質が測定される場所であればよく、排水路、熱交換器の出口及び復水器の出口の少なくとも一箇所で実施することが好ましい。 In the adhesion prevention method of the present invention, the measurement location of peracetic acid concentration, acetic acid concentration and/or hydrogen peroxide concentration in seawater utilization equipment is not particularly limited, and the water quality of seawater downstream from the chemical addition location in the present invention is measured. It is preferable to carry out at least one of the drainage channel, the outlet of the heat exchanger, and the outlet of the condenser.

本発明の海生生物の付着防止方法では、本発明の効果を阻害しない範囲において、当該技術分野で公知の他の添加剤を併用してもよい。
例えば、環境への影響が生じない程度の低濃度のハロゲン系薬剤(例えば、次亜塩素酸、次亜臭素酸、海水電解液、モノクロラミン等の結合塩素や結合臭素、N―クロロスルファマート等の安定化塩素や安定化臭素、二酸化塩素等)、ジアルキルジチオカルバミン酸塩、カチオン系界面活性剤等の海生生物付着防止剤、鉄系金属腐食防止剤、消泡剤などが挙げられる。
In the method for preventing adhesion of marine organisms of the present invention, other additives known in the art may be used in combination as long as the effects of the present invention are not impaired.
For example, low concentrations of halogen-based chemicals that do not affect the environment (e.g., hypochlorous acid, hypobromous acid, seawater electrolyte, combined chlorine and combined bromine such as monochloramine, N-chlorosulfamate (e.g., stabilized chlorine, stabilized bromine, chlorine dioxide, etc.), dialkyldithiocarbamates, marine biofouling inhibitors such as cationic surfactants, iron-based metal corrosion inhibitors, antifoaming agents, and the like.

本発明の方法において、海水中の成分濃度(過酢酸濃度、酢酸濃度及び過酸化水素濃度等)は、公知の方法により測定することができる。 In the method of the present invention, the component concentrations in seawater (peracetic acid concentration, acetic acid concentration, hydrogen peroxide concentration, etc.) can be measured by known methods.

以下、実施例を用いて本開示をさらに説明する。ただし、本開示は以下の実施例に限定して解釈されない。 The present disclosure is further described below using examples. However, the present disclosure should not be construed as being limited to the following examples.

[モデル水路を用いた評価試験]
太平洋に面した和歌山県沿岸の某所に、水路試験装置を設け、試験を行った。水中ポンプを用いて揚水した未濾過の海水(pH8)を、10系統に分岐させた水路(試験区)に流量1m/hで78日間(2020年8月~同年10月)、一過式に通水し、各水路に表1に記載の薬剤を、表1に示す海水中の濃度、および一日当たりの添加時間になるように添加した(参考例1~3、比較例1、実施例1~6)。
また、水中ポンプを用いて揚水した未濾過の海水(pH8)を、6系統に分岐させた水路(試験区)に流量1m/hで76日間(2021年4月~同年6月)、一過式に通水し、各水路に表1に記載の薬剤を、表1に示す海水中の濃度、および一日当たりの添加時間になるように添加した(実施例7~11)。
[Evaluation test using model channel]
A hydrographic test equipment was installed at a certain place on the coast of Wakayama Prefecture facing the Pacific Ocean, and tests were conducted. Unfiltered seawater (pH 8) pumped using a submersible pump was pumped into 10 channels (test zones) at a flow rate of 1 m 3 /h for 78 days (August 2020 to October 2020). , and the chemicals listed in Table 1 were added to each channel so that the concentration in seawater and the addition time per day shown in Table 1 were obtained (Reference Examples 1 to 3, Comparative Example 1, Example 1-6).
In addition, unfiltered seawater (pH 8) pumped using a submersible pump was sent to a channel (test area) branched into 6 systems at a flow rate of 1 m 3 /h for 76 days (April 2021 to June 2021). Water was passed through the system, and the chemicals shown in Table 1 were added to each channel so that the concentration in seawater and the addition time per day shown in Table 1 were obtained (Examples 7 to 11).

水路試験装置の各水路内(各試験区内)には、付着生物調査用にアクリル製のカラム(内径64mm×長さ300mm×厚さ2mm、表面積:602.88cm、半円状に半割しその片方の内面に目合5mm、糸径1mmのビニロン網を張りつけたものを再度円柱状にしたもの)を挿入し、通水終了後にカラムに付着した海生生物(ヒドロ虫類)を測定し、海生生物の付着防止効果を評価した。
また、各水路内には、スライム汚れ防止効果確認用にチタン管からなるテストチューブ(内径23.4mm、長さ1000mm、肉厚1.0mm)を設置し、通水終了後にテストチューブの内面に形成されたスライムを主体とする汚れ量を測定し、スライムの付着防止効果を評価した。なお、ブランクとして薬剤無添加についても試験した。
得られた結果を、海水中の過酢酸濃度、酢酸濃度及び過酸化水素濃度、並びに、一日当たりの添加時間と共に表1に示す。
In each waterway (inside each test area) of the waterway test apparatus, an acrylic column (inner diameter 64 mm × length 300 mm × thickness 2 mm, surface area: 602.88 cm 2 , divided into half in a semicircular shape) is used for the investigation of attached organisms. A plastic net with a mesh size of 5 mm and a thread diameter of 1 mm was attached to the inner surface of one side of the perilla, and then re-formed into a column), and after water flow was completed, marine organisms (hydrozoans) adhering to the column were measured. and evaluated the effect of preventing adhesion of marine organisms.
In addition, a test tube made of titanium (inner diameter: 23.4 mm, length: 1000 mm, wall thickness: 1.0 mm) was installed in each water channel to check the effect of preventing slime stains. The amount of dirt mainly composed of formed slime was measured to evaluate the slime adhesion prevention effect. In addition, as a blank, the test was also performed without the addition of the drug.
The obtained results are shown in Table 1 together with peracetic acid concentration, acetic acid concentration and hydrogen peroxide concentration in seawater, and addition time per day.

(過酢酸を含有する薬剤(過酢酸溶液1~5)の調製)
下記手順で過酢酸を含有する薬剤として、過酢酸溶液1~5を調製した。
(過酢酸溶液1)
過酢酸溶液1は、35%過酸化水素11%、酢酸33%、水54%、硫酸1%、60%HEDP(1-ヒドロキシエチリデン-1,1-ジホスホン酸)水溶液1%となるよう混合し、室温で2日間放置することで調製した。調製した過酢酸溶液1の過酸化水素及び総過酸化物濃度を、従来公知の滴定法によって測定し、得られた結果から組成を算出したところ、過酸化水素2.8%、過酢酸1.3%、酢酸32.0%であった。
(過酢酸溶液2)
過酢酸溶液2は、35%過酸化水素11%、酢酸55%、水32%、硫酸1%、60%HEDP(1-ヒドロキシエチリデン-1,1-ジホスホン酸)水溶液1%となるよう混合し、室温で2日間放置することで調製した。調製した過酢酸溶液2の過酸化水素及び総過酸化物濃度を、従来公知の滴定法によって測定し、得られた結果から組成を算出したところ、過酸化水素1.9%、過酢酸3.0%、酢酸52.7%であった。
(過酢酸溶液3)
過酢酸溶液3は、35%過酸化水素20%、酢酸52%、水26%、硫酸1%、60%HEDP(1-ヒドロキシエチリデン-1,1-ジホスホン酸)水溶液1%となるよう混合し、室温で2日間放置することで調製した。調製した過酢酸溶液3の過酸化水素及び総過酸化物濃度を、従来公知の滴定法によって測定し、得られた結果から組成を算出したところ、過酸化水素3.8%、過酢酸5.1%、酢酸48.2%であった。
(過酢酸溶液4)
過酢酸溶液4は、35%過酸化水素31%、酢酸37%、水30%、硫酸1%、60%HEDP(1-ヒドロキシエチリデン-1,1-ジホスホン酸)水溶液1%となるよう混合し、室温で2日間放置することで調製した。調製した過酢酸溶液4の過酸化水素及び総過酸化物濃度を、従来公知の滴定法によって測定し、得られた結果から組成を算出したところ、過酸化水素8.0%、過酢酸6.0%、酢酸32.0%であった。
(過酢酸溶液5)
過酢酸溶液5は、35%過酸化水素60%、酢酸38%、硫酸1%、60%HEDP(1-ヒドロキシエチリデン-1,1-ジホスホン酸)水溶液1%となるよう混合し、室温で2日間放置することで調製した。調製した過酢酸溶液5の過酸化水素及び総過酸化物濃度を、従来公知の滴定法によって測定し、得られた結果から組成を算出したところ、過酸化水素14.4%、過酢酸14.4%、酢酸26.7%であった。
(Preparation of drugs containing peracetic acid (peracetic acid solutions 1 to 5))
Peracetic acid solutions 1 to 5 were prepared as agents containing peracetic acid by the following procedure.
(Peracetic acid solution 1)
Peracetic acid solution 1 is 35% hydrogen peroxide 11%, acetic acid 33%, water 54%, sulfuric acid 1%, 60% HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) aqueous solution 1%. , was prepared by standing at room temperature for 2 days. The hydrogen peroxide and total peroxide concentrations of the prepared peracetic acid solution 1 were measured by a conventionally known titration method, and the composition was calculated from the obtained results. 3% and 32.0% acetic acid.
(Peracetic acid solution 2)
Peracetic acid solution 2 is 35% hydrogen peroxide 11%, acetic acid 55%, water 32%, sulfuric acid 1%, 60% HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) aqueous solution 1%. , was prepared by standing at room temperature for 2 days. The hydrogen peroxide and total peroxide concentrations of the prepared peracetic acid solution 2 were measured by a conventionally known titration method, and the composition was calculated from the obtained results. 0% and 52.7% acetic acid.
(Peracetic acid solution 3)
Peracetic acid solution 3 is 35% hydrogen peroxide 20%, acetic acid 52%, water 26%, sulfuric acid 1%, and 60% HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) aqueous solution 1%. , was prepared by standing at room temperature for 2 days. The hydrogen peroxide and total peroxide concentrations of the prepared peracetic acid solution 3 were measured by a conventionally known titration method, and the composition was calculated from the obtained results. 1% and 48.2% acetic acid.
(Peracetic acid solution 4)
Peracetic acid solution 4 is 35% hydrogen peroxide 31%, acetic acid 37%, water 30%, sulfuric acid 1%, 60% HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) aqueous solution 1%. , was prepared by standing at room temperature for 2 days. The hydrogen peroxide and total peroxide concentrations of the prepared peracetic acid solution 4 were measured by a conventionally known titration method, and the composition was calculated from the obtained results. 0% and 32.0% acetic acid.
(Peracetic acid solution 5)
Peracetic acid solution 5 was prepared by mixing 35% hydrogen peroxide 60%, acetic acid 38%, sulfuric acid 1%, and 60% HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) aqueous solution 1%. It was prepared by leaving it for days. The hydrogen peroxide and total peroxide concentrations of the prepared peracetic acid solution 5 were measured by a conventionally known titration method, and the composition was calculated from the obtained results. 4% and 26.7% acetic acid.

調製した各過酢酸溶液1~5は、付着防止効果確認用アクリル製カラムの手前に、定量ポンプを用いて、表1に示す海水中の濃度、および一日当たりの添加時間(24時間)になるように水路(試験区)に添加された。 Each of the prepared peracetic acid solutions 1 to 5 was placed in front of an acrylic column for checking the anti-adhesion effect, using a metering pump, to the concentration in seawater shown in Table 1 and the addition time per day (24 hours). It was added to the waterway (test plot) as follows.

(過酸化水素)
過酸化水素は、市販品の35%過酸化水素溶液を適宜純水で希釈することで海水に添加する薬剤濃度に調整し、同様に付着防止効果確認用アクリル製カラムの手前に、定量ポンプを用いて、表1に示す海水中の濃度、および一日当たりの添加時間が24時間になるように添加した。
(hydrogen peroxide)
Hydrogen peroxide was adjusted to the chemical concentration to be added to seawater by appropriately diluting a commercially available 35% hydrogen peroxide solution with pure water. was added so that the concentration in seawater shown in Table 1 and the addition time per day was 24 hours.

[評価]
(ヒドロ虫類の被覆率の計測)
回収したカラムからヒドロ虫類の被覆率(%)の計測を行った。ヒドロ虫類の被覆率(%)は、通水終了後のカラムに5mm目合いのネットを押し当て、被覆面と非被覆面の目数を計数し、カラムの表面積602.88cmを100%として被覆率を算出した。算出結果に基づき下記のように評価をした。
[evaluation]
(Measurement of hydrozoan coverage)
Hydrozoan coverage (%) was measured from the collected columns. The hydrozoan coverage (%) is obtained by pressing a net with a mesh size of 5 mm against the column after the completion of water passage, counting the number of meshes on the coated surface and the uncoated surface, and dividing the surface area of 602.88 cm 2 of the column into 100%. The coverage was calculated as Based on the calculation results, evaluation was made as follows.

(ヒドロ虫類)
被覆率が5%以下の場合に「〇」、被覆率が5~10%の場合に「△」、被覆率が10%を超える場合に「×」と評価した。評価が「△」であれば、ヒドロ虫類の付着障害防止効果があると判断でき、評価が「〇」であれば、ヒドロ虫類の付着防止効果が充分にあると判断できる。得られた結果を表1に記載した。
(hydrozoans)
It was evaluated as “◯” when the coverage was 5% or less, “Δ” when the coverage was 5 to 10%, and “×” when the coverage exceeded 10%. If the evaluation is "Δ", it can be judged that there is an effect of preventing hydrozoan adhesion failure, and if the evaluation is "◯", it can be judged that the hydrozoan adhesion prevention effect is sufficient. The results obtained are listed in Table 1.

(スライムの計測)
試験後、水路から取り外したテストチューブの内面に形成されたスライムを主体とする汚れを掻き取り、100mLのメスシリンダーに回収し、4時間静置後の湿体積を計量した。
ブランクにおいて掻き取ったスライムは主にテストチューブに付着した微生物に由来する。カラムでの付着防止効果の確認と同様に、テストチューブの内面に付着したスライムにもデトリタスが含まれるが、テストチューブのチタン管径はカラム径の約1/3であり、その管内の海水の流速は速く、ムラサキイガイなどのイガイ類やフジツボ類、コケムシ類などの海生付着生物の付着はないことを確認している。
ブランクでのスライムの付着状況から、本試験例では湿体積が5mL以下の場合に「〇」、湿体積が5mLを超え10mL以下の場合に「△」、湿体積が10~21mLの場合に「×」と評価し、湿体積が21mLを超え、ブランクよりも悪化する場合に「××」と評価した。評価が「△」であれば、スライムの付着障害防止効果があると判断でき、評価が「〇」であれば、スライムの付着防止効果が充分にあると判断できる。得られた結果を表1に記載した。
(Slime measurement)
After the test, the dirt mainly composed of slime formed on the inner surface of the test tube removed from the water channel was scraped off, collected in a 100 mL graduated cylinder, and the wet volume after standing still for 4 hours was measured.
The slime scraped off in the blank originated mainly from microorganisms adhering to the test tube. Similar to the confirmation of the adhesion prevention effect in the column, the slime adhering to the inner surface of the test tube also contains detritus, but the titanium tube diameter of the test tube is about 1/3 of the column diameter, and the seawater in the tube The current is fast, and it has been confirmed that there are no mussels such as purple mussels, barnacles, bryozoans, or other marine organisms adhering to them.
From the state of slime adhesion on the blank, in this test example, "○" when the wet volume is 5 mL or less, "△" when the wet volume is more than 5 mL and 10 mL or less, and " when the wet volume is 10 to 21 mL. When the wet volume exceeded 21 mL and was worse than the blank, it was evaluated as "xx". If the evaluation is ".DELTA.", it can be judged that there is a slime adhesion prevention effect, and if the evaluation is ".largecircle.", it can be judged that the slime adhesion prevention effect is sufficient. The results obtained are listed in Table 1.

Figure 0007228148000001
Figure 0007228148000001

表1に示すように、海水の過酢酸濃度が0.1~10mg/Lになるように過酢酸を含有する薬剤(過酢酸溶液)が添加されている実施例1~11にかかる試験例は、ヒドロ虫類の評価が「△」又は「〇」であり、低濃度の過酢酸によるヒドロ虫類に対する付着抑制効果を確認した。
一方、過酸化水素のみが添加されている参考例2、参考例3、及び、過酢酸溶液(過酢酸を含有する薬剤に該当)を添加しても海水中の過酢酸濃度が0.1mg/L未満であった比較例1にかかる試験例では、ヒドロ虫類のような海生生物に対する付着抑制効果が得られなかった。
また、実施例2の結果から、過酢酸を含有する薬剤を海水に添加することにより、1日当たり添加される酢酸の積算濃度が70mg/Lを大きく超える場合、ブランク(参考例1)と比較してスライムの付着が増加しており、酢酸によるスライムの増加を確認した。また、実施例1及び実施例11の結果から、過酢酸を含有する薬剤を海水に添加することにより、1日当たり添加される酢酸の積算濃度が70mg/Lを超える場合、スライムの量はブランクと同様であり、酢酸によるスライムの増加は確認できなかった。しかし、過酢酸によるスライム抑制効果も確認されなかった。
また、実施例3~10の結果から、1日当たり添加される酢酸の積算濃度が70mg/L以下となるように過酢酸を含有する薬剤(過酢酸溶液3~5)が海水に添加された場合、酢酸によるスライムの増加作用よりも過酢酸によるスライム付着防止作用の方が大きく、ヒドロ虫類及びスライムなどの海生生物等の海水利用設備への付着を効果的に抑制できた。
そのため、過酢酸及び酢酸を含有する薬剤を海水に添加する場合、1日当たり添加される酢酸の積算濃度を70mg/L以下とすることで、ヒドロ虫類及びスライムのような海生生物等の海水利用設備への付着を効果的に低減できることを確認した。


As shown in Table 1, the test examples according to Examples 1 to 11 in which a chemical containing peracetic acid (peracetic acid solution) is added so that the peracetic acid concentration in seawater is 0.1 to 10 mg / L , The evaluation of hydrozoans was "△" or "○", confirming the effect of low-concentration peracetic acid on inhibiting the adhesion of hydrozoa.
On the other hand, the peracetic acid concentration in seawater was 0.1 mg/ In the test example according to Comparative Example 1 in which it was less than L, no effect of suppressing adhesion to marine organisms such as hydrozoans was obtained.
Further, from the results of Example 2, when the cumulative concentration of acetic acid added per day greatly exceeds 70 mg/L by adding a chemical containing peracetic acid to seawater, compared with the blank (Reference Example 1) It was confirmed that acetic acid increased slime adhesion. Further, from the results of Examples 1 and 11, by adding a peracetic acid-containing agent to seawater, when the cumulative concentration of acetic acid added per day exceeds 70 mg / L, the amount of slime is blank. Similarly, an increase in slime due to acetic acid could not be confirmed. However, no slime inhibitory effect was confirmed by peracetic acid.
Further, from the results of Examples 3 to 10, when the peracetic acid-containing agent (peracetic acid solutions 3 to 5) was added to seawater so that the cumulative concentration of acetic acid added per day was 70 mg/L or less. , the slime-adhesion-preventing action of peracetic acid was greater than the slime-increasing action of acetic acid, and the adhesion of marine organisms such as hydrozoans and slimes to seawater utilization facilities could be effectively suppressed.
Therefore, when a chemical containing peracetic acid and acetic acid is added to seawater, by setting the cumulative concentration of acetic acid added per day to 70 mg / L or less, seawater such as hydrozoans and marine organisms such as slimes It was confirmed that adhesion to the equipment used can be effectively reduced.


Claims (3)

海生生物の付着防止剤であって、
過酢酸を含有し、
前記過酢酸の濃度が1質量%以上であり、
海水利用設備を流通する海水へ前記海水の前記過酢酸濃度が0.1~10mg/Lになるように添加され
前記海生生物がヒドロ虫類である
ことを特徴とする海生生物の付着防止剤。
An antifouling agent for marine organisms,
contains peracetic acid,
The concentration of peracetic acid is 1% by mass or more,
added to seawater flowing through the seawater utilization facility so that the peracetic acid concentration of the seawater is 0.1 to 10 mg / L ,
said marine organism is a hydrozoan
An antifouling agent for marine organisms characterized by:
さらに酢酸を含有し、前記酢酸の濃度が過酢酸濃度の25倍以下である請求項1に記載の海生生物の付着防止剤。 2. The antifouling agent for marine organisms according to claim 1, further comprising acetic acid, wherein the concentration of said acetic acid is 25 times or less the concentration of peracetic acid. さらに過酸化水素を含有し、前記過酸化水素の濃度が1質量%以上である請求項1又は2に記載の海生生物の付着防止剤
The antifouling agent for marine organisms according to claim 1 or 2, further comprising hydrogen peroxide, wherein the concentration of said hydrogen peroxide is 1% by mass or more .
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JP2021183336A (en) 2017-02-02 2021-12-02 株式会社片山化学工業研究所 Method for preventing adhesion of marine organisms and antiadhesive agent used therefor
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