KR101941575B1 - Method for removal of algal bloom using copper nano - Google Patents

Abstract

The present invention relates to a method for removing green algae using copper nano. The method comprises: a first step of sterilizing by chemical formula H_2O_2+2H^++2e=2H_2O or chemical formula H_2O_2+2e=2OH^-; a second step of sterilizing by chemical formula H_2O_2+2e=2OH^- and chemical formula PO_4^3-+3H_2O=H_3PO_4+3OH^-; and a third step of removing fungi by chemical formula H_3PO_4=3H^++PO+4^(3-). By the green algae removing method using copper nano, green algae fungi can be sterilized and removed, and malodor also can be removed.

Description

[0001] The present invention relates to a method of removing algal blooms using copper nano,

The present invention relates to a method of removing green algae using a copper nano, which is capable of easily sterilizing and removing green algae and removing odors from the composition by mixing a mixture of hydrogen peroxide and phosphoric acid in copper nano will be.

Recently, as a part of the 'social problem solving project', the future creation science department has been putting out various policies for producing clean tap water from which green algae is removed from water taken from rivers, rivers, dams and reservoirs.

The algal bloom (green tide) occurs when the concentration of nutrients in the water is higher than when it is in a natural state. The problem of green tide in rivers can occur when the water is stagnant or when nutrients are accumulated in large quantities. Also, in summer when the water temperature rises rapidly, green tides occur. These green algae have been exposed to many problems in the process of producing tap water by destroying aquatic ecosystem by reducing carbon dioxide and oxygen in water.

In order to remove these algae safely and cleanly, KG Chemical Co., Ltd. has developed an environmentally friendly coagulation agent in which aluminum hydroxide is bonded to silicon. In the case of copper flocculants, it is important to improve the reactivity with algae in water by attaching an organic polymer (polymetaphosphoric acid) to silicon to increase mass of aluminum hydroxide (increase in basicity), taking into account that algae- I will. In addition, it has been optimized for domestic aquatic characteristics through research and experiment, and it has an advantage that it is suitable for treatment of various water resources by improvement of precipitation of algae contained in the source water and a wide agglutination pH range (pH 5 ~ 9).

On the other hand, according to Korean Registered Patent Publication (B1) No. 10-0925988 (2009.11.10), a method of optimizing algae suppression using silver nano has been proposed.

However, this patented technique has a problem that silver nanoparticles are expensive to inhibit algae, and that silver nanoparticles must be continuously treated so that the range of 0.005 to 0.03 ppm can be maintained at the time of occurrence of a green algae alert.

Therefore, the present invention proposes a completely new method of removing green algae to solve the above-mentioned problems.

It is an object of the present invention to improve the problems of the prior art, and more particularly, to provide a method of sterilizing and removing a green tide easily by controlling the mixing ratio of a composition comprising hydrogen peroxide water and phosphoric acid in copper nano, So as to provide a method of removing green algae using copper nano.

Another object of the present invention is to solve the problems of the prior art, and more particularly, to provide a method of removing green algae using copper nano which can sterilize and remove green tanks easily by mixing only hydrogen peroxide with copper nano .

According to an aspect of the present invention for achieving the above object, there is provided a copper nano-sized copper nano-scale material obtained by dissolving a metal ion reducing agent in water and then collecting spherical copper nano- (H ₂ O ₂ ) and phosphoric acid (H ₃ PO ₄ ) are mixed in the particles, and the hydrogen peroxide water is added to the green nanotubes in which the high potential of the copper nano surface and a reduction reaction are caused on the surface of the copper nano The first step of sterilizing by the formula H ₂ O ₂ + 2H ⁺ + 2e = 2H ₂ O which promotes oxidation or by the formula H ₂ O ₂ + 2e = 2OH ^- ; The hydrogen peroxide is reacted with water at the copper nano surface by the formula H ₂ O ₂ + 2e = 2OH ^- and the phosphoric acid is represented by the formula PO ₄ ^3- + 3H ₂ O = H ₃ PO ₄ + 3OH- A second step of sterilizing the green tide; The phosphoric acid is hydrogenated on the copper nano surface by the formula H ₃ PO ₄ = 3 H ⁺ + PO ₄ ^3- And a third step of forming ions and removing the algae fungus. The present invention also provides a method of removing green algae using copper nano.

According to another embodiment of the present invention, the mixed composition for removing green algae comprises 86.5 wt% of water (H ₂ O), 0.5 wt% of copper (Cu), 10 wt% of hydrogen peroxide water (H ₂ O ₂ ) 2% by weight of H ₃ PO ₄ , and 1% by weight of impurities including protein, fat and calcium.

According to another embodiment of the present invention, the mixed composition for removing green algae comprises 83.2 wt% of water (H ₂ O), 0.8 wt% of copper (Cu), 12 wt% of hydrogen peroxide water (H ₂ O ₂ ) 3 wt% of H ₃ PO ₄ , and 1 wt% of impurities including protein, fat and calcium.

According to another embodiment of the present invention, the mixed composition for removing green algae comprises 81 wt% of water (H ₂ O), 1 wt% of copper (Cu), 14 wt% of hydrogen peroxide water (H ₂ O ₂ ) 3 wt% of H ₃ PO ₄ , and 1 wt% of impurities including protein, fat and calcium.

According to another embodiment of the present invention, the mixed composition for removing green algae comprises 79.5 wt% of water (H ₂ O), 1.5 wt% of copper (Cu), 15 wt% of hydrogen peroxide water (H ₂ O ₂ ) 3 wt% of H ₃ PO ₄ , and 1 wt% of impurities including protein, fat and calcium.

According to another embodiment of the present invention, the mixed composition for removing green algae comprises 76 wt% of water (H ₂ O), 3 wt% of copper (Cu), 16 wt% of hydrogen peroxide water (H ₂ O ₂ ) 4% by weight of H ₃ PO ₄ , and 1% by weight of impurities including protein, fat and calcium.

The method of removing green algae using copper nano of the present invention has the following effects.

(1) The present invention can easily sterilize and remove green tanks by controlling the mixing ratio of a composition obtained by mixing hydrogen peroxide and phosphoric acid in copper nano.

(2) The present invention can sterilize a green algae by mixing the copper nano with only hydrogen peroxide to accelerate oxidation by utilizing a high potential difference and a reduction reaction of the copper nano surface, and forming a hydroxide ion (OH ^- ).

(3) Copper nanoparticles, hydrogen peroxide water and phosphoric acid of the present invention generate bad odor when green tide is generated, and odor can be removed at the same time in the process of sterilizing and removing green fungus fungus.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram of a whole flow chart of a greenhouse removal method using copper nano according to an embodiment of the present invention;
2 is a graph showing a first experiment on a method of removing green algae using copper nano according to an embodiment of the present invention
3 is a graph showing a second experiment on a method of removing green algae using copper nano according to an embodiment of the present invention
4 is a graph showing a third experiment on a method of removing green algae using copper nano according to an embodiment of the present invention
5 is a graph showing a fourth experiment on a method of removing green algae using copper nano according to an embodiment of the present invention
6 is a graph showing a fifth experiment of a method of removing green algae using copper nano according to an embodiment of the present invention

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, like reference numerals refer to like elements throughout. Although the same reference numerals are used in the different drawings, the same reference numerals are used throughout the drawings. The prior art should be interpreted by itself. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

1 to 6, core technical means for a method of removing green algae using copper nano according to a preferred embodiment of the present invention include copper nano (Cu nano), hydrogen peroxide water (H ₂ O ₂ ), phosphoric acid (H ₃ PO ₄ ).

Until now, green algae have been difficult to remove. The reason is that when putting an excessive amount of disinfectant in order to achieve sterilization and insecticidal effect, not only a green tide but also a small fish are killed. However, it is difficult to remove a green tide because a green tide is survived when a small amount is put.

In the case of using loess, loess also has effect of absorbing and alleviating the algae, but when the temperature and conditions are formed, the algae is revived and only 30% of the effect is removed.

Therefore, the present invention proposes a method of effectively removing a green veneer by utilizing copper nano.

1, a method of removing green algae using copper nano according to a preferred embodiment of the present invention includes dissolving a metal ion reducing agent in water, and then dissolving copper nanoparticles (H ₂ O ₂ ) and phosphoric acid (H ₃ PO ₄ ) are mixed with Cu nanoparticles having a size of one size of the copper nanoparticles, and the hydrogen peroxide water has a high potential on the copper nanoparticles and a reduction reaction on the surface of the copper nanoparticles (S100) for sterilizing by the chemical formula H ₂ O ₂ + 2H ⁺ + 2e = 2H ₂ O or the formula H ₂ O ₂ + 2e = 2OH ^- which promotes the oxidation of the green tanks coming into contact with the copper nano surface . The hydrogen peroxide is reacted with water at the copper nano surface by the formula H ₂ O ₂ + 2e = 2OH ^- and the phosphoric acid is represented by the formula PO ₄ ³ + 3H ₂ O = H ₃ PO ₄ + 3OH ^- And sterilizing the greenhouse (S200). In addition, the phosphoric acid has a third step (S300) of forming a hydrogen ion by the formula H ₃ PO ₄ = 3H ⁺ + PO ₄ ^3- on the copper nano surface to remove green algae fungus.

Specifically, the copper nano according to the embodiment of the present invention is obtained by dissolving a metal ion reducing agent (additive - trisodium citrate or the like) capable of reducing copper ion in water and then reducing the spherical copper It is obtained by collecting nanoparticles.

The hydrogen peroxide solution (H ₂ O ₂ ) is neutral in acidity as shown in equation (1), but reduced in alkali as shown in equation (2).

H ₂ O ₂ + 2H ⁺ + 2e = 2H ₂ O (1)

H ₂ O ₂ + 2e = 2OH ^- (2)

Equation (1) or (2) can occur very rapidly on the surface of copper (Cu), resulting in a very high electrical potential of the copper surface.

The potential of the copper surface increased by the reduction reaction of hydrogen peroxide water promotes the oxidation of life forms that contact the copper surface, thereby exhibiting sterilization characteristics.

Therefore, it is possible to remove the fungus by causing a reduction reaction on the surface of the nanocatalyst particle having a high specific surface area as the hydrogen peroxide serving as the oxidizing agent.

Also, the hydrogen peroxide water can perform the sterilizing function by the hydroxide ion (OH < ^- & gt ^; ) formed on the surface of the nanoporous particles by the formula (2).

Here, in the embodiment of the present invention, the first step of mixing the copper nano and the hydrogen peroxide only to sterilize the surface of the copper nanoparticles by accelerating the oxidation by utilizing the high potential difference and the reduction reaction of the copper nano surface, (OH < ^- & gt ^; ) is formed and sterilized by the second step.

Further, the phosphoric acid (H ₃ PO ₄ ) can perform a sterilizing function by reacting water with phosphoric acid ion (PO ₄ ^3- ) on the copper surface as in the formula (3) to form hydroxide ions.

PO ₄ ^{3 -} + 3H ₂ O = H ₃ PO ₄ + 3OH ^- (3)

In addition, the phosphoric acid (H ₃ PO ₄ ) may form hydrogen ions on the copper surface to remove fungus as shown in Equation (4).

H ₃ PO ₄ = 3H ⁺ + PO ₄ ^{3 -} (4)

As described above, the copper nano (Cu Nano), hydrogen peroxide water (H ₂ O ₂ ) and phosphoric acid (H ₃ PO ₄ ) according to the embodiment of the present invention are sterilized by the above chemical formulas (1) And the copper nano, hydrogen peroxide, and phosphoric acid generate a bad odor when a green tide is generated, and the malodor can be removed simultaneously during sterilization and removal of the green algae fungus.

[Example]: A method of removing a green alga

In the examples of the present invention, the activity of the microorganism and the anabenanth green were determined using the phosphoric acid additive, and the data according to the example of the present invention were the data of the microsystite green tide.

1. The first experiment

In the first experiment of the present invention, a mixture of 86.5 wt% of water (H ₂ O), 0.5 wt% of copper (Cu), 10 wt% of hydrogen peroxide water (H ₂ O ₂ ), ₂ wt% of phosphoric acid (H ₃ PO ₄ ) And a mixture composition as shown in Table 1 in which 1 wt% of calcium-containing impurities was used.

water
(H ₂ O) Copper nano
(Cu Nano) Hydrogen peroxide water
(H ₂ O ₂ ) Phosphoric acid
(H ₃ PO ₄ ) impurities Sum 86.5 0.5 10 2 One 100 wt%

Referring to FIG. 2, A shows a population of 5000 cells / ml when a greenhouse is small, B shows a population of 10000 to 500000 cells / ml when a greenhouse is large, C has a population of 500000 cells / ml or more Respectively.

Experimental results show that the copper nanoparticles are removed when the ratio of copper nanoparticles is small, but only a part of the copper nanoparticles are removed and some of them are not removed. In other words, A was removed by almost 100% when the population was small, B was removed by 70% when the population was large, and C was removed by 30% when the population was very large.

In addition, it is observed that the green algae are removed from the normal 4 hours, and the algae are removed from 6 hours to 12 hours, and all the algae are removed within 1 day (1DAY).

2. The second experiment

In the second experiment of the present invention, the water content (H ₂ O) of 83.2% by weight, copper (Cu) of 0.8% by weight, hydrogen peroxide water (H ₂ O ₂ ) of 12% by weight, phosphoric acid (H ₃ PO ₄ ) And a mixture composition as shown in Table 2 in which 1 wt% of calcium-containing impurities was used.

water
(H ₂ O) Copper nano
(Cu Nano) Hydrogen peroxide water
(H ₂ O ₂ ) Phosphoric acid
(H ₃ PO ₄ ) impurities Sum 83.2 0.8 12 3 One 100 wt%

3, A shows a population of 5000 cells / ml when a greenhouse is small, B shows a population of 10000-500000 cells / ml when a greenhouse is large, C has a population of 500000 cells / ml or more when a greenhouse is very large Respectively.

When the ratio of copper nanoparticles and the number of green algae were small, all of the green algae were removed, but only a part was removed and some were not removed. That is, A is 100% removed when the population is small, B is removed by 80% when the population is large, and C is removed when the population is very large.

In addition, it can be seen that the green algae are observed to be killed from 4 hours later, and most of them are removed within 6 hours to 12 hours, and all of them are removed within 24 hours of 1 day.

3. The third experiment

In the third experiment of the present invention, a mixture of 81 wt% of water (H ₂ O), 1 wt% of copper (Cu), 14 wt% of hydrogen peroxide water (H ₂ O ₂ ), 3 wt% of phosphoric acid (H ₃ PO ₄ ) And a mixture composition as shown in Table 3 in which 1 wt% of calcium-containing impurities was used.

water
(H ₂ O) Copper nano
(Cu Nano) Hydrogen peroxide water
(H ₂ O ₂ ) Phosphoric acid
(H ₃ PO ₄ ) impurities Sum 81 One 14 3 One 100 wt%

4, A shows a population of 5000 cells / ml when a greenhouse is small, B shows a population of 10000 to 500000 cells / ml when a greenhouse is large, C has a population of 500000 cells / ml or more when a greenhouse is very large Respectively.

Experimental results show that copper nanoparticles have a small number of copper nanoparticles, but most of the copper nanoparticles have been removed. In other words, A is 100% removed when the population is small, B is 100% removed when the population is large, and C is 80% removed when the population is very large.

Therefore, it can be seen that, in the embodiment of the present invention, when the proportion of copper nanoparticles is increased, the green algae removal rate is increased by that much.

4. The fourth experiment

In the fourth experiment of the present invention, the water content was determined to be 79.5 wt% of water (H ₂ O), 1.5 wt% of copper (Cu), 15 wt% of hydrogen peroxide water (H ₂ O ₂ ), ₃ wt% of phosphoric acid (H ₃ PO ₄ ) And a mixture composition as shown in Table 4 in which 1% by weight of impurities containing calcium was used.

water
(H ₂ O) Copper nano
(Cu Nano) Hydrogen peroxide water
(H ₂ O ₂ ) Phosphoric acid
(H ₃ PO ₄ ) impurities Sum 79.5 1.5 15 3 One 100 wt%

Referring to FIG. 5, A indicates the number of individuals when the green tide is low, 5000 cells / ml when the green tide is low, B indicates the number of 10000-500000 cells / ml when the green tide is high, C indicates the number of the population is 500000 cells / Respectively.

As a result, most of the green algae were removed within 1 day when the copper nanoparticles were 1 ~ 1.5%, and only partially survived when the algae swelled over the surface of the water. In other words, A is 100% removed when the population is small, B is 100% removed when the population is large, and C is removed when the population is very large.

In addition, it is usually seen to be removed after 4 hours, and it is confirmed most at 6 ~ 12 hours and completely eliminated within 24 hours.

5. The fifth experiment

In the 5th experiment according to the present invention, water (H ₂ O) 76 wt%, copper (Cu) 3 wt%, hydrogen peroxide water (H ₂ O ₂ ) 16 wt%, phosphoric acid (H ₃ PO ₄ ) 4 wt %, And 1% by weight of an impurity containing protein fat calcium, as shown in Table 5.

water
(H ₂ O) Copper nano
(Cu Nano) Hydrogen peroxide water
(H ₂ O ₂ ) Phosphoric acid
(H ₃ PO ₄ ) impurities Sum 76 3 16 4 One 100 wt%

Referring to FIG. 6, the number of individuals A is 5000 cells / ml when greenhouse is small, B is 10000-500000 cells / ml when greenhouse is large, C is 500000 cells / ml or more when greenhouse is very large Respectively.

As a result, the number of copper nanoparticles was an important variable in the case of 2 ~ 3% of copper nanoparticles because all green algae were removed even if the number of green algae was large. In other words, A is 100% removed when the population is small, B is 100% removed when the population is large, and C is removed when the population is very large.

In addition, it was observed that most of the green algae collected on the surface of the water were not removed, but they were usually removed after 4 hours, and most of them were removed between 6 hours and 12 hours. there was.

Therefore, it can be confirmed through the first to fifth experiments according to the embodiment of the present invention that when the copper nano is mixed with the hydrogen peroxide solution and sprinkled, the reaction with the hydrogen peroxide occurs rapidly on the copper surface and the potential of the copper surface becomes very high, It accelerates the oxidation of life-forms that come into contact with the surface, and it has sterilization characteristics. This can remove the fungus by causing a reduction reaction on the surface of nanoporous catalyst particles having a high specific surface area as hydrogen peroxide serving as an oxidizing agent.

In addition, the sterilization function can be performed by hydroxide ions (OH-). The nanoparticles have a size of about one billionth of that of the green algae with a green algae particle size of about 2 μm or more, This is because there are enough populations to be sterilized.

As described above, in the embodiment of the present invention, the copper nanoparticles themselves can remove the green alga, but the copper nanoparticles are mixed with hydrogen peroxide water and phosphoric acid to cause a reduction reaction on the surface of the copper nanoparticles and the surface of the copper nanoparticles, It is possible to sterilize and sterilize living organisms contacting with the surface, sterilize by forming hydroxide ions secondarily, and sterilize and remove the green algae fungus by forming hydrogen ions on the copper nano surface thirdly, During the removal process, the odor of the green algae can be removed at the same time.

According to an embodiment of the present invention, there is provided a method for manufacturing a copper nanoparticle comprising: a first step of mixing only copper nano and hydrogen peroxide to sterilize copper nanoparticles by accelerating oxidation by utilizing a high potential difference and a reduction reaction of copper nanoparticles; (OH ^- ) is formed and sterilized by the second step.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the scope of the present invention but to limit the scope of the technical idea of the present invention. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (7)

Hydrogen peroxide (H ₂ O ₂ ) and phosphoric acid (H ₂ O ₂ ) were added to Cu nanoparticles of a size of 1 / 100,000,000 m obtained by dissolving a metal ion reducing agent in water and then collecting spherical copper nanoparticles to be reduced. _{3 < / RTI} > PO4)
The hydrogen peroxide has the formula ^{_{H 2 O 2 + 2H + +}} 2e = 2H 2 O , or the general formula H ₂ which causes a reduction reaction at high potential and the particle surface of the copper nano-surface to promote the oxidation of the green algae in contact with the copper nano-surface O ₂ + 2e = 2OH ^- ;
The hydrogen peroxide is reacted with water at the copper nano surface by the formula H ₂ O ₂ + 2e = 2OH ^- and the phosphoric acid is represented by the formula PO ₄ ^3- + 3H ₂ O = H ₃ PO ₄ + 3OH- A second step of sterilizing the green tide;
The phosphoric acid is hydrogenated on the copper nano surface by the formula H ₃ PO ₄ = 3 H ⁺ + PO ₄ ^3- And a third step of removing the green algae fungus by forming ions.
The method according to claim 1,
The mixed composition for removing green algae contained 86.5 wt% of water (H ₂ O), 0.5 wt% of copper (Cu), 10 wt% of hydrogen peroxide (H ₂ O ₂ ), ₂ wt% of phosphoric acid (H ₃ PO ₄ ) And 1 wt% of an impurity containing protein, fat, and calcium.
The method according to claim 1,
The mixed composition for removing green algae contained 83.2 wt% of water (H ₂ O), 0.8 wt% of copper (Cu), 12 wt% of hydrogen peroxide water (H ₂ O ₂ ), ₃ wt% of phosphoric acid (H ₃ PO ₄ ) And 1 wt% of an impurity containing protein, fat, and calcium.
The method according to claim 1,
The mixed composition for removing green algae contained 81 wt% of water (H ₂ O), 1 wt% of copper (Cu), 14 wt% of hydrogen peroxide (H ₂ O ₂ ), 3 wt% of phosphoric acid (H ₃ PO ₄ ) And 1 wt% of an impurity containing protein, fat, and calcium.
The method according to claim 1,
The mixed composition for removing green algae contained 79.5 wt% of water (H ₂ O), 1.5 wt% of copper (Cu), 15 wt% of hydrogen peroxide water (H ₂ O ₂ ), ₃ wt% of phosphoric acid (H ₃ PO ₄ ) And 1 wt% of an impurity containing protein, fat, and calcium.
The method according to claim 1,
The mixed composition for removing green algae contained 76 wt% of water (H ₂ O), 3 wt% of copper (Cu), 16 wt% of hydrogen peroxide (H ₂ O ₂ ), 4 wt% of phosphoric acid (H ₃ PO ₄ ) And 1 wt% of an impurity containing protein, fat, and calcium. delete

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