JPH0366601A - Marine organism adhesion inhibitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides an introduction path for a system that uses seawater as cooling water;
This invention relates to an agent that suppresses the adhesion of marine organisms to marine structures such as water pipes and plants.

<Conventional Technology> As is well known, in thermal power plants, pig iron and steel mills, oil refineries, petrochemical plants, chemical plants, etc. that use seawater, marine organisms attach to their cooling water systems and disrupt their functions. It is decreasing.

Examples of the above-mentioned marine organisms include shellfish such as mussels, barnacles, and oysters, and examples of sessile organisms include hydrobugs and bryozoans. These marine creatures create waterways,
When they breed in water pipes or plants, they can narrow the pipes and reduce the flow of seawater, fall off and clog the heat exchanger tubes, and corrode heat exchanger tubes, water pipes, etc. .

Therefore, after a certain period of operation, the operation was stopped and cleaning was performed by physical methods to remove the above-mentioned attached organisms and wash the corroded inner walls.

<Problem to be solved by the invention> However, the above-mentioned cleaning requires the suspension of operations, which takes time and effort, and the above-mentioned marine organisms grow in a short period of time, so cleaning is not carried out frequently. There was a problem that it had to be cleaned.

In addition, in recent years, aliphatic amines, ethylene oxide adducts of β-hydroxy-substituted aliphatic amines, ethylene oxide adducts of N-mono-substituted propylene diamine, It has been proposed to add trace amounts of amines such as aliphatic oxybropylene amine, aliphatic ethylene diamine, secondary aliphatic amine, tertiary aliphatic amine, and quaternary ammonium salts.

However, these water-soluble amine salts can be used as is, or with water,
Even if diluted with methyl alcohol or ethyl alcohol and injected into the seawater line intermittently or continuously, marine organisms such as mussels, barnacles, water bugs, bryozoans, and sea squirts will temporarily stop their living functions to prevent the passage of poisonous substances. Even if you wait or ingest poisonous substances, the growth will only be suppressed and you will not be killed.
Injecting 10 times more can kill marine organisms and prevent them from adhering to marine structures, but adding such a large amount can kill marine fish, carapaces, molluscs,
A problem arises in that other organisms such as shellfish are also killed, and furthermore, processing costs increase, making it economically unfavorable.

<Means for Solving the Problems> The present invention has been proposed in view of the above, and includes a composition in which amine salts are dissolved in less toxic propylene glycol, glycerin, or a mixture of both, which is intermittently introduced into a seawater line. Alternatively, the present invention relates to a marine organism adhesion inhibitor that is continuously injected to suppress the adhesion of marine organisms to marine structures.

As mentioned above, by dissolving amine salts in less toxic propylene glycol, glycerin, or a mixture of both, the amount of injection into seawater can be reduced compared to when amine salts are dissolved in water. This is because amine salts are dissolved and dispersed in water when dissolved in propylene glycol, glycerin, or a mixture of both, which causes marine organisms to reject the toxicity.
This is because it slows down the activation of the repellent response. When amines are ingested by marine organisms, they can kill them or significantly inhibit their growth.

Therefore, for example, the effects conventionally obtained by intermittent injection once a day can be obtained by using the adhesion inhibitor of the present invention with intermittent injection once every 3 to 7 days. When performing continuous injection, the injection amount can be reduced as described above.

In addition, since propylene glycol, glycerin, and the mixture of both used in the present invention are highly viscous solvents, methyl alcohol, ethyl alcohol, isopropyl alcohol, water, etc. are also used as viscosity modifiers to facilitate injection of the composition. can be used.

Examples of amine compounds that can be used as the marine organism adhesion inhibitor of the present invention by adding them to the above-mentioned solvents such as propylene glycol and glycerin include β-
Ethylene oxide adduct of hydroxy-substituted aliphatic amine or its acid addition salt, N-monosubstituted propylene diamine ethylene oxide adduct or its acid addition salt, aliphatic amine or its monobasic acid salt, aliphatic oxypropylamine or its acid addition salt. Acid addition salts, tertiary aliphatic amines, N
Examples include -monosubstituted propylene diamine or a salt thereof, N-monosubstituted ethylenediamine or a salt thereof, and a quaternary ammonium salt.

In addition, the general formula % formula % (in the above formula, R is a straight chain or branched alkyl group having 12 to 18 carbon atoms, m is an integer of 1 to 4, Ro is hydrogen (H) or a methyl group (CUt), or ethyl It has been found that higher fatty acid aminoamides or derivatives thereof and their acid adducts represented by the following groups (CJs) can also be used in the marine organism adhesion inhibitor of the present invention.

Examples of the above-mentioned compounds include higher fatty acid aminoethylamide and its acid adduct, higher fatty acid aminopropylamide and its acid adduct, higher fatty acid dimethylaminoethylamide and its acid adduct, higher fatty acid dimethylaminopropylamide and its acid adduct. There are acid adducts, higher fatty acid diethylaminoethylamide and its acid adducts, higher fatty acid diethylaminopropylamide and its acid adducts, etc.
Examples of higher fatty acids that are raw materials for the aminoamides mentioned above include beef fatty acids, coconut oil fatty acids, oleic acid, stearic acid, lauric acid, and capric acid.

A composition prepared by blending propylene glycol with the above-mentioned compound has an extremely high effect of inhibiting adhesion to marine organisms.

Also, a combination of N-alkyl-substituted diaminobutane and propylene glycol represented by the general formula % (in the above formula, R represents a straight chain or branched alkyl group having 12 to 18 carbon atoms), especially N-alkyl 0 parts of propylene glycol to 1 part of substituted diaminobutane,
It was found that 5 to 2 parts had a high effect of inhibiting the adhesion of marine organisms. Further, examples of the alkyl group of the above-mentioned N-alkyl-substituted diaminobutane include alkyl groups such as beef tallow alkyl, coconut oil alkyl, oleyl, stearyl, and lauryl.

Furthermore, a reaction obtained by adding equimolar sulfuric acid to N-alkyl-substituted propylene diamine represented by the general formula % formula % (in the above formula, R represents a linear or branched alkyl group having 12 to 18 carbon atoms) Although the product is not soluble in water, it can be made into a homogeneous aqueous composition using, for example, an alcohol (such as a -hydric alcohol or a polyhydric alcohol). However, when a small amount of the above-mentioned composition is added to a large amount of water or seawater, it cannot be dissolved uniformly, but the reaction product obtained by adding equimolar amounts of sulfuric acid to the above-mentioned N-alkyl-substituted propylene diamine, When the acetic acid addition reaction product of R-CONH-(CH*)s-N((:l5)i and a polyhydric alcohol such as propylene glycol or glycerin are blended, it can be dissolved uniformly in a large amount of water or seawater. , and the effect of inhibiting marine biofouling can be obtained.

Moreover, the mixing ratio of the above-mentioned amine compound and propylene glycol is preferably in the range of 0.5 to 2 parts of propylene glycol to 1 part of the amine compound.

The composition in which the amine salts of the present invention as described above are dissolved in propylene glycol, glycerin, or a mixture of both can be continuously or intermittently injected at 0.05 to 20 ppm into seawater in water conduits, water pipes, or plants. By doing so, attachment of various marine organisms can be suppressed.

Examples of the various marine organisms whose adhesion is inhibited by the composition of the present invention include shellfish such as mussels, Fujitbo, sea squirts, and oysters, and examples of adherent organisms include water worms, bryozoans, bacteria, and algae.

Further, the composition of the present invention is added to seawater as described above, and the amount of the composition added is generally 0.01 to 20 ppm relative to the flow rate of seawater, and is added within 1 to 7 days. 1
It may be injected for ~24 hours. In the intermittent injection period described above, if the amount added is less than O, Ol ppm, the effect will be low, and if the amount added is more than 20 ppm, there will be no further effect, and furthermore, it will be bad economically.

The amount of the composition of the present invention added is determined by the f! Depending on the type, the above amounts may need to be reduced or increased. For example, if the attached organisms are bryozoans, water bugs, etc., a small amount may be added; however, if the attached organisms are mussels, fujibos, etc., and the amount of these organisms is particularly large, it is necessary to increase the amount added.

A feature of the effectiveness of the compositions of the invention is that they prevent the adhesion of shellfish and periphyton. That is, the composition can be used to kill shellfish in their larval stage and to suppress the growth of shellfish that have already grown up, since the composition is ingested into the living body.

<Example> Polyvinyl chloride 100X 100mm square, length 2.
A test plant containing a test piece (cedar board) was used in a 5 m waterway, and seawater was passed through it. Seawater flow fi 7.5n+'
The composition of the present invention was injected using a metering pump at a flow rate of 0.35 m/hr. The amount of marine sessile organisms over 30 days was compared to a blank.

The composition of the composition of the present invention and the attached 1110 ffi are listed in Table 1 along with the results.

As is clear from Table 1 above, the composition of the present invention exhibits a remarkable effect in suppressing the adhesion of marine organisms such as mussels and Fujitbo.

<Effects of the Invention> As explained above, the composition of the present invention can suppress the adhesion of marine organisms simply by injecting it into a seawater cooling water system.

Therefore, it is possible to remove attached marine organisms without stopping the operation of the marine horizontal structure, which has great time and economic advantages compared to conventional cleaning methods.

Further, the addition of the composition of the present invention to seawater is extremely simple, as it is only necessary to mix a fixed amount.

Claims (1)

[Claims] A marine organism adhesion inhibitor characterized by containing propylene glycol, glycerin, or a mixture of both.