JPWO2020022217A1 - Adhesion prevention method for marine organisms, adhesion prevention agent and adhesion prevention kit - Google Patents

Abstract

While reducing the amount of halogen-based chemicals such as chlorine and bromine and chlorine dioxide, and reducing the amount of aliphatic quaternary ammonium salt and N-mono-substituted alkylenediamine, both effects can be achieved. Provided are a method for preventing the adhesion of marine organisms and the like, which can be maintained for a long period of time and can prevent the adhesion of a wide range of marine species and slime, and an adhesion inhibitor and an adhesion prevention kit used for the method. A method for preventing the adhesion of marine organisms and slime to a seawater cooling water system, wherein an aliphatic quaternary ammonium salt represented by the general formula (I) and an N-mono-substituted alkylenediamine represented by the general formula (II) are used. Prevention of adhesion of marine organisms and the like by adding a first agent having at least one and a second agent having at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide to the seawater of the seawater cooling water system. Method. (In the formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R1 and R3 are alkyl groups having 1 to 4 carbon atoms, and R2 is the same as R. Alternatively, it is an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.) In R-NH- (CH2) nNH2 (II) (formula (II)). , R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, and n is an integer of 1 to 4.) [Chemical formula 1]

Description

The present invention relates to a method for preventing adhesion of marine organisms and the like, an anti-adhesion agent for marine organisms and the like, and a kit for preventing adhesion of marine organisms and the like.

Many power plants, steelworks, petrochemical plants, etc. that use seawater as cooling water are constructed in places facing the inland sea or the bay to avoid waves. When seawater is taken in the inland sea or bay, marine organisms such as mussels, barnacles, mussels, and hydroins and slimes that live in the seawater are found in seawater intake channels, pipes and headraces, heat exchangers, condenser tubes, etc. It adheres to the waterways of the sea and causes various obstacles. For example, the attached marine organisms grow and block the headraces such as heat exchanger tubes to obstruct the passage of seawater and cause turbulence, causing obstacles such as erosion corrosion. In addition, the attached marine organisms, etc. are stripped off by water pressure, flow velocity, etc., causing blockage of the tube and strainer of the heat exchanger, obstructing the passage of seawater, and deteriorating the original function of the heat exchanger. cause.
It is said that the normal attached breeding season of the above marine organisms is around April to October, but the above-mentioned obstacles occur due to breeding even in winter due to high seawater temperature and influx of alien species. cause.

In order to prevent the formation (adhesion) of the above marine species, conventional chlorine generators such as sodium hypochlorite, electrolytic chlorine or chlorine gas (also referred to as "chlorine agents"), hydrogen peroxide or peroxide A hydrogen generating agent (also referred to as “hydrogen peroxide agent”) has been added (Patent Document 1 and Patent Document 2).

Further, for example, Patent Document 3 describes a technique relating to an aqueous solution-adhering biological control agent containing chlorine dioxide or a chlorine dioxide generating agent as an active ingredient, and Patent Document 4 describes fresh water or fresh water installed in a facility using fresh water or seawater. A technique relating to a method for preventing or controlling the adhesion of organisms adhering to a water channel, which comprises continuously or intermittently injecting a chlorine dioxide aqueous solution into a water channel through which seawater passes, is disclosed.
Chlorine dioxide used here has a strong bactericidal activity and does not form a compound such as trihalomethane, so that it has an advantage of having a small impact on the environment.
However, chlorine dioxide is extremely unstable as a chemical substance, and there is a problem in sustaining the effect of preventing the adhesion of marine organisms.
In addition, the applicant has proposed a method for preventing the adhesion of marine organisms in which chlorine dioxide and hydrogen peroxide are used in combination, and an anti-adhesion agent used therein (Patent Document 5).

Further, for example, in Patent Document 6 and the like, sodium chlorosulfamic acid and the like are described as slime control agents capable of preventing biofouling disorders without causing deterioration of RO membranes used in seawater desalination equipment and the like. Stabilized bromine agents such as stabilized chlorinating agents and sodium bromosulfamate have been proposed.

In addition, quaternary ammonium compounds and higher aliphatic amine compounds have also been proposed as highly safe anti-adhesion agents for marine attached organisms (Patent Document 7).

Japanese Unexamined Patent Publication No. 11-376666 Special Publication No. 61-2439 Japanese Unexamined Patent Publication No. 1-2755004 Japanese Unexamined Patent Publication No. 6-153759 Japanese Patent No. 5879596 Japanese Unexamined Patent Publication No. 2006-263510 Japanese Patent No. 2634958

In order to prevent the adhesion of marine organisms, there is a movement to avoid the use of halogen-based agents such as chlorine agents and bromine agents in consideration of the impact on the environment. You may have to use.
Under such circumstances, a method for preventing the adhesion of marine organisms and slime, which can exert an excellent effect of preventing the adhesion of marine organisms and slime, while reducing the amount of halogen-based agents such as chlorine agents and bromine agents. Development is desired.
Further, a drug of a quaternary ammonium salt or a higher aliphatic amine compound is relatively expensive, and addition of a high concentration or a large amount of the drug is not economically preferable, and an inexpensive method is desired.

The present invention reduces the amount of halogen-based agents such as chlorine agents and bromine agents and chlorine dioxide, and reduces the amount of aliphatic quaternary ammonium salts and N-mono-substituted alkylenediamines. To provide a method for preventing the adhesion of marine organisms, etc., which can maintain the effects of both for a long period of time and prevent the adhesion of a wide range of marine species and slime, and the adhesion inhibitor and adhesion prevention kit used for the method. Make it an issue.

The inventor of the present invention has a first agent having at least one of an aliphatic quaternary ammonium salt and an N-mono-substituted alkylenediamine, and at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide. By using the two drugs in combination, it is possible to effectively prevent the adhesion of a wide range of marine species including mussels such as purple mussels and fujitsubo, and the adhesion of slime. Reduced drug addition compared to the single use of either the class ammonium salt or the N-mono-substituted alkylenediamine and the single use of at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide. We have found that an effective anti-adhesion effect of marine organisms and slime can be sufficiently obtained even if they are allowed to do so, and have completed the present invention.

（式（Ｉ）において、Ｒは炭素数１０〜２０の飽和又は不飽和の直鎖状脂肪族炭化水素基であり、Ｒ^１及びＲ^３は炭素数１〜４のアルキル基、Ｒ^２はＲと同じか又は炭素数１〜４のアルキル基であり、ＸはＣｌ、Ｂｒ、Ｉ、メチルサルフェート、エチルサルフェート又はパラトルエンスルホネートである。）
Ｒ−ＮＨ−（ＣＨ_２）_ｎＮＨ_２ （ＩＩ）
（式（ＩＩ）において、Ｒは炭素数１０〜２０の飽和又は不飽和の直鎖状脂肪族炭化水素基であり、ｎは１〜４の整数である。）
また、本発明の海生生物の付着防止方法では、海水中の第一薬剤の濃度が、０．００１〜０．３ｍｇ／Ｌとなるように１日当たり少なくとも１２時間、第一薬剤を海水冷却水系の海水に添加することが好ましい。
また、海水中の第二薬剤の濃度が、０．００２〜３．０ｍｇ／Ｌとなるように１日当たり少なくとも１時間、第二薬剤を海水冷却水系の海水に添加することが好ましい。
また、上記第二薬剤における塩素剤又は上記臭素剤は、（ａ）塩素ガス、次亜塩素酸カルシウム、次亜塩素酸ナトリウム、塩素化イソシアヌル酸、ジクロロイソシアヌル酸ナトリウム、ジクロロイソシアヌル酸カリウム、モノクロロイソシアヌル酸ナトリウム、モノクロロイソシアヌル酸カリウム、トリクロロイソシアヌル酸ナトリウム及びトリクロロイソシアヌル酸カリウムの中から選択される一種以上の水中で次亜塩素酸を生成する物質、（ｂ）次亜臭素酸ナトリウム、臭化ナトリウムと次亜塩素酸ナトリウムとの反応物及び臭素水から選択される一種以上の水中で次亜臭素酸を生成する物質、（ｃ）海水電解液、又は、（ｄ）モノクロラミン、ジクロラミン、トリクロラミン、モノブロラミン、ジブロラミン、トリブロラミン、Ｎ-クロロスルファマート及びＮ-ブロモスルファマートから選択される一種以上の結合塩素または結合臭素、であることが好ましい。That is, the present invention is a method for preventing the adhesion of marine organisms and slime to a seawater cooling water system, and is an aliphatic quaternary ammonium salt represented by the general formula (I) and N represented by the general formula (II). -Adding a first agent having at least one of mono-substituted alkylenediamines and a second agent having at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide to the seawater of the seawater cooling water system. This is a method for preventing the adhesion of marine organisms and the like.

In the formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R ¹ and R ³ are alkyl groups having 1 to 4 carbon atoms, and R ² is R. Is the same as or is an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.)
R-NH- (CH ₂ ) _n NH ₂ (II)
(In formula (II), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, and n is an integer of 1 to 4).
Further, in the method for preventing the adhesion of marine organisms of the present invention, the first drug is used in a seawater cooling water system for at least 12 hours per day so that the concentration of the first drug in seawater is 0.001 to 0.3 mg / L. It is preferable to add it to the seawater of.
Further, it is preferable to add the second drug to the seawater of the seawater cooling water system for at least 1 hour per day so that the concentration of the second drug in the seawater becomes 0.002 to 3.0 mg / L.
The chlorine agent or the bromine agent in the second drug is (a) chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, monochloroisocyanuric. Sodium hypochlorite, potassium monochloroisocyanurate, sodium trichloroisocyanurate and potassium trichloroisocyanurate, which are selected from one or more substances that produce hypochlorite in water, (b) sodium hypochlorite, sodium bromide and A substance that produces hypobromic acid in one or more waters selected from a reaction product with sodium hypochlorite and bromine water, (c) seawater electrolyte, or (d) monochloroamine, dichloramine, trichloroisocyanuric, It is preferably one or more bound chlorine or bound bromine selected from monobrolamin, dibroramine, tribroramine, N-chlorosulfamate and N-bromosulfamate.

Further, the present invention is an adhesion preventive agent for marine organisms and the like used in the adhesion prevention method for marine organisms and the like, and is an aliphatic quaternary ammonium salt represented by the general formula (I) and the general. Adhesion of marine organisms or the like containing at least one of the N-mono-substituted alkylenediamine represented by the formula (II) and at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide as active ingredients. It is also an inhibitor.

Further, the present invention is a kit for preventing adhesion of marine organisms and the like used in the method for preventing adhesion of marine organisms and the like, and comprises an aliphatic quaternary ammonium salt represented by the general formula (I) and the above. A first agent having at least one of the N-mono-substituted alkylenediamine represented by the general formula (II) and a second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide. It is also a kit for preventing the adhesion of marine organisms contained in it.

According to the method for preventing the adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent for marine organisms and the anti-adhesion kit for use in this method for preventing the adhesion of marine organisms, a wide range of marine organism species (for example, mussels) It is possible to prevent the adhesion of mussels, mussels, mussels) and slimes.
Further, according to the method for preventing the adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent for marine organisms and the anti-adhesion kit for use in this method for preventing adhesion, the above general formula (I) is used. The amount of the primary agent having at least one of the aliphatic quaternary ammonium salt and the N-mono-substituted alkylenediamine represented by the above general formula (II), and the halogen-based agent such as a chlorine agent or a bromine agent. The amount of the second drug having at least one selected from the group consisting of and chlorine dioxide is reduced as compared with the case where the first drug or the second drug is used alone, while the first drug and the second drug are used. The effects of both can be sustained.
In addition, at power plants, chlorine agents or bromine agents are added to the seawater taken in to prevent the adhesion of seawater organisms, but due to the regulation of the concentration of residual chlorine in wastewater, sufficient chlorine agents or bromine agents are added. Cannot be added, and the required chlorine or bromine concentration cannot be retained in the heat exchanger (condenser), so that a sufficient effect of preventing the adhesion of marine organisms may not be obtained. Therefore, according to the present invention, by adding a first agent containing at least one of the above aliphatic quaternary ammonium salt and N-mono-substituted alkylenediamine to such a seawater system, the concentration of residual chlorine is within the above-mentioned regulation. Also, a sufficient effect of preventing the adhesion of marine organisms can be obtained.

(Method of preventing adhesion of marine organisms, etc.)
The method for preventing adhesion of marine organisms and the like according to the present invention is at least one of an aliphatic quaternary ammonium salt represented by the general formula (I) and an N-mono-substituted alkylenediamine represented by the general formula (II). The first agent having the above and the second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide are added to the seawater of the seawater cooling water system.
The first agent and the second agent are preferably added so as to have a concentration that prevents the adhesion of marine organisms and the adhesion of slime in the seawater of the seawater cooling water system. In addition, the first drug and the second drug can be added to the same place or different places at the same time zone or different time zones.

The "seawater cooling water system" used in the present specification refers to, in one or more embodiments, from, for example, water intake system equipment, equipment to be cooled such as a condenser and a heat exchanger, and water discharge system equipment. Become. The water intake system equipment includes a headrace, a screen for removing foreign substances in seawater, a circulating water pump (water intake pump), a circulating water pipe (water intake pipe), and the like.
Further, the "seawater of the seawater cooling water system" used in the present specification means, for example, seawater used as cooling water in equipment to be cooled such as a condenser and a heat exchanger.

The first drug having at least one of the above aliphatic quaternary ammonium salt and the above N-mono-substituted alkylenediamine added to the seawater cooling water system sufficiently prevents adhesion to large marine organisms such as mussels and fujitsubo. Although it shows an effect, it may not show a sufficient effect of preventing adhesion against stains caused by slime or the like. On the other hand, the second agent having at least one selected from the group consisting of chlorine agent, bromine agent and chlorine dioxide shows a sufficient adhesion prevention effect against stains caused by slime and the like, but large seas such as mussels and barnacles. It may not show a sufficient anti-adhesion effect on living organisms. The first drug is safer than the second drug, and tends to show selectivity for marine organisms and the like that exhibit the above-mentioned anti-adhesion effect.
In the method for preventing adhesion of marine organisms and the like in the present invention, by using the first agent and the second agent, the first agent and the second agent cover each other's shortcomings and the effects of both are maintained for a long time. It is thought that it can prevent the adhesion of a wide range of marine species and slime. In particular, by setting the concentrations of the first drug and the second drug in seawater within a specific range, the effects of both drugs can be maintained for a long time without causing overuse of either drug or both drugs. It is thought that it can prevent the adhesion of a wide range of marine species and slime.
That is, it is considered that the use of the first agent and the second agent can obtain a synergistic effect on the prevention of marine organism adhesion and the prevention of slime adhesion.

In the technical field to which the present invention belongs, the empirical rule that only the excellent effects of each drug are exhibited by the combined use of a plurality of drugs having different selectivity for attached marine organisms, etc. is not clear and is actually confirmed. You can't understand it unless you try it. In fact, when a drug having selectivity for attached marine organisms and the like is added to seawater, the number of attached marine organism species other than the target organisms increases, and in many cases, it becomes predominant. Therefore, in the technical field of the present invention, it is not possible to simply combine a plurality of drugs to obtain a combination of excellent effects of these drugs, and what kind of results can be obtained without actual confirmation. I don't know.

(First drug)
[Aliphatic quaternary ammonium salt]
The aliphatic quaternary ammonium salt used in the adhesion prevention method for marine organisms, the adhesion prevention agent, and the adhesion prevention kit of the present invention is represented by the following general formula (I) in one or more embodiments. Is.

In formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R ¹ and R ³ are alkyl groups having 1 to 4 carbon atoms, and R ² is R. Alkyl groups of the same or 1 to 4 carbon atoms, where X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.

In the general formula (I), the saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms includes decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, icosyl, and henicosyl. , Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl and other linear saturated aliphatic hydrocarbon groups; Examples thereof include saturated or unsaturated linear aliphatic hydrocarbon groups derived from natural substances such as chain unsaturated aliphatic hydrocarbon groups, beef fat alkyl groups, hardened beef fat alkyl groups, and coconut alkyl groups.

The "beef fat alkyl group" and "hardened beef fat alkyl group" mainly contain 16 to 18 carbon atoms, and the "coconut alkyl group" mainly contains saturated or unsaturated linear aliphatic hydrocarbon groups in the range of 12 to 16 carbon atoms. means. The compound having the "beef tallow alkyl group", "hardened beef tallow alkyl group" or "coconut alkyl group" is a mixed aliphatic quaternary ammonium salt produced from beef tallow or coconut oil or coconut fat by known means.

In the general formula (I), examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

One or more embodiments of the aliphatic quaternary ammonium salt represented by the general formula (I) that can be used in the adhesion prevention method for marine organisms and the like, the adhesion prevention agent, and the adhesion prevention kit of the present invention. In, decyltrimethylammonium salt, dodecyltriethylammonium salt, tetradecyltrimethylammonium salt, tetradecyltriethylammonium salt, hexadecyltrimethylammonium salt, hexadecyltriethylammonium salt, octadecyltrimethylammonium salt, octadecyltriethylammonium salt, palm alkyltrimethylammonium salt. Salt, Palm Alkyl Triethyl Ammonium Salt, Beef Alkyl Triethyl Ammonium Salt, Beef Alkyl Triethyl Ammonium Salt; Didecyl Dimethyl Ammonium Salt, Didodecyl Dimethyl Ammonium Salt, Dihexadecyl Dimethyl Ammonium Salt, Dioctadecyl Ammonium Salt, Diyashi Alkyl Ammonium Salt Examples thereof include salts and di-beef fat alkyldimethylammonium salts.

[Method of adding aliphatic quaternary ammonium salt]
The aliphatic quaternary ammonium salt represented by the general formula (I) that can be used in the adhesion prevention method for marine organisms and the like, the adhesion prevention agent and the adhesion prevention kit in the present invention is an aqueous preparation dissolved in water. , It is preferable to use it as an aqueous preparation dissolved in water with a hydrophilic organic solvent such as ethyl alcohol or isopropyl alcohol in terms of workability, transportability, handleability, economy and effect. When hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium paratoluenesulfonate, hexadecyltrimethylammonium methylsulfate and octadecyltrimethylammonium methylsulfate are used as the aliphatic quaternary ammonium salt, these aliphatic quaternary ammonium salts are used. Since the quaternary ammonium salt is sparingly soluble in water, it is preferable to use it as an aqueous preparation when it is added to seawater in terms of workability, transportability, handleability and effect. As this aqueous preparation, it is preferable to use the aqueous preparation described in Japanese Patent No. 5621119.

[N-mono-substituted alkylene diamine]
The N-mono-substituted alkylenediamine used in the adhesion prevention method for marine organisms, the adhesion prevention agent, and the adhesion prevention kit of the present invention is represented by the following general formula (II) in one or more embodiments. Is.
R-NH- (CH ₂ ) _n NH ₂ (II)

In formula (II), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms. Examples of the saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms include those similar to those in the formula (I).
In formula (II), n is an integer of 1 to 4.

As the N-mono-substituted alkylenediamine that can be used in the adhesion prevention method for marine organisms and the like, the adhesion prevention agent and the adhesion prevention kit of the present invention, in one or more embodiments, N-coconut alkylethylenediamine, N- N-mono-substituted ethylenediamines such as beef fat alkylethylenediamine and N-hardened beef fat alkylethylenediamine; N-mono-substituted propylenediamines such as N-coconut alkylpropylenediamine, N-beef fat alkylpropylenediamine, N-hardened beef fat alkylpropylenediamine; Examples thereof include N-mono-substituted trimethylenediamines such as coconut alkyl butylene diamine, N-beef alkyl butylene diamine, and N-hardened beef alkyl butylene diamine.

The N-mono-substituted alkylene diamines may be their acid addition salts in one or more embodiments. Examples of the acid include inorganic acids such as hydrochloric acid and hydrobromic acid; and organic acids such as formic acid, acetic acid, lactic acid, methacrylic acid and amino acids. Examples of amino acids include L-aspartic acid and L-glutamic acid. Among these, N-beef alkylpropylene diamine acetate is preferable from the viewpoint of preventing the adhesion of marine organisms in the copper alloy pipe and the corrosion prevention of the copper alloy pipe.

[Method of adding N-mono-substituted alkylenediamine]
The N-mono-substituted alkylenediamine represented by the general formula (II) that can be used in the adhesion prevention method for marine organisms, the adhesion prevention agent, and the adhesion prevention kit of the present invention is an aqueous preparation dissolved in water. It is preferable to use it as an aqueous preparation dissolved in water with a hydrophilic organic solvent such as ethyl alcohol or isopropyl alcohol in terms of workability, transportability, handleability, economy and effect.

In the adhesion prevention method, adhesion prevention agent, and adhesion prevention kit for marine organisms of the present invention, a first agent having at least one of the above aliphatic quaternary ammonium salt and the above N-mono-substituted alkylenediamine is used. That is, the above aliphatic quaternary ammonium salt and the above N-mono-substituted alkylene diamine may be used alone or in combination.

Further, in the method for preventing adhesion of marine organisms, etc. of the present invention, at least one of the above aliphatic quaternary ammonium salt and the above N-mono-substituted alkylenediamine used as the first agent is attached to the marine organisms and the like. It can be selected as appropriate according to the season.

The addition concentration of the first agent containing at least one of the aliphatic quaternary ammonium salt and the N-mono-substituted alkylenediamine is the concentration of the first agent in the seawater of the seawater cooling water system in one or more embodiments. It can be referred to and adjusted as appropriate. The concentration of the first drug in seawater is preferably 0.001 to 0.3 mg / liter, more preferably 0.005 to 0.1 mg, from the viewpoint of the effect of preventing the adhesion of marine organisms to the seawater cooling water system. / Liter, more preferably 0.01-0.03 mg / liter.

The addition time of the first drug tends to be inversely proportional to the addition concentration, but within the above addition concentration range, 12 hours or more is preferable, and 16 hours or more is preferable from the viewpoint of preventing the adhesion of marine organisms per day. More preferably, 18 hours or more is further preferable. The addition time is 24 hours or less, 22 hours or less, and 20 hours or less per 24 hours a day. The addition may be continuous addition or intermittent addition.

The place where the first chemical is added is not particularly limited, and in one or a plurality of embodiments, any place before the taken seawater is sent to the seawater cooling water system pipe by a pump or the like can be mentioned. From the viewpoint of the effect of preventing damage due to the adhesion of marine organisms, for example, the vicinity of the intake port of the intake pump, the inlet of the heat exchanger or the condenser is preferable.

The concentration of the first chemical in seawater can be obtained by, for example, measuring the concentration in seawater in equipment to be cooled such as a condenser or a heat exchanger using a general measuring method. be able to.

(Second drug)
[Chlorine or bromine]
Examples of the chlorine agent or bromine agent that can be used in the adhesion prevention method for marine organisms, the adhesion prevention agent, and the adhesion prevention kit of the present invention include known chlorine agents or bromine agents.
(A) Chloric gas, hypochlorate (calcium hypochlorate, sodium hypochlorate, etc.), chlorinated isocyanuric acid, dichloroisocyanurate (sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.), monochloroisocyanuric Substances that produce dichloroisocyanuric acid in water, such as acid salts (sodium monochloroisocyanurate, potassium monochloroisocyanurate, etc.), trichloroisocyanuric acidate (sodium trichloroisocyanurate, potassium trichloroisocyanurate, etc.),
(B) Sodium hypobromous acid, a reaction product of sodium bromide and sodium hypochlorite, and a substance that produces hypobromous acid in water such as bromine water.
(C) Seawater electrolyte (electrolyte containing hypochlorous acid obtained by electrolyzing seawater in an electrolytic cell), and (d) Monochloramine, dichloramine, trichloramine, monochloramine, dichloramine, tribrolamin, N-chloro. Bound chlorine (stabilized chlorine) or bound bromine (stabilized bromine) such as sulfamate and N-bromosulfamate
Can be mentioned. Among these, (a), (b) and (c) are preferable from the practical viewpoints such as the effect of preventing the adhesion of marine organisms, economy, and handleability, and the following are preferable from the viewpoint of industrial availability. Sodium chlorite and potassium hypochlorite are particularly preferable. Among (d), monochrome lamin and monobrolamin are preferable, and then N-chlorosulfomate and N-bromosulfomate are preferable from the viewpoint of the effect of preventing the adhesion of marine organisms.
The "chlorine agent" in the present specification means a known "chlorine agent" used based on the common general technical knowledge belonging to the technical field of the present invention, and does not include chlorine dioxide.

N-chlorosulfamate and N-bromosulfamate can be prepared by known methods, for example, Japanese Patent Application Laid-Open No. 2003-503323, JP-A-2006-022097, Japanese Patent Application Laid-Open No. 11-506139, Japanese Patent Application Laid-Open No. 2001-2001. It can be prepared by the methods described in JP-A-501869, JP-A-2003-507326, JP-A-2014-101251 and JP-A-2017-159276.
In the present invention, the reaction product of sulfamic acid and hypochlorous acid and / or hypobromous acid can be preferably used.
Bound chlorine such as monochlorolamin can be prepared by the methods described in Japanese Patent No. 4914146, Japanese Patent Application Laid-Open No. 2017-119245, Japanese Patent Application Laid-Open No. 2017-53054, and the like.

The above chlorine and bromine agents may be diluted or dissolved in seawater or fresh water so as to have a desired concentration at the time of addition.
When (a) a substance that produces hypochlorous acid in water or (c) a seawater electrolyte is added to seawater, hypochlorous acid reacts with bromide ions existing in seawater and rapidly chlorine and bromine. Replaces. For example, when sodium hypochlorite is added to seawater, it quickly becomes sodium hypobromite. Therefore, the effect of preventing adhesion to marine organisms is the same regardless of which of (a), (b) and (c) is used.

[Chlorine dioxide]
Chlorine dioxide, which can be used in the adhesion prevention method for marine organisms, the adhesion prevention agent, and the adhesion prevention kit of the present invention, is an extremely unstable chemical substance, and therefore its storage and transportation are extremely difficult. Therefore, it is preferable to produce (produce) chlorine dioxide on the spot by a known method and adjust the addition concentration before use.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (equipment) can also be used.
(1) Reaction of sodium hypochlorite, hydrochloric acid and sodium chlorite NaOCl + 2HCl + 2NaClO2 → 2ClO2 + 3NaCl + H2O
(2) Reaction of sodium chlorite with hydrochloric acid 5NaClO2 + 4HCl → 4ClO2 + 5NaCl + 2H2O
(3) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO3 + H2O2 + H2SO4 → 2ClO2 + Na2SO4 + O2 + 2H2O

The above-mentioned second agent that can be used in the adhesion prevention method for marine organisms and the like, the adhesion prevention agent and the adhesion prevention kit of the present invention may be appropriately set depending on the state of seawater to be added, but a chlorine agent and a bromine agent. It is preferable to add at least one selected from the group consisting of chlorine dioxide and chlorine dioxide to a concentration of 0.002 to 3.0 mg / L with respect to seawater.
The concentration of the second drug in seawater means "effective chlorine concentration" when the second drug is a chlorine agent and / or a bromine agent.
If the concentration of the second drug is less than 0.002 mg / L, the effect of preventing the adhesion of marine organisms and slime may not be sufficiently obtained. On the other hand, if the concentration of the second drug exceeds 3.0 mg / L, no further effect can be expected, which is not preferable from the economical point of view.
A more preferred concentration of the second agent is 0.01 to 1.0 mg / L, more preferably 0.01 to 0.3 mg / L.

The addition time of the second drug may be appropriately set depending on the concentration of the first drug to be added, the state of the seawater to be added, and the like, but is usually 1 hour or more and 20 hours or less per day.
If the addition time is less than 1 hour per day, the effect of preventing the adhesion of marine organisms and slime by the combined use with the first drug may not be sufficiently obtained.
The addition time of the second drug is more preferably 1 hour or more and 8 hours or less per day, and more preferably 1 hour or more and 4 hours or less per day.

The place where the second chemical is added is not particularly limited, and in one or a plurality of embodiments, any place before the taken seawater is sent to the seawater cooling water system pipe by a pump or the like can be mentioned. From the viewpoint of the effect of preventing damage due to the adhesion of marine organisms, for example, the vicinity of the intake port of the intake pump, the inlet of the heat exchanger or the condenser is preferable.

The concentration of the second chemical in seawater can be obtained, for example, by measuring the concentration in seawater in equipment to be cooled such as a condenser or a heat exchanger using a general measuring method. be able to.

(Other additives)
In the method for preventing the 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.
Examples thereof include marine biofouling inhibitors such as dialkyldithiocarbamate, iron-based metal corrosion inhibitors, and defoamers.

(Addition method)
Examples of the method of adding each drug include a method using an injection pump, an air diffuser, a sprayer, and the like. In the present invention, conventional physical means can be used to diffuse a trace amount of the drug into the seawater cooling water system quickly and substantially uniformly. Specific examples thereof include installation of a diffuser, a stirrer, a baffle plate, etc. in the water system. In addition, since the equipment corresponding to these is attached to the seawater cooling water system, it may be diverted.

The present invention will be specifically described with reference to the following test examples, but the present invention is not limited thereto.

[Test Example 1]
N-mono-substituted alkylenediamine was used in combination as the first agent, and chlorine agent, bromine agent or chlorine dioxide was used in combination as the second agent, and the effect of preventing the adhesion of marine organisms and the effect of cleaning slime were confirmed.
A waterway test device was installed somewhere along the coast of Wakayama Prefecture facing the Pacific Ocean, and tests were conducted.
Unfiltered seawater (pH 8) pumped using a submersible pump is transiently passed through a channel (test plot) branched into 17 systems at a flow rate of 1 m ³ / h for 70 days using a pump. Additives prepared as shown below were added to each water channel at the daily addition time shown in Table 1 so as to have the drug concentrations shown in Table 1.
The chemical concentration is the set concentration in the acrylic column for confirming the adhesion prevention effect below, and the concentration of hypochlorite used as the chlorine agent is the effective chlorine concentration.
In addition, the amount of the drug added in the test group having the same drug concentration is the same. For example, the amount of chlorine added in Example 2 and Comparative Example 3 is the same, and the amount of chlorine dioxide added in Example 6 and Comparative Example 5 is the same.

In addition, an acrylic column (inner diameter 64 mm x length 300 mm x thickness 2 mm, surface area 602.88 cm ² ) for confirming the adhesion prevention effect is inserted into each water channel, and slime is further downstream of the acrylic column. A titanium tube (inner diameter 23.4 mm, length 1000 mm, wall thickness 10 mm) for confirming the cleaning effect was inserted. The drug effect was evaluated by measuring the amount of biomass adhering to the column and the wet volume of slime adhering to the inner surface of the titanium tube after the completion of water flow.
In addition, it was also tested that no drug was added as a blank.
The results obtained are shown in Table 1 along with the concentrations of each drug and their addition times.

(Additive drug)
N-Beef alkylpropylene diamine (drug: A) as N-mono-substituted alkylenediamine, sodium hypochlorite (drug: B) and N-chlorosulfamate (drug: D) as chlorinating agent, N- as bromine agent Bromosulfamate (drug: E) and chlorine dioxide (drug: C) generated by mixing sodium chlorite and hydrochloric acid as chlorine dioxide were used as additional chemicals.
Specifically, N-beef tallow alkylpropylene diamine was appropriately diluted with pure water to adjust the concentration of the drug to be added to seawater, and was added from the front of the acrylic column for confirming the adhesion prevention effect using a metering pump.
Sodium hypochlorite is adjusted to the concentration of chemicals added to seawater by appropriately diluting an aqueous solution of sodium hypochlorite with an effective chlorine concentration of 12% with pure water, and similarly, an acrylic column for confirming the adhesion prevention effect. It was added from the front using a metering pump.
For chlorine dioxide, an aqueous solution obtained by appropriately diluting sodium chlorite and hydrochloric acid with pure water is mixed in a tube before the chemical addition point so that the chlorine dioxide concentration shown in Table 1 can be obtained, and the residence time is 1 hour. The chlorine dioxide aqueous solution generated by the addition was added from the front of the acrylic column for confirming the adhesion prevention effect. Regarding the generation of chlorine dioxide, we confirmed the generation in a preliminary test and confirmed that sodium chlorite does not remain at a concentration that affects the effect.
N-chlorosulfamate and N-bromosulfamate are produced by a known method (for example, the method described in JP-A-2017-159276), and then added to seawater by appropriately diluting with pure water. The concentration of the drug was adjusted to be adjusted, and the concentration was added from the front of the acrylic column for confirming the adhesion prevention effect using a metering pump.

(Confirmation of marine organism adhesion prevention effect)
After the test, the mass W1 (g) of the column removed from the water channel was measured. The attached biomass (g) was calculated by the following formula together with the mass W0 of the column at the time of drying, which was measured in advance before the test.
Adhered biomass (g) = W1-W0
The sessile organisms attached to the blank are mainly derived from mussels such as mussels and marine sessile organisms such as barnacles and bryozoa. In addition, detritus-like substances containing a large amount of organic matter such as adhering organisms, slime excreta and carcasses, and extracellular secretions, and viscous particles and suspended matter contained in seawater also adhered, but these are also included in the amount of attached biomass.
From the state of attachment of marine organisms in the blank, it can be judged that in this test example, there is a sufficient effect of preventing the attachment of marine organisms when the amount of attached organisms is 15 g or less.
(Confirmation of slime cleaning effect)
After the test, the slime adhering to the inner surface of the titanium tube removed from the water channel was scraped off, collected in a 10 to 100 ml graduated cylinder, and the wet volume after standing for 4 hours was measured to evaluate the cleaning effect.
The slime scraped from the blank is mainly derived from microorganisms attached to the titanium tube. Similar to the confirmation of the adhesion prevention effect on the column, the slime adhering to the inner surface of the titanium tube also contains detritus-like substances, but the titanium tube diameter is about 1/3 of the column diameter, and the seawater cooling water inside the titanium tube. It has been confirmed that there is no attachment of mussels such as mussels and marine sessile organisms such as barnacles and mussels.
From the slime adhesion state on the blank, it can be judged that in this test example, there is a sufficient slime cleaning effect when the slime volume is 10 mL or less.

From the results in Table 1 above, the following was confirmed.
(1) In Comparative Examples 1 and 2 in which N-mono-substituted alkyldiamine was used alone as the first agent, a certain degree of marine biofouling prevention effect was compared with the blank to which no agent was added (Reference Example 1). Was confirmed, but a sufficient effect of preventing marine biofouling was not obtained. Moreover, the slime cleaning effect could hardly be confirmed.
(2) On the other hand, as in Comparative Examples 1 and 2, N-mono-substituted alkylenediamine was added at an addition concentration of 0.02 mg / L or 0.03 mg / L for 18 hours, and a second drug was also added. For 2, 3, 4, 8 and 9, a sufficient effect of preventing marine biofouling and a sufficient slime cleaning effect were confirmed.
(3) Further, in Comparative Examples 3 to 7 in which the second agent was applied alone, a sufficient slime cleaning effect could be confirmed, but a sufficient effect on prevention of marine organism adhesion could not be obtained. From the results of Comparative Example 3 and Comparative Example 4, it is better to add the second drug at a certain concentration for a short time than to add it at a low concentration for a long time to prevent marine organisms from adhering and to wash the slime. It was confirmed that the effect was obtained.
(4) From the results of Examples 1 to 9, when the first drug and the second drug are used in combination, the addition concentration of the first drug is 0.01 to 0.03 mg / L for 18 to 24 hours. By adding / day and adding the second drug at a concentration of 0.01 to 0.3 mg / L for 2 to 18 hours / day, a sufficient effect of preventing marine organisms from adhering and a sufficient slime cleaning effect can be obtained. Was confirmed.
From the above Examples and Comparative Examples, N-mono-substituted alkylenediamine (N-beef alkylpropylene diamine) was used as the first drug, and sodium hypochlorite, N-chlorosulfamate, and N-bromosulfa were used as the second drug. By using mart or chlorine dioxide in combination, a wide range of marine species (for example, mussels such as mussels, mussels, and mussels) are compared with the case where the first drug and the second drug are used alone. It was confirmed that the adhesion of marine organisms) and slime can be prevented.
In addition, it was confirmed that by using the first drug and the second drug in combination, a long-lasting effect of preventing the adhesion of marine organisms and slime can be sufficiently obtained for 70 days without increasing the amount of both. ..

[Test Example 2]
The following additive agents were used as the first agent and the second agent, and the effect of preventing the adhesion of marine organisms and the effect of cleaning slime were confirmed in the same manner as in Test Example 1 except that the test period was 55 days.
The results obtained are shown in Table 2 along with the concentrations of each drug and their addition times.

(Additive drug)
Hexadecyltrimethylammonium chloride (drug: a) as an aliphatic quaternary ammonium salt, sodium hypochlorite (drug: b) and monochloroamine (drug: d) as a chlorinating agent, and monobrolamin as a brominating agent (drug: e). ), Chlorine dioxide (drug: c) generated by mixing sodium chlorite and hydrochloric acid as chlorine dioxide was used as an additive.
Specifically, hexadecyltrimethylammonium chloride was appropriately diluted with pure water to adjust the concentration of the drug to be added to seawater, and was added from the front of the acrylic column for confirming the adhesion prevention effect using a metering pump.
Monochlorolamin and monobrolamin are produced by a known method (for example, the method described in JP-A-2017-53054), and then appropriately diluted with pure water to adjust the concentration of the drug to be added to seawater and adhered. It was added using a metering pump from the front of the acrylic column for confirming the preventive effect.
Sodium hypochlorite and chlorine dioxide were adjusted and added in the same manner as in Test Example 1.

From the results in Table 2 above, the following was confirmed.
(1) In Comparative Examples 11 and 12 in which the aliphatic quaternary ammonium salt was used alone as the first drug, a certain degree of prevention of marine biofouling was prevented as compared with the blank to which no drug was added (Reference Example 2). Although the effect was confirmed, a sufficient effect of preventing marine biofouling was not obtained. Moreover, the slime cleaning effect could hardly be confirmed.
(2) Further, in Comparative Examples 13 to 17 in which the second agent was applied alone, a sufficient slime cleaning effect could be confirmed, but a sufficient effect on prevention of marine organism adhesion could not be obtained. From the results of Comparative Example 13 and Comparative Example 14, it is better to add the second drug at a certain concentration for a short time than to add it at a low concentration for a long time to prevent marine organisms from adhering and to wash the slime. It was confirmed that the effect was obtained.
(3) On the other hand, from the results of Examples 11 to 19, when the first drug and the second drug are used in combination, the addition concentration of the first drug is 0.01 to 0.03 mg / L for 18 to 24 hours. By adding / day and adding the second drug at a concentration of 0.01 to 0.3 mg / L for 2 to 20 hours / day, a sufficient effect of preventing marine organisms from adhering and a sufficient slime cleaning effect can be obtained. Was confirmed.
From the above Examples and Comparative Examples, an aliphatic quaternary ammonium salt (hexadecyltrimethylammonium chloride) is used as the first drug, and sodium hypochlorite, monochloroamine, monobrolamin or chlorine dioxide are used in combination as the second drug. By doing so, compared to the case where the first drug and the second drug are used alone, a wide range of marine species (for example, mussels such as purple mussels, mussels, and sea mussels) and slimes It was confirmed that adhesion could be prevented.
In addition, it was confirmed that by using the first drug and the second drug in combination, a long-lasting effect of preventing the adhesion of marine organisms and slime can be sufficiently obtained for 55 days without increasing the amount of both. ..

Claims (6)

A method for preventing the adhesion of marine organisms and slime to the seawater cooling water system.
A first agent having at least one of an aliphatic quaternary ammonium salt represented by the general formula (I) and an N-mono-substituted alkylenediamine represented by the general formula (II).
A second agent having at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide,
A method for preventing the adhesion of marine organisms and the like, which comprises adding the above-mentioned seawater to the seawater of the seawater cooling water system.

In the formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R ¹ and R ³ are alkyl groups having 1 to 4 carbon atoms, and R ² is R. Is the same as or is an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.)
R-NH- (CH ₂ ) _n NH ₂ (II)
(In formula (II), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, and n is an integer of 1 to 4). The first aspect of claim 1, wherein the first agent is added to the seawater of the seawater cooling water system for at least 12 hours per day so that the concentration of the first agent in the seawater becomes 0.001 to 0.3 mg / L. How to prevent the adhesion of marine organisms. Claim 1 or 2 comprising adding the second agent to the seawater of the seawater cooling water system for at least one hour per day so that the concentration of the second agent in the seawater becomes 0.002 to 3.0 mg / L. The described method for preventing adhesion of marine organisms, etc. The chlorine agent or bromine agent in the second agent is
(A) Chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanuric acid, potassium dichloroisocyanuric acid, sodium monochloroisocyanuric acid, potassium monochloroisocyanuric acid, sodium trichloroisocyanuric acid and trichloroisocyanuric acid. A substance that produces hypochlorite in one or more waters selected from potassium acid,
(B) A substance that produces hypobromous acid in one or more waters selected from sodium hypobromous acid, a reaction product of sodium bromide and sodium hypochlorite, and bromine water.
(C) Seawater electrolyte or (d) One or more bound chlorine or bonds selected from monochloramine, dichloramine, trichloramine, monochloramine, dichloramine, tribrolamin, N-chlorosulfamate and N-bromosulfamate. The method for preventing adhesion of marine organisms or the like according to claim 1, 2 or 3, which is bromine. An anti-adhesion agent for marine organisms, etc. used in the method for preventing adhesion of marine organisms, etc. according to claim 1, 2, 3 or 4.
At least one of the aliphatic quaternary ammonium salt represented by the general formula (I) and the N-mono-substituted alkylenediamine represented by the general formula (II).
At least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide,
Anti-adhesion agent for marine organisms, etc. containing as an active ingredient.

In the formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R ¹ and R ³ are alkyl groups having 1 to 4 carbon atoms, and R ² is R. Is the same as or is an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.)
R-NH- (CH ₂ ) _n NH ₂ (II)
(In formula (II), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, and n is an integer of 1 to 4). A kit for preventing adhesion of marine organisms, etc., which is used in the method for preventing adhesion of marine organisms, etc. according to claim 1, 2, 3 or 4.
A first agent having at least one of an aliphatic quaternary ammonium salt represented by the general formula (I) and an N-mono-substituted alkylenediamine represented by the general formula (II).
A second agent having at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide,
Kit for preventing adhesion of marine organisms including.

In the formula (I), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, R ¹ and R ³ are alkyl groups having 1 to 4 carbon atoms, and R ² is R. Is the same as or is an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.)
R-NH- (CH ₂ ) _n NH ₂ (II)
(In formula (II), R is a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms, and n is an integer of 1 to 4).