Method for preventing adhesion of marine organisms and the like, anti-adhesion agent, and anti-adhesion kit

Abstract

The purpose of the present invention is to provide: a method which is for preventing the adhesion of marine organisms and the like, and by which the used amounts of chlorine dioxide and a halogen-based chemical agent, such as a chlorine agent and a bromine agent, are reduced, the used amount of a higher aliphatic tertiary amine is reduced, both effects can be maintained for a long period of time, and the adhesion of a wide range of marine organism species and slime can be prevented; and an adhesion preventive agent and an adhesion preventive kit, which are used in said method. The present invention pertains to a method for preventing the adhesion of marine organisms and slime to a seawater cooling water system, the method being characterized by comprising adding, to seawater for the seawater cooling water system, a first chemical agent having a higher aliphatic tertiary amine represented by general formula (I), and a second chemical agent having at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide.

Description

Technical Field

[0001] 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.

Background Art

[0002] Power plants, steel mills, petrochemical plants, etc. that use seawater as cooling water are mostly constructed in places facing inland seas or bays in order to avoid waves and the like. When seawater is taken in from inland seas or bays, marine organisms such as purple mussels, barnacles, bryozoans, hydroids, etc. and slime that inhabit the seawater adhere to water passages such as seawater intake pipes, pipes, aqueducts, heat exchangers, and condenser tubes, causing various obstacles. For example, the attached marine organisms and the like grow and block the water passages such as heat exchanger tubes, inhibiting the flow of seawater, generating turbulent flow, and causing obstacles such as erosion corrosion. In addition, when the attached marine organisms and the like are peeled off due to water pressure, flow velocity, etc., it also causes blockage of the tubes and strainers of the heat exchanger, inhibits the flow of seawater, and causes a decrease in the original function of the heat exchanger. It is said that the normal adhesion and breeding period of the above-mentioned marine organisms in the coastal waters of Japan is around April to October. However, due to the increase in seawater temperature or the inflow of alien species, they also breed in winter, causing the above-mentioned obstacles.

[0003] In order to prevent the settlement (adhesion) of the above-mentioned marine organism species, conventionally, the addition of chlorine generators (also referred to as "chlorine agents") such as sodium hypochlorite, electrolytic chlorine, or chlorine gas, hydrogen peroxide, or hydrogen peroxide generators (also referred to as "hydrogen peroxide agents") has been carried out (Patent Document 1 and Patent Document 2).

[0004] For example, Patent Document 3 discloses a technology related to an aquatic fouling control agent containing chlorine dioxide or a chlorine dioxide generator as an active ingredient, and Patent Document 4 discloses a technology related to a method for preventing or controlling the adhesion of organisms adhering to a water channel through which fresh water or seawater passes, which is installed in a facility using fresh water or seawater, and which comprises continuously or intermittently injecting an aqueous chlorine dioxide solution or a relatively high-concentration aqueous chlorine dioxide solution into the water channel. The chlorine dioxide used here has a strong bactericidal power and does not form compounds such as trihalomethanes, so it has the advantage of having little impact on the environment. However, chlorine dioxide is extremely unstable as a chemical substance, and there are problems with the persistence of the effect of preventing the adhesion of marine organisms. In addition, the applicant of the present application has proposed a method for preventing the adhesion of marine organisms by using a combination of chlorine dioxide and hydrogen peroxide and an anti-adhesion agent used therefor (Patent Document 5).

[0005] For example, Patent Document 6 etc. propose stabilized chlorine agents such as sodium chlorosulfamate and stabilized bromine agents such as sodium bromosulfamate as slime control agents that can prevent biofouling damage without causing deterioration of RO membranes used in seawater desalination devices etc.

[0006] In addition, quaternary ammonium compounds and higher aliphatic amine compounds have also been proposed as highly safe anti-adhesion agents for marine fouling organisms (Patent Document 7).

[0007] In addition, aiming at the problem of efficiently suppressing foaming occurring in a seawater cooling water system etc. that prevents the adhesion of marine organisms by adding a chlorine generator, a method for suppressing foaming in a seawater cooling water system in which a specific higher aliphatic tertiary amine is added to a seawater cooling water system in which foaming has occurred due to the addition of a chlorine generator has been proposed (Patent Document 8). However, this document was made with the problem of providing a method for suppressing foaming in a seawater cooling water system that can efficiently suppress foaming, and is not implemented in a seawater cooling water system in which foaming does not occur, and the addition of the higher aliphatic tertiary amine is not aimed at preventing the adhesion of marine organisms.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Summary of the Invention

Problems to be Solved by the Invention

[0009] In the prevention of adhesion of marine organisms, while there is a movement to avoid the use of halogen-based chemicals such as chlorine agents and bromine agents in consideration of the impact on the environment, in the current situation, chlorine agents and bromine agents may have to be used because of the use of old plant facilities. In such a situation, it is desired to develop 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 usage amount of halogen-based chemicals such as chlorine agents and bromine agents. In addition, chemicals such as quaternary ammonium salts and higher aliphatic amine compounds are relatively expensive, and the addition of high-concentration or large amounts of chemicals is not economically preferable, and an inexpensive method is desired.

[0010] The present invention aims to provide a method for preventing the attachment of marine organisms and the like, an anti-attachment agent used therefor, and an anti-attachment kit, which can maintain the effects of both a halogen-based agent such as a chlorine agent or a bromine agent and chlorine dioxide for a long period while reducing the usage amounts of both, and can prevent the attachment of a wide range of marine biological species and slime.

Means for Solving the Problems

[0011] The inventor of the present invention has found that by using in combination a first agent having a higher aliphatic tertiary amine 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 possible to effectively prevent the attachment of a wide range of marine biological species including mussels such as Mytilus edulis and barnacles, and the attachment of slime. Furthermore, compared with the conventional single use of a higher aliphatic tertiary amine and the single use of at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide, an effective anti-attachment effect on marine organisms and slime can be sufficiently obtained even when the dosage of the agent is reduced, and thus the present invention has been completed.

[0012] That is, the present invention is a method for preventing the attachment of marine organisms and slime to a seawater cooling water system, which comprises adding a first agent having a higher aliphatic tertiary amine represented by the general formula (I) and a second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide to the seawater in the seawater cooling water system.

Chemical formula

[0013] The present invention is also an anti-adhesion agent for marine organisms and the like used in the method for preventing adhesion of marine organisms and the like, which contains at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide, and a higher aliphatic tertiary amine represented by the general formula (I) as active ingredients.

[0014] The present invention is also an anti-adhesion kit for marine organisms and the like used in the method for preventing adhesion of marine organisms and the like, which contains a first agent containing a higher aliphatic tertiary amine represented by the general formula (I), and a second agent containing at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide.

Effects of the Invention

[0015] According to the method for preventing adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent and anti-adhesion kit for marine organisms and the like used for this anti-adhesion method, adhesion of a wide range of marine biological species (for example, marine organisms such as mussels like Mytilus edulis, barnacles, and bryozoans) and slime can be prevented. Furthermore, according to the method for preventing adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent and anti-adhesion kit for marine organisms and the like used for this anti-adhesion method, the usage amount of the first agent having a higher aliphatic tertiary amine represented by the general formula (I), and the usage amount of the second agent having at least one selected from the group consisting of halogen-based agents such as chlorine agents and bromine agents and chlorine dioxide, can be reduced compared to the case where the first agent or the second agent is used alone, while the effects of both the first agent and the second agent can be sustained. In power plants and the like, in order to obtain an effect of preventing adhesion of marine organisms, a chlorine agent or a bromine agent is added to the seawater taken in. However, due to the regulation of the concentration of residual chlorine in the drainage, sufficient addition of the chlorine agent or the bromine agent cannot be achieved, and the necessary chlorine or bromine concentration cannot be retained in the heat exchanger (condenser), and thus a sufficient effect of preventing adhesion of marine organisms may not be obtained. Therefore, according to the present invention, by adding a first agent containing a higher aliphatic tertiary amine to such a seawater system, a sufficient effect of preventing adhesion of marine organisms can be obtained even within the above-mentioned regulation of the concentration of residual chlorine. According to the method for preventing adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent and anti-adhesion kit for marine organisms and the like used for this anti-adhesion method, in a seawater cooling water system that uses a large amount of seawater, while reducing the usage amounts of the first agent and the second agent, adhesion of a wide range of marine biological species (for example, marine organisms such as mussels like Mytilus edulis, barnacles, and bryozoans) and slime can be prevented, so that excellent cost performance can be obtained while taking environmental considerations.

Mode for Carrying Out the Invention

[0016] (Method for Preventing Adhesion of Marine Organisms) The method for preventing adhesion of marine organisms and the like of the present invention is characterized in that a first agent having a higher aliphatic tertiary amine represented by the above general formula (I) 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 the seawater in a seawater cooling water system. It is preferable that the first agent and the second agent are added so as to have concentrations that achieve both prevention of adhesion of marine organisms and prevention of slime adhesion in the seawater of the seawater cooling water system. Further, the first agent and the second agent can be added to the same location or different locations in the same time zone or different time zones.

[0017] As used herein, the "seawater cooling water system" consists of, for example, a water intake system facility, equipment to be cooled such as a condenser and a heat exchanger, etc. in one or more embodiments. The water intake system facility consists of a water conduit, a screen for removing foreign substances in seawater, a circulating water pump (water intake pump) and a circulating water pipe (water intake pipe), etc. Also, as used herein, the "seawater of the seawater cooling water system" refers to, for example, the seawater used as cooling water in equipment to be cooled such as a condenser and a heat exchanger. According to the present invention, while reducing the usage amounts of the first agent and the second agent, it is possible to prevent the adhesion of a wide range of marine organism species (for example, marine organisms such as mussels like Mytilus edulis, barnacles, and bryozoans) and slime to the seawater cooling water system. Therefore, in a seawater cooling water system that uses a large amount of seawater, it is possible to prevent the adhesion of marine organism species and slime in the seawater cooling water system while suppressing the chemical concentration in the seawater that is constantly drained to an extremely low level, and to obtain excellent cost performance while considering the environment.

[0018] The first agent containing the higher aliphatic tertiary amine represented by the general formula (I) added to the seawater cooling water system shows a certain degree of anti-adhesion effect on large marine organisms such as barnacles and mussels, but there are cases where a sufficient anti-adhesion effect cannot be obtained. Also, there are cases where a sufficient anti-adhesion effect cannot be obtained against fouling by slime and the like. On the other hand, the second agent having at least one selected from the group consisting of chlorine agents, bromine agents, and chlorine dioxide shows an anti-adhesion effect against fouling by slime and the like, but shows no anti-adhesion effect or has an insufficient effect on large marine organisms such as barnacles and mussels. In the method for preventing adhesion of marine organisms and the like in the present invention, by using the above-described first agent and second agent, the first agent and the second agent cover each other's drawbacks and the effects of both are maintained for a long time, and it is considered that adhesion of a wide range of marine biological species and slime can be prevented. In particular, by setting the concentrations of the first agent and the second agent in seawater within a specific range, the effects of both agents can be maintained for a long time without causing excessive use of either one of the agents or both agents, and it is considered that adhesion of a wide range of marine biological species and slime can be prevented. That is, it is considered that by using the first agent and the second agent, a synergistic effect can be obtained for preventing adhesion of marine organisms and adhesion of slime.

[0019] In the technical field to which the present invention pertains, it is not clear that an empirical rule that only the excellent effects of each agent are exhibited by the combined use of a plurality of agents having different selectivities for attached marine organisms and the like can be obtained, and it cannot be known without actually confirming. In fact, when a chemical having selectivity for attached marine organisms and the like is added to seawater, there are many cases where the attached marine biological species other than the target organism increase and become dominant. Therefore, in the technical field of the present invention, simply combining a plurality of agents does not result in a combination of the excellent effects of those agents, and it is not known what results will be obtained without actual confirmation.

[0020] In the present invention, the first agent and the second agent may be added at a location in the seawater cooling water system where an anti-fouling effect on marine organisms and an anti-slime fouling effect can be obtained. The addition locations of the first agent and the second agent may be the same location or different locations in the seawater cooling water system. From the viewpoint of further improving the anti-fouling effect on marine organisms and the anti-slime fouling effect, specific addition locations of the first agent and the second agent are preferably added to the intake port of the intake pump of the seawater cooling water system and / or the vicinity of the intake port, the heat exchanger and / or the inlet of the condenser. Here, the same location in the seawater cooling water system means the same equipment, the same tank, and the same pipe (the pipe between equipment). Note that the vicinity of the intake port of the intake pump of the seawater cooling water system means the location where the added agent is taken into the intake port.

[0021] (First agent) [Higher aliphatic tertiary amine] The higher aliphatic tertiary amine used in the method for preventing adhesion of marine organisms and the like, the anti-fouling agent, and the anti-fouling kit of the present invention is represented by the general formula (I) in one or more embodiments.

[0022] Examples of the higher aliphatic tertiary amine represented by the general formula (I) used in the method for preventing adhesion of marine organisms and the like, the anti-adhesive agent, and the anti-adhesive kit of the present invention include specifically octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, pentadecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, icosyldimethylamine, docosyldimethylamine, coconut alkyl dimethylamine, tallow alkyl dimethylamine, hydrogenated tallow alkyl dimethylamine, didecylmethylamine, didodecylmethylamine, dioctadecylmethylamine, dioleylmethylamine, ditallow alkylmethylamine, dicy coconut alkylmethylamine, dodecyltetradecylmethylamine, dodecyloctadecylmethylamine, tetradecylhexadecylmethylamine, dodecylmethylpropylamine, tallow alkyl ethylpropylamine, tallow alkyldiethylamine, tallow alkyldipropylamine, tallow alkyldibutylamine, coconut alkyl dihexylamine, trioctylamine, tridecylamine, β-hydroxy dodecyldimethylamine, β-hydroxy hexadecyldimethylamine, β-hydroxy octadecyldimethylamine, di(β-hydroxy hexadecyl)methylamine, di(β-hydroxy octadecyl)methylamine, tallow alkyloxypropyl dimethylamine, tallow alkyloxypropyl diethylamine, 3-(2-ethylhexyloxy)propyl dimethylamine, 3-(2-ethylhexyloxy)propyl diethylamine, 3-dodecyloxyethyl dimethylamine, 3-dodecyloxyethyl diethylamine, 3-(coconut alkyloxy)propyl dimethylamine, 3-(coconut alkyloxy)propyl diethylamine and the like.

[0023] The substituent R in the general formula (I) 1 and R 2 are more preferably alkyl groups having 1 to 4 carbon atoms, and the substituent R 3 is more preferably a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 22 carbon atoms.

[0024] Specific examples of the higher aliphatic tertiary amine represented by the above general formula (I) that are more preferably used include octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, pentadecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, icosyldimethylamine, docosyldimethylamine, dodecylmethylpropylamine, coconut alkyl dimethylamine, tallow alkyl dimethylamine, hydrogenated tallow alkyl dimethylamine, tallow alkyl diethylamine, tallow alkyl dipropylamine, tallow alkyl dibutylamine, and tallow alkyl ethylpropylamine, etc.

[0025] The "tallow alkyl group" and "hydrogenated tallow alkyl group" mainly mean saturated or unsaturated linear aliphatic hydrocarbon groups in the range of 16 to 18 carbon atoms, and the "coconut alkyl group" mainly means those in the range of 12 to 16 carbon atoms. Compounds having this "tallow alkyl group", "hydrogenated tallow alkyl group" or "coconut alkyl group" are mixed aliphatic tertiary amines produced from tallow or hydrogenated tallow or coconut oil by known means.

[0026] The higher aliphatic tertiary amine represented by the above general formula (I) may be used in the form of salts such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oleic acid, naphthenic acid, adipic acid, lactic acid, citric acid, and saccharin. For example, in the case of acetate, it can be obtained by reacting the higher aliphatic tertiary amine represented by the above general formula (I) with an equimolar amount of acetic acid. When adding these to a seawater cooling water system, these compounds may be appropriately diluted or dissolved in seawater or fresh water to a desired concentration before use.

[0027] [Method for Adding the First Agent Containing the Higher Aliphatic Tertiary Amine Represented by the Above General Formula (I)] The first agent having a higher aliphatic tertiary amine represented by the above general formula (I), which can be used in the method for preventing adhesion of marine organisms and the like, the anti-adhesion agent, and the anti-adhesion kit of the present invention, is preferably used as an aqueous preparation dissolved in water or an aqueous preparation dissolved in a hydrophilic organic solvent such as ethyl alcohol or isopropyl alcohol and water in terms of workability, transportability, handleability, economy, and effect.

[0028] In one or more embodiments, the addition concentration of the first agent containing the higher aliphatic tertiary amine represented by the above general formula (I) can be appropriately adjusted with reference to the concentration of the first agent in the seawater of the seawater cooling water system. As the concentration of the first agent in the seawater, 0.001 to 0.3 mg / L is preferable, more preferably 0.005 to 0.1 mg / L, and still more preferably 0.01 to 0.03 mg / L from the viewpoint of the effect of preventing the adhesion of marine organisms to the seawater cooling water system.

[0029] The addition time of the first agent tends to be inversely proportional to the addition concentration. However, within the above addition concentration range, from the viewpoint of preventing the adhesion of marine organisms, 12 hours or more per day is preferable, 14 hours or more is more preferable, and 16 hours or more is still more preferable. And the addition time may be 24 hours or less, 22 hours or less, 20 hours or less per 24 hours of a day. The addition may be continuous addition or intermittent addition.

[0030] The addition location of the first agent is not particularly limited. In one or more embodiments, any location before the taken seawater is sent to the seawater cooling water system piping by a pump or the like can be mentioned. From the viewpoint of the effect of preventing obstacles due to the adhesion of marine organisms, for example, the vicinity of the intake of the intake pump, the inlet of the heat exchanger or the condenser is preferable.

[0031] The concentration of the first agent in seawater can be obtained, for example, by measuring the concentration of the first agent in seawater in facilities to be cooled such as condensers and heat exchangers using a general measurement method.

[0032] (Second agent) [Chlorinating agent or brominating agent] Examples of the chlorine agent or bromine agent that can be used in the method for preventing adhesion of marine organisms and the like, the anti-adhesion agent, and the anti-adhesion kit of the present invention include known chlorine agents or bromine agents. For example, (a) Substances that generate hypochlorous acid in water, such as chlorine gas, hypochlorites (calcium hypochlorite, sodium hypochlorite, etc.), chlorinated isocyanuric acid, dichloroisocyanurate salts (sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.), monochloroisocyanurate salts (sodium monochloroisocyanurate, potassium monochloroisocyanurate, etc.), trichloroisocyanurate salts (sodium trichloroisocyanurate, potassium trichloroisocyanurate, etc.); (b) Substances that generate hypobromous acid in water, such as sodium hypobromite, the reaction product of sodium bromide and sodium hypochlorite, and bromine water; (c) Seawater electrolytic solution (an electrolytic solution containing hypochlorous acid obtained by electrolyzing seawater in an electrolytic cell), and (d) Bound chlorine (stabilized chlorine) or bound bromine (stabilized bromine) such as monochloramine, dichloramine, trichloramine, monobromamine, dibromamine, tribromamine, N-chlorosulfamate, and N-bromosulfamate. Among these, from a practical perspective such as the anti-adhesion effect of marine organisms, economy, and handleability, (a), (b), and (c) are preferred. From the perspective of easy industrial availability, sodium hypochlorite and potassium hypochlorite are particularly preferred. Among (d), monochloramine and monobromamine are preferred, and next, N-chlorosulfamate and N-bromosulfamate are preferred. In addition, the "chlorine agent" in this specification means a known "chlorine agent" used based on the common general knowledge in the technical field of the present invention, and does not include chlorine dioxide.

[0033] N-chlorosulfamate and N-bromosulfamate can be prepared by known methods, for example, the methods described in Japanese Patent Publication No. 2003-503323, Japanese Patent Application Laid-Open No. 2006-022097, Japanese Patent Publication No. Hei 11-506139, Japanese Patent Publication No. 2001-501869, Japanese Patent Publication No. 2003-507326, Japanese Patent Application Laid-Open No. 2014-101251, and Japanese Patent Application Laid-Open No. 2017-159276. In the present invention, a reaction product of sulfamic acid and hypochlorous acid and / or hypobromous acid can be preferably used. Combined chlorine such as monochloramine can be prepared by the methods described in Japanese Patent No. 4914146, Japanese Patent Application Laid-Open No. 2017-119245, and Japanese Patent Application Laid-Open No. 2017-53054.

[0034] The above chlorine agents 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 and used. When a substance that generates hypochlorous acid in water or a seawater electrolysis solution is added to seawater, hypochlorous acid reacts with bromide ions present in seawater, and chlorine and bromine are rapidly substituted. For example, when sodium hypochlorite is added to seawater, it rapidly becomes sodium hypobromite. Therefore, the anti-adhesion effect on marine organisms is the same regardless of which of (a), (b), and (c) is used.

[0035] [Chlorine Dioxide] Chlorine dioxide that can be used in the method for preventing adhesion of marine organisms and the like, the anti-adhesion agent, and the anti-adhesion kit of the present invention is a very unstable chemical substance, so its storage and transportation are very difficult. Therefore, it is preferable to produce (generate) chlorine dioxide by a known method on-site and adjust it to the addition concentration for use. For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (device) 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 of sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO3 + H2O2 + H2SO4 → 2ClO2 + Na2SO4 + O2 + 2H2O

[0036] The above-mentioned second agent that can be used in the method for preventing adhesion of marine organisms and the like, the anti-adhesion agent and the anti-adhesion kit of the present invention may be appropriately set according to the state of the seawater to be added, etc., but at least one selected from the group consisting of chlorine agents, bromine agents and chlorine dioxide is preferably added to the seawater in the seawater cooling water system so as to have a concentration of 0.002 to 3.0 mg / L. In addition, the concentration of the above-mentioned second agent in seawater means "available chlorine concentration" when the above-mentioned second agent is a chlorine agent and / or a bromine agent. If the concentration of the above-mentioned second agent in seawater 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 above-mentioned second agent exceeds 3.0 mg / L, no further effect can be expected, which is not preferable from an economic point of view. A more preferable concentration of the above-mentioned second agent is 0.01 to 1.0 mg / L, and more preferably 0.01 to 0.3 mg / L.

[0037] The addition time of the above-mentioned second agent may be appropriately set according to the addition concentration of the above-mentioned first agent used in combination, the state of the seawater to be added, etc., but usually it is 1 hour or more and 24 hours or less per day. If the addition time is less than 1 hour per day, there is a possibility that the effect of preventing the adhesion of marine organisms and slime by the combined use with the above-mentioned first agent cannot be sufficiently obtained. A more preferable addition time of the above-mentioned second agent is 1 hour or more and 22 hours or less per day. In addition, when the addition concentration of the second agent is 0.05 mg / L or more, preferably 0.1 mg / L or more, more preferably 0.2 mg / L or more, the addition time of the second agent can be 1 hour or more and 5 hours or less per day, preferably 1 hour or more and 4 hours or less. Regarding the second agent, by setting the addition concentration to a certain high concentration, the effects of the present invention can be obtained even if the addition time is shortened. Further, by setting the addition concentration of the second agent to such a certain high concentration and adding it for a short time, an excellent slime adhesion prevention effect can be obtained.

[0038] The addition location of the second agent is not particularly limited, and in one or more embodiments, examples include any location before the seawater taken in is pumped into the seawater cooling water system piping by a pump or the like. From the viewpoint of preventing obstacles due to the adhesion of marine organisms, for example, the vicinity of the intake of the intake pump, the inlet of the heat exchanger or the condenser is preferable.

[0039] Note that the concentration of the second agent in seawater can be obtained, for example, by measuring the concentration of seawater in facilities to be cooled such as condensers and heat exchangers using a general measurement method (for example, the DPD method).

[0040] (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 inhibited. For example, marine organism adhesion preventives such as dialkyldithiocarbamate, iron-based metal corrosion preventives, defoamers, and the like can be mentioned.

[0041] (Addition method) Examples of the addition method of each agent include methods using an injection pump, an air diffuser, a sprayer, etc. In the present invention, in order to rapidly and substantially uniformly diffuse a small amount of the agent into the seawater cooling water system, conventional physical means can be used. Specifically, examples include the installation of a diffuser, a stirring device, a baffle plate, etc. in the water system. Further, since the equipment corresponding to these is attached to the seawater cooling water system, this can be diverted.

Example

[0042] The present invention will be specifically described by the following test examples, but the present invention is not limited thereto.

[0043] [Test Example 1] N,N-dimethyltallow alkylamine (tallow alkyldimethylamine) was used as the above first agent, and a chlorine agent, a bromine agent, or chlorine dioxide was used in combination as the above second agent to confirm the anti-adhesion effect of marine organisms and the anti-adhesion effect of slime. A waterway test device was installed at a certain place on the coast of Wakayama Prefecture facing the Pacific Ocean, and the test was conducted. Unfiltered seawater (pH 8) pumped up using an underwater pump was branched into 19 waterways (test sections), and the flow rate was 1 m 3 / h for 79 days, and the prepared additive chemicals shown below were added to each waterway at the addition time per day shown in Table 1 so that the chemical concentrations shown in Table 1 were obtained. The chemical concentration is the set concentration in the acrylic column for confirming the anti-adhesion effect described below, and the concentration of the hypochlorite used as the chlorine agent is the available chlorine concentration. Also, the chemical addition amounts in the test sections with the same chemical concentration are the same. For example, the addition amounts of chlorine dioxide in Example 1 and Comparative Example 5 are the same, and the addition amounts of hypochlorous acid in Example 4 and Comparative Example 8 are the same.

[0044] In addition, an acrylic column for confirming the anti-adhesion effect (inner diameter 64 mm × length 300 mm × thickness 2 mm, surface area 602.88 cm 2 ) was inserted into each waterway, and further, a titanium pipe (inner diameter 23.4 mm, length 1000 mm, wall thickness 10 mm) for confirming the anti-slime adhesion effect was inserted immediately downstream of the acrylic column. After the water flow was completed, the amount of attached organisms adhering to the column and the wet volume of the slime adhering to the inner surface of the titanium pipe were measured to evaluate the chemical effect. Note that a test was also conducted for no chemical addition as a blank. The obtained results are shown in Table 1 together with each chemical concentration and their addition times.

[0045] (Added agent) As the higher aliphatic tertiary amine in the first agent, N,N-dimethyl tallow alkylamine (carbon number 12-18), as the chlorine agent in the second agent, sodium hypochlorite and monochloramine, as the bromine agent in the second agent, N-bromosulfamate, and as the chlorine dioxide in the second agent, chlorine dioxide generated by mixing sodium chlorite and hydrochloric acid were used as the added agent. Specifically, N,N-dimethyl tallow alkylamine was adjusted to the agent concentration to be added to seawater by appropriately diluting it with pure water, and added using a metering pump from in front of the acrylic column for confirming the anti-adhesion effect. Sodium hypochlorite was adjusted to the agent concentration to be added to seawater by appropriately diluting an aqueous solution of sodium hypochlorite with an available chlorine concentration of 12% with pure water, and added in the same manner using a metering pump from in front of the acrylic column for confirming the anti-adhesion effect. For chlorine dioxide, an aqueous solution obtained by appropriately diluting sodium chlorite and hydrochloric acid with pure water respectively was mixed in the tube before the agent addition point so that the chlorine dioxide concentration shown in Table 1 was obtained, and the generated aqueous chlorine dioxide solution was added from in front of the acrylic column for confirming the anti-adhesion effect after giving a residence time of 1 hour. Regarding the generation of chlorine dioxide, it was confirmed in a preliminary test that the generation occurred and that sodium chlorite did not remain at a concentration that affects the effect. Monochloramine and N-bromosulfamate were each generated by a known method (for example, the methods described in JP-A-2017-53054 and JP-A-2017-159276), and then adjusted to the agent concentration to be added to seawater by appropriately diluting with pure water, and added using a metering pump from in front of the acrylic column for confirming the anti-adhesion effect.

[0046] (Confirmation of anti-fouling effect of marine organisms) After the test, the mass W1 (g) of the column removed from the water channel was measured. Together with the mass W0 of the column at the time of drying measured in advance before the test, the fouling organism amount (g) was calculated by the following formula. Fouling organism amount (g) = W1 - W0 The fouling organisms on the blank mainly originate from marine fouling organisms such as mussels like Mytilus edulis, barnacles, and bryozoans. In addition, detritus-like substances containing a large amount of organic matter such as excreta, carcasses, and extracellular secretions of fouling organisms and slime, as well as viscous particles and suspended matter contained in seawater, also adhered, and these are also included in the fouling organism biomass. From the situation of marine organism fouling on the blank, in this test example, it can be judged that when the fouling organism biomass is 15 g or less, there is a sufficient anti-fouling effect on marine organisms. (Confirmation of slime anti-fouling 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 100 mL colorimetric tube, and the anti-fouling effect was evaluated by measuring the wet volume after standing for 4 hours. The slime scraped from the blank mainly originates from the microorganisms adhering to the titanium tube. Similar to the confirmation of the anti-fouling effect in the column, the slime adhering to the inner surface of the titanium tube also contains detritus-like substances. However, the titanium tube diameter is about 1 / 3 of the column diameter, the flow rate of seawater cooling water in the titanium tube is fast, and it has been confirmed that there is no adhesion of marine fouling organisms such as mussels like Mytilus edulis, barnacles, and bryozoans. From the situation of slime fouling on the blank, in this test example, it can be judged that when the slime volume is 10 mL or less, there is a sufficient anti-fouling effect on slime.

[0047]

Table 1

[0048] From the results in Table 1 above, the following were confirmed. (1) In Comparative Examples 1, 2, 3, and 4 where N,N-dimethyltallow alkylamine was used alone as the first agent, compared with the blank (reference example) without adding the agent, a certain degree of anti-fouling effect on marine organisms was observed, but a sufficient anti-fouling effect on marine organisms was not obtained. Also, as for the slime anti-fouling effect, it was not sufficient. (2) For Example 3 where N,N-dimethyl tallow alkylamine was added at 0.02 mg / L (20 h) in the same manner as Comparative Example 2, Example 2 where N,N-dimethyl tallow alkylamine was added at 0.01 mg / L (20 h) in the same manner as Comparative Example 3, and Example 7 where N,N-dimethyl tallow alkylamine was added at 0.03 mg / L (16 h) in the same manner as Comparative Example 4, since a second agent was used in combination, a sufficient anti-fouling effect against marine organisms and a sufficient anti-slime adhesion effect were confirmed. (3) Also, in Comparative Examples 5, 7, 9 to 11 where the second agent was used alone, although a sufficient anti-slime adhesion effect was confirmed, a sufficient effect for preventing marine organism fouling could not be obtained. For Comparative Examples 6 and 8, neither the anti-slime adhesion effect nor the anti-fouling effect against marine organisms was sufficient. Also, from the results of Comparative Example 6 and Comparative Example 7, and Comparative Example 8 and Comparative Example 9, it was confirmed that the second agent has a higher anti-slime adhesion effect when added at a certain higher concentration for a short time rather than added at a low concentration for a long time. (4) Also, from the results of Examples 1 to 7, when the first agent and the second agent are used in combination, by adding the first agent at a concentration of 0.01 to 0.03 mg / L for 16 to 20 hours per day and adding the second agent at a concentration of 0.01 to 0.3 mg / L for 1 to 22 hours per day, it was confirmed that sufficient anti-fouling effects against marine organisms and sufficient anti-slime adhesion effects can be obtained. (5) From the results in Table 1 above, by using N,N-dimethyl tallow alkylamine as the first agent in combination with chlorine agents such as chlorine dioxide, sodium hypochlorite, and monochloramine, and bromine agents such as N-bromosulfamate as the second agent, compared with the case of using each of the first agent or the second agent alone, it was confirmed that fouling by a wide range of marine species (e.g., mussels such as Mytilus edulis and Mytilus galloprovincialis, barnacles, and marine organisms such as bryozoans) and slime adhesion can be prevented. Also, by using the first agent and the second agent in combination, it was confirmed that a sufficient and continuous anti-fouling effect against marine organisms and slime can be obtained over 79 days without increasing the usage amounts of both.

[0049] From the above results, according to the method for preventing adhesion of marine organisms and the like of the present invention, and the anti-adhesion agent and anti-adhesion kit for marine organisms and the like used for this anti-adhesion method, while reducing the usage amounts of the above first agent and the above second agent added to the seawater cooling water system, it was confirmed that the adhesion of a wide range of marine biological species (for example, marine organisms such as mussels like Mytilus edulis, barnacles, and bryozoans) and slime to the seawater cooling water system can be prevented over a long period of time.

Claims

1. A method for preventing the attachment of marine organisms and slime to a seawater cooling water system, comprising: adding a first agent having a higher aliphatic tertiary amine represented by the general formula (I) as an active ingredient and a second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide to the seawater of the seawater cooling water system; the first agent is added such that the concentration of the higher aliphatic tertiary amine in seawater is 0.001 mg / L or more and less than 0.1 mg / L; A method for preventing the attachment of marine organisms and the like, characterized by the above. 【Chemical 1】 (In the formula (I), the substituents R1 and R2 are methyl groups, and the substituent R3 is a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 22 carbon atoms.)

2. The method for preventing the attachment of marine organisms and the like according to claim 1, comprising adding the first agent to the seawater of the seawater cooling water system for at least 12 hours per day.

3. The method for preventing the attachment of marine organisms and the like according to claim 1 or 2, comprising adding the second agent to the seawater of the seawater cooling water system for at least 1 hour per day such that the concentration of the second agent in seawater is 0.002 to 3.0 mg / L.

4. The chlorine agent or bromine agent in the second agent is (a) one or more substances selected from the group consisting of chlorine gas, calcium hypochlorite, sodium hypochlorite, chlorinated isocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium monochloroisocyanurate, potassium monochloroisocyanurate, sodium trichloroisocyanurate, and potassium trichloroisocyanurate, which generate hypochlorous acid in water; (b) one or more substances selected from the group consisting of sodium hypobromite, a reaction product of sodium bromide and sodium hypochlorite, and bromine water, which generate hypobromous acid in water; (c) seawater electrolytic solution, or (d) one or more of combined chlorine or combined bromine selected from the group consisting of monochloramine, dichloramine, trichloramine, monobromamine, dibromamine, tribromamine, N-chlorosulfamate, and N-bromosulfamate. The method for preventing the attachment of marine organisms and the like according to claim 1, 2, or 3.

5. An anti-fouling agent for marine organisms and the like used in the method for preventing the attachment of marine organisms and the like according to claim 1, 2, 3, or 4, comprising: an anti-fouling agent for marine organisms and the like containing at least one selected from the group consisting of a chlorine agent, a bromine agent, and chlorine dioxide and a higher aliphatic tertiary amine represented by the general formula (I) as active ingredients. [Chemical 2] (In formula (I), substituents R1 and R2 are methyl groups, and substituent R3 is a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 22 carbon atoms.)

6. An anti-fouling kit for marine organisms etc. used in the method for preventing adhesion of marine organisms etc. according to claim 1, 2, 3 or 4, a first agent having a higher aliphatic tertiary amine represented by the general formula (I), a second agent having at least one selected from the group consisting of a chlorine agent, a bromine agent and chlorine dioxide, and an anti-fouling kit for marine organisms etc. containing the same. 【Chemical Formula 3】 (In formula (I), substituents R1 and R2 are methyl groups, and substituent R3 is a saturated or unsaturated linear aliphatic hydrocarbon group having 8 to 22 carbon atoms.)

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