WO2020022217A1 - Method, agent and kit each for preventing attachment of marine organism and others - Google Patents

Abstract

Provided are: a method for preventing the attachment of a marine organism and others, whereby it becomes possible to keep both of the effects of a halogen agent, e.g., a chlorine disinfectant and a bromine disinfectant, and chlorine dioxide and the effects of an aliphatic quaternary ammonium salt and a N-monosubstituted alkylene diamine for a long period while reducing the use amounts of the halogen agent and chlorine dioxide and also reducing the use amounts of the aliphatic quaternary ammonium salt and the N-monosubstituted alkylene diamine, and it also becomes possible to prevent the attachment of wide varieties of marine organism species and slime; an attachment preventing agent and an attachment preventing kit, each of which can be used for the method. A method for preventing the attachment of a marine organism and slime to a sea water coolant system, the method comprising adding a first chemical agent comprising an aliphatic quaternary ammonium salt represented by general formula (I) and/or a N-monosubstituted alkylene diamine represented by general formula (II) and a second chemical agent comprising at least one component selected from the group consisting of a chlorine disinfectant, a bromine disinfectant and chlorine dioxide to sea water in the sea water coolant system. (In formula (I), R represents a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms; R¹ and R³ independently represent an alkyl group having 1 to 4 carbon atoms; R² represents the same group as R or an alkyl group having 1 to 4 carbon atoms; and X represents Cl, Br, I, a methylsulfate group, an ethylsulfate group or a para-toluenesulfonate group.) R-NH-(CH₂)_nNH₂ (II) (In formula (II), R represents a saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms; and n represents an integer of 1 to 4.)

Description

Method for preventing adhesion of marine organisms, adhesion inhibitor and kit for preventing adhesion

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

Many power plants, steelworks, petrochemical plants, and the like that use seawater as cooling water have been constructed in places facing the inland seas and bays to avoid waves. When seawater is taken in the inland sea or in the bay, marine organisms such as mussels, barnacles, bryozoans, and hydroids that inhabit the seawater, slime, etc. are converted into seawater intake channels, pipes and conduits, heat exchangers, condenser tubes, etc. Attached to the waterway, causing various obstacles. For example, the attached marine organisms and the like grow and obstruct water passages such as heat exchanger tubes, thereby impeding the passage of seawater and causing turbulence, thereby causing obstacles such as erosion corrosion. In addition, the marine organisms that have adhered can be stripped off due to water pressure, flow rate, etc., causing blockage of the heat exchanger tubes and strainers, impeding the passage of seawater, and reducing the original function of the heat exchanger. cause.
The normal breeding season of the marine organisms is said to be around April to October. However, the seawater temperature increases and breeding occurs in winter due to the introduction of alien species. cause.

Conventionally, in order to prevent the above-mentioned marine species from forming (adhering), chlorine generating agents such as sodium hypochlorite, electrolytic chlorine or chlorine gas (also referred to as “chlorinating agents”), hydrogen peroxide or peroxide have been used. A hydrogen generator (also referred to as a “hydrogen peroxide agent”) has been added (Patent Documents 1 and 2).

Further, for example, Patent Document 3 discloses a technique relating to an in-water biocontrol agent containing chlorine dioxide or a chlorine dioxide generator as an active ingredient, and Patent Document 4 discloses freshwater or freshwater installed in a facility using freshwater or seawater. There is disclosed a technique relating to a method for preventing or controlling organisms adhering to a waterway, comprising continuously or intermittently injecting a chlorine dioxide aqueous solution into a waterway through which seawater passes.
Chlorine dioxide used here has an advantage that it has a strong bactericidal activity and does not form a compound such as trihalomethane, and thus has little effect on the environment.
However, chlorine dioxide is extremely unstable as a chemical substance, and has a problem in sustaining the effect of preventing marine organisms from adhering.
The present applicant has also proposed a method for preventing marine organisms from adhering using chlorine dioxide and hydrogen peroxide in combination, and an antiadhesion agent used for the method (Patent Document 5).

Further, for example, Patent Literature 6 and the like describe sodium chlorosulfamate or the like as a slime control agent capable of preventing biofouling failure without causing deterioration of an RO membrane used in a seawater desalination apparatus or the like. Stabilizing bromine agents such as stabilized chlorine agents and sodium bromosulfamate have been proposed.

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

JP-A-11-37666 JP-B-61-2439 JP-A 1-275504 JP-A-6-153759 Japanese Patent No. 5879596 JP 2006-263510 A Japanese Patent No. 2634958

In preventing marine organisms from adhering, there is a trend to avoid the use of chlorine agents and bromine agents, etc. in consideration of the impact on the environment. May have to be used.
Under such circumstances, a method for preventing the adhesion of marine organisms and the like that can exhibit an excellent effect of preventing the adhesion of marine organisms and slime while reducing the amount of use of halogen-based chemicals such as chlorine agents and bromine agents. Development is desired.
In addition, quaternary ammonium salts and higher aliphatic amine compound drugs are relatively expensive, and it is not economically preferable to add a high concentration or a large amount of drugs, and an inexpensive method is desired.

The present invention reduces the use of halogen-based agents such as chlorine agents and bromine agents and chlorine dioxide, and also reduces the use of aliphatic quaternary ammonium salts and N-monosubstituted alkylenediamines. It is an object of the present invention to provide a method for preventing the adhesion of marine organisms and the like which can maintain the effects of both for a long period of time and can prevent the adhesion of a wide range of marine species and slime, and an anti-adhesion agent and an anti-adhesion kit used therefor. Make it an issue.

The inventors of the present invention provide a first agent having at least one of an aliphatic quaternary ammonium salt and an N-monosubstituted alkylenediamine, and a first agent having at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide. By using the two agents in combination, it is possible to effectively prevent the adhesion of a wide range of marine species including mussels such as mussels and barnacles, and the adhesion of slime. The amount of drug added is reduced as compared with the use of either one of a quaternary ammonium salt and an N-monosubstituted alkylenediamine alone and at least one of a group selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide. It has been found that the effect of effectively preventing the adhesion of marine organisms and slime can be sufficiently obtained, and the present invention has been completed.

That is, the present invention relates to a method for preventing marine organisms and slime from adhering to a seawater cooling water system, and comprises an aliphatic quaternary ammonium salt represented by the general formula (I) and N 2 represented by the general formula (II). Adding a first agent having at least one of a mono-substituted alkylenediamine and a second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide to seawater of the seawater cooling water system; This is a method for preventing 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 Or 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 the 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 adhesion of marine organisms of the present invention, the first agent is added to the seawater cooling water system for at least 12 hours per day so that the concentration of the first agent in seawater is 0.001 to 0.3 mg / L. Is preferably added to seawater.
Further, it is preferable to add the second drug to the seawater of the seawater cooling water system for at least one hour per day so that the concentration of the second drug in the seawater becomes 0.002 to 3.0 mg / L.
Further, the chlorine agent or the bromine agent in the second agent is (a) chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, monochloroisocyanurate. A substance that produces hypochlorous acid in one or more waters selected from sodium oxalate, potassium monochloroisocyanurate, sodium trichloroisocyanurate and potassium trichloroisocyanurate, (b) sodium hypobromite, sodium bromide A substance that produces hypobromite in one or more waters selected from a reaction product with sodium hypochlorite and bromine water, (c) a seawater electrolyte, or (d) monochloramine, dichloramine, trichloramine, Monobrolamine, dibrolamine, tribrolamine, N-clo It is preferably one or more bonded chlorine or bonded bromine selected from rosulfamate and N-bromosulfamate.

The present invention also relates to an agent for preventing adhesion of marine organisms and the like used in the method for preventing adhesion of marine organisms and the like, wherein the aliphatic quaternary ammonium salt represented by the general formula (I) and Attachment of marine organisms and the like containing as active ingredients at least one of N-monosubstituted alkylenediamine represented by the formula (II) and at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide. It is also an inhibitor.

The present invention also relates to a kit for preventing the adhesion of marine organisms and the like used in the method for preventing adhesion of marine organisms and the like, comprising the aliphatic quaternary ammonium salt represented by the general formula (I) and A first agent having at least one of an N-monosubstituted 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 adhesion of marine organisms and the like.

According to the method for preventing adhesion of marine organisms and the like, and the agent for preventing adhesion of marine organisms and the like for use in the method for preventing adhesion of the present invention, a wide variety of marine species (for example, mussels) Such as mussels, barnacles, and bryozoans) and slime.
Further, according to the method for preventing adhesion of marine organisms and the like, and the agent for preventing adhesion of marine organisms and the like for use in the method for preventing adhesion of the present invention, the kit for preventing adhesion is represented by the general formula (I). The amount of the first agent having at least one of the aliphatic quaternary ammonium salt to be used and the N-monosubstituted alkylenediamine represented by the general formula (II), and a halogen-based agent such as a chlorine agent or a bromine agent And the amount of the second drug having at least one selected from the group consisting of chlorine dioxide and the first drug and the second drug while reducing the amount of use of the first drug or the second drug alone, respectively. Both effects can be maintained.
In addition, in power plants and the like, chlorinating agents or brominating agents are added to withdrawn seawater in order to obtain the effect of preventing seawater organisms from adhering. Cannot be added, the required chlorine or bromine concentration cannot be left in the heat exchanger (condenser), and a sufficient effect of preventing adhesion of seawater organisms may not be obtained. Therefore, according to the present invention, by adding a first agent containing at least one of the aliphatic quaternary ammonium salt and the N-monosubstituted alkylenediamine to such a seawater system, the concentration of the residual chlorine is regulated. Thus, a sufficient effect of preventing the adhesion of seawater organisms can be obtained.

(Method of preventing marine organisms from adhering)
The method for preventing adhesion of marine organisms and the like according to the present invention comprises at least one of the aliphatic quaternary ammonium salt represented by the general formula (I) and the N-monosubstituted 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 are added to seawater of a seawater cooling water system.
In addition, it is preferable that the first agent and the second agent are added in the seawater of the seawater cooling water system so as to have a concentration at which prevention of adhesion of marine organisms and prevention of slime adhesion are compatible. Further, the first drug and the second drug can be added to the same place or different places in the same time zone or different time zones.

The `` seawater cooling water system '' used in the present specification is, in one or a plurality of embodiments, for example, an intake system facility, a facility to be cooled such as a condenser or a heat exchanger, and a water discharge facility. 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 refers to, for example, seawater used as cooling water in equipment to be cooled such as a condenser or a heat exchanger.

The first agent having at least one of the above-mentioned aliphatic quaternary ammonium salt and the above-mentioned N-monosubstituted alkylenediamine added to the seawater cooling water system can sufficiently prevent adhesion to large marine organisms such as mussels and barnacles. Although it shows an effect, it may not show a sufficient anti-adhesion effect on stains caused by slime and the like. On the other hand, the second chemical agent having at least one selected from the group consisting of chlorinating agents, bromine chemicals and chlorine dioxide exhibits a sufficient anti-adhesion effect on dirt due to slime or the like, but has a large seawater such as mussel or barnacle. It may not show sufficient adhesion-preventing effect on living organisms. The first drug has higher safety than the second drug, and tends to easily exhibit selectivity for marine organisms and the like that exhibit the above-described adhesion preventing 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 defects and maintain the effects of both for a long time. It is thought that the adhesion of a wide range of marine species and slime can be prevented. In particular, by making the concentration of the first drug and the second drug in seawater within a specific range, without causing excessive use of either drug or both drugs, the effects of both drugs are maintained for a long time, It is thought that it can prevent the attachment of a wide range of marine species and slime.
That is, it is considered that a synergistic effect can be obtained by using the first agent and the second agent with respect to prevention of marine organism adhesion and 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 selectivities to attached marine organisms is not clear, and it is actually confirmed. If you don't try it you won't know. In fact, when an agent having selectivity for attached marine organisms is added to seawater, the number of attached marine species other than the target organism increases in many cases and becomes dominant. Therefore, in the technical field of the present invention, simply combining a plurality of drugs does not provide a combination of excellent effects possessed by the drugs, and any result can be obtained unless actually confirmed. I do not know.

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

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 an alkyl group having 1 to 4 carbon atoms, and R ² is It is the same or an alkyl group having 1 to 4 carbon atoms, and X is Cl, Br, I, methyl sulfate, ethyl sulfate or paratoluene sulfonate.

In the general formula (I), examples of the saturated or unsaturated linear aliphatic hydrocarbon group having 10 to 20 carbon atoms include decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and henicosyl. Linear saturated aliphatic hydrocarbon groups such as docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, and octacosyl; decenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl and eicosenyl; Saturated or unsaturated linear aliphatic hydrocarbon groups derived from natural products such as chain unsaturated aliphatic hydrocarbon groups, tallow alkyl groups, hardened tallow alkyl groups, and coco alkyl groups.

The “tallow alkyl group” and the “hardened tallow alkyl group” are mainly C18 to C18, and the “coconut alkyl group” is a saturated or unsaturated linear aliphatic hydrocarbon group having mainly C12 to C16. means. The compound having the "tallow alkyl group", "hardened tallow alkyl group" or "coconut alkyl group" is a mixed aliphatic quaternary ammonium salt produced from tallow or coconut oil or coconut fat by known means.

に お い て 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.

The aliphatic quaternary ammonium salt represented by the general formula (I) which can be used in the method for preventing adhesion of marine organisms and the like, the adhesion inhibitor and the kit for preventing adhesion according to the present invention includes one or more embodiments In, decyl trimethyl ammonium salt, dodecyl triethyl ammonium salt, tetradecyl trimethyl ammonium salt, tetradecyl triethyl ammonium salt, hexadecyl trimethyl ammonium salt, hexadecyl triethyl ammonium salt, octadecyl trimethyl ammonium salt, octadecyl triethyl ammonium salt, coco alkyl trimethyl ammonium Salt, coconut alkyltriethylammonium salt, tallowalkyltrimethylammonium salt, tallowalkyltriethylammonium salt; didecyldimethylammonium salt, didodecyldimethyl Cylammonium salt, dihexadecyldimethylammonium salt, dioctadecyldimethylammonium salt, dicocoalkyldimethylammonium salt, ditallowalkyldimethylammonium salt are exemplified.

[Method of adding aliphatic quaternary ammonium salt]
The aliphatic quaternary ammonium salt represented by the general formula (I), which can be used in the method for preventing adhesion of marine organisms, the adhesion inhibitor and the kit for preventing adhesion in the present invention, is a water preparation dissolved in water. It is preferably used as an aqueous preparation dissolved in water and a hydrophilic organic solvent such as ethyl alcohol or isopropyl alcohol in terms of workability, transportability, handling, economy and effect. When hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium / paratoluenesulfonate, hexadecyltrimethylammonium / methyl sulfate and octadecyltrimethylammonium / methyl sulfate are used as the aliphatic quaternary ammonium salt, these aliphatic quaternary ammonium salts are used. Since the quaternary ammonium salt is hardly soluble in water, it is preferably used as an aqueous preparation when added to seawater in terms of workability, transportability, handling properties and effects. As this aqueous preparation, it is preferable to use the aqueous preparation described in Japanese Patent No. 562119.

[N-monosubstituted alkylenediamine]
The N-monosubstituted alkylenediamine used in the method for preventing adhesion of marine organisms, the adhesion inhibitor and the kit for preventing adhesion according to the present invention is represented by the following general formula (II) in one or more embodiments. It is.
R-NH- (CH ₂ ) _n NH ₂ (II)

In the 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 the formula (I).
In the formula (II), n is an integer of 1 to 4.

The N-monosubstituted alkylenediamine that can be used in the method for preventing adhesion of marine organisms, the adhesion inhibitor and the kit for preventing adhesion of the present invention includes, in one or more embodiments, N-cocoalkylethylenediamine, N- N-monosubstituted propylene diamines such as tallow alkyl ethylene diamine and N-hardened tallow alkyl ethylene diamine; N-mono substituted propylene diamines such as N-cocoalkyl propylene diamine, N-tallow alkyl propylene diamine, N-hardened tallow alkyl propylene diamine; N-monosubstituted trimethylenediamines such as coconut alkyl butylene diamine, N-tallow alkyl butylene diamine, and N-hardened tallow alkyl butylene diamine.

The N-monosubstituted alkylenediamine, in one or more embodiments, may be their acid addition salts. 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 the amino acid include L-aspartic acid, L-glutamic acid and the like. Among these, N-tallow alkyl propylene diamine acetate is preferred from the viewpoint of preventing marine organisms from adhering to the copper alloy pipe and preventing corrosion of the copper alloy pipe.

[Method of adding N-monosubstituted alkylenediamine]
The N-monosubstituted alkylenediamine represented by the general formula (II), which can be used in the method for preventing adhesion of marine organisms, the adhesion inhibitor and the kit for preventing adhesion of the present invention, comprises an aqueous preparation dissolved in water, It is preferable to use 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.

に お い て In the method for preventing adhesion of marine organisms, the adhesion preventing agent and the kit for preventing adhesion of the present invention, the first agent having at least one of the aliphatic quaternary ammonium salt and the N-monosubstituted alkylenediamine is used. That is, the aliphatic quaternary ammonium salt and the N-monosubstituted alkylenediamine may be used alone or in combination.

Further, in the method for preventing adhesion of marine organisms and the like according to the present invention, at least one of the aliphatic quaternary ammonium salt and the N-monosubstituted alkylenediamine used as the first agent is attached to a marine organism or the like. And can be appropriately selected according to the season.

In one or more embodiments, the concentration of the first drug containing at least one of the aliphatic quaternary ammonium salt and the N-monosubstituted alkylenediamine may be, in one or more embodiments, the concentration of the first drug in seawater of a seawater cooling water system. It can be adjusted as appropriate with reference to FIG. The concentration of the first agent 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 marine organisms from adhering to the seawater cooling water system. / Liter, more preferably 0.01 to 0.03 mg / liter.

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

(4) The place where the first chemical is added is not particularly limited, and in one or a plurality of embodiments, may be any place before the taken seawater is sent to the seawater cooling water system piping by a pump or the like. From the viewpoint of the effect of preventing damage due to the attachment of marine organisms, for example, the vicinity of the intake port of an intake pump, the entrance of a heat exchanger or a condenser is preferable.

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

(Second drug)
[Chlorine or bromine]
Examples of the chlorinating agent or brominating agent that can be used in the method for preventing adhesion of marine organisms and the like of the present invention, an antiadhesion agent and an antiadhesion kit include known chlorinating agents and brominating agents.
(A) chlorine gas, hypochlorite (calcium hypochlorite, sodium hypochlorite, etc.), chlorinated isocyanuric acid, dichloroisocyanurate (sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.), monochloroisocyanurate Substances that produce hypochlorous acid in water, such as acid salts (such as sodium monochloroisocyanurate and potassium monochloroisocyanurate) and trichloroisocyanurates (such as sodium trichloroisocyanurate and potassium trichloroisocyanurate)
(B) sodium hypobromite, a substance that produces hypobromite in water such as a reaction product of sodium bromide and sodium hypochlorite, and bromine water,
(C) a seawater electrolytic solution (an electrolytic solution containing hypochlorous acid obtained by electrolyzing seawater in an electrolytic cell); and (d) monochloramine, dichloramine, trichloramine, monobrolamine, dibrolamine, tribrolamine, N-chloroform. Bound chlorine (stabilized chlorine) or bromine (stabilized bromine) such as sulfamate and N-bromosulfamate
Is mentioned. Among them, (a), (b) and (c) are preferable from the practical viewpoints such as the effect of preventing marine organisms from adhering, economical efficiency, and handleability. From the viewpoint of industrial availability, the following are preferred. Sodium chlorite and potassium hypochlorite are particularly preferred. Among (d), from the viewpoint of the effect of preventing marine organisms from adhering, monochloramine and monobrolamine are preferred, and then N-chlorosulfate and N-bromosulfate are preferred.
The “chlorinating agent” in the present specification means a known “chlorinating agent” used based on 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 obtained by known methods, for example, JP-T-2003-503323, JP-A-2006-022097, JP-T-11-506139, and JP-T-2001-2001. It can be prepared by the methods described in JP-A-501869, JP-T-2003-507326, JP-A-2014-101251 and JP-A-2017-159276.
In the present invention, a reaction product of sulfamic acid with hypochlorous acid and / or hypobromous acid can be suitably used.
Bound chlorine such as monochloramine can be prepared by the methods described in Japanese Patent No. 4914146, JP-A-2017-119245, JP-A-2017-53054 and the like.

The above-mentioned chlorine agent and bromine agent may be used after being diluted or dissolved with seawater or fresh water so as to have a desired concentration at the time of addition.
When (a) a substance that generates hypochlorous acid in water or (c) a seawater electrolyte is added to seawater, hypochlorous acid reacts with bromide ions present in the seawater, and quickly reacts with 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 whether any of (a), (b) and (c) is used.

[Chlorine dioxide]
Chlorine dioxide which can be used in the method for preventing adhesion of marine organisms and the like, the antiadhesive agent, and the kit for preventing adhesion of the present invention is an extremely unstable chemical substance, so that storage and transportation thereof are extremely difficult. Therefore, it is preferable to produce (generate) chlorine dioxide on the spot by a known method and to adjust the concentration to be used.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (apparatus) 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 method for preventing adhesion of marine organisms and the like of the present invention, the second agent which can be used in the anti-adhesion agent and the anti-adhesion kit, may be appropriately set depending on the state of seawater to be added, etc. And at least one selected from the group consisting of chlorine dioxide and chlorine dioxide is preferably added to seawater at a concentration of 0.002 to 3.0 mg / L.
In addition, the density | concentration with respect to seawater of a 2nd chemical | medical agent means "effective chlorine concentration", when a 2nd chemical | medical agent is a chlorine agent and / or a bromine agent.
If the concentration of the second agent 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 an economical viewpoint.
A more preferred concentration of the second drug is 0.01 to 1.0 mg / L, and still more preferably 0.01 to 0.3 mg / L.

The addition time of the second agent may be appropriately set depending on the addition concentration of the first agent to be used in combination, the state of seawater to be added, and the like, and 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 agent may not be sufficiently obtained.
The addition time of the second agent is more preferably 1 hour or more and 8 hours or less, more preferably 1 hour or more and 4 hours or less per day.

場所 The location of addition of the second chemical is not particularly limited, and in one or a plurality of embodiments, may be any location before the taken seawater is sent to the seawater cooling water system piping by a pump or the like. From the viewpoint of the effect of preventing damage due to the attachment of marine organisms, for example, the vicinity of the intake port of an intake pump, the entrance of a heat exchanger or a condenser is preferable.

The concentration of the second agent in seawater is 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 measurement method. be able to.

(Other additives)
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 inhibited.
For example, a marine organism adhesion inhibitor such as a dialkyldithiocarbamate, an iron-based metal corrosion inhibitor, an antifoaming agent and the like can be mentioned.

(Addition method)
Examples of a method for adding each drug include a method using an infusion pump, a diffuser tube, a nebulizer, and the like. In the present invention, conventional physical means can be used to rapidly and substantially uniformly diffuse a trace amount of a drug into a seawater cooling water system. Specifically, installation of a diffuser, a stirrer, a baffle plate, and the like in the water system may be mentioned. Further, since the equipment corresponding to these is provided in 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]
Using an N-monosubstituted alkylenediamine as the first agent and a chlorine agent, bromine agent or chlorine dioxide as the second agent, the effect of preventing marine organisms from adhering and the effect of washing slime were confirmed.
A waterway test device was installed at a certain location along the coast of Wakayama Prefecture facing the Pacific Ocean, and the test was conducted.
Unfiltered seawater (pH 8) pumped using a submersible pump is passed through a waterway (test zone) branched into 17 systems at a flow rate of 1 m ³ / h for 70 days using a pump, in a transient manner. The added drug prepared as described below was added to each channel at the addition time per day shown in Table 1 so as to have the drug concentration shown in Table 1.
The chemical concentration is a set concentration in an acrylic column for confirming the adhesion preventing effect described below, and the concentration of hypochlorite used as a chlorine agent is an effective chlorine concentration.
In addition, the amount of drug added in the test plots 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 anti-adhesion effect was inserted into each channel, and slime was immediately downstream of the acrylic column. A titanium tube (inner diameter 23.4 mm, length 1000 mm, wall thickness 10 mm) for checking the cleaning effect was inserted. After the passage of water, the drug effect was evaluated by measuring the amount of attached organisms attached to the column and the wet volume of slime attached to the inner surface of the titanium tube.
In addition, it tested also about addition of no drug as a blank.
The results obtained are shown in Table 1 together with the concentration of each drug and the time of their addition.

(Additives)
N-tallow alkylpropylenediamine (drug: A) as N-monosubstituted alkylenediamine, sodium hypochlorite (drug: B) and N-chlorosulfamate (drug: D) as chlorinating agents, and N-chlorobromide as N-brominating agents Bromosulfamate (drug: E) and chlorine dioxide generated by mixing sodium chlorite and hydrochloric acid as chlorine dioxide (drug: C) were used as added drugs.
Specifically, N-tallow alkylpropylenediamine was appropriately diluted with pure water to adjust the concentration of the drug to be added to seawater, and was added using a metering pump before the acrylic column for checking the antiadhesion effect.
Sodium hypochlorite is adjusted to the concentration of the drug added to seawater by appropriately diluting an aqueous solution of sodium hypochlorite having an effective chlorine concentration of 12% with pure water. It was added from the front using a metering pump.
Chlorine dioxide was prepared by mixing aqueous solutions prepared by appropriately diluting sodium chlorite and hydrochloric acid with pure water in a tube before the drug addition point so that the chlorine dioxide concentrations shown in Table 1 were obtained, and a residence time of 1 hour. The aqueous solution of chlorine dioxide generated by the addition of water was added in front of an acrylic column for checking the anti-adhesion effect. Regarding the generation of chlorine dioxide, the generation was confirmed in a preliminary test, and it was confirmed that sodium chlorite did not remain at a concentration that affected the effect.
N-chlorosulfamate and N-bromosulfamate are each produced by a known method (for example, a method described in JP-A-2017-159276), and then appropriately diluted with pure water to be added to seawater. The drug concentration was adjusted to a desired level, and added using a metering pump before the acrylic column for confirming the adhesion preventing effect.

(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 amount of attached organisms (g) was calculated according to the following equation together with the mass W0 of the dried column measured before the test.
Attached biomass (g) = W1-W0
The attached organisms in the blank are mainly derived from mussels such as mussels and marine organisms such as barnacles and bryozoans. Detritus-like substances containing a large amount of organic matter such as excrement and dead body of attached organisms and slime, extracellular secretions and the like, and viscous particles and suspended matters contained in seawater also adhered, and these are also included in the amount of attached organisms.
In this test example, it can be determined from the blank marine organism attachment state that the blank has an 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 adhered to the inner surface of the titanium tube removed from the water channel was scraped off, collected in a 10 to 100 ml measuring cylinder, and the washing effect was evaluated by measuring the wet volume after standing for 4 hours.
The slime scraped from the blank is mainly derived from microorganisms attached to the titanium tube. Similar to the confirmation of the effect of preventing adhesion on the column, the slime adhered to the inner surface of the titanium tube also contains a detritus-like substance, but the diameter of the titanium tube is about 1/3 of the column diameter, and the seawater cooling water in the titanium tube It has been confirmed that there is no attachment of mussels such as mussels and marine organisms such as barnacles and bryozoans.
In addition, from the slime adhesion state in the blank, it can be determined in this test example that the slime washing effect is sufficient 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-monosubstituted alkyldiamine was used alone as the first agent, a certain degree of effect of preventing marine organisms from adhering to the blank (Reference Example 1) in which no agent was added. However, sufficient marine organism adhesion preventing effect was not obtained. Further, almost no slime cleaning effect was confirmed.
(2) On the other hand, in the same manner as in Comparative Examples 1 and 2, N-monosubstituted alkylenediamine was added at an addition concentration of 0.02 mg / L or 0.03 mg / L for 18 hours, and further, a second drug was also added. With respect to 2, 3, 4, 8 and 9, a sufficient marine organism adhesion preventing effect and a sufficient slime washing effect were confirmed.
(3) In Comparative Examples 3 to 7, in which the second agent was applied alone, a sufficient slime washing effect was confirmed, but a sufficient effect in preventing marine organism adhesion was not obtained. From the results of Comparative Example 3 and Comparative Example 4, it is more effective to add the second agent at a certain concentration for a short period of time than at a low concentration for a long period of time, as compared with the case where the second agent is added at a low concentration. 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 the second agent at a concentration of 0.01 to 0.3 mg / L for 2 to 18 hours / day, a sufficient marine organism adhesion preventing effect and a sufficient slime washing effect can be obtained. Was confirmed.
From the above Examples and Comparative Examples, N-monosubstituted alkylenediamine (N-tallow alkylpropylenediamine) was used as the first drug, and sodium hypochlorite, N-chlorosulfamate, and N-bromosulfamate were used as the second drug. By using mart or chlorine dioxide in combination, a wider range of marine species, such as mussels such as mussels, barnacles, and bryozoans, as compared with the case where the first and second agents are used alone. Of marine organisms) and slime can be prevented.
In addition, it was confirmed that the combined use of the above-mentioned first drug and second drug can sufficiently achieve the effect of preventing the adhesion of marine organisms and slime over a period of 70 days without increasing the amount of use of both. .

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

(Additives)
Hexadecyltrimethylammonium chloride (drug: a) as an aliphatic quaternary ammonium salt, sodium hypochlorite (drug: b) and monochloramine (drug: d) as chlorinating agents, and monobrolamine (drug: e) as a brominating agent ) And chlorine dioxide (drug: c) generated by mixing sodium chlorite and hydrochloric acid as chlorine dioxide.
Specifically, hexadecyltrimethylammonium chloride was adjusted to a drug concentration to be added to seawater by appropriately diluting with pure water, and was added using a metering pump before the acrylic column for checking the antiadhesion effect.
Monochloramine and monobrolamine are each 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, thereby causing adhesion. It was added using a metering pump from just before the acrylic column for checking the prevention effect.
Sodium hypochlorite and chlorine dioxide were adjusted and added in the same manner as in Test Example 1.

The following was confirmed from the results in Table 2 above.
(1) In Comparative Examples 11 and 12 in which an aliphatic quaternary ammonium salt was used alone as the first agent, some degree of prevention of marine organism adhesion was observed as compared with the blank (Reference Example 2) in which the agent was not added. Although the effect was confirmed, a sufficient marine organism adhesion preventing effect was not obtained. Further, almost no slime cleaning effect was confirmed.
(2) In Comparative Examples 13 to 17, in which the second agent was applied alone, a sufficient slime washing effect was confirmed, but a sufficient effect on prevention of marine organism adhesion was not obtained. From the results of Comparative Examples 13 and 14, it was found that adding the second agent at a certain concentration for a short period of time was more effective in preventing marine organism adhesion and slime washing than adding the second agent at a lower concentration for a longer period of time. 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. / Day addition, the concentration of the second drug is 0.01 to 0.3 mg / L for 2 to 20 hours / day, so that a sufficient marine organism adhesion preventing effect and a sufficient slime washing 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 agent, and sodium hypochlorite, monochloramine, monobrolamine or chlorine dioxide is used in combination as the second agent. By doing so, a wider range of marine species (for example, mussels such as mussels, barnacles, and bryozoans) and slimes are compared with the case where the first and second drugs are used alone. It was confirmed that adhesion could be prevented.
In addition, it was confirmed that the combined use of the first drug and the second drug can sufficiently achieve the effect of preventing the adhesion of marine organisms and slime over a period of 55 days without increasing the amounts of both used. .

Claims (6)

1. A method for preventing marine organisms and slime from adhering to a 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-monosubstituted 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,
   Is added 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 Or 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 the 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.)
2. The method according to claim 1, comprising adding the first drug to the seawater of the seawater cooling water system for at least 12 hours per day so that the concentration of the first drug in the seawater is 0.001 to 0.3 mg / L. A method for preventing marine organisms from adhering.
3. 3. The method according to claim 1, further comprising adding the second drug to the seawater in the seawater cooling water system for at least one hour per day so that the concentration of the second drug in the seawater is 0.002 to 3.0 mg / L. The method for preventing adhesion of marine organisms and the like as described in the above.
4. Chlorine or bromine in the second drug,
   (A) chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium monochloroisocyanurate, potassium monochloroisocyanurate, sodium trichloroisocyanurate and trichloroisocyanurate A substance that produces hypochlorous acid in one or more types of water selected from potassium silicates,
   (B) sodium hypobromite, a substance that produces hypobromite in one or more waters selected from a reaction product of sodium bromide and sodium hypochlorite, and bromine water;
   (C) seawater electrolyte, or (d) one or more bond chlorine or bond selected from monochloramine, dichloramine, trichloramine, monobrolamine, dibrolamine, tribrolamine, 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.
5. An antiadhesion agent for marine organisms used in the method for preventing adhesion of marine organisms according to claim 1, 2, 3, or 4,
   At least one of an aliphatic quaternary ammonium salt represented by the general formula (I) and an N-monosubstituted alkylenediamine represented by the general formula (II);
   At least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide,
   An anti-adhesive agent for marine organisms and the like, containing
   

   

   (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 Or 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 the 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.)
6. A kit for preventing adhesion of marine organisms used in the method for preventing adhesion of marine organisms 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-monosubstituted 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 kit for preventing marine organisms from adhering.
   

   

   (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 Or 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 the 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.)