JP3126423B2 - Prevention method for marine organisms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preventing the adhesion of marine organisms. More specifically, the present invention relates to a method for preventing the adhesion of marine organisms, especially kansetsu kansetsu, using a hydrogen peroxide supply compound and a water-soluble cationic polymer as active ingredients in a seawater system.

[0002]

2. Description of the Related Art In recent years, in a closed bay, kansane kansashi, a kind of marine organisms, has become more and more attached. In a factory using seawater as cooling water, pitting occurs due to the attachment to the cooling tubes of a heat exchanger. Causes corrosion. Conventionally, electrolytic chlorine and the like have been used. However, chlorine-based chemicals are highly toxic to various marine marine organisms, and control of barnacles and mussels as well as kanashi kanashi was carried out. However, injection of a chlorine-based drug is feared for the generation of halomethane and possibly for the generation of dioxin, and both are bioaccumulated, which is not preferable in terms of environmental pollution prevention.
As a method for preventing the adhesion of marine organisms, simultaneous use of hydrogen peroxide and a quaternary ammonium compound is disclosed in
According to Japanese Patent No. 161592, the combination use of hydrogen peroxide and a biguanide polymer which is a water-soluble cationic polymer is disclosed in
They are both known by JP-97598.

[0003]

However, in the cooling water system that takes in seawater from the inside of a closed bay, obstacles caused by kansane kansashi have increased in recent years. The effect could not be expected. Here, "Kasane Kansashi," which is a kind of marine periphyton, is a marine periphyton belonging to the annelids, polychaete, and scrophulariaceae in classification.
The larva swims in the sea and attaches when it contacts the attachment base,
They secrete calcareous living vessels and grow. It is not unusual for the thickness of the adhesion layer to reach 10 cm or more in about two months in the case of Kansane Kansashi. In view of the current situation and recognition, the present invention intends to provide an effective method for preventing the adhesion of Kanashika Kanashi to a seawater cooling system in a sea area to which Kansai Kanzaki preferentially adheres, which has low toxicity to humans and animals and low environmental pollution. Is what you do.

[0004]

Thus, according to the present invention, a reaction between a hydrogen peroxide supply compound, a polyamine represented by the following general formula (I) and epihalohydrin or dihalogenoethyl ether in a seawater cooling water system is provided. A method for preventing marine fouling organisms from adhering, comprising adding together at least one water-soluble cationic polymer obtained by the method.

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and A represents 1 to 5 carbon atoms)
Represents a linear or branched alkylene group, wherein n is 1 to
Indicates an integer of 5. )

[0005] In the present invention, the hydrogen peroxide supply compound is a compound that generates hydrogen peroxide in water, and examples thereof include hydrogen peroxide, sodium percarbonate, and peracetic acid.

The water-soluble cationic polymer used in the present invention is known as an aqueous algal growth inhibitor in JP-B-55-49042 and JP-B-53-23377. It is also known as an activated sludge bulking inhibitor.

Specific examples of the alkylene polyamine (n = 1) belonging to the polyamine of the general formula (I) used in the present invention include ethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, propylenediamine, , N-dimethylpropylenediamine,
N, N, N ′, N′-tetramethylethylenediamine and the like. On the other hand, specific examples of the polyalkylenepolyamine (n = 2 to 5) belonging to the polyamine of the general formula (I) include diethylenetriamine, triethylenetetramine,
Examples thereof include tetraethylenepentamine and pentaethylenehexamine. Any of these polyamines can be used in combination of two or more.

As the halogen of epihalohydrin, any of fluorine, chlorine, bromine and iodine is effective.
Epichlorohydrin is economically preferred. As dihalogenoethyl ether, dichloroethyl ether is preferred in terms of economy.

In order to obtain the water-soluble cationic polymer used in the present invention, the above-mentioned polyamine is reacted with epihalohydrin or dihalogenoethyl ether in an amount of 1 mol of the polyamine (total amount of 1 mol when the polyamine is a mixture). Mol) with 0.5 to 1.75 mol of epihalohydrin or dihalogenoethyl ether.

In order to obtain a polymer, a polyamine is charged into a closed reaction vessel, the atmosphere in the vessel is replaced with an inert gas, and epihalohydrin or diamine is adjusted with stirring so as not to raise the reaction temperature excessively. The halogenoethyl ether is preferably added continuously or in a divided manner, and the polymerization is preferably carried out at a reaction temperature of 30 to 110 ° C.

The water-soluble cationic polymer thus obtained can be obtained by changing the polymerization conditions to a polymer having an average molecular weight of about 500-10000. The molecular weight of this polymer can be determined by dissolving it in a 2 mol / liter aqueous potassium bromide solution and determining the intrinsic viscosity [η]. Further, it is possible to replace halogen (derived from epihalohydrin or dihalogenoethyl ether) as a counter ion with another anion, or to remove the counter ion to convert the water-soluble cationic polymer to a hydroxide. .

The water-soluble cationic polymer obtained as described above can be used as a solid, but the one prepared as an aqueous solution may be used as it is or may be diluted with water as needed to obtain an appropriate concentration, for example. It can be adjusted to an aqueous solution of about 1 to 70% by weight and injected with a chemical pump.

In the present invention, the ratio of the hydrogen peroxide supply compound to the water-soluble cationic polymer is from 0.1 to 5 in terms of weight ratio with respect to the amount of hydrogen peroxide to be generated, but preferably a synergistic effect can be expected when used in combination. The range is 0.2-3. When the proportion of the water-soluble cationic polymer is less than 0.1 or more than 5, no synergistic effect is exhibited, which is not preferred.

The amount of hydrogen peroxide to be added to the seawater cooling system is generally 0.05 to ₂ ppm, preferably 0.1 to 1.5 ppm in terms of H ₂ O ₂ , based on the flow rate of seawater, and is 12 to 24 ppm per day.
It is preferable to inject for a time. The water-soluble cationic polymer to be added in combination is 0.005 to 1 ppm, preferably 0.01 to 0.8 ppm.
ppm may be infused for 8 to 24 hours a day. Although the amount of addition may slightly increase or decrease depending on the conditions in the sea area, it is desirable to increase the amount if the amount of Kansane Kansashi is extremely large. However, in any situation, the concentration of the active ingredient to be added is ₂ ppm as H ₂ O ₂ and the addition amount of the water-soluble cationic polymer up to 1 ppm is sufficient. Is also not preferred. It is preferred that both hydrogen peroxide and the water-soluble cationic polymer be dissolved or diluted in water so as to be uniformly dispersed in seawater in the seawater cooling system. The method of the present invention can be effectively used not only for seawater-borne organisms, but also for freshwater-based organisms (for example, zebra muscles and shore clams).

In the addition method, the hydrogen peroxide supply compound may be added simultaneously or separately before and after each. Particularly, in a factory where water in a contaminated sea area is used as cooling water, a hydrogen peroxide supply compound is added. Thereafter, it is more effective to add a water-soluble cationic polymer. The method of the present invention can be effectively used not only for seawater-borne organisms, but also for freshwater-based organisms (for example, zebra muscles and shore clams).

[0016]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 1 l equipped with a stirrer, a cooler, a thermometer and a dropping funnel
116 g (1 mol) of N, N, N ', N'-tetramethylethylenediamine was placed in a flask having a capacity, and 101.4 g of 36% hydrochloric acid was added dropwise with stirring while maintaining the liquid temperature at 30 to 40 ° C. After replacing the air in the container with nitrogen gas, the liquid temperature is raised to 80 to 90 ° C.
Under stirring, 92.5 g (1 mol) of epichlorohydrin was gradually added dropwise with stirring, and after completion of the addition, polymerization was carried out for 10 hours while maintaining the liquid temperature at 90 to 100 ° C. to obtain a water-soluble cationic polymer A.
The average molecular weight of this polymer A was 4,000. Using the same equipment as above, N, N-dimethylethylenediamine 132
g (1.5 mol), and 67.7 g of pure water was added while maintaining the liquid temperature at 20 to 30 ° C. After the atmosphere in the vessel was replaced with nitrogen gas, 138.7 g (1.5 mol) of epichlorohydrin was added dropwise with stirring while maintaining the liquid temperature at 70 to 80 ° C. Thereafter, while maintaining the liquid temperature at 80 to 90 ° C., polymerization was carried out for 6 hours to obtain a polymer B. The average molecular weight of the obtained polymer B is 95
It was 0. Hereinafter, each polymer was obtained by the same operation.
That is, the molar ratio of the polyamine compound and epihalohydrin or dihalogenoethyl ether used to obtain the polymers C to G, and the average molecular weight of the obtained polymer are as follows. Polymer C: N, N, N ', N'-tetramethylethylenediamine 116 g (1 mol) Dichloroethyl ether 143 g (1 mol) The average molecular weight of the polymer was 2000 Polymer D: N, N-dimethyl 1,3 -Propanediamine 10
2 g (1 mol) Epichlorohydrin 92.5 g (1 mol) Polymer has an average molecular weight of 2500 Polymer E: triethylenetetramine 146 g (1 mol) Epichlorohydrin 92.5 g (1 mol) Polymer has an average molecular weight of 1500 Polymer F : N, N-dimethylethylenediamine 44 g (0.5 g)
Mol) triethylenetetramine 73 g (0.5 mol) epichlorohydrin 92.5 g (1 mol) The average molecular weight of the polymer is 1200 Polymer G: N, N-dimethylethylenediamine 44 g (0.5 mol)
Mol) N, N, N ', N'-tetramethylethylenediamine 58 g (0.
5 mol) 36% HCl 50.6 g (0.5 mol) Epichlorohydrin 92.5 g (1 mol) The average molecular weight of the polymer is 7,500.

Example 2 The living body of the kansetsu Kansashi was collected, the living tube was removed, the soft part was taken out, and the soft part was allowed to stand in filtered seawater to induce ovulation and spermation to obtain eggs and sperm. The eggs and sperm were fertilized in filtered seawater, excess sperm were washed with filtered seawater, and the fertilized eggs were placed in a thermostat at 22 ± 1 ° C. and left for 24 hours. Then, using the obtained trochophore larvae, the killing effectiveness of the various drugs prepared in Example 1 against them was tested by the following procedure. That is, 30 liters of filtered seawater to which each agent was added to a chalet having a diameter of 90 mm and a height of 15 mm so as to have a predetermined concentration was added, and NXX- was placed in one of the thick glass tubes having a diameter of 60 mm and a height of 20 mm. Put the equipment with 25 mueller gauze on it, then kanko kanko trocophore
-10 larvae were placed. After leaving it in a constant temperature bath at 22 ± 1 ° C for 6 hours, it was changed to filtered seawater, and bred for 24 hours in a constant temperature bath, and the number of swimming larvae was counted under a microscope to determine the efficacy of each drug. . When the number of swimming individuals is 0, it indicates that all of them have been killed. The results are shown in Tables 1 and 2 .

[0019]

[Table 1]

[0020]

[Table 2]

[Consideration of test results] From the test results, it was found that the combined use of the hydrogen peroxide-supplying compound and the water-soluble cationic polymer at a weight ratio of 1: 0.3 to 3 significantly reduced the larvae of the moss Kanesashi. A synergistic effect was observed.

Example 3 A test channel was made with a PVC pipe having an inner diameter of 75 mm and a length of 20 m.
Tests were performed for the case where hydrogen peroxide and the water-soluble cationic polymer were added simultaneously and the case where they were added staggered. That is, when adding to the same location, both chemicals are injected into the tip of the test channel. When displacing, injection was performed by providing a chemical injection point at each of the tip and center of the test channel. Then, a test net was placed at the rear end of the test channel to determine the effect of the concomitant drug. In other words, the seawater is pumped from the seawater channel of the factory in Tokyo Bay with a submersible pump,
Seawater is passed through for one day for 40 days (approx. 3 tons / hour each)
Then, each drug was injected by a chemical pump, and the number of kanashikanashi and other attached organisms attached at that time were counted. The results are as shown in Table 3 .

[0023]

[Table 3]

Example 4 A test was performed using a seawater cooling system waterway (seawater volume of 30,000 tons / hour) in the Tokyo Bay area. Chemicals were injected by a chemical pump into the tip part and two places in front of burs screen 10 m after the tip part due to the chemical injection pipe. The test was carried out for 60 days during the attachment period of the kanashi-kanashi. That is, from the tip of the headrace
2 ppm of 35% aqueous hydrogen peroxide was continuously injected, and 0.1 ppm of a 30% aqueous solution of a water-soluble cationic polymer was also injected before bursculin. In order to investigate the effect, the test net was immersed near the head of the headrace as no addition, and the test net was immersed in the pump pit after travel screen where both chemicals were mixed, and the effect was examined. Table 4 shows the results.

[0025]

[Table 4]

[Consideration of results of water channel test] From the results of the water channel experiment, it is found that the addition of hydrogen peroxide and the water-soluble cationic polymer can prevent the adhesion of Kanashi Kanashi with a small amount of addition. In comparison, the addition of hydrogen peroxide or a water-soluble cationic polymer alone had no effect on Kansai Kanzaki. In particular, it is better to inject hydrogen peroxide first and then inject the water-soluble cationic polymer.
It turns out that it is also effective against other attached organisms.

[0027]

According to the present invention, it is possible to extremely effectively prevent a trouble in the seawater cooling water system due to marine fouling organisms.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toru Yasunaga 2- 10-15 Higashiawaji, Higashiyodogawa-ku, Osaka-shi Inside Katayama Chemical Industry Laboratory Co., Ltd. (72) Inventor Kunio Nishimura 2--10 Higashiawaji, Higashiyodogawa-ku, Osaka-shi No. 15 Inside Katayama Chemical Industry Co., Ltd. (56) References JP-A-56-97598 (JP, A) JP-A-51-138799 (JP, A) JP-A-3-151306 (JP, A) JP-A-62-36128 (JP, A) JP-A-4-312502 (JP, A) JP-A-59-98791 (JP, A) JP-A-3-186391 (JP, A) JP-A-57-32202 (JP , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C02F 1/00 C02F 1/50 A01N 59/00 A01N 33/00

Claims (5)

(57) [Claims] 1. A compound for supplying hydrogen peroxide and a compound represented by the general formula (I): (Wherein, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and A represents a linear or branched alkylene group having 1 to 5 carbon atoms) , n represents Ri Do from the addition of one or more water-soluble cationic polymer obtained by reacting a polyamine with epihalohydrin or dihalogeno ether represented by an integer from 1 to 5.) seawater cooling system Addition of hydrogen peroxide supply compound
Pressurizing amount 0.05 seawater cooling water per ton H ₂ O ₂ conversion
2 g, and the added amount of the water-soluble cationic polymer is 0.00
A method for preventing marine fouling organisms from 5-1 g . 2. The method according to claim 1 , wherein the hydrogen peroxide supply compound is hydrogen peroxide. 3. The water-soluble cationic polymer is 500 to 100.
The method for preventing adhesion according to claim 1 or 2 , having an average molecular weight of 00. 4. After the addition of the hydrogen peroxide feed compound, adhesion preventing method according to any one of claims 1 to 3 the addition of a water-soluble cationic polymers. 5. The method according to any one of claims 1 to 4, wherein the marine fouling organism is a moss Kanesi.