WO2022203298A1 - Green tide removal agent, and method for producing same - Google Patents

Green tide removal agent, and method for producing same Download PDF

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WO2022203298A1
WO2022203298A1 PCT/KR2022/003872 KR2022003872W WO2022203298A1 WO 2022203298 A1 WO2022203298 A1 WO 2022203298A1 KR 2022003872 W KR2022003872 W KR 2022003872W WO 2022203298 A1 WO2022203298 A1 WO 2022203298A1
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algae
remover
green algae
sulfate
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PCT/KR2022/003872
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French (fr)
Korean (ko)
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정행문
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주식회사 우석환경
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used

Definitions

  • the present invention relates to an algae remover and a method for manufacturing the same, and more particularly, to an algae remover capable of having an excellent effect of removing algae even in a small amount, preventing the occurrence of algae, and preventing contamination of secondary microorganisms, and a method for manufacturing the same will be.
  • Green tide ( ⁇ , green tide) refers to a phenomenon in which the color of water changes to dark green due to excessive growth of blue-green algae in rivers or lakes.
  • Red algae refers to a phenomenon in which the oxygen concentration in the area where the river meets the sea decreases, causing suffocation and death of fish and shellfish, whereas green algae covers the surface of the river to block the inflow of oxygen, resulting in the death of aquatic organisms and the rotting of the water, resulting in a foul odor. .
  • Green algae is caused by a complex action of various factors such as the influx of pollutants (nutrients, eutrophication), water temperature, solar radiation, and water cycle stagnation (increased residence time).
  • pollutants nutrients including nitrogen and phosphorus
  • water temperature water temperature
  • solar radiation solar radiation
  • water cycle stagnation increased residence time
  • Microcystis a major blue-green algae that causes green algae, can be amplified by eutrophication, thereby forming colonies and growing while floating on the water surface, blocking oxygen in the water. Microcystis causes an unpleasant odor, and leaches microcystin, a liver disease toxin substance, into water and accumulates in aquatic organisms, which can cause serious ecological and environmental problems.
  • Another method for removing algae is to remove algae using an algae control line, but there is a problem in that it is inconvenient to constantly manage the control line, so that its usefulness is not high both humanly and economically.
  • the present invention is intended to solve the above problems, and relates to an algae removal agent capable of preventing secondary contamination while having an excellent effect of removing algae even when sprayed in a small amount, at a low cost, and a method for manufacturing the same.
  • it is a technical solution to improve the water quality of rivers through the effective removal of microcystis that produce toxic substances.
  • the present invention is composed of 5 to 30% by weight of zinc sulfate, 0.1 to 2% by weight of potassium sulfate, 0.1 to 2% by weight of magnesium sulfate, and the balance water, characterized in that the pH is 5.0 to 6.5
  • hydrogen peroxide (based on a 30% solution) 1 to 10% by weight, EDTA 0.1 to 3% by weight, nutrients 0.1 to 1.0% by weight, magnesium silicate 0.1 to 1.0% by weight, but further comprising, the nutrients sodium gluconate, sodium alginate And it provides an algae remover, characterized in that at least one nutrient selected from the group consisting of chitosan.
  • an algae remover characterized in that it further comprises 0.1 to 2% by weight of titanium dioxide.
  • the green algae remover is characterized in that it kills blue-green algae.
  • the green algae remover prepared according to an embodiment of the present invention can be mass-produced at a relatively low cost, and has an excellent effect of removing algae in a large area even when a small amount is sprayed. In addition, since it does not contain toxic substances, damage to aquatic organisms is minimized, and nutrients that help restore the ecosystem of aquatic organisms after removal of algae are included, and secondary pollution can also be prevented.
  • FIG. 1 is a flowchart of a method for manufacturing an algae remover according to an embodiment of the present invention.
  • Figure 2 is a photograph showing the degree of algae removal according to the lapse of time (immediately after injection, 1 day, 2 days, 3 days) by varying the polymerization ratio of the disinfectant added to the algae remover.
  • 3 is a photograph showing the degree of algae removal according to the passage of time (immediately after injection, after 6 hours, after 1 day, after 3 days) by varying the titanium dioxide addition polymerization ratio of the algae remover.
  • the algae remover prepared according to an embodiment of the present invention includes zinc sulfate (ZnSO 4 ), potassium sulfate (K 2 SO 4 ), magnesium sulfate (MgSO 4 ), and the like.
  • Zinc sulfate has excellent sterilization and killing effects on microorganisms and blue-green algae, which are the causative substances of green algae.
  • cyanobacteria or cyanobacteria such as the genus Microcystis and the genus anabaena. It is preferable to include 5 to 30% by weight, and when it is less than 5% by weight, the sterilization effect is insignificant, and when it exceeds 30% by weight, it adversely affects the bacteria and aquatic animals and plants by excessive sterilization, thereby causing damage to the aquatic ecosystem. There is a risk of giving
  • Potassium sulfate has the same effect of removing and sterilizing blue-green algae as zinc sulfate, and is added as an auxiliary sterilizing agent that assists in the sterilization of zinc sulfate. It is preferable to include 0.1 to 2% by weight, and when it is less than 0.1% by weight, the role as a sterilizing aid is insignificant, and when it exceeds 2% by weight, the dispersibility of the algae remover may be deteriorated.
  • Magnesium sulfate like potassium sulfate, is used as an auxiliary disinfectant by assisting zinc sulfate.
  • it is substituted with Mg ions and OH ions in aqueous solution and reacts with phosphate groups that are food for blue-green algae, cyanobacteria, or microorganisms that cause green algae to make them inactive.
  • zinc sulfate, potassium sulfate, or magnesium sulfate alone has a sterilizing effect, but when the algae remover is prepared with a mixture of the three compounds in an appropriate ratio, the effect is more excellent than when used alone .
  • Hydrogen peroxide (H 2 O 2 ) generates active oxygen in water to decompose organic matter and can be used as an auxiliary sterilizer. It is preferable to include 1 to 10% by weight of hydrogen peroxide (based on a 30% solution), and when it is less than 1% by weight, the degree of decomposition of organic matter is insignificant, and when it is more than 10% by weight, the dispersibility of the algae remover may be deteriorated.
  • EDTA acts as a metal stabilizing group as a chelate functional group of a metal component that acts as an antioxidant. It is preferable to include 0.1 to 3% by weight of EDTA, and when it is less than 0.1% by weight, the antioxidative and metal stabilizer effect is insignificant, and even if it exceeds 3% by weight, the antioxidative and metal stabilizer effect does not increase any more.
  • Nutrients play a role in restoring the aquatic ecosystem by supplying nutrients to the surrounding aquatic ecosystem after removing the algae.
  • the nutrient preferably includes 0.1 to 1% by weight of at least one nutrient selected from the group consisting of sodium gluconate, sodium alginate and chitosan. If it is less than 0.1% by weight, nutrients may not be sufficiently supplied, and if it is more than 1% by weight, nutrients may be excessive and the aquatic environment may be rather turbid.
  • any substance that can be used as a nutritional supplement can be used.
  • Magnesium silicate increases the dispersibility of the algae remover and acts as a dispersant to evenly disperse it in the spraying area.
  • titanium dioxide to be described later is evenly dispersed in the bottom of a river or lake to help prevent secondary pollution. It is preferable to include 0.1 to 1% by weight, and when it is less than 0.1% by weight, the role of the dispersant is insignificant, and when it is more than 1% by weight, the green algae and the algae remover may not react sufficiently.
  • Titanium dioxide (TiO 2 ) is a representative photocatalyst and responds to light in the ultraviolet (UV) region.
  • UV ultraviolet
  • hydroxyl groups OH radicals
  • This hydroxyl group has a very strong oxidizing ability, so it decomposes organic matter and pollutants.
  • -OH hydroxy
  • the sterilization action of the algae remover when the sterilization action of the algae remover is completed and the algae and the algae remover are precipitated together, it serves to suppress the generation of secondary pollutants through photocatalysis.
  • it has a higher specific gravity than water (rutile type specific gravity 3.8, anatase type specific gravity 4.2), when titanium dioxide is included, it effectively sinks dead algae.
  • rutile type specific gravity 3.8, anatase type specific gravity 4.2 when titanium dioxide is included, it effectively sinks dead algae.
  • only faint sunlight from the bottom of a river or lake enables photosynthesis, creating an environment for photosynthesis in water.
  • the pH adjusting agent may be calcium oxide (CaO) or sodium carbonate (Na 2 CO 3 ), but is not limited thereto, and any pH adjusting agent capable of adjusting the pH may be used. It is preferable to adjust the pH of the algae remover prepared according to an embodiment of the present invention to 5.0 to 6.5 for an appropriate underwater pH, and if the pH is less than 5.0, it may adversely affect the aquatic ecosystem by an excessively acidic environment, and the pH of 6.5 In the case of exceeding this, as it becomes non-acidic, the agitation of the compound is not easy, so the dispersibility is poor, and the sterilization properties in a wide range may not be expressed.
  • CaO calcium oxide
  • Na 2 CO 3 sodium carbonate
  • a green algae remover containing zinc sulfate, potassium sulfate, and magnesium sulfate prepared according to an embodiment of the present invention at a concentration of 1 to 10 ppm and inject it into an area where algae are generated.
  • concentration is less than 1ppm, the sterilization effect is insignificant and an excessive amount of algae remover must be added, so the economic feasibility is deteriorated.
  • Limiting the upper limit of the concentration of the algae remover to 10 ppm is a threshold value for protecting the environment from potential dangers caused by excessive concentrations of constituents included in the algae remover, and The removal effect does not decrease.
  • the green algae remover prepared according to an embodiment of the present invention can particularly effectively remove blue-green algae, cyanobacteria, and the like, and when it is added before the occurrence of algae, the full-scale occurrence of algae can be prevented.
  • the nutrient is preferably at least one selected from the group consisting of sodium gluconate, sodium alginate and chitosan.
  • a step of adjusting the pH to 5.0 to 6.5 by adding a pH adjusting agent is performed to prepare a green algae remover.
  • the other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 10 wt% of zinc sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
  • the other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 0.5 wt% of magnesium sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
  • the other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 0.5 wt% of potassium sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
  • the LCC-500MP device was used to maintain the water temperature at 25°C under the conditions of the batch experiment, and 250 mL of a sample containing blue-green algae (4,000,000 to 5,000,000 cells/ml in number) was used to measure the occurrence of algae.
  • the number of algae measured using the microscopic counting method was compared (water quality process contamination test method), and the concentration of chlorophyll-a (Chl-a), an algae concentration index, was compared to measure the degree of the effect of removing algae.
  • Chlorophyll-a is a type of chlorophyll that is common to all algae, and is one of the indicators that can relatively easily determine the occurrence of green algae. The higher the measured value, the more green algae was produced, and the lower the measured value, the less the green algae product was produced.
  • green algae having values of 4,512,000 cells/ml and 497.68 mg/m 3 were used.
  • Example 1 Referring to Table 1, in Example 1, it can be seen that the number of algae decreased by about 95% to 232,500 cells/ml after 3 days after the addition of the algae remover, and Chl-a was also reduced to 24.12 mg/m 3 It can be seen that the concentration decreased by about 95%.
  • Example 2 is a photograph showing the degree of removal of green algae with the lapse of time after 1 day, 2 days, and 3 days in Example 1 and Comparative Examples 1 to 4 of Test Example 1 with the naked eye. In Example 1, it can be seen that the color of the green algae is remarkably pale.
  • the green algae remover was prepared at 3 ppm and added.
  • the other additives were the same as in Example 2, and 3 ppm of an algae remover to which 0.5 wt% of titanium dioxide was added was prepared and added.
  • the other additives were the same as in Example 2, and 3 ppm of an algae remover to which 1 wt% of titanium dioxide was added was prepared and added.
  • the other additives were the same as in Example 2, but 3 ppm of a green algae remover without titanium dioxide was added.
  • Test Example 2 zinc sulfate 10% by weight, potassium sulfate 0.5% by weight, magnesium sulfate 0.5% by weight, hydrogen peroxide 2% by weight, EDTA 0.2% by weight, magnesium silicate 0.1% by weight, sodium gluconate 0.1% by weight, and the remainder water.
  • the green algae remover prepared at 3 ppm by varying the weight of titanium dioxide added to the algae remover is summarized in Table 2 below.
  • Example 2 Algae remover containing 0.1% by weight of titanium dioxide
  • Example 3 Algae remover containing 0.5 wt% of titanium dioxide
  • Example 4 Algae remover containing 1 wt% of titanium dioxide
  • Example 5 Algae remover without titanium dioxide Comparative Example 5 -
  • FIG. 3 is a photograph showing the degree of removal of algae with the lapse of time, such as after 6 hours, 1 day, and 3 days in Test Example 2 with the naked eye.
  • up to 1 wt% of titanium dioxide was uniformly dispersed without agglomeration, and it was confirmed that the algae were effectively removed. It can be clearly distinguished that titanium dioxide has been removed. Titanium dioxide can act as a photocatalytic compound, but its main purpose is to prevent the formation of secondary pollutants, so it is expected to be more effective in actual rivers and lakes.
  • the present invention relates to an algae remover and a method for manufacturing the same, and more particularly, can be used in an industrial field capable of preventing algae occurrence and contamination of secondary microorganisms by having an excellent effect of removing algae even in a small amount.

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Abstract

The present invention relates to a green tide removal agent characterized by comprising: 5 to 30 wt% of zinc sulfate; 0.1 to 2 wt% of potassium sulfate; and 0.1 to 2 wt% of magnesium sulfate, with the balance being water, wherein the pH of the green tide removal agent is 5.0 to 6.5. Accordingly, it is possible to produce a large amount of the green tide removal agent at a relatively low cost, and the green tide removal agent exhibits an excellent green tide removal effect over a wide area even when sprayed in a small amount.

Description

녹조제거제 및 그 제조방법Green algae remover and its manufacturing method
본 발명은 녹조제거제 및 그 제조방법에 관한 것으로, 더욱 상세하게는 소량으로도 녹조제거효과가 우수하고 녹조 발생을 예방할 수 있으며 2차 미생물의 오염을 방지할 수 있는 녹조제거제 및 그 제조방법에 관한 것이다.The present invention relates to an algae remover and a method for manufacturing the same, and more particularly, to an algae remover capable of having an excellent effect of removing algae even in a small amount, preventing the occurrence of algae, and preventing contamination of secondary microorganisms, and a method for manufacturing the same will be.
녹조(綠潮, green tide)는 강이나 호수에 남조류의 과다 성장으로 물의 색이 짙은 녹색으로 변하는 현상을 말한다. 적조는 하천과 바다가 접하는 지역의 산소 농도가 옅어져 어패류가 질식해 폐사하는 반면, 녹조는 하천의 표면을 덮어 산소 유입을 차단하여 결과적으로 수중생물이 사멸되고 물이 썩어 악취가 나는 현상을 일컫는다.Green tide (綠潮, green tide) refers to a phenomenon in which the color of water changes to dark green due to excessive growth of blue-green algae in rivers or lakes. Red algae refers to a phenomenon in which the oxygen concentration in the area where the river meets the sea decreases, causing suffocation and death of fish and shellfish, whereas green algae covers the surface of the river to block the inflow of oxygen, resulting in the death of aquatic organisms and the rotting of the water, resulting in a foul odor. .
녹조는 오염물질의 유입(영양물질, 부영양화), 수온, 일사량, 물 순환 정체(체류시간 증가) 등 다양한 원인들이 복합적으로 작용하여 발생한다. 특히, 질소와 인을 포함한 영양물질들이 강이나 호수로 흘러들어 부영양화가 발생하고 이와 함께 강한 햇빛, 높아진 수온, 물 순환의 정체 등 남조류가 성장하기 좋은 환경이 조성되는 경우 녹조현상이 일어나게 된다.Green algae is caused by a complex action of various factors such as the influx of pollutants (nutrients, eutrophication), water temperature, solar radiation, and water cycle stagnation (increased residence time). In particular, when nutrients including nitrogen and phosphorus flow into rivers or lakes, eutrophication occurs, and a favorable environment for blue-green algae growth is created, such as strong sunlight, elevated water temperature, and stagnant water circulation.
녹조현상을 유발하는 주요 남조류인 마이크로시스티스(microcystis)는 부영양화에 의해 증폭될 수 있고 이에 따라 군체를 형성하여 수표면에 부유하면서 성장하여 수중의 산소를 차단한다. 마이크로시스티스는 불쾌한 냄새를 유발하고, 간 질환 독소물질인 마이크로시스틴(microcystin)을 수중으로 용출하여 수생 생물에 축적되어 생태계 및 환경적으로 심각한 문제를 일으킬 수 있다.Microcystis, a major blue-green algae that causes green algae, can be amplified by eutrophication, thereby forming colonies and growing while floating on the water surface, blocking oxygen in the water. Microcystis causes an unpleasant odor, and leaches microcystin, a liver disease toxin substance, into water and accumulates in aquatic organisms, which can cause serious ecological and environmental problems.
녹조가 발생하는 경우 하천의 색깔이 탁해지고 수면에 찌꺼기가 생기면서 수면을 뒤덮은 조류가 햇빛을 차단하여 깊은 물 속의 수생식물들이 광합성을 충분히 하지 못하게 되고, 물속의 산소 소비량이 상대적으로 많아짐에 따라 산소부족에 의한 동·식물의 폐사율이 높아지는 문제가 발생한다.When algae occur, the color of the river becomes cloudy and debris forms on the water surface, and the algae covering the water surface blocks sunlight, preventing sufficient photosynthesis for aquatic plants in deep water. There is a problem that the mortality rate of animals and plants due to the shortage increases.
종래 녹조를 제거하는 한 방법으로 황토 및 백토를 살포하는 방법 등이 사용되어왔으나, 황토의 콜로이드 입자가 녹조흡착 후 침전이 되면서 부패가 진행되거나 다시 부유하여 2차 오염이 발생한다는 단점이 있다.Conventionally, a method of spraying loess and white soil has been used as a method of removing green algae. However, as colloidal particles of loess are adsorbed and then precipitated, decay proceeds or floats again, resulting in secondary pollution.
또 다른 녹조 제거 방법으로는 녹조 방제선을 이용하여 녹조를 제거하는 방법이 있으나, 방제선을 꾸준히 관리해줘야 하는 불편함이 있어 인적으로도 경제적으로도 활용성이 높지 못한 문제점이 있었다.Another method for removing algae is to remove algae using an algae control line, but there is a problem in that it is inconvenient to constantly manage the control line, so that its usefulness is not high both humanly and economically.
본 발명은 상기와 같은 문제점을 해결하고자 한 것으로, 소량을 살포하여도 녹조 제거 효과가 뛰어나면서 비용이 저렴함과 동시에 2차 오염을 방지할 수 있는 녹조제거제 및 그 제조방법에 관한 것이다. 특히 독성물질을 생성하는 마이크로시스티스의 효과적인 제거를 통해 하천의 수질을 개선하는 것을 기술적 해결과제로 한다. 또한, 녹조의 피해를 최소화하고 녹조 제거 후 2차 오염 발생을 방지하는 것을 또 다른 기술적 해결과제로 한다.The present invention is intended to solve the above problems, and relates to an algae removal agent capable of preventing secondary contamination while having an excellent effect of removing algae even when sprayed in a small amount, at a low cost, and a method for manufacturing the same. In particular, it is a technical solution to improve the water quality of rivers through the effective removal of microcystis that produce toxic substances. In addition, it is another technical solution to minimize damage to algae and prevent secondary pollution after removal of algae.
본 발명은 상기한 기술적 과제를 달성하고자, 황산아연 5 내지 30 중량%, 황산칼륨 0.1 내지 2 중량%, 황산마그네슘 0.1 내지 2 중량% 및 잔량 물로 구성되되, pH가 5.0 내지 6.5인 것을 특징으로 하는 녹조제거제를 제공한다.In order to achieve the above technical problem, the present invention is composed of 5 to 30% by weight of zinc sulfate, 0.1 to 2% by weight of potassium sulfate, 0.1 to 2% by weight of magnesium sulfate, and the balance water, characterized in that the pH is 5.0 to 6.5 We provide an algae remover.
또한, 과산화수소(30% 용액 기준) 1 내지 10 중량%, EDTA 0.1 내지 3 중량%, 영양제 0.1 내지 1.0 중량%, 마그네슘실리케이트 0.1 내지 1.0 중량%를 더 포함하되, 상기 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 구성된 군으로부터 선택된 하나 이상의 영양제인 것을 특징으로 하는 녹조제거제를 제공한다.In addition, hydrogen peroxide (based on a 30% solution) 1 to 10% by weight, EDTA 0.1 to 3% by weight, nutrients 0.1 to 1.0% by weight, magnesium silicate 0.1 to 1.0% by weight, but further comprising, the nutrients sodium gluconate, sodium alginate And it provides an algae remover, characterized in that at least one nutrient selected from the group consisting of chitosan.
또한, 이산화티타늄 0.1 내지 2 중량%를 더 포함하는 것을 특징으로 하는 녹조제거제를 제공한다.In addition, it provides an algae remover, characterized in that it further comprises 0.1 to 2% by weight of titanium dioxide.
이때, 상기 녹조제거제는 남조류의 사멸작용을 하는 것을 특징으로 하는 녹조제거제를 제공한다.In this case, the green algae remover is characterized in that it kills blue-green algae.
본 발명의 다른 일 구현예로, (a) 반응용기에 황산아연 5 내지 30 중량%, 황산칼륨 0.1 내지 2 중량%, 황산마그네슘 0.1 내지 2 중량% 및 잔량 물로 구성되는 혼합물을 넣고 30분 내지 2시간동안 교반하는 단계; (b) 과산화수소(30% 용액 기준) 1 내지 10 중량%, EDTA 0.1 내지 3 중량%, 마그네슘실리케이트 0.1 내지 1 중량%, 영양제 0.1 내지 1 중량%, 이산화티타늄 0.1 내지 2 중량%를 더 첨가하고 교반하는 단계; 및 (c) pH를 5.0 내지 6.5로 조절하는 단계;를 포함하되, 상기 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 녹조제거제 제조방법을 제공한다.In another embodiment of the present invention, (a) put a mixture consisting of 5 to 30% by weight of zinc sulfate, 0.1 to 2% by weight of potassium sulfate, 0.1 to 2% by weight of magnesium sulfate, and the remainder of water in a reaction vessel for 30 minutes to 2 stirring for a period of time; (b) 1 to 10% by weight of hydrogen peroxide (based on a 30% solution), 0.1 to 3% by weight of EDTA, 0.1 to 1% by weight of magnesium silicate, 0.1 to 1% by weight of nutrients, 0.1 to 2% by weight of titanium dioxide are further added and stirred to do; and (c) adjusting the pH to 5.0 to 6.5; including, wherein the nutrient is at least one selected from the group consisting of sodium gluconate, sodium alginate and chitosan.
본 발명의 일 실시예에 따라 제조된 녹조제거제는, 비교적 저렴한 비용으로 대량생산이 가능하고 소량을 살포하여도 넓은 지역에서의 녹조 제거 효과가 우수하다. 또한, 독성물질이 포함되어 있지 않아 수중생물의 피해를 최소화하였으며 녹조제거후 수중생물의 생태계 복원을 도와주는 영양성분이 포함되고 2차 오염 또한 방지할 수 있다.The green algae remover prepared according to an embodiment of the present invention can be mass-produced at a relatively low cost, and has an excellent effect of removing algae in a large area even when a small amount is sprayed. In addition, since it does not contain toxic substances, damage to aquatic organisms is minimized, and nutrients that help restore the ecosystem of aquatic organisms after removal of algae are included, and secondary pollution can also be prevented.
도 1은 본 발명의 일 실시예에 따른 녹조제거제 제조방법의 흐름도이다.1 is a flowchart of a method for manufacturing an algae remover according to an embodiment of the present invention.
도 2는 녹조제거제에 들어가는 살균제 첨가 중합비를 달리하여 시간의 경과(투입 직후, 1일 후, 2일 후, 3일 후)에 따른 녹조제거 정도를 나타낸 사진이다.Figure 2 is a photograph showing the degree of algae removal according to the lapse of time (immediately after injection, 1 day, 2 days, 3 days) by varying the polymerization ratio of the disinfectant added to the algae remover.
도 3은 녹조제거제의 이산화티타늄 첨가 중합비를 달리하여 시간의 경과(투입 직후, 6시간 후, 1일 후, 3일 후)에 따라 녹조제거 정도를 나타낸 사진이다.3 is a photograph showing the degree of algae removal according to the passage of time (immediately after injection, after 6 hours, after 1 day, after 3 days) by varying the titanium dioxide addition polymerization ratio of the algae remover.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는바, 특정 실시예들을 도면에 예시하고 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 각 도면을 설명하면서 유사한 참조부호를 유사한 구성요소에 대해 사용하였다.Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention. In describing each figure, like reference numerals have been used for like elements.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not
본 발명의 일 실시예에 따라 제조된 녹조제거제는 황산아연(ZnSO4), 황산칼륨(K2SO4), 황산마그네슘(MgSO4) 등을 포함한다.The algae remover prepared according to an embodiment of the present invention includes zinc sulfate (ZnSO 4 ), potassium sulfate (K 2 SO 4 ), magnesium sulfate (MgSO 4 ), and the like.
황산아연은 녹조의 원인물질인 미생물 및 남조류에 대한 살균·사멸 효과가 우수하여 적절한 농도로 희석하여 사용하는 경우 그 효과가 탁월한 녹조제거제로 사용할 수 있다. 특히, 마이크로시스티스 속, 아나베나(anabaena) 속 등의 남조류 또는 남세균을 효과적으로 제거할 수 있다. 5 내지 30 중량%를 포함하는 것이 바람직하며, 5 중량% 미만일 경우 살균효과가 미미하고, 30 중량%를 초과하는 경우 과도한 살균에 의해 호세균, 수중 동·식물까지 악영향을 주어 수중생태계에 피해를 줄 우려가 있다.Zinc sulfate has excellent sterilization and killing effects on microorganisms and blue-green algae, which are the causative substances of green algae. In particular, it is possible to effectively remove cyanobacteria or cyanobacteria, such as the genus Microcystis and the genus anabaena. It is preferable to include 5 to 30% by weight, and when it is less than 5% by weight, the sterilization effect is insignificant, and when it exceeds 30% by weight, it adversely affects the bacteria and aquatic animals and plants by excessive sterilization, thereby causing damage to the aquatic ecosystem. There is a risk of giving
황산칼륨은 황산아연과 동일한 남조류 제거 및 살균효과를 가지고 있으며, 황산아연의 살균역할을 보조하는 보조살균제로 첨가한다. 0.1 내지 2 중량%를 포함하는 것이 바람직하며, 0.1 중량% 미만일 경우 살균보조제로서의 역할이 미미하고, 2 중량%를 초과하는 경우 녹조제거제의 분산성이 떨어질 수 있다.Potassium sulfate has the same effect of removing and sterilizing blue-green algae as zinc sulfate, and is added as an auxiliary sterilizing agent that assists in the sterilization of zinc sulfate. It is preferable to include 0.1 to 2% by weight, and when it is less than 0.1% by weight, the role as a sterilizing aid is insignificant, and when it exceeds 2% by weight, the dispersibility of the algae remover may be deteriorated.
황산마그네슘은 황산칼륨과 마찬가지로 황산아연을 보조하여 보조살균제로 사용된다. 특히, 수용액에서 Mg 이온과 OH 이온으로 치환되어 녹조의 원인인 남조류, 남세균 또는 미생물의 먹이가 되는 인산기와 반응하여 불활성 상태로 만든다. 0.1 내지 2 중량%를 포함하는 것이 바람직하며, 0.1 중량% 미만일 경우 인산기와 반응하는 양이 미미해 보조살균제로서 불충분하고, 2 중량%를 초과하는 경우 녹조제거제의 분산성이 떨어질 수 있다Magnesium sulfate, like potassium sulfate, is used as an auxiliary disinfectant by assisting zinc sulfate. In particular, it is substituted with Mg ions and OH ions in aqueous solution and reacts with phosphate groups that are food for blue-green algae, cyanobacteria, or microorganisms that cause green algae to make them inactive. It is preferable to include 0.1 to 2% by weight, and when it is less than 0.1% by weight, the amount of reaction with the phosphoric acid group is insignificant, which is insufficient as an auxiliary disinfectant, and when it exceeds 2% by weight, the dispersibility of the algae remover may be deteriorated.
후술하는 실시예 1과 같이 황산아연, 황산칼륨 또는 황산마그네슘 자체만으로도 살균효과가 있으나 세 화합물을 적절한 비율로 배합한 혼합물로 녹조제거제를 제조할 경우, 단독으로 사용하는 경우보다 그 효과가 더 탁월하다.As in Example 1 to be described later, zinc sulfate, potassium sulfate, or magnesium sulfate alone has a sterilizing effect, but when the algae remover is prepared with a mixture of the three compounds in an appropriate ratio, the effect is more excellent than when used alone .
과산화수소(H2O2)는 수중에서 활성산소를 생성해 유기물을 분해하는 역할을 하고 보조살균제로서도 사용할 수 있다. 과산화수소(30% 용액 기준) 1 내지 10 중량%를 포함하는 것이 바람직하며, 1 중량% 미만일 경우 유기물 분해정도가 미미하고, 10 중량% 초과일 경우 녹조제거제의 분산성이 떨어질 수 있다.Hydrogen peroxide (H 2 O 2 ) generates active oxygen in water to decompose organic matter and can be used as an auxiliary sterilizer. It is preferable to include 1 to 10% by weight of hydrogen peroxide (based on a 30% solution), and when it is less than 1% by weight, the degree of decomposition of organic matter is insignificant, and when it is more than 10% by weight, the dispersibility of the algae remover may be deteriorated.
EDTA는 산화방지 역할을 하는 금속성분의 킬레이트 작용기로서 금속안정화 작용을 한다. EDTA 0.1 내지 3 중량%를 포함하는 것이 바람직하며, 0.1 중량% 미만일 경우 산화방지 및 금속안정제 효과가 미미하고, 3 중량% 초과하더라도 산화방지 및 금속안정제 효과가 더 이상 증가하지 않는다.EDTA acts as a metal stabilizing group as a chelate functional group of a metal component that acts as an antioxidant. It is preferable to include 0.1 to 3% by weight of EDTA, and when it is less than 0.1% by weight, the antioxidative and metal stabilizer effect is insignificant, and even if it exceeds 3% by weight, the antioxidative and metal stabilizer effect does not increase any more.
영양제는 녹조를 제거한 후 주변 수중생태계에 영양분을 공급함으로써 수중생태계를 복원하는 역할을 한다. 이때, 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 이루어진 군으로부터 선택된 하나 이상의 영양제를 0.1 내지 1 중량%를 포함하는 것이 바람직하다. 0.1 중량% 미만일 경우 영양분이 충분히 공급되지 못할 수 있고, 1 중량% 초과일 경우 영양분이 과도하여 오히려 수중환경이 혼탁해질 수 있다. 글루콘산나트륨, 알긴산나트륨 또는 키토산 외에도 영양제로 사용될 수 있는 모든 물질을 사용할 수 있다.Nutrients play a role in restoring the aquatic ecosystem by supplying nutrients to the surrounding aquatic ecosystem after removing the algae. At this time, the nutrient preferably includes 0.1 to 1% by weight of at least one nutrient selected from the group consisting of sodium gluconate, sodium alginate and chitosan. If it is less than 0.1% by weight, nutrients may not be sufficiently supplied, and if it is more than 1% by weight, nutrients may be excessive and the aquatic environment may be rather turbid. In addition to sodium gluconate, sodium alginate or chitosan, any substance that can be used as a nutritional supplement can be used.
마그네슘실리케이트는 녹조제거제의 분산성을 높여 살포지역에 고르게 분산시키는 분산제 역할을 한다. 특히, 후술하는 이산화티타늄을 강 또는 호수의 저부에서 고르게 분산시켜 2차 오염 방지를 보조한다. 0.1 내지 1 중량%를 포함하는 것이 바람직하며, 0.1 중량% 미만일 경우 분산제 역할이 미미하며, 1 중량% 초과일 경우 오히려 녹조와 녹조제거제가 충분히 반응하지 못할 수 있다.Magnesium silicate increases the dispersibility of the algae remover and acts as a dispersant to evenly disperse it in the spraying area. In particular, titanium dioxide to be described later is evenly dispersed in the bottom of a river or lake to help prevent secondary pollution. It is preferable to include 0.1 to 1% by weight, and when it is less than 0.1% by weight, the role of the dispersant is insignificant, and when it is more than 1% by weight, the green algae and the algae remover may not react sufficiently.
이산화티타늄(TiO2)은 대표적인 광촉매로 자외선(UV)영역의 빛에 반응한다. 이산화티타늄에 자외선을 쬐면 광촉매 표면에 결합되어 있는 물 분자로부터 수산기(OH radical)가 생성된다. 이 수산기는 매우 강한 산화능력을 가지고 있어 유기물 및 오염물질 분해힌다. 또한, 태양광에 의하여 물과 반응하여 하이드록시(-OH)로 변화되어 친수성을 띄게 되면서 물표면에 넓게 분포하게 되어, 넓은 범위에서의 살균작용을 용이하게 만드는 효과가 있다.Titanium dioxide (TiO 2 ) is a representative photocatalyst and responds to light in the ultraviolet (UV) region. When titanium dioxide is exposed to ultraviolet rays, hydroxyl groups (OH radicals) are generated from water molecules bound to the surface of the photocatalyst. This hydroxyl group has a very strong oxidizing ability, so it decomposes organic matter and pollutants. In addition, by reacting with water by sunlight, it is changed to hydroxy (-OH) and becomes hydrophilic and widely distributed on the water surface, thereby facilitating sterilization in a wide range.
한편, 녹조제거제의 살균작용이 완료되어 녹조와 녹조제거제가 함께 침전되었을 경우, 광촉매작용을 통해 2차 오염물질 발생을 억제하는 역할을 한다. 특히, 물보다 비중이 높아(루타일형 비중 3.8, 아나타제형 비중 4.2) 이산화티타늄이 포함될 경우 사멸된 녹조를 효과적으로 가라앉게 해준다. 이때, 강이나 호수의 저부에서 희미한 햇빛만으로도 광합성을 가능하게 해주어 수중에서도 광합성을 할 수 있는 환경을 조성해준다. 0.1 내지 2 중량%를 포함하는 것이 바람직하며, 0.1 중량% 미만일 경우 광합성량이 미미하여 2차 오염물질 발생을 효과적으로 억제할 수 없고, 2 중량%를 초과할 경우 녹조제거제의 분산성이 저하된다.On the other hand, when the sterilization action of the algae remover is completed and the algae and the algae remover are precipitated together, it serves to suppress the generation of secondary pollutants through photocatalysis. In particular, as it has a higher specific gravity than water (rutile type specific gravity 3.8, anatase type specific gravity 4.2), when titanium dioxide is included, it effectively sinks dead algae. At this time, only faint sunlight from the bottom of a river or lake enables photosynthesis, creating an environment for photosynthesis in water. It is preferable to include 0.1 to 2% by weight, and when it is less than 0.1% by weight, the amount of photosynthesis is insignificant, so that the generation of secondary pollutants cannot be effectively suppressed, and when it exceeds 2% by weight, the dispersibility of the algae remover is reduced.
pH 조절제는 산화칼슘(CaO) 또는 탄산나트륨(Na2CO3)을 사용할 수 있으나 이에 한정되지 않고 pH를 조절할 수 있는 모든 pH 조절제를 사용할 수 있다. 적절한 수중 pH를 위해 본 발명의 일 실시예에 따라 제조된 녹조제거제의 pH를 5.0 내지 6.5로 조절하는 것이 바람직하며, 5.0 pH 미만일 경우 과도한 산성환경에 의해 수중생태계에 악영향을 미칠 수 있고, 6.5 pH를 초과하는 경우 비산성화 됨에 따라 화합물의 교반이 수월하지 못해 분산성이 떨어져 광범위에서의 살균특성이 발현되지 않을 수 있다.The pH adjusting agent may be calcium oxide (CaO) or sodium carbonate (Na 2 CO 3 ), but is not limited thereto, and any pH adjusting agent capable of adjusting the pH may be used. It is preferable to adjust the pH of the algae remover prepared according to an embodiment of the present invention to 5.0 to 6.5 for an appropriate underwater pH, and if the pH is less than 5.0, it may adversely affect the aquatic ecosystem by an excessively acidic environment, and the pH of 6.5 In the case of exceeding this, as it becomes non-acidic, the agitation of the compound is not easy, so the dispersibility is poor, and the sterilization properties in a wide range may not be expressed.
본 발명의 일 실시예에 따라 제조된 황산아연, 황산칼륨, 황산마그네슘이 포함된 녹조제거제를 1 내지 10ppm의 농도로 제조하여 녹조가 생성된 지역에 투입하는 것이 바람직하다. 이때, 1ppm 농도 미만일 경우 살균효과가 미미하여 과량의 녹조제거제를 투입해야하므로 경제성이 떨어지고, 10ppm을 초과하는 경우 살균제의 과다 살포로 인해 수중생태계에 악영향을 미칠 수 있다. 이때, 녹조가 발생한 지역의 녹조농도에 비례하여 1ppm에서 10ppm 까지 정량적으로 살포할 수 있다. 상기 녹조제거제 농도의 상한선을 10ppm로 제한한 것은, 녹조제거제에 포함된 구성물질의 과도한 농도에 의한 잠재적 위험성으로부터 환경을 보호하기 위한 임계값이지, 본 발명의 일 실시예에 따라 제조된 녹조제거제의 제거효과가 감소하는 것은 아니다.It is preferable to prepare a green algae remover containing zinc sulfate, potassium sulfate, and magnesium sulfate prepared according to an embodiment of the present invention at a concentration of 1 to 10 ppm and inject it into an area where algae are generated. At this time, if the concentration is less than 1ppm, the sterilization effect is insignificant and an excessive amount of algae remover must be added, so the economic feasibility is deteriorated. At this time, it is possible to quantitatively spray from 1ppm to 10ppm in proportion to the concentration of algae in the area where the algae is generated. Limiting the upper limit of the concentration of the algae remover to 10 ppm is a threshold value for protecting the environment from potential dangers caused by excessive concentrations of constituents included in the algae remover, and The removal effect does not decrease.
한편, 본 발명의 일 실시예에 따라 제조된 녹조제거제는 특히 효과적으로 남조류, 남세균 등을 제거할 수 있으며, 녹조발생 전에 투입하게 될 경우 녹조의 본격적인 발생을 예방할 수 있다. On the other hand, the green algae remover prepared according to an embodiment of the present invention can particularly effectively remove blue-green algae, cyanobacteria, and the like, and when it is added before the occurrence of algae, the full-scale occurrence of algae can be prevented.
본 발명의 다른 일 구현예로 녹조제거제의 제조방법이 있다.In another embodiment of the present invention, there is a method for producing an algae remover.
먼저, 반응용기에 황산아연 5 내지 30 중량%, 황산칼륨 0.1 내지 2 중량%, 황산마그네슘 0.1 내지 2 중량% 및 잔량 물로 구성되는 혼합물을 넣고 30분 내지 2시간동안 교반하는 단계를 실시한다.First, a mixture consisting of 5 to 30% by weight of zinc sulfate, 0.1 to 2% by weight of potassium sulfate, 0.1 to 2% by weight of magnesium sulfate, and the remainder of water is put into a reaction vessel and stirred for 30 minutes to 2 hours.
그 후, 과산화수소(30% 용액 기준) 1 내지 10 중량%, EDTA 0.1 내지 3 중량%, 마그네슘실리케이트 0.1 내지 1 중량%, 영양제 0.1 내지 1 중량%, 이산화티타늄 0.1 내지 2 중량%를 더 첨가하고 교반하는 단계를 실시한다. 상기 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 이루어진 군으로부터 선택된 하나 이상인 것이 바람직하다.Then, 1 to 10% by weight of hydrogen peroxide (based on a 30% solution), 0.1 to 3% by weight of EDTA, 0.1 to 1% by weight of magnesium silicate, 0.1 to 1% by weight of nutrients, 0.1 to 2% by weight of titanium dioxide are further added and stirred carry out the steps The nutrient is preferably at least one selected from the group consisting of sodium gluconate, sodium alginate and chitosan.
마지막으로, pH조절제를 첨가하여 pH를 5.0 내지 6.5로 조절하는 단계를 실시하여 녹조제거제를 제조한다.Finally, a step of adjusting the pH to 5.0 to 6.5 by adding a pH adjusting agent is performed to prepare a green algae remover.
이하에서는, 본 발명인 녹조제거제의 녹조제거효과에 대해 실시예를 바탕으로 상세히 서술하기로 한다. 다만, 이하의 실시예는 본 발명의 이해를 돕기 위한 예시일 뿐, 이에 의하여 본 발명의 권리범위가 한정되는 것은 아니다.Hereinafter, the algae removal effect of the algae remover according to the present invention will be described in detail based on Examples. However, the following examples are only examples to help the understanding of the present invention, and the scope of the present invention is not limited thereby.
<실시예 1><Example 1>
반응용기에 황산아연 10 중량%, 황산칼륨 0.5 중량%, 황산마그네슘 0.5 중량%를 물에 첨가하여 1시간 동안 교반한 후, 과산화수소 2 중량%, EDTA 0.2 중량%, 이산화티타늄 0.5 중량%, 마그네슘실리케이트 0.1 중량%, 글루콘산나트륨 0.1 중량%를 더 첨가하여 교반하였으며, pH를 5.5로 조절한 녹조제거제를 3ppm으로 제조하여 녹조에 투입하였다.10% by weight of zinc sulfate, 0.5% by weight of potassium sulfate, and 0.5% by weight of magnesium sulfate were added to water in a reaction vessel and stirred for 1 hour, followed by 2% by weight of hydrogen peroxide, 0.2% by weight of EDTA, 0.5% by weight of titanium dioxide, and magnesium silicate 0.1% by weight and 0.1% by weight of sodium gluconate were further added and stirred, and 3 ppm of a green algae remover adjusted to pH 5.5 was added to the green algae.
<비교예 1><Comparative Example 1>
녹조제거제를 첨가하지 않은 대조군으로서, 녹조 외에 어떠한 화합물도 첨가하지 않았다.As a control to which no green algae remover was added, no compound other than green algae was added.
<비교예 2><Comparative Example 2>
실시예 1과 다른 첨가물은 동일하고, 살균제 역할을 하는 황산아연, 황산마그네슘, 황산칼륨 중 황산아연만을 10 중량% 첨가한 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 10 wt% of zinc sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
<비교예 3><Comparative Example 3>
실시예 1과 다른 첨가물은 동일하고, 살균제 역할을 하는 황산아연, 황산마그네슘, 황산칼륨 중 황산마그네슘만을 0.5 중량% 첨가한 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 0.5 wt% of magnesium sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
<비교예 4><Comparative Example 4>
실시예 1과 다른 첨가물은 동일하고, 살균제 역할을 하는 황산아연, 황산마그네슘, 황산칼륨 중 황산칼륨만을 0.5 중량% 첨가한 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 1, and 3 ppm of a green algae remover containing only 0.5 wt% of potassium sulfate among zinc sulfate, magnesium sulfate, and potassium sulfate serving as a disinfectant was prepared and added.
<시험예 1><Test Example 1>
본 시험예 1에서는 실시예 1 및 비교예 1 내지 4에 따른 조류 개체수 및 Chl-a 농도를 측정하여 하기 표 1과 같이 나타내었다.In this Test Example 1, the number of algae and the Chl-a concentration according to Example 1 and Comparative Examples 1 to 4 were measured and shown in Table 1 below.
실험환경은 batch experiment의 조건에서 LCC-500MP 장치를 사용해 25℃ 수온을 유지하였으며, 녹조의 발생정도를 측정하기 위해 남조류가 포함된 시료 250mL(개체수 4,000,000~5,000,000 cells/ml)를 사용했다. 현미경계수법을 이용하여 측정된 조류 개체수를 비교(수질공정오염시험법)하였고, 조류농도지표인 클로로필-a(Chl-a)의 농도를 비교하여 녹조제거 효과의 정도를 측정하였다.In the experimental environment, the LCC-500MP device was used to maintain the water temperature at 25°C under the conditions of the batch experiment, and 250 mL of a sample containing blue-green algae (4,000,000 to 5,000,000 cells/ml in number) was used to measure the occurrence of algae. The number of algae measured using the microscopic counting method was compared (water quality process contamination test method), and the concentration of chlorophyll-a (Chl-a), an algae concentration index, was compared to measure the degree of the effect of removing algae.
클로로필-a는 모든 조류에 공통적으로 존재하는 엽록소의 한 종류로서, 녹조의 발생 정도를 비교적 쉽게 파악할 수 있는 지표 중 하나이다. 측정된 수치가 높을수록 녹조가 많이 생성되었고, 낮을수록 녹조생성물이 적게 생성되었음을 의미한다.Chlorophyll-a is a type of chlorophyll that is common to all algae, and is one of the indicators that can relatively easily determine the occurrence of green algae. The higher the measured value, the more green algae was produced, and the lower the measured value, the less the green algae product was produced.
종류type 조류 개체수(cells/ml)Algae population (cells/ml) Chl-a(mg/m3)Chl-a (mg/m 3 )
투입전before input 3일후3 days later 투입전before input 3일후3 days later
실시예 1Example 1 녹조제거제
(3ppm)algae remover
(3ppm) 		4,512,0004,512,000 232,500232,500 497.68497.68 24.1224.12
비교예 1Comparative Example 1 -- 4,971,0004,971,000 512.68512.68
비교예 2Comparative Example 2 ZnSO4
(3ppm)ZnSO 4
(3ppm) 		4,125,0004,125,000 453.45453.45
비교예 3Comparative Example 3 MgSO4
(3ppm)MgSO 4
(3ppm) 		4,250,0004,250,000 480.45480.45
비교예 4Comparative Example 4 K2SO4
(3ppm)K 2 SO 4
(3ppm) 		4,651,0004,651,000 480.12480.12
녹조의 제거정도를 측정하기 위해 4,512,000cells/ml 및 497.68mg/m3의 수치를 가지는 녹조를 사용하였다.To measure the degree of removal of green algae, green algae having values of 4,512,000 cells/ml and 497.68 mg/m 3 were used.
표 1을 참조하면 실시예 1은, 녹조제거제를 첨가한 후 3일 후의 조류 개체수가 232,500cells/ml 로 약 95%의 개체수가 감소하였음을 알 수 있고, Chl-a 또한 24.12mg/m3 으로 약 95%의 농도가 감소하였음을 알 수 있다.Referring to Table 1, in Example 1, it can be seen that the number of algae decreased by about 95% to 232,500 cells/ml after 3 days after the addition of the algae remover, and Chl-a was also reduced to 24.12 mg/m 3 It can be seen that the concentration decreased by about 95%.
비교예 1에서, 3일 후의 조류개체수는 4,971,000cells/ml 로 약 10% 증가하였고, Chl-a 또한 512.68mg/m3 으로 약 3% 증가하였다..In Comparative Example 1, the number of algae after 3 days increased by about 10% to 4,971,000 cells/ml, and Chl-a also increased by about 3% to 512.68 mg/m 3 .
비교예 2에서, 3일 후의 조류개체수는 4,125,000cells/ml 로 약 8.6% 감소하였고, Chl-a 또한 약 8.9% 감소하였다.In Comparative Example 2, the number of algae after 3 days was reduced by about 8.6% to 4,125,000 cells/ml, and Chl-a was also reduced by about 8.9%.
비교예 3에서, 3일 후의 조류개체수는 4,250,000cells/ml 로 약 5.8% 감소하였고, Chl-a 또한 약 3.5% 감소하였다.In Comparative Example 3, the number of algae after 3 days was reduced by about 5.8% to 4,250,000 cells/ml, and Chl-a was also reduced by about 3.5%.
비교예 4에서, 3일 후의 조류개체수는 4,651,000cells/ml 로 약 3% 증가하였고, Chl-a는 약 3.5% 감소하였다.In Comparative Example 4, the number of algae after 3 days increased by about 3% to 4,651,000 cells/ml, and Chl-a decreased by about 3.5%.
시험예 1로부터, 살균제 역할을 하는 황산아연, 황산마그네슘 및 황산칼륨을 각각 첨가하는 경우 대체적으로 조류 개체수 및 Chl-a의 농도가 감소하였으나, 본 발명의 일 실시예에 따라 제조된 3ppm의 녹조제거제의 조류 개체수 및 Chl-a 농도 감소율에는 미미한 정도임을 알 수 있다.From Test Example 1, when zinc sulfate, magnesium sulfate, and potassium sulfate acting as disinfectants were added, the number of algae and the concentration of Chl-a were generally decreased, but 3 ppm of the green algae remover prepared according to an embodiment of the present invention It can be seen that the rate of decrease in the number of algae and Chl-a concentration is insignificant.
도 2는 본 시험예 1의 실시예 1 및 비교예 1 내지 4의 1일 후, 2일 후, 3일 후의 시간의 경과에 따른 녹조의 제거정도를 육안으로 확인할 수 있는 사진이다. 실시예 1에서 눈에 띄게 녹조의 색이 옅어짐을 알 수 있다.2 is a photograph showing the degree of removal of green algae with the lapse of time after 1 day, 2 days, and 3 days in Example 1 and Comparative Examples 1 to 4 of Test Example 1 with the naked eye. In Example 1, it can be seen that the color of the green algae is remarkably pale.
<실시예 2><Example 2>
황산아연 10 중량%, 황산칼륨 0.5 중량%, 황산마그네슘 0.5 중량%, 과산화수소 2 중량%, EDTA 0.2 중량%, 이산화티타늄 0.1 중량%, 마그네슘실리케이트 0.1 중량%, 글루콘산나트륨 0.1 중량% 및 잔량 물로 구성되는 녹조제거제를 3ppm으로 제조하여 투입하였다.Zinc sulfate 10% by weight, potassium sulfate 0.5% by weight, magnesium sulfate 0.5% by weight, hydrogen peroxide 2% by weight, EDTA 0.2% by weight, titanium dioxide 0.1% by weight, magnesium silicate 0.1% by weight, sodium gluconate 0.1% by weight and the balance water The green algae remover was prepared at 3 ppm and added.
<실시예 3><Example 3>
실시예 2와 다른 첨가물은 동일하고, 이산화티타늄 0.5 중량%가 첨가된 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 2, and 3 ppm of an algae remover to which 0.5 wt% of titanium dioxide was added was prepared and added.
<실시예 4><Example 4>
실시예 2와 다른 첨가물은 동일하고, 이산화티타늄 1 중량%가 첨가된 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 2, and 3 ppm of an algae remover to which 1 wt% of titanium dioxide was added was prepared and added.
<실시예 5><Example 5>
실시예 2와 다른 첨가물은 동일하나, 이산화티타늄을 첨가하지 않은 녹조제거제를 3ppm으로 제조하여 투입하였다.The other additives were the same as in Example 2, but 3 ppm of a green algae remover without titanium dioxide was added.
<비교예 5><Comparative Example 5>
녹조제거제를 첨가하지 않은 대조군으로서, 녹조 외에 어떠한 화합물도 첨가하지 않았다.As a control to which no green algae remover was added, no compound other than green algae was added.
< 시험예 2 ><Test Example 2>
본 시험예 2에서는 황산아연 10 중량%, 황산칼륨 0.5 중량%, 황산마그네슘 0.5 중량%, 과산화수소 2 중량%, EDTA 0.2 중량%, 마그네슘실리케이트 0.1 중량%, 글루콘산나트륨 0.1 중량% 및 잔량 물로 구성되는 녹조제거제에 이산화티타늄의 첨가 중량을 달리하여 제조된 녹조제거제를 3ppm으로 제조한 것을 하기 표 2로 정리하였다.In Test Example 2, zinc sulfate 10% by weight, potassium sulfate 0.5% by weight, magnesium sulfate 0.5% by weight, hydrogen peroxide 2% by weight, EDTA 0.2% by weight, magnesium silicate 0.1% by weight, sodium gluconate 0.1% by weight, and the remainder water. The green algae remover prepared at 3 ppm by varying the weight of titanium dioxide added to the algae remover is summarized in Table 2 below.
samplesample 첨가 화합물additive compound
실시예 2Example 2 이산화티타늄 0.1 중량%가 포함된 녹조제거제Algae remover containing 0.1% by weight of titanium dioxide
실시예 3Example 3 이산화티타늄 0.5 중량%가 포함된 녹조제거제Algae remover containing 0.5 wt% of titanium dioxide
실시예 4Example 4 이산화티타늄 1 중량%가 포함된 녹조제거제Algae remover containing 1 wt% of titanium dioxide
실시예 5Example 5 이산화티타늄이 포함되지 않은 녹조제거제Algae remover without titanium dioxide
비교예 5Comparative Example 5 --
도 3은 본 시험예 2의 6시간 후, 1일 후, 3일 후와 같이 시간의 경과에 따른 녹조 제거정도를 육안으로 확인할 수 있는 사진이다. 실시예 2 내지 4에서 볼 수 있듯이 이산화티타늄 1 중량% 까지는 응집되지 않고 균일하게 분산되어 녹조가 효과적으로 제거되었음을 확인할 수 있으며, 이산화티타늄이 포함되지 않은 실시예 5 또한 비교예 5와 비교하였을 때 녹조가 제거되었음을 확연히 구분할 수 있다.이산화티타늄은 광촉매 화합물로 작용할 수는 있으나, 2차 오염물질 생성을 방지하는 것을 주 목적으로 하므로, 실제 강이나 호수 등에서 효과를 더욱 발휘할 수 있을 것으로 예상된다.3 is a photograph showing the degree of removal of algae with the lapse of time, such as after 6 hours, 1 day, and 3 days in Test Example 2 with the naked eye. As can be seen in Examples 2 to 4, up to 1 wt% of titanium dioxide was uniformly dispersed without agglomeration, and it was confirmed that the algae were effectively removed. It can be clearly distinguished that titanium dioxide has been removed. Titanium dioxide can act as a photocatalytic compound, but its main purpose is to prevent the formation of secondary pollutants, so it is expected to be more effective in actual rivers and lakes.
이상의 설명은 본 발명의 기술적 사상을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서 본 발명에 개시된 실시예는 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것도 아니다. 본 발명의 보호범위는 특허청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the technical idea of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the claims, and all technical ideas within the equivalent range should be construed as being included in the scope of the present invention.
본 발명은 녹조제거제 및 그 제조방법에 관한 것으로, 더욱 상세하게는 소량으로도 녹조제거효과가 우수하고 녹조 발생을 예방할 수 있으며 2차 미생물의 오염을 방지할 수 있는 산업분야에서 이용가능하다.The present invention relates to an algae remover and a method for manufacturing the same, and more particularly, can be used in an industrial field capable of preventing algae occurrence and contamination of secondary microorganisms by having an excellent effect of removing algae even in a small amount.

Claims (2)

  1. 녹조제거제에 있어서,In the green algae remover,
    황산아연 5 내지 30 중량%, 황산칼륨 0.1 내지 2 중량%, 황산마그네슘 0.1 내지 2 중량%, 과산화수소(30% 용액 기준) 1 내지 10 중량%, EDTA 0.1 내지 3 중량%, 영양제 0.1 내지 1 중량%, 마그네슘실리케이트 0.1 내지 1 중량%, 이산화티타늄 0.1 내지 1 중량% 및 잔량 물로 구성되되,Zinc sulfate 5 to 30% by weight, potassium sulfate 0.1 to 2% by weight, magnesium sulfate 0.1 to 2% by weight, hydrogen peroxide (based on a 30% solution) 1 to 10% by weight, EDTA 0.1 to 3% by weight, nutrients 0.1 to 1% by weight , consisting of 0.1 to 1% by weight of magnesium silicate, 0.1 to 1% by weight of titanium dioxide and the balance water,
    상기 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 구성된 군으로 부터 선택된 하나이상 포함되며,The nutrients include at least one selected from the group consisting of sodium gluconate, sodium alginate and chitosan,
    상기 녹조제거제는 pH가 5.0 내지 6.5 이고 농도가 1~3ppm을 가짐으로써 남조류 사멸작용과 광촉매 작용을 통해 2차 오염 물질 발생을 억제하는 효과를 갖는 것을 특징으로 하는 녹조제거제.The green algae remover has a pH of 5.0 to 6.5 and a concentration of 1 to 3 ppm, and has an effect of inhibiting the generation of secondary pollutants through the killing of blue-green algae and the photocatalytic action.
  2. 녹조제거제 제조방법에 있어서,In the method for manufacturing a green algae remover,
    (a) 반응용기에 황산아연 5 내지 30 중량%, 황산칼륨 0.1 내지 2 중량%, 황산마그네슘 0.1 내지 2 중량% 및 잔량 물로 구성되는 혼합물을 넣고 30분 내지 2시간동안 교반하는 단계;(a) putting a mixture consisting of 5 to 30% by weight of zinc sulfate, 0.1 to 2% by weight of potassium sulfate, 0.1 to 2% by weight of magnesium sulfate, and the remainder of water in a reaction vessel and stirring for 30 minutes to 2 hours;
    (b) 과산화수소(30% 용액 기준) 1 내지 10 중량%, EDTA 0.1 내지 3 중량%, 마그네슘실리케이트 0.1 내지 1 중량%, 영양제 0.1 내지 1 중량%, 이산화티타늄 0.1 내지 1 중량%를 더 첨가하고 교반하는 단계; 및(b) 1 to 10% by weight of hydrogen peroxide (based on a 30% solution), 0.1 to 3% by weight of EDTA, 0.1 to 1% by weight of magnesium silicate, 0.1 to 1% by weight of nutrients, 0.1 to 1% by weight of titanium dioxide are further added and stirred to do; and
    (c) pH를 5.0 내지 6.5로 조절하는 단계;를 포함하되,(c) adjusting the pH to 5.0 to 6.5; including,
    상기 영양제는 글루콘산나트륨, 알긴산나트륨 및 키토산으로 이루어진 군으로부터 선택된 하나 이상이며,The nutrient is at least one selected from the group consisting of sodium gluconate, sodium alginate and chitosan,
    상기 방법으로 제조된 녹조제거제는 농도가 1~3ppm을 가짐으로써 남조류 사멸작용과 광촉매 작용을 통해 2차 오염 물질 발생을 억제하는 효과를 갖는 것을 특징으로 하는 녹조제거제 제조방법.The method for producing an algae remover, characterized in that the algae remover prepared by the above method has an effect of inhibiting the generation of secondary pollutants through the cyanobacteria killing action and the photocatalytic action by having a concentration of 1 to 3 ppm.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101274071B1 (en) * 2012-12-11 2013-06-12 정동성 Red tide removal materials and manufacturing method thereof
US20150099632A1 (en) * 2013-10-03 2015-04-09 Dong-Suek JUNG Blue-green algae remover and method for manufacturing the same
CN104542705A (en) * 2013-10-22 2015-04-29 郑东成 Blue-green algae removing agent and preparation method thereof
KR20160107974A (en) * 2015-03-06 2016-09-19 정동성 Agent for removing cyanobacteria and removing method of the same.
KR20180119726A (en) * 2017-04-25 2018-11-05 이명희 Water clarifying agent for removing water-bloom and red tide
CN110526355A (en) * 2018-05-26 2019-12-03 王忠厚 A kind of Novel pollution-free water purification agent prescription and preparation method thereof
KR102355146B1 (en) * 2021-03-24 2022-02-08 주식회사 우석환경 Green tide remover and its manufacturing method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101274071B1 (en) * 2012-12-11 2013-06-12 정동성 Red tide removal materials and manufacturing method thereof
US20150099632A1 (en) * 2013-10-03 2015-04-09 Dong-Suek JUNG Blue-green algae remover and method for manufacturing the same
CN104542705A (en) * 2013-10-22 2015-04-29 郑东成 Blue-green algae removing agent and preparation method thereof
KR20160107974A (en) * 2015-03-06 2016-09-19 정동성 Agent for removing cyanobacteria and removing method of the same.
KR20180119726A (en) * 2017-04-25 2018-11-05 이명희 Water clarifying agent for removing water-bloom and red tide
CN110526355A (en) * 2018-05-26 2019-12-03 王忠厚 A kind of Novel pollution-free water purification agent prescription and preparation method thereof
KR102355146B1 (en) * 2021-03-24 2022-02-08 주식회사 우석환경 Green tide remover and its manufacturing method

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