KR101048627B1 - Composition for controlling harmful algae containing nanosilver as an active ingredient and method for controlling the same - Google Patents

Abstract

The present invention is a composition for controlling harmful algae containing nano silver as an active ingredient, more specifically, a nano-sized silver metal or silver oxide that does not contain nitrogen (N) or phosphorus (P), which is a problem in eutrophication, as an active ingredient. The present invention relates to a composition for controlling harmful algae and a method for controlling harmful algae using the same, wherein the composition for controlling harmful algae of the present invention uses nanosilver without nitrate, which is selective for inhibiting growth and environment-friendly and harmful algae. It can be usefully used as a harmful algae control agent having excellent efficacy.

Nano silver, harmful algae, nitrogen, phosphorus, silver metal, silver oxide

Description

Composition comprising nano-silver compounds for enhansing control of harmful algae and method for controlling harmful algae using the same

The present invention is a composition for controlling harmful algae containing nano silver as an active ingredient, more specifically, a nano-sized silver metal or silver oxide that does not contain nitrogen (N) or phosphorus (P), which is a problem in eutrophication, as an active ingredient. The present invention relates to a composition for controlling harmful algae and a method for controlling harmful algae using the same.

Harmful algal blooms (HABs) are causing various industrial problems, depending on their habitat. The outbreak of harmful algae in lakes, streams, reservoirs, fish farms, etc., 1) causes aquatic deaths (Duke et al., Weed Sci. 50: 138-151, 2002); 2) to produce off-flavor substances, reducing the quality of drinking water and farmed fish (Duke et al., Weed Sci. 50: 138-151, 2002); 3) toxins that are harmful to humans and animals (Haider et al., Chemosphere 52: 1-21, 2003); 4) causing discomfort and impeding leisure and industrial activity due to the coloring of water and the formation of scum; 5) Over-treatment of chlorine is necessary due to filter paper closure and inhibition of flocculation precipitation during water treatment, resulting in economic losses; 6) In the construction and industrial facilities, harmful algae can cause various damages such as water pollution, machine malfunctions, aging, and aesthetic damage.

In order to effectively cope with the problem of the generation of harmful algae, physical, biological or chemical methods have been attempted at various angles, but there are still no satisfactory results. Until now, the main algae control method applied to Korea is the most widely used method of spraying ocher powder to settle algae together with a cutlery. In addition, separation by flocculant, unsaturated fatty acid and sodium silicate of aluminum, kaolin Algae adsorption sedimentation method using algae, algae adsorbent and mechanical device mixed with a mixture of magnesium hydroxide, calcium carbonate and clay, adsorption using inorganic oxide ceramics, separation using dissolved air flotation, centrifugation A method of removing algae generated in water by using a physical method such as separation and the like has been proposed or used. As a chemical method, an algae killing method by spraying copper sulfate or sodium hypochlorite solution is used.

However, the algae removal method by the physical method has the disadvantage that the removal efficiency of algae is not very high or the installation cost for the physical method using the machine is very high and the economic efficiency is greatly reduced. It has a problem that cannot be prevented. Particularly, when powders such as ocher or inorganic oxides with high specific gravity are used, they can be economically available due to the low price, but have a disadvantage in that the algae removal rate is very low due to insufficient adsorption time with algae after spraying in water.

Chemical methods such as copper sulphate or sodium hypochlorite can maximize the removal rate of algae and prevent algae damage in advance, but copper sulphate is a specific harmful substance that accelerates heavy metal contamination by water deterioration and food chains. Hullebusch et al. Water, Air, and Soil Pollution 150: 3-22, 2003) have a problem that can greatly deteriorate the water ecosystem.In the case of sodium hypochlorite, the bleaching and sterilizing effect is large, which maximizes the killing effect of algae. It has the advantage of being able to cause discomfort caused by odor of chlorine gas, and chlorine acts with organic substances (humic acid, fulvic acid, etc.) in water to increase the possibility of generating carcinogenic trihalomethanes. In addition, organic synthetic herbicides such as simazine and diuron (Aquaculture 163: 85-99, 2004; Aquaculture 233: 197-203, 2004) may be toxic in some cases, Safety is an issue. Therefore, among the compounds that are currently used, many compounds that are desired to be replaced in the future in consideration of phosphorus toxicity or environmental stability are many circumstances.

In order to kill algae by an environmentally friendly method or to suppress algae generation or to prevent algae more efficiently, Korean Laid-Open Patent Publication No. 2006-0108409 discloses a photocatalyst, silver, or silver on a porous biostone surface. It is proposed to remove green algae and red tide by coating copper and to remove green algae and red tide efficiently. Korean Laid-Open Patent Publication No. 2005-0121091 proposes seafood products of kelp, seaweed and mussels, and black beans, bamboo shoots and acorns. Natural solutions are mixed with each solution obtained in hot water extraction, and raw potato juice is added to it and matured for 6 months to 1 year at a temperature of 30 to 45 ° C. Red tide of fresh water, green algae for fresh water and water purification and soil improving agent And a method of manufacturing the same, and in Korean Laid-Open Patent Publication No. 2003-0038276, a living organism widely used in an industrial wastewater storage plant is currently disclosed. In the case of membranes, as the media uses stones, slags, ceramic products, or plastic products as biofilms, the biofilms lose their function by attaching moss and green algae to the biofilms. (Silver) is proposed a method for producing a biofilm dyed.

The Korean Laid-Open Patent Publication No. 2006-0108409 can be described as a somewhat environmentally friendly method by photocatalyst, silver and copper coating on biostone, but it is porous in controlling algae. Even though photocatalysts, silver and copper are coated on the surface of biostones, the possibility of sunlight being exposed to the water by the depth of freshwater lakes or sea level or by the large amount of turbidity is rare, and the photocatalyst of titanium dioxide is generally very inactive. Therefore, there is a problem that the possibility of removing algae is very thin, and since the silver (Ag) or copper (Cu) which is bactericidal is coated on the carrier of the biostone, the contact surface with the algae generated in the water is extremely low, The time is so short that the killing effect of algae is actually very low.

The Korean Laid-Open Patent Publication No. 2005-0121091, which is biochemically manufactured, has the advantages of being environmentally friendly, pollution-free, and harmless to the environment even when used in large quantities. However, algae are generated in the composition of the improving agent and the water purification and soil improving agent. In the case of inputting into the water, the composition consists of all organic materials, so when a large amount is added to the water, a large chemical oxygen demand is required, and the manufacturing period is required for a long period of time, which has the disadvantage of very low economic efficiency.

The Korean Laid-Open Patent Publication No. 2003-0038276 discloses a semi-permanent function of the inorganic antimicrobial agent without the drop of silver salts on the surface of the biofilm so as not to be washed or rubbed, but as described above, it is coated on the coated object of the biofilm. Since the surface area is not large, the role of the inorganic antimicrobial agent due to silver (Ag) is substantially low, and it has a drawback that its use is very rare in huge waters such as freshwater lakes and sea levels where algae are generated.

As mentioned above, a number of methods for overcoming the problems of algae generation due to eutrophication have been proposed and used. However, although the algae treatment efficiency is insufficient, the water environment deteriorates further, and the economic burden increases, the conventional methods Efficient and environmentally friendly algae algae composition and a method for producing the same while overcoming the problems have been very poor to date.

However, the biggest cause of algal outbreaks is eutrification, and the causative agents that cause this are nutrients such as nitrogen (N), phosphorus (P), trace elements, and vitamins. The major contaminants that influence are known as nitrogen (N) and phosphorus (P). Therefore, in order to minimize eutrophication of algae control composition, a method of manufacturing such that nitrogen compounds and phosphorus (P) is not required is necessary. First of all, it is possible to minimize the amount of compound input into the environment by actively developing technology for the utilization of compounds that can selectively control only harmful birds, and by searching for compound combinations that have synergistic effects on harmful birds. New technologies must continue to be developed. Particularly, for this purpose, a technique for preventing the initial occurrence of algae from a preventive level rather than after algae occurrence using a safer compound is required.

It is an object of the present invention to provide a composition for controlling harmful algae, a composition for controlling harmful algae containing nanosilver as an active ingredient, and a method for controlling harmful algae using the same.

More specifically, an object of the present invention is to produce a nano-sized silver metal or silver oxide that does not contain nitrogen (N) or phosphorus (P), which is a problem in eutrophication, and synergistically with the nano-silver to be treated at a lower concentration The present invention provides a composition for controlling environmentally friendly harmful algae mixed with a control compound having the same and provides a method for controlling harmful algae to be used for suppressing or preventing generation of harmful algae using the same.

Accordingly, the present inventors provide a composition for controlling harmful algae comprising nano silver which does not contain nitric acid (NO ₃ ) as an active ingredient, and when the control compound is further included as an active ingredient in the control composition for harmful algae, harmful algae control The present invention was completed by confirming that not only a synergistic effect but also nano silver was treated at a lower concentration while controlling harmful algae selectively and effectively.

In accordance with the above object, in the present invention, a natural product or a biochemical agent is added to the harmful algae control composition or the harmful algae control composition comprising nano-sized silver metal or silver oxide as an active ingredient, thereby synergistically controlling harmful algae. Eggplant provides a composition for controlling harmful algae.

According to the other object, the present invention provides a method for controlling harmful algae comprising treating the harmful algae control composition in water or soil.

Hereinafter, the present invention will be described in more detail.

The present invention provides a composition for controlling harmful algae, comprising nanosilver as an active ingredient and not containing nitrogen and phosphorus.

The harmful algae composition for dissolving a silver salt in distilled water;

Supplying carbonate or carbon dioxide, filtration and washing to remove nitrogen and phosphorus from the dissolved silver salt; And

Adding an inorganic reducing agent or persulfate and hydroxide to the filtered and washed silver salt, and then forming the silver salt into nanometer size;

Refer to Figure 1 as being prepared, including.

The nano silver is a nano-sized silver metal or silver oxide, and the raw material of the silver metal or silver oxide is silver salt selected from silver acetate, silver nitrate, silver carbonate, and silver citrate. It is preferable to use silver acetate or silver carbonate as it is more than a species and in accordance with the technical idea of the present invention. However, silver salts except silver nitrate have disadvantages of low economical efficiency because they are very expensive. In order to overcome such economics, silver nitrate is supplied with carbonate and carbonic acid gas as in Scheme 1 to form insoluble silver carbonate, and then filtered and washed so that nitric acid is not included. acetic acid) can be added and dissolved, and in another method, an anionic by-product can be removed from the nanoalgae for controlling algae prepared by the present invention to remove nitrates.

At this time, in order to form insoluble silver carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate ( Ammonium bicarbonate), one or more kinds of carbonates or carbonic acid gas selected from CO ₂ gas may be used, and when ammonium carbonate or ammonium bicarbonate is used in the carbonates, the ammonium carbonate may be treated with a cation exchange resin to remove ammonium ions. It can be said of course.

The dissolving step of dissolving the silver salt provided in the feeding step is that silver salts dissolved in water react with anions such as chlorine salt, fluoride salt, sulfate salt and the like, and are insoluble or have very low solubility. As it forms a silver salt, it is advantageous to have as little impurities as possible in the water. Therefore, the water required for the dissolution step should be reverse osmosis (RO) or distilled water treated in a secondary distiller.

The nano-sized silver metal or silver oxide has a concentration of 0.01 to 15% by weight relative to the total weight of the total composition of silver salts corresponding to the mole of silver salts / mole of silver ratio. Weigh and dissolve. In this case, the silver salt corresponding to the nano-sized silver metal or silver oxide may be dissolved such that the concentration of the silver metal or silver oxide is 0.01 to 15 wt%, preferably 0.05 to 0.15 wt%, and most preferably 0.075 to 0.12 wt% It is advantageous to dissolve so that the content of nano silver is low. If the nano silver content is manufactured at a low concentration of less than 0.01% by weight, it requires not only the huge equipment necessary for the production of nano silver, but also a large logistics cost when transporting to the water where the algae is generated. When the nano silver content is prepared at a high concentration of more than 15 wt%, nanometer-sized silver particles included in the composition for controlling harmful algae are not dispersed in water but aggregated with each other, thereby forming Nano silver particles are likely to settle, making them less commercially viable and lowering the specific surface area It has a problem that could fall.

Reduction step for forming the dissolved silver salt (Silver salt) nano-sized silver metal (TEMED; TEMED; N, N, N ', N'-Tetramethyl-ethylenediamine), hydrazine hydrate (Hydrazine one or more reducing agents selected from hydrate, sodium borohydride, formaldehyde, acetaldehyde, citric acid, ascorbic acid, tannic acid In the case of organic reducing agents such as hydrazine hydrate, formaldehyde, acetaldehyde, etc. For this reason, it is advantageous not to use reducing agents composed of environmentally harmful substances, and other reducing agents are not particularly limited.

The reducing agent is added above the stoichiometric amount of the silver salt dissolved in the silver salt dissolving step, and if the concentration of the reducing agent is high, the reduction rate proceeds very fast and the particle size of silver (Ag) may increase. Since it may depart from the technical idea of the present application, it is preferable to dilute to 10 to 250 times based on the amount of the reducing agent and then slowly dropping.

In the next step, persulfate and hydroxide are added to form the dissolved silver salt into silver oxide (Ag ₄ O ₄ ), and 2 moles of persulfate and 8 moles of hydroxide are supplied to 4 moles of nitrate as shown in Scheme 2 below. Is made.

The persulfate for forming the silver salt into silver oxide (Ag ₄ O ₄ ) is at least one selected from sodium persulfate, potassium persulfate, and ammonium persulfate, preferably The use of sodium persulfate or potassium persulfate can eliminate the cause of eutrophication due to the production of by-products of ammonium salts.

In addition, the hydroxide is one or more selected from sodium hydroxide, potassium hydroxide, ammonia water, preferably using sodium hydroxide or potassium hydroxide can reduce the nutrients of the water caused by odor or by-products of ammonium salts caused by odor have.

Agitation is performed to form the nano-sized silver metal or silver oxide, and the stirring is not particularly limited, but particles of silver oxide (Ag ₄ O ₄ ) formed by the supply of silver metal or persulfate and hydroxide formed by supplying a reducing agent. It is not possible to grow, it is stirred at high speed to form nanometer-sized particles, it is advantageous to stir at room temperature in the case of nanometer-sized silver metal, at a temperature of 70 ℃ or more in the case of nanometer-sized silver oxide It is desirable to.

The stirring speed may vary depending on the concentration of silver salt dissolved in distilled water or the amount of distilled water relative to the container. The stirring speed is stirred at a speed of 500 to 100,000 rpm, preferably at a stirring speed of 750 to 75,000 rpm, more preferably at a stirring speed of 2,500 rpm to 50,000 rpm, and when the stirring speed is less than 500 rpm, In the process of mixing a reducing agent for forming a silver metal and a persulfate and a hydroxide for forming a silver oxide, a non-uniform phase is formed, and thus, there is a possibility that a nanometer-sized harmful algae for controlling algae proposed in the present invention is produced. In addition, it has the disadvantage that the algae of harmful algae is low because it can form particles of uneven silver metal and silver oxide, and for the control of uniform high concentration of harmful algae of nanometer size when the stirring speed exceeds 100,000 rpm Nano silver has the advantage that it can be manufactured, but the economical efficiency may be lowered because the stirrer is expensive In addition, since the stirring at a very high speed, not only safety measures are required, but also has a disadvantage in that a large amount of nano silver for controlling harmful algae cannot be manufactured.

The harmful algae control composition comprising nanosilver according to the present invention as an active ingredient can be used as the composition alone, but in order to enhance the efficacy of chrysophanol (chrysophanol), emodin (emodin), menadione sodium (menadione sodium) bisulphite, menadione salt (MSB)), menadione (menadione), hydrogen peroxide, acetic acid or a mixture of these compounds further comprises an active ingredient, the control compound (B) is the nano silver (A) 0.1 to 99.5%: 99.9 to 0.5% (A: B) by weight ratio is mixed, preferably 0.1 to 30%: 99.9 to 70% (A: B) by weight ratio to prepare a mixed control composition for synergy It is. In the case where the weight ratio is less than 0.1% or more than 99.9%, the synergy effect due to mixing may be insignificant, and therefore, mixing in the above range is preferable.

Among the control compounds, chrysopanol and emimodine may be substances synthesized or extracted from plants or concentrates thereof, more preferably Rumex , Rheum , Rhamnus , Rhamnus , knotgrass in (Polygonum), iron knee in (Achyranthes), aloe in (Aloe), Ardisia japonica in (Ardisia), Michaelmas daisy in (Aster), tea pulsok (Cassia), chrysanthemum in (chrysanthemum), stapes hawthorn (Eupatorium), tetradium daniellii selected from the genus (Evodia), waedang Bind (Ligusticum), Tung hawthorn (paulownia), coltsfoot in (Petasites), mint in (Mentha), geumbulcho in (Inula), daylily (Hemerocallis) and military camp made of a mixture thereof It can be prepared by extracting the whole plant, roots, seeds or dried products thereof of the plant to be a solvent.

In the prymouth , Rumex crispus , Rumex japonicus , Rumex aquaticus , Rumex longifolius , Rumex conglomeratus , Rumex maritimus Rumex obtusifolius , Rumex gmelini , Rumex acetosa , Rumex acetosella are preferred to use the roots. Rheum undulatum , Rheum coreanum , Rheum palmatum , Rheum emodi , Rheum officinale , Rheum hotaoense , Rheum hotaoense , Rheum hotaoense Rheum nanum , Rheum glabricaule , Rheum ribes , Rheum spiciforme , Rheum tanguticum , or Rheum wittrochii It is preferable to use roots.

As a biochemical that can be mixed with nanosilver among the control compounds, menadione salt (menadione sodium bisulphite, menadione salt (MSB)), menadione (menadione), hydrogen peroxide, acetic acid or peracetic acid can be purchased and mixed on the market. . Especially in the case of acetic acid, glacial acetic acid, fruit vinegar, edible vinegar is also possible, and more preferably use glacial acetic acid.

The composition for controlling harmful algae comprising nano-sized silver metal or silver oxide as an active ingredient according to the present invention has a selective control effect on harmful algae.

The harmful alga from the group consisting of algae of the genus Microcystis , Anabaena , Oscillatoria , Oscillatoria , Aphanizomenon , Nodularia and Cochlodinium In particular, it has a very high control effect against cyanobacteria such as Microcystis spp., Anabaena spp. And the like, and is not harmful Chlorella spp., Senedmus. Green algae such as Senedesmus spp. Have relatively low control effects. The selective control effect of the compounds on algae varies slightly from compound to compound.

The mixed composition for controlling harmful algae of the present invention is a pharmaceutically acceptable solid carrier and liquid carrier for stable expression of the effect, enhancement of adhesion to the organism to be applied, and simplicity of transportation and treatment within the range of not inhibiting the effect of the mixture. , Surfactants such as liquid diluents, liquefied gas diluents, solid diluents, or other suitable auxiliaries such as emulsifiers, dispersants or foaming agents.

The control composition of the present invention may preferably be formulated in emulsion, hydrated, granulated, powdered, capsule and gelled formulations, and is preferably provided as a contact through a formulation such as a donut for buoyancy of the formulation. .

The present invention provides a harmful algae control method for controlling harmful algae by treating the composition for harmful algae according to the present invention in water or soil in which harmful algae as illustrated above. At this time, it is preferable to block the mass growth in advance by treating the composition in the early stage of the generation of harmful algae.

The harmful algae control method according to the present invention may have a low harmful algae control effect when the concentration of the active ingredient in the water or soil where the harmful algae is generated is too low, and when the concentration of the active ingredient is too high, Since it may adversely affect the ecosystem, it is preferable to treat the composition for controlling harmful algae to a concentration of 0.01 µg / ml to 100 µg / ml in the water or soil where algae is generated based on the active ingredient, which is a kind of harmful algae. It can be appropriately adjusted in consideration of the density of development, the degree of growth, and the water environment.

The composition for controlling harmful algae comprising nanosilver as an active ingredient according to the present invention has better effect lasting than when treated with silver ions or silver salts itself, and thus contributes to environmental and shrinkage safety because nano silver is used without nitrate.

In addition, the composition for controlling harmful algae of the present invention can be treated with nano-silver and synergistic control compounds (natural or biochemicals) as an active ingredient, which can be used as well as a smaller amount of nano silver. It is expected to reduce the side effects on the environment because less compound that can be decomposed more easily, and economic efficiency can be improved because the selective algae activity against harmful algae is enhanced, which is both friendly and eco-friendly and effective. It can be usefully used as a good pest control agent.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1 Preparation of 100 ppm Nano-Sized Silver Metal Solution

5 g of silver nitrate (Tunsei Co .; AgNO ₃ ) was weighed into a 500 ml beaker washed with clean water, and 250 ml of distilled water was supplied, followed by dissolution while stirring. Separately, 10 g of sodium carbonate (Dongyang Steel Chemical Co .; Na ₂ CO ₃ ) was weighed in a 200 ml beaker and completely dissolved. While stirring the solution containing silver nitrate at a speed of 500rpm, slowly dropping the dissolved sodium carbonate solution to form silver carbonate, which was washed five times with a reduced pressure filter, and then dried in a dry oven at 100 ° C. Drying completely gave nitrate-free silver carbonate. 0.1278 g of the prepared silver carbonate was weighed into a clean, one-liter beaker, 700 ml of distilled water was supplied, and acetic acid was supplied with slow stirring to completely dissolve the silver carbonate, so that the pH in the water was maintained at 4.5.

Here, a stoichiometric amount of sodium carbonate (Merck, Sodium borohydride) reducing agent was dissolved in distilled water, and then slowly added dropwise to a solution containing silver carbonate while rotating at a stirring speed of 50,000 rpm to obtain brown nanosilver. A solution was prepared, and the solution was transferred to a total volume of 1 liter of volumetric flask and then shaken up and down to prepare a 100 ppm silver metal solution (nanosilver solution) for controlling green algae.

Example 2 Preparation of 500 ppm Nanoscale Silver Metal Solution

Sodium hydrogen carbonate (NaHCO ₃ ) was used in place of sodium carbonate in Example 1, except that 0.6391g of the prepared silver carbonate was measured in the same manner as in Example 1.

Example 3 Preparation of 1,000 ppm (0.1 wt%) Nanoscale Silver Metal Solution

Potassium carbonate (K ₂ CO ₃ ) was used in place of sodium carbonate in Example 1, and the same procedure as in Example 1 was performed except that 1.2782 g of the prepared silver carbonate was measured.

Example 4 Preparation of 5,000 ppm (0.5 wt%) Nanoscale Silver Metal Solution

Potassium hydrogen carbonate (KHCO 3) was used instead of sodium carbonate in Example 1, and the same procedure as in Example 1 was performed except that 6.3910 g of the prepared silver carbonate was measured.

Example 5 Preparation of nanometer sized silver oxide solution of 1,000 ppm as Ag (reaction at 70 ° C)

700 ml of distilled water was supplied to a clean beaker of 1,000 ml, and the temperature was maintained at 70 ° C. by a hot palte while stirring at a speed of 850 rpm with a mechanical stirrer. acetate) was accurately weighed and dissolved. Separately, 1 mol of sodium persulfate and 1 mol of sodium persulfate were dissolved in 100 ml of distilled water, respectively, and then supplied to an aqueous solution of 70 ° C. in which silver acetate was dissolved. A silver oxide solution (nanosilver solution) for controlling Ag ₄ O ₄ (black gray) green algae was prepared.

Example 6 Preparation of a Nanometer Silver Oxide Solution of 1,000 ppm as Ag (reaction at 85 ° C)

The reaction was carried out in the same manner as in Example 5 except that the reaction temperature was performed at 85 ° C.

Example 7 Preparation of nanometer sized silver oxide solution of 1,000 ppm as Ag (reaction at 100 ° C)

The reaction was carried out in the same manner as in Example 5 except that the reaction temperature was performed at 100 ° C.

[Comparative Example 1] Preparation of 100 ppm nanosized silver metal solution by silver nitrate as starting material (silver salt)

0.1575 g of silver nitrate (Tunsei Co., AgNO ₃ ) was weighed into a 1-liter beaker that was washed thoroughly, and 700 ml of distilled water was supplied, followed by dissolution while stirring. Separately, a stoichiometric amount of sodium nitrate (Merck, Sodium borohydride) reducing agent was dissolved in distilled water, and then slowly added dropwise to a solution containing silver nitrate while rotating at a stirring speed of 50,000 rpm to prepare a brown nanosilver solution. Then, this was transferred to a volume of 1 liter of volumetric flask (Volumetric flask) and shaken up and down to prepare a 100ppin nanosilver solution.

[Comparative Example 2] Preparation of 500 ppm nano-sized silver metal solution using silver nitrate as starting material

The same procedure as in Comparative Example 1 was conducted except that 0.7874 g of silver nitrate was measured.

Comparative Example 3 Preparation of 1,000 ppm Nano-Sized Silver Metal Solution by Silver Nitrate

The same procedure as in Comparative Example 1 was conducted except that 1.5748 g of silver nitrate was measured.

[Comparative Example 4] Preparation of 5,000 ppm nanoscale silver metal solution using silver nitrate as starting material

Silver nitrate was carried out in the same manner as in Comparative Example 1 except that 7.8740 g of silver nitrate was measured.

[Comparative Example 5] Preparation of nanometer-sized silver oxide solution of 1,000 ppm as Ag using silver nitrate as a starting material (reaction at 70 ° C)

The same procedure as in Example 5 was carried out except that 1.5748 g of silver nitrate was dissolved as a starting material.

Comparative Example 6 Preparation of nanometer-sized silver oxide solution of 1,000 ppm as Ag using silver nitrate as a starting material (reaction at 85 ° C)

The same procedure as in Example 6 was carried out except that 1.5748 g of silver nitrate was dissolved as a starting material.

Comparative Example 7 Preparation of nanometer-sized silver oxide solution of 1,000 ppm as Ag using silver nitrate as a starting material (reaction at 100 ° C)

The same procedure as in Example 7 was carried out except that 1.5748 g of silver nitrate was dissolved as a starting material.

Nano silver solutions of the silver metal and silver oxide prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were confirmed the content of nitric acid (NO ₃ ) by Metrohm's Ion Liquid Chromatograph, the particles of nano silver prepared for controlling harmful algae The size was observed by transmission electron microscope (Tecnai G2, FEI). The silver silver and silver oxide of the nanosilver solutions prepared by Examples 1 to 7 and Comparative Examples 1 to 7 were completely dissolved by acid treatment with nitric acid, and then Jobin-Yvon Ultima-C Inductively Coupled Plasma- The content of silver (Ag) was confirmed by an Atomic Emission Spectrometer (ICP-AES), and the analysis results are shown in Table 1 and FIG. 2.

As shown in Table 1, it was confirmed that the preparation of the nanoalgae solution for controlling harmful algae of the present invention could include silver (Ag) of a required concentration relatively accurately, and finally using silver nitrate as a starting material. Nano-sized silver metal or silver oxide solution composition with little nitric acid could be prepared and confirmed in FIG. 2. On the other hand, the nano silver particle size of the prepared silver metal or silver oxide belongs to the size range of 5 to 50 nm as can be seen in FIG.

Example 7 Room Algae Activity Experiment of Nano-Sized NanoSilver Solution

Copper sulphate is a representative inorganic killing agent that has been used for a long time. However, as the accumulation of copper into the environment and constriction has been a problem recently, its use has been limited, and therefore, the search for an alternative algae is required. This study was carried out to find out how much the silver metal nano silver prepared in Example 3 in the algae activity compared to copper sulfate.

First, we compared the activity of the representative harmful cyanobacteria microsis in Korea. The cyanobacteria species used were in the form of single cells distributed by the Korea Research Institute of Bioscience and Biotechnology and were microcistis aeruginosa UTEX 2388. The algae under passage were inoculated in the culture medium (Allen medium) so that the algae concentration was about 0.06 at 670 nm. 10 ml of the culture solution was dispensed into 100 ml culture bottles, and the nano-sized silver metal solution prepared in Example 3 and the solution prepared with copper sulfate (CuSO ₄ 5H ₂ O) were administered to the strain culture solution to make various concentrations. , 25 ° C., 14 hours photoperiod, incubated under conditions of luminous intensity 40-60 μmol −2 s −1 and 100 rpm. The absorbance of the culture solution was measured on the 6th day of culture, and the growth level was investigated through the previously set absorbance-building correlation (Kim et al., Aquatic Botany 85: 1-6, 2006) (Equation 1). The control effect on freshwater algae was expressed as percent inhibition of dry matter in the control group.

As can be seen in Table 2 below, the copper sulfate treatment showed 98.6% inhibition at 0.25 ug / mL, but the nano silver treatment showed a similar effect in the 0.06 ug / mL treatment, and the nanosilver showed about four times stronger activity than the copper sulfate.

On the other hand, using the cyanobacteria growing in the field was compared the difference in efficacy between the nano-sized silver metal solution prepared in Example 3 and copper sulfate. To this end, microcistis nige colonies collected from small ponds were used as test birds. In other words, the suspended cyanobacteria were collected and diluted in an allen medium, which was then dispensed in 200 mL each into a 1 L water bottle. At this time, the algae concentration was 83.3 ± 2.2 ug / L based on the chlorophyll content.

Those placed after nanoeun and copper sulfate solution, while the rating process to handle (CuSO ₄ .5H ₂ O) created a journey concentration to 27 ℃ growth chamber. After 7 days and 14 days, a certain amount of algal culture was taken, filtered through a GF / F filter, ethanol was added to extract chlorophyll, and then absorbance was measured at 750 nm, 664.6 nm, and 648.5 nm by spectral spectrophotometry. 1984. A manual of chemical and biological methods for Seawater analysis. 1st ed.Pergamon Press Ltd., Oxford. In the present experiment, because the algae and the high salt culture medium were used, the algae predominantly prevailed, but the new green algae and brown algae tended to be more prominent in the late stage of culture (around 10 days). The results of the experiment under these conditions are shown in Table 3 below. On the 7th day after the treatment, the nano silver and copper sulfate 0.1ug / mL treatment showed 80% growth inhibition effect, respectively, and no significant difference in activity was observed. However, on day 14, the difference between treatments was remarkable, showing a 17.7% growth inhibition effect in 1.0 ug / mL of copper sulfate, while maintaining a high killing capacity of 99.5% in nanosilver. From these results, it was confirmed that the nano silver had a better killing effect than copper sulfate, and thus it was possible to process low concentrations, and the effect was more pronounced when using the field algae.

On the other hand, in order to find out how much the killing effect lasts when nanosilver is treated, it showed continuous effect over 20 days regardless of the presence of sediment when experimenting with microcystis single cell and colony. In addition, it had an effect of suppressing harmful algae reproduction until about 20 days after treatment. This indicates that the efficacy is maintained for a considerably long time when compared with an average of about 10 days of treatment with ultrasonication, copper sulfate, and other organic / inorganic compounds. According to Gibbins & Warner (Medical Device & Diagnostic Industry Magazine, August, 2005), nanosilver particles produced in biofilms in medical devices have long been antibacterial for as long as 100 to 200 days, while silver ions are only effective for a few days. It was shown.

Example 8 Comparison of Efficacy Between Nanosized Silver Metal (NS-01) and Silver Oxide (SO-01) Solution on Growth Inhibition Activity of Freshwater Algae

To investigate and compare fresh algae growth inhibitory ability between silver oxide (SO-01) solution prepared in silver oxide form and silver metal (NS-01) solution prepared in silver metal form during nanosilver synthesis Experiment.

The silver metal (NS-01) solution and silver oxide (SO-01) solution used in the test were prepared in Example 3 and Example 7, respectively. 500 mL of algae growth solution (4 times dilution of Allen medium) is placed in a 1 L beaker and Chlorella vulgaris , a green algae, and Microcystis aeruginosa , a cyanobacteria, are grown indoors. Small amount (about 1 million cells / mL) was added. Thereafter, the silver metal (NS-01) solution and the silver oxide (SO-01) solution were treated at various concentrations, and then grown in greenhouse conditions (minimum 15 ° C./maximum 30 ° C.) for 8 days. The growth inhibition of algae was investigated through the lunar survey based on the degree of green expression.

As a result, as can be seen in Table 4, the silver oxide (SO-01) solution in the form of silver oxide showed overall good activity, and in particular, the growth inhibition activity against chlorella was better. However, the silver oxide (SO-01) solution should be prepared at a high temperature, and depending on the conditions, the silver concentration may be lowered according to the silver mirror reaction. Therefore, it was determined that the silver metal (NS-01) solution prepared at room temperature would be more practical.

Example 9 Growth Inhibition Activity of Five Freshwater Algae of Nano-sized Silver Metal Solution (NS-01)

Two experiments, indoor and field tests, were conducted to determine whether nano-sized silver metal solution had selective growth inhibitory activity against freshwater algae species.

(Indoor experiment)

Several freshwater algae species growing indoors were investigated for the difference of inhibitory activity of silver metal (NS-01) solution as follows.

Freshwater algae in this test were three harmful algae ( Microcystis aeruginosa , UTEX 2388) and Microcystis aeruginosa (NIES107). And Anabaena affinis and two beneficial green algae ( Chlorella vulgaris and Scenedesmus spp.). Each of the algae in the subculture was inoculated in a culture medium (Allen medium), so that the algae concentration was about 0.08 at 670 nm. 10 ml of the culture solution was dispensed into 50 ml culture bottles, and 10 µl of the test solution and the control solution were respectively administered to the strain culture medium, followed by a 25 ° C., 14 hour photoperiod, luminous intensity of 40 to 60 μmol-2s-1 and 100 rpm. Cultured under conditions. For 5 days for green algae and 6 days for cyanobacteria, the absorbance of the algae was determined by measuring the absorbance of the culture solution after the incubation was completed. The correlation between the absorbance and the building (Kim et al., Aquatic Botany 85: 1-6, 2006) (Equations 1 to 4), and then calculated as the percent inhibition of dry matter in the control group (Equation 1-microsistis aeruginosa, Equation 2- Chlorella Vulgaris, Equation 3-Senedesmus, Equation 4-Anabena Apinis).

As can be seen from the results shown in Fig. 4, the blue alga was more sensitive than the green alga, and the selectivity was about 4 to 5 times. Among the algae, Ma (NIES107) showed the most sensitive reaction, followed by Microcystis aeruginosa (UTEX 2388), and Anabaena affinis. Chlorella vulgaris showed more sensitive reactions than Scenedesmus spp. In this test condition, 0.06 to 0.25 ppm was required to suppress southern algae, and 0.5 to 1 ppm treatment was required to control algae. The selectivity width was on the order of 4-5 times.

[Example 10] Growth inhibition effect according to the microalgal concentration at the time of nano silver treatment

Removing the algae in a large amount of money would require a lot of money and effort, and processing the compound would be expensive. Therefore, in order to solve the problem of green algae, it is necessary to suppress the initial occurrence, which will have a difference in effect depending on the nature of the material used. In this experiment, the experiment was conducted to determine the control effect of nano silver at low algae concentration.

Using algae Chlorella vulgaris were used (Chlorella vulgaris) as rugi Labor (Microcystis aeruginosa, UTEX 2388) and the micro-algae as cyanobacteria during seutiseu Oh received pre-sale at the Korea Research Institute of Bioscience and Biotechnology. Diluting the algae cultured in the allen medium to prepare a low to high concentration of single-cell algal culture medium, and then directly administering the nano-sized silver metal solution prepared in Example 3 to 10mL medium contained in a 100mL glass bottle In the case of 0.006ug / mL, 0.1ug / mL for green algae was treated for 6 days in the growth room conditions (25 ℃ constant temperature, photoperiod 14 hours, luminous intensity 40 to 50μmolm-2s-1). All treatments were performed in three replicates. After 6 days of culture the effect of the drug was assayed as in Example 9 above.

Overall, the lower the algal initial concentration, the lower the concentration of nanosilver needed for control. In other words, when the monocytic microcystis aeruginosa (UTEX 2388) is present at a level of 150,000 / mL or less, the experiments in this condition showed that the nanoparticles could be 100% inhibited even at 6 ppb concentration. On the other hand, as can be seen in Figure 5 Chlorella vulgaris ( Clorella vulgaris ) also showed a similar tendency to cyanobacteria, at the level of 850,000 cells / mL, 100% nano-controlled at 1ppm concentration, but a single cell Chlorella vulgaris algae When the concentration was about 110,000 / mL, the nano silver was 100% inhibited even at 0.1 ppm treatment. This is considered to be the result showing that the treatment of the compound at the early stage of algae generation can block algae generation at a lower concentration, and the impact on the aquatic environment is very weak due to the low concentration of algae.

So far, the experiments have been conducted in single cell algae cultured in the room and low nutrient solution conditions. In order to find out whether this tendency is the same in the experiments near the field, the following experiment was conducted.

Microcystis nigea colonies collected from a small pond of the Korea Research Institute of Chemical Technology were diluted in allenzymes at different concentrations and dispensed 20mL each in 100mL PET bottles. At this time, the algal concentration was 7.7 to 512.5 ug / L based on the chlorophyll content.

Then, the nano-sized silver metal solution prepared in Example 3 was treated to a final concentration of 0.1 ug / mL. This was incubated for 8 days in a 27 ℃ growth chamber (14 hours photoperiod, light intensity 40-50μmolm-2s-1,). Take a certain amount of algae culture solution of each algae concentration and nano silver treatment group, filter it through GF / F filter, extract chlorophyll by adding ethanol, measure absorbance at 750nm, 664.6nm, 648.5nm, and quantitate chlorophyll. (Parsons et al. 1984. A manual of chemical and biological methods for Seawater analysis. 1st ed. Pergamon Press Ltd., Oxford). On the 8th day after the treatment, green algae and brown flagella algae began to develop along with the algae, and the growth inhibition of the whole was as shown in Table 5 below when the chlorophyll content was analyzed. In other words, the nano silver showed 51.2%, 96.8%, and 99.0% inhibitory effects when the chlorophyll a content was 512.5, 138.5, and 40.5ug / L at the time of 0.1ug / mL treatment, respectively. . Based on the above results, it was concluded that nano silver should be treated at a time when the initial concentration of algae is 221 ug / L or less in order to obtain a 90% algae effect with 0.1 ug / mL treatment.

Therefore, the above results indicate that the treatment of nano silver in the field can be enhanced when it occurs less than when algae are generated. In addition, it can be advantageous in terms of economic efficiency and environmental friendliness because it can be treated in low concentration when treated early. Shows.

Example 11 Investigation of Mixing Effect for Improving Algal Activity of Nano Silver

Nano silver has a very good killing effect, but the raw material price is high. And because of its broad activity against many organisms, it can kill all the beneficial organisms of the aquatic ecosystem at high concentrations. Therefore, as low concentration as possible is required. For this, a method of searching for and using a compound having a synergy with nano silver should be devised. Since the synergistic effect of a drug depends on many factors, it cannot be easily predicted and may vary depending on the organism and compound type. Studies conducted for this purpose have been conducted to search for and report synergistic compounds with silver ions / silver salts in antimicrobial experiments (de Souza A. et al. 2006. Current Sci. 91: 926-929; Pedahzur et al. 1995. Water Science and Technology 31: 123-129; Orta De Velasquez et al. 2008, Environ. Tech. 29: 1209-1217. Representative studies show that antibiotic Ceftizidime synergizes with silver against growth inhibition of multidrug resistant E. coli and Pseudimonas aeruginosa . Kanamycin is synergistic with silver against multidrug resistant E. coli growth. Amikacin also synergizes with silver against MRSA (Methicillin-resistant Staphylococcus aureus) (de Souza A. et al. 2006. Current Sci. 91: 926-929).

Experiment 1: Experiment with Cyanobacteria in Indoor Culture

Nano silver solution was used nano-sized silver metal solution prepared in Sykes Example 3, and other test compounds were purchased from Sigma-Aldrich reagent company. Water-soluble compounds (menadione salt (MSB), H ₂ O ₂ , Acetic acid) were dissolved in water, but chrysophanol and emodin were dissolved in acetone mixed with surfactant Tween 20. Final concentrations were 0.5% acetone, 0.5 ppm tween 20.

Specifically, the nanosilver solution has a final concentration of 0.0-0.05 µg / ml, chrysophanol and emodine in the final concentration range of 0.0-0.5 µg / ml, and the menadione salt (MSB) has a final concentration of 0.0-0.25 µg / ml. After the preparation of a mixture of various concentrations by adding each compound to the nanosilver material in the ㎖ range, it was confirmed the growth inhibitory activity against microcystis aeruginosa UTEX 2388 as a harmful algae. In other words, the culture medium (Allen medium) was inoculated with microcistis aeruginosa subcultured at this time, the initial concentration of the algae was absorbed at a concentration of about 0.06 at 670 nm using a microplate reader It was made. This was dispensed with 10 ml in a 50 ml culture bottle, and the test agent was administered and then cultured under 25 ° C., 14 hour photoperiod, and light intensity of 40 to 60 μmolm-2s-1. 6 days after treatment of the test solution, the absorbance was measured and the degree of growth of each algae was investigated through the absorbance-building correlation equation (Equation 1), which was set in advance, and the algae control effect of the control composition was compared to that of the control group. It was calculated as the degree of inhibition (%).

The interaction between the two mixtures was evaluated by Colby S.R .. Weeds 15: 20-22, 1967. If the actual control value (observed value) shown by the mixing agent treatment is greater than the expected value (expected value calculated by Equation 5, expected value), it shows synergy, if it is equal, it is antagonistic action. will be.

As a result, when the two components of nanosilver and chrysopanol were mixed, there was also a concentration where additive functionality was observed, as shown in the results of FIG. 6, but the synergy was good depending on the combination of concentrations (eg, nano silver 0.0125 µg / ml + chrysophanol). 0.25 μg / ml). In addition, when the two components of nanosilver and emodine were mixed, as shown in the result of FIG. 7, the synergy (eg, nanosilver 0.0125 µg / ml + Emodine 0.25 to 0.5 µg / ml) showed not only a good synergy. Mixing of the two components of dione salt (MSB) shows good synergy at most concentration combinations (eg, nano silver 0.0125 μg / ml + menadione salt (MSB) 0.06 to 0.25 μg / ml, nano silver 0.025 μg / ml) + Menadione salt (MSB) 0.06 μg / ml). This tendency was similarly confirmed in mixing with menadione, an active ingredient of menadione salt (MSB).

Experiment 2: Nano silver + hydrogen peroxide mixture experiment using field algae

On the other hand, the effects of the mixed treatment with hydrogen peroxide were tested using the cyanobacteria colonies growing in the field. For this purpose, microcistis nige colony predominant material collected from small pond of Korea Research Institute of Chemical Technology was used as the algae to be tested. That is, the suspended algae predominant algae were collected and diluted in the allen medium (at which the algae concentration was 216.9 ± 11.6 ug / L based on the chlorophyll a content) and 50 mL were dispensed in 200mL PET bottles. Afterwards, the nanosilver solution was prepared in a concentration range of 0.0 to 0.4 ug / ml, and hydrogen peroxide in a range of 0 to 40 ug / ml. The culture solution thus treated was grown in a 27 ° C. constant temperature growth room (14 hours of light cycle, conditions of 40-50 μmolm-2s-1 light intensity). At 7 and 14 days of culture, a certain amount of algal culture was taken, filtered through a GF / F filter, chlorophyll was extracted by adding ethanol, and then absorbance was measured at 750 nm, 664.6 nm, and 648.5 nm by spectrophotometer. 1984. A manual of chemical and biological methods for Seawater analysis. 1st ed.Pergamon Press Ltd., Oxford. The killing ability of each treatment was expressed as% inhibition relative to the chlorophyll content of the control, and the interaction between the two mixtures was evaluated by Colby method as described above. As can be seen in FIG. 9, in all cases irradiated at 7 and 14 days of culture, nanosilver and hydrogen peroxide have a very strong synergistic effect on microalgae growth inhibitory activity in the field conditions in which various algae including algae are mixed. Confirmed. A report on the synergy associated with microbial killing between silver ions and hydrogen peroxide has been reported in fecal coliforms (Pedahzur et al. 1995. Water Science and Technology 31: 123-129) and various pathogenic microorganisms ( Vibrio cholerae , Salmonella spp., Shigella spp., Pseudomonas aeruginosa has been reported (Orta De Velasquez et al. 2008, Environ. Tech. 29: 1209-1217). Synergy in freshwater algae including harmful algae has not been reported yet. This report is the first time that research has the same effect.

Experiment 3: Nano silver + acetic acid or peracetic acid mixture experiment using field algae

Acetic acid is an acidic substance, which has been used for a long time because of its weak toxic toxicity, odor removal, and antibacterial effect. However, in the present invention, the experiment was conducted to investigate what kind of interaction of acetic acid or peracetic acid material was mixed with nano silver. In the case of this experiment, the material of the algae colonies growing in the field, that is, the microcistis nige colonies collected from the small pond of Korea Research Institute of Chemical Technology, was used as the test algae. The collected test algae were diluted in allen medium (the algal concentration at this time was 164.5 ug / L based on the chlorophyll a content) and 20 mL were dispensed in 100 mL vials. The nanosilver solution is then in the concentration range of 0.0 to 0.4 ug / ml, acetic acid (Sigma-Aldrich, 99% purity) or peracetic acid (manufactured in our laboratory, purity 5%) in the concentration range of 0 to 100 ug / ml, respectively. Several concentration combinations were made either alone or in combination. The culture solution thus treated was grown in a 27 ° C. constant temperature growth room (14 hours of light cycle, conditions of 40-50 μmolm-2s-1 light intensity). At 6 or 12 days of culture, a certain amount of algal culture was taken, filtered through a GF / F filter, chlorophyll was extracted by adding ethanol, and then absorbance was measured at 750 nm, 664.6 nm, and 648.5 nm by spectrophotometer, and then chlorophyll was quantified (Parsons et. 1984. A manual of chemical and biological methods for Seawater analysis. 1st ed.Pergamon Press Ltd., Oxford. The killing ability of each treatment was expressed as% inhibition relative to the chlorophyll content of the control, and the interaction between the two mixtures was evaluated by Colby method as described above.

As a result, acetic acid had the effect of rapidly settling the cells of floating cyanobacteria. This means that it may have a secondary effect of weakening the photosynthetic performance of harmful cyanobacteria to induce growth inhibition. Acetic acid, on the other hand, increases the acidity of the solution, and therefore appears to play a role in detrimental growth of harmful algae that grow well in relatively high alkalinity. On the sixth day after the treatment between the nano silver and acetic acid, good synergy was observed in the concentration range of 0.1 ppm + 50 ppm acetic acid. On the other hand, in the case of the mixed treatment between nano silver and peracetic acid, as shown in the results of FIG. 10, an additive action appeared on the 8th day after the treatment, but a strong synergy was observed on the 12th day after the treatment.

Silver ions and peracetic acid had a synergistic effect on the inactivation of pathogenic microorganisms, and mixed treatments were reported to be the most effective in removing parasite eggs (Orta De Velasquez et al. 2008, Environ. Tech. 29: 1209-1217). Synergy in freshwater algae killing, including algae, has not been reported yet, and this report is the first time that nanosilver has the same effect.

Example 12 Algal Activity Characteristics of Nanosilver + Menadione Salt (MSB) Mixture Treatment at Field Conditions

As shown in Example 11, the nano silver + menadione salt (MSB) has a synergistic effect on the harmful algae killing ability and both compounds have higher selectivity to inhibit the growth of algae than green algae. Therefore, field experiments were conducted to confirm whether these characteristics are well reflected in actual field conditions.

The experiment set up a 4.5 tonne capacity mesocosm upstream of the lake and filled 3.375 tons of field water within the mesocism. Thereafter, the nanoscale silver metal solution prepared in Example 3 and the mixed concentration so that the final concentration of the menadione salt (MSB) to 0.5, 10ug / mL level respectively. On the 20th day after the treatment, samples were taken from each test fixture and fixed. Then, the number of generated and remaining algae was determined by microscopy and the ratio of the relative distribution to the untreated was plotted. That is, the surface water of the field was collected by Van Dorn water collector, fixed with Lugol iodine solution, settled in the laboratory for 72 hours or more, and concentrated 2 to 5 times according to the algae concentration of the sample. The concentrated sample was mixed well, 1 ml of the sample was transferred to a Sedgwick-Rafter Counting Chamber, and then precipitated for 10 minutes or longer, and the number of colonies or cells was counted under an optical microscope.

Algae predominantly occupied with southern algae (83.1 to 90.5%) before algae treatment, and a little green algae (5.0 to 8.2) and euglena (3.0 to 6.1%) appeared. The most predominant species was investigated as Microcystis aeruginosa . When the nanosilver and menadione salt (MSB) are mixed, the present mixture composition is compared to the green alga Scenedesmus ecornis and the diatom Cyclotella spp. ( Microcystis aeruginosa ) and Phormidium sp. Were selectively inhibited higher. The growth of green algae seemed to increase due to drug treatment, but showed a high inhibitory effect of over 98% for algae.

1 is a schematic diagram of a process for preparing a nanosilver solution having little nitric acid and a composition for controlling harmful algae containing the same.

2 is a transmission electron micrograph of the nano-sized silver metal solution prepared in Example 3 of the present invention.

(A: before dispersant treatment, B: after dispersant treatment)

3 is a transmission electron micrograph of the nano-size silver oxide solution prepared in Example 7 of the present invention

Figure 4 is a diagram showing the growth inhibitory activity for five freshwater algae (three algae, two green algae) of the nano-size silver metal solution (NS-01).

Figure 5 is a diagram showing the difference in growth inhibition effect according to the concentration of unicellular microalgae at the time of nanosilver treatment according to the present invention.

Figure 6 is a diagram showing the synergistic effect of the growth inhibition activity of the microcistis of the nanosilver solution and chrysophanol mixing treatment according to the present invention.

Figure 7 is a diagram showing the synergistic action of the growth inhibitory activity of the microcistis of the nanosilver solution and emodine mixed treatment according to the present invention.

8 is a diagram showing the synergistic effect of the growth inhibition activity of the microcistis in the nano silver solution and menadione salt (MSB) mixed treatment according to the present invention on the growth inhibitory activity of cyanobacteria microsis.

9 is a diagram showing the synergistic action of the growth inhibitory activity of the microsis of the nanosilver solution and hydrogen peroxide mixed treatment according to the present invention.

10 is a diagram showing the synergistic action of the growth inhibitory activity of the microcistis of the nano silver solution and peracetic acid mixed treatment according to the present invention.

Claims (12)

Dissolving silver salt in distilled water; Supplying carbonate or carbon dioxide, filtration and washing to remove nitrogen and phosphorus in the dissolved silver salt; And Adding an inorganic reducing agent or persulfate and hydroxide to the filtered and washed silver salt, and then forming the silver salt into nanometer size; Harmful algae control composition comprising a nano-silver prepared as an active ingredient. delete The method of claim 1, The nano silver is a composition for controlling harmful algae, characterized in that the nano-sized silver metal or silver oxide. The method of claim 3, The nano silver is a harmful algae control composition, characterized in that 0.01 to 15% by weight based on the total weight of the composition. delete The method of claim 1, The silver salt is at least one selected from silver acetate, silver nitrate, silver carbonate, silver citrate, and the persulfate is sodium persulfate and potassium persulfate ( Potassium persulfate), at least one selected from ammonium persulfate, and the hydroxide is a composition for controlling harmful algae, characterized in that at least one selected from sodium hydroxide, potassium hydroxide, ammonia water. The method of claim 1, The harmful algae control composition is chrysophanol (chrysophanol), emodin (emodin), menadione salt (menadione sodium bisulphite, menadione salt (MSB)), menadione (menadione), hydrogen peroxide, acetic acid, peracetic acid or these Further comprising a control compound selected from a mixture of as an active ingredient, the control compound (B) is characterized in that the weight ratio of 0.1 to 99.5%: 99.9 to 0.5% (A: B) relative to the nanosilver (A) Algae control composition. The method of claim 7, wherein The chrysophanol (chrysophanol) and emodin (emodin) is a composition for controlling harmful algae, characterized in that the substance or concentrate separated from the plant extract. The method of claim 8, The plant extract is curly dock in (Rumex), rhubarb in (Rheum), buckthorn (Rhamnus), knotgrass in (Polygonum), hinge knee in (Achyranthes), Aloe genus (Aloe), Ardisia japonica in (Ardisia), Michaelmas daisy in (Aster), car pulsok (Cassia), chrysanthemum genus (chrysanthemum), spine hawthorn (Eupatorium), tetradium daniellii in (Evodia), waedang Bind (Ligusticum), paulownia hawthorn (paulownia), butterbur in (Petasites), mint in (Mentha ), Inula , Hemerocallis , and mixtures of plants selected from the group consisting of the whole plant, roots, seeds or their dried products for the control of harmful algae, characterized in that prepared by the extraction Composition. The method of claim 1, The harmful alga is from a group consisting of algae of the genus Microcystis , Anabaena , Oscillatoria , Oscillatoria , Aphanizomenon , Nodularia and Cochlodinium . A composition for controlling harmful algae, characterized in that selected. The harmful algae control composition of any one of claims 1, 3 to 4, 6 to 10 is selected from Microcystis , Anabaena , Oscillatoria , Aphanizomenon ( Aphanizomenon ) , Nodularia ( Nodularia ) or Cochlodinium ( Cochlodinium ) A method for controlling harmful algae, including the treatment in the water or soil inhabit the algae. The method of claim 11, The harmful algae control composition for controlling harmful algae, characterized in that the treatment to control to 0.01㎛ / ㎖ to 100㎍ / ㎖ in water or soil on the basis of the active ingredient.

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