JPS6046082B2 - Treatment agent for algae-producing industrial water - Google Patents

Description

[Detailed description of the invention] The present invention relates to a treatment agent for algae-producing industrial water.

More specifically, the present invention provides methylene bisthiocyanate and -'-'--' which prevent algal damage to industrial waters.
゛ 1., 1 吋,, 1/ Book 14-1
Book 1-1■15'4 means those with 6 to 18 carbon atoms), and methylene bisthiocyanate and bromoacetic acid alkyl ester (alkyl group has 6 to 18 carbon atoms). ) to alkylamine (
The present invention relates to a processing agent characterized by adding an alkyl group having 8 to 18 carbon atoms. Algae have a green pigment called chlorophyll inside their alga bodies and commonly live in surface water, but they differ from bacteria, fungi, yeast, etc. in that they require light.

Most algae thrive in the presence of trace amounts of nutrients such as phosphorus, nitrogen, potassium, magnesium, and iron in addition to light.
Groups form after ~4 hours. When such algae proliferate in treated water for general industry or plant water, it causes serious problems such as contamination of products, corrosion of iron equipment, deterioration of their functionality, and blockage of flow paths.

For example, when water in which algae have grown is used as washing water, extractant, etc. in the treatment of products, it not only affects the purification efficiency but also contaminates the product and significantly reduces its quality. In particular, when algae proliferate, increases in organic precipitates in the system, increases in dissolved oxygen in water due to photosynthesis, changes in Pll, changes in the amount of carbon dioxide gas and calcium carbonate in water, etc. indirectly promote corrosion of iron. cause it to happen. For example, the increase in dissolved oxygen caused by algae forms an oxygen concentration cell, which can be used to produce iron bits, equipment,
Significantly accelerates corrosion of equipment, etc. Furthermore, due to the need to conserve water, when plant water is circulated in a closed system, it is said that if algae adheres to the pipe walls of the cooler, it will reduce the cooling function, and if it adheres to the pump piping, it will block the flow path. I have a disability. Alternatively, it adheres to the surface of cooling towers and sprinkler doors in wastewater treatment facilities, reducing their functionality. Furthermore, if even a small amount of algae is present in water from natural wells or swimming pools, it forms so-called green water, which gives an unpleasant taste and odor and causes pollution. Many drugs have been developed and used to kill the algae that cause these problems, but the main ones are inorganic salts, organometallic compounds, rosin amines, quinones, amide derivatives, phenols, metal salts of pentachlorophenol, Chlorine, etc. Among these, chlorine, which is the most widely used algaecide, acts on the protein system that is a component of algae and produces chloramine, which has a remarkable algaecide effect.However, since chlorine is a strong oxidizing agent, it If organic or inorganic metal salts are present, they will be oxidized by chlorine to form metal oxides, producing unpleasant pigments in the water and rendering the chlorine inactive. Therefore, when chlorine is used as a commercial algaecide, the demand for chlorine is large, requiring constant chlorine replenishment, which has the disadvantage of causing accelerated corrosion of iron. The present inventors conducted research on an industrially practical algaecide that does not have the above-mentioned drawbacks, and previously filed a patent application in 1987-6887.
In No. 8, halogenoacetic acid esters were proposed as useful algaecides.

This compound again. By adding a slime control agent to the water intake or recovery bit of a paper mill, and adding a slime control agent to the bit or water used in the papermaking process, it is possible to prevent and kill the growth of algae and slime in the papermaking water, thereby causing damage to paper. How to eliminate them and use algaecides. Special application 1980-8
168 and filed the application. The inventors of this application have filed a patent application in 1983-
We have continued to study the effects and usability of the algaecide invented by 8168 Unagi, and have now invented the algaecide of the present application, which is extremely effective against algae that grow and proliferate in various types of industrial water. The purpose of the present invention is to provide an algaecide that is non-irritating, stable, and has a remarkable algicidal effect in a small amount compared to conventional general industrial water algaecides. The purpose is to apply it to industrial water generated to prevent its problems. As mentioned above, the present invention provides that the two components, methylene bisthiocyanate and bromoacetate, have a more pronounced synergistic effect on killing algae in water when used in combination than when used alone. admitted.

It is also known that some alkylamines have a killing effect on algae. However, the experiments of the present inventors have shown that, similar to the case of jointly using two components of bromoacetate and methylene bisthiocyanate, the joint use of these three components and alkylamine is more significant than the case of using each component alone. It was confirmed that results were obtained, and it was found that, depending on the type of algae, the combination of three components had a more pronounced killing effect than the combination of two components.
In the present invention, the alkyl group of the bromoacetic acid alkyl ester shown above includes n-hexyl, n-octyl,
Straight chain alkyl groups such as n-decyl, n-lauryl, n-myristyl and n-cetyl, and their well-known branched alkyl groups are included, among which the most preferred compound is lauryl bromoacetate. .

Bromoacetic acid ester is generally used as a single compound, but two alcohols are used as raw materials for production.
Two or more types of bromoacetic esters may be used if they are available at low cost as a mixture of two or more types. Furthermore, in the present invention, the alkyl group of the alkylamine includes straight chain alkyl groups such as n-octyl, n-decyl, n-lauryl, n-myristyl, and n-cetyl, and among these, the most preferred compound is laurylamine. be. The drug component of the present invention can be used in various dosage forms.

That is, in actual use, the drug compounds can be added to industrial water separately or simply mixed together, either continuously or in an impact manner, but preferably in a liquid form such as an organic solvent solution or a hydrated state. It is used either as a granule or a powder in a water-dispersible fixative. The three types of compounds that are the active ingredients of this invention can be used in organic solvents such as dimethylformamide, diethylene glycol, dipropylene glycol, dioctyl phthalate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, toluene, acetone, xylene, or ethyl alcohol. Since they are soluble, they are used as suitable diluents when preparing liquid preparations, and commonly used surfactants, particularly nonionic surfactants, are added to maintain good dispersibility in water. In addition, when preparing granules or powders, examples of fixatives include kaolin, bentonite chalk, dolomite, aluminum or calcium silicate, silica gel, diatomaceous earth, and talc, which are mixed with appropriate dispersants. It will be done. In the present invention, the compounding ratio that exhibits a synergistic effect compared to when each component compound is used alone is 2:8 to 8:2 by weight in the case of methylene bisthiocyanate and bromoacetic ester, The ratio is preferably 3:7 to 7:3, particularly preferably 5:5.

In addition, in the case of methylene bisthiocyanate, bromoacetate and alkylamine, each compound has a weight ratio of 2 to 5.
The ratio is particularly preferably 3:3:4. Although the amount of the active ingredient added in this invention varies slightly depending on the type of algae, water quality, season, etc., it is usually sufficient to add about 10 to 30 ppm, and there is no particular upper limit, but it is not necessary to add more than 100 ppm.

Next, this invention will be explained using experimental examples and examples. Preparation Form Example Experimental Example - Dissolve 1.25 g each of potassium nitrate, magnesium sulfate (heptahydrate), and sodium monohydrogen phosphate in pure water 1e of cultured algae Chlorella pyrenoidosa, Spirogyla variens, and add 1.25 g each of each .0m1 (7) Fe liquid (1) and modified human fluid (2)
Prepare a nutrient solution with the addition of and adjust the pH to 6.0.
It was sterilized for one batch at 0°C.

After sterilization, 1ase of chlorella per 10mt of nutrient solution
Pyrenoidosa (ChlOrella●Pyr'EnOi
dOsa) and Spirogyra Variance (SpirO
gyra●Varials) and were allowed to sufficiently propagate in a culture flask at a temperature of 25° C. and with shaking under a light intensity of 2500 lux.

B. Oscillatoria Tenu r.s., Anabaena Siri
Potassium nitrate, magnesium sulfate (
Heptahydrate), potassium monohydrogen phosphate, sodium chloride and calcium chloride dihydrate were dissolved, and 1.0% each
A nutrient solution was prepared by adding m1 of Fe solution (1) and modified human solution (2), the pH was adjusted to 8.0, and the solution was sterilized for one batch at 120°C.

After sterilization, add 1 dose of Oscillatoria tenuis per 10 ml of nutrient solution.
is) and Anabaena cylindrica (Anabaen cylindrica)
A Cyllndrica) were inoculated and allowed to grow sufficiently in a culture flask at a temperature of 25° C. and a light intensity of 2,500 lux and shaking. (1) Fe
Liquid: 1e of water with magnesium iron sulfate (heptahydrate)
Solution prepared by adding 2.0g and 4 drops of concentrated sulfuric acid (2) Modification A
5 liquids: 1 e of water, 2.86 g of boric acid, 1.81 g of manganese chloride (tetrahydrate), 1 zinc sulfate (heptahydrate), 0
．． 222g 1 molybdic acid 0.0177g 1 copper sulfate (pentahydrate) 0.079g and cobalt chloride 1.00g
10 cc of the sufficiently grown algae were aseptically dispensed into a sterilization test, and each test drug at a predetermined concentration diluted with dimethylformamide to 100 ppm was added to each test tube.

The test tube was shaken once a day to confirm the concentration of the test drug added that completely killed algae within 10 days, and the efficacy of the drug was determined based on this concentration. Example 1 A large amount of green algae grew in a dormant pool after the season had passed, forming green water and emitting an unpleasant odor.

This green algae was collected and identified as Chlorella Pyr'EnOidOsa.
, Chlamydomonas sp.
PP), Palmera●Mucosa (Pafme'Fa●M
ucOsa), Cosmaryum Potoliteis (COs)
marium◆BOtrytis). child. For every 1000 tons of water stored in a swimming pool, 10 parts by weight of lauryl monobromoacetate (the same applies below), 38 parts of dimethylformamide, 38 parts of diethylene glycol, and 1 part of surfactant. 1 drug formulated in
0ppm (purity equivalent) impact addition. After 3 days, the algae died, the green water disappeared, and the odor disappeared.
Example 2 Chlorella pyrenoidosa (C
heOrella●PyrenOidOsa), Palmera species (Pa'MeI7eaSPP), Uroshritus●
U'0thrix-ZOnata, the blue-green algae Oscillatoria tenuis (0scieeat0ri)
a-Tenuis), Anarchisteis species (ATlaCy
StiSSPP) and the diatom Diatoma species (DiatO
10 parts by weight of lauryl monobromoacetate (the same applies hereinafter), 10 parts of laurylamine, 2 parts of methylene bisthiocyanate, 3 parts of dimethylformamide, and 3 parts of ethylene glycol monobromoacetate were added to the natural well water (10 tons of stored water) generated in large quantities by maSPP). 28 parts of ethyl ether, 1 part of surfactant? When the drug formulated in 10 ppm (purity equivalent) was added to the water storage volume, an abnormality was observed in the distribution of algae on the first day, and on the third day, the algae turned white and died. did.

Claims (1)

[Scope of Claims] 1. Algae-producing industrial water ( (excluding water used in the paper manufacturing process). 2. The processing agent according to claim 1, wherein the alkyl bromoacetate is lauryl bromoacetate. 3 Methylene bisthiocyanate and bromoacetic acid alkyl ester (alkyl group means one having 6 to 18 carbon atoms), alkylamine (alkyl group means one having 8 to 1 carbon atoms)
A treatment agent for algae-producing industrial water (excluding water for paper manufacturing process), characterized by adding 8 of them. 4. The processing agent according to claim 3, wherein the alkyl bromoacetate is lauryl bromoacetate. 5. The processing agent according to claim 3 or 4, wherein the alkylamine is laurylamine.