KR101355178B1 - Water treating agent of food wastewater and for removing green algae, red algae and odors - Google Patents

Abstract

The present invention relates to a water treatment agent for removing green and red algae and/or odors and a water treatment method using the same, more specifically to: a water treatment agent for removing green and red algae and/or odors which includes sea water, yellow soil, white clay, sea shell powder, marine soil, caustic soda, charcoal powder, aluminum sulfate, and bay salt; and a water treatment method using the same. according to the present invention, the water treatment agent absorbs and decomposes microorganisms which causes green and red algae for offering a contamination treatment effect in short time, and does not generate a secondary contamination problem or produce harmful materials by using eco-friendly natural minerals. The water treatment agent uses natural mineral materials which can be unlimitedly and economically obtained from the nature, does not need a large scale production facility, has an easy usage method, and is useful to remove green and red algae and/or odors.

Description

Water Treatment Agent for Food Wastewater and for Removing Green Algae, Red Algae and Odors}

The present invention relates to a water treatment agent for treatment of effluent and green algae and / or odor removal, and a water treatment method using the same, more specifically seawater, loess, white soil, shell shell powder, marine soil, caustic soda, charcoal powder, sulfuric acid It relates to a green algae and / or odor removal water treatment agent containing aluminum and sun salt and the like and a water treatment method using the same.

In Korea, due to industrialization, the outflow of polluted water such as factories formed along rivers is intensifying. Existing crops and livestock waste water are causing serious water pollution on narrow lands along with living sewage including negative waste water. If eutrophication and green algae occur at the time of increase in the lakes and dams, and when typhoons of similar scale to cicada occur again, the result will be due to non-point sources such as turbidity including hardly decomposable organic matter, phosphorus and suspended earth. Water pollution is a very serious reality.

As an example, the recent Doam Dam in the Namhan River water system, along with the Imha Dam in the Nakdong River water system, called the first East Coast hydroelectric power plant in Korea, costing KRW 122.6 billion by requiring the closure of dams due to pollution, not only by local residents, civil society but also by local governments. Of course, since March 29, 2001, power generation disruption caused by the discontinuation of power generation has caused more than 10 billion won in losses per year. It is a serious case.

The high concentrations of nitrogen and phosphorus, which are the causes of eutrophication, have been pointed out that the effluent from Doam Dam is the major source of pollutants in the Songyang and Donggang waters, including Songcheon. The reason why the water quality of Doam Dam is not improved is located in the upstream area of Doam Dam. Soils mixed with fertilizer and pesticides in highland vegetable complexes are influxing during heavy rains, but it is analyzed that they are not equipped with environmental basic facilities upstream of the dam.

The Doam Dam, which lost its self-cleaning capacity, discharges more than a second grade of water, but the sedimentation tank provided by the dam's self-purification facility is only 3 tons per second, which causes worsening water quality. In particular, during the dry season, the Songcheon water system is depleted, which causes ecosystem damage. Almost all dams and lakes in Korea show similar patterns.

Once contaminated lakes and dams are difficult to purify themselves due to the nature of the stagnant water system. In addition to maintaining ecosystems and water quality, such as lakes and dams, nutrients and turbidity are required to maintain the quality of dam discharged water. In the case of the target material in the lake dam, the biological process is followed by many processes for high efficiency purification due to constraints such as the time required for the application of the microorganism lake dam.

Among them, naturally occurring green algae and red algae are caused by abnormal growth of phytoplankton, which is a food for fish, by eutrophication and the like, and have a fatal effect on fish farming in offshore farms. That is, the amount of dissolved oxygen in the water is greatly reduced as the phytoplankton, which is a food for fish, is increased, thereby killing fish and aquatic organisms.

Green algae is a phenomenon in which algae microorganisms multiply in water and release green paint in the upper part of the water. Fertilizers and pesticides such as decaying organic pollutants, trace metals and growth promoting substances such as phosphorus (P) and nitrogen (N) When living sewage, which contains a large amount of nutrients, is abundantly introduced into the water and the water temperature rises to create an environment suitable for the growth of plankton, a large amount of algae microorganisms are reproduced in a short time. Green algae-causing organisms (phytoplankton) are mostly southern algae, but are often caused by ciliary reptiles, a kind of protozoa.

Hundreds of billions of billion won of environmental damages are caused by harmful green algae that occur from May to October every year. Green algae are easily generated at high or slow flow rates, such as solidified dams, reservoirs, lakes, golf course hazards, ponds, freshwater farms, and fishing grounds. Most of the green algae found in Korea are a kind of southern algae.

When algae begin to develop, the rate of reproduction of algae microbes increases exponentially, and most of the algae absorb the oxygen content of the water, causing the water to rapidly eutrophicate (oxygen deficiency), causing severe odors. Fishes in the water, due to lack of oxygen and algae attached to the gills, have difficulty breathing due to the change of water temperature due to difficulty in breathing. The frequency, area and duration of green algae are increasing all over the world. Increasing nutrients during heat waves and droughts causes algal blooms in rivers and lakes to destroy ecosystems in aquatic environments as well as cause problems for terrestrial animals.

The presently used method to solve the green algae is shown in Table 1.

Algae removal technology Kinds system Advantages Disadvantages One Aberration Rotating like a watermill, artificially mixing water. Oxygen supply to the bottom Prevents phosphorus from melting out of the riverbed and prevents death of fish Water quality improvement effect against installation cost 2 ultrasonic wave Destroy the algae's air pockets, sinking the algae under water Eco-friendly green algae removal Unavailable in large area, high maintenance cost 3 Green algae Installation and operation of green algae suction rack recovery device on ship Environmentally friendly treatment High maintenance costs 4 ocher Clumping exhausted Temporary green algae removal effect Blocks sunlight to disrupt ecosystems and cause secondary pollution 5 Agicide Destruction of algae with copper sulfate Algal growth inhibition, fast treatment effect Ecological damage concerns, high disposal costs

Red tide is a phenomenon in which the seawater is red due to the explosive generation of plankton, which is rich in perishable organic contaminants, trace metals, and growth-promoting substances, such as domestic sewage such as phosphorus (P) and nitrogen (N). If the environment is suitable for propagation of plankton by the inflow of seawater and rising of seawater temperature, the plankton is reproduced in large quantities in a short time. Most of the organisms causing red tide (phytoplankton) are flagella algae and diatoms, but ciliary reptiles, which are euglenas or protozoa, may be the cause.

Hundreds of billions of fishermen's damage is caused by the harmful red tide that occurs between June and September every year. Red tide starts to occur early in the vicinity of Yeosu and Wando, Jeonnam, when the sea water temperature exceeds 23 ℃ for an average of three days, and spreads very quickly to the waters near Pohang when it is severely located in Masan and Tongyeong. Although red tide occurs not only in Korea but also in Japan, the United States, Kenya, and Mexico every year, the red tide is very toxic enough to kill meat in many fish farms at once. It's been a long time. In Korea, the frequency, area, and period of red tide are increasing year by year, and the amount of damage and the pain of fishermen are increasing.

Table 2 summarizes the methods currently used as red tide removal methods to solve the red tide phenomenon.

How to remove red tide division Contents characteristic Remarks One Wavelength Remove red tide using electromagnetic waves / ultrasound Reduction of Coclodinium as a Red Tide Caused by Microwave High red tide relief 2 Electrolysis Electrolyze seawater to create sterilizing substance NaOCl "to remove red tide Sterilize and eliminate red tide Unlike the yellow soil spray method, there is little possibility of secondary environmental pollution 3 Zeolite
How to use A method of relieving red tide by adsorbing red tide and depositing it into the sea by using zeolites widely used as detergents, catalysts and adsorbents. 95% red tide precipitation rate 10 times higher red tide sedimentation rate with less than yellow soil 4 Magnesium hydroxide
Usage Red tide remedy by extracting magnesium in seawater and using magnesium hydroxide Indirect remedy method to remove red tide by blocking the food chain by reducing phosphorus (P) and nitrogen (N) components that feed red tide organisms Effect of inhibiting the dissolution of heavy metals such as chromium (Cr) and lead (Pb) contained in marine sediments 5 Natural enemies
How it worked How to get rid of red tide by using animal plankton, which is a natural enemy of phytoplankton that causes red tide, and natural microorganisms that are highly specific to red tide. Environmentally friendly Low cost 6 Ozone treatment Red tide remedy by using sterilizing power of ozone (O3) May adversely affect other microorganisms as well as red tide Low cost 7 Ocher Spray Red tide rescue by colloidal particles of ocher flocculating red tide Some red tide rises again or settles in the sea after precipitation, causing secondary environmental pollution. Low cost 8 Ocher + flocculation aids Method for preparing red tide remover by inserting various coagulant aids into loess as additive Utilizes to add red tide coagulant effect or decrease turbidity by adding adjuvant to loess Increased red tide effect 9 Bio Control Method How to remove red tide by extracting active or bactericidal substances from marine microorganisms or plants Environmentally friendly High relief 10 Chemical spraying Red tide relief by using highly efficient chemicals to remove red tide Difficult to research and develop environmentally friendly chemicals High relief efficiency
Low cost
Red tide relief in a short time

Existing methods of removing and removing red tide organisms include chemical spraying, ultrasonic treatment, ozone treatment, and bio-control, which destroy or kill red tide, but for industrial use, mass production, large scale spraying and It must be competitive in price because it should not affect the seabed ecosystem, be easy to transport and simple to use.

In Korea, live loess spreading method was used to prevent and remove green algae. In general, loess is a material that can be easily obtained anywhere, harmless to living organisms, and proved to be harmless in the dissolution test under the Japan Marine Pollution Prevention Act. The role of the material circulation and natural purification is great, and in particular, the colloidal particles of ocher have the advantage of adsorbing and agglomerating the suspended substances of seawater, which can be used as a material to remove the green algae microorganisms.

However, if the raw raw clay, which is not refined and processed, is applied to the sea as it is, the loess and impurities are settled as it is, so there is no time for adsorption and flocculation of the green algae, and thus the efficiency of removing the green algae decreases and becomes unprotected. Due to dumping at sea, there is a problem that can cause secondary environmental pollution of the seabed.

Water treatment agents are chemicals used to facilitate physical, chemical and biological water treatment. In the case of drinking water, it is important to satisfy the water quality standards of raw water and purified water in the case of drinking water and to prove the safety of health. In the case of sewage treatment, it is necessary to consider the water quality of influent and effluent. In Korea, the discharged water quality standards of sewage treatment plants are uniformly applied according to the provisions of the Water Environment Conservation Act, and in the future, it is expected to apply the differential standard considering the characteristics of each water system and region by implementing the total pollutant regulation system. For example, in the United States and European Union countries, the discharge water quality standards are differentially applied according to the pollutant loads on the receiving streams by region and water system.In Japan, the national discharge water quality standards are similar to those of Korea, but separate by local governments. The discharge water quality standard of the country is applied.

In Korea, 20 species are designated as water treatment agents, 7 species including aluminum sulfate as a flocculant, 5 species including chlorine as a disinfectant disinfectant, 1 species as antirust agent, and 7 types including activated carbon as other agents. In addition, there are 17 kinds of items in which two or more kinds of water treatment agents have been approved for self-quality standards and specifications (Table 3).

Status of Water Treatment System in Korea Usage Product Name Notice Let's have quality system 20 17 Yes Polyaluminum Chloride
Aluminum sulfate
Polyaluminum Silicate
Polyaluminum Hydroxide
Ferric Sulphate
Ferric Chloride
Sodium alginate

Polyorganic Aluminum Sulfate
Organic Polymer Aluminum Sulfate
Polyorganic Aluminum Sulfate-M
Poly Aluminum Magnesium Sulfate
-Name of Coa
-DMC
Ferric Aluminum Sulfate
-PAC Ferric Sulphate Mixture Composition
Chitosan-based polyaluminum chloride
Chitosan liquid aluminum sulfate
Polysilica aluminum Sterilization
·
disinfectant Highly bleached powder
Liquid Chlorine
Sodium hypochlorite
Chlorine Dioxide
-ozone Antirust agent Antirust Other Calcium hydroxide (slaked lime)
Activated Carbon
-Hwangsandong
Sodium hydroxide (liquid)
Zeolite
-Light
-Sulfuric acid -SCI-62
-HANCLEAN
-FILDCLEAN
-HANCLEAN-X
-Earth Tec
Zeocarbon

In addition to hate facilities such as wastewater treatment plants, there are many kinds of odor-producing substances, including ammonia, in our surroundings. Normally, even odors generated in the human body include sulfur compounds such as hydrogen sulfide and mercaptan, nitrogen compounds such as ammonia, scatol and amine, and fatty acids such as formic acid and acetic acid. In recent years, as the standard of living improves, the unpleasant odor of life is regarded as pollution, and the regulation by relevant laws is tightened.

Conventional deodorization methods for removing such odors include chemical deodorization (masking), which is supplemented by olfactory smell or fragrance, and chemical deodorization and activated carbon decomposed by oxidation, reduction, neutralization, and side reactions. It is roughly classified into a physical adsorption method using a porous material such as silica gel and a biological deodorization method using a microorganism or an enzyme.

However, natural and synthetic fragrances in chemical deodorization have so many kinds that the ingredients are not known, but respiratory and skin troubles are easily caused by toxicity, and the physical adsorption method again increases with increasing temperature and pressure during use. It is easy to regenerate, and the biological deodorization method is not stable due to the large difference in activity depending on the temperature and humidity conditions.

Chemical deodorization is one of the most promising areas for development, but it still has its own limitations in ensuring satisfactory deodorizing power.

The deodorant used in such a deodorant method is to use a deodorant mainly composed of chemical components, the deodorant composed of this chemical component is made of strong acid, harmful to the human body has a problem that is unsafe and causes many side effects in use have.

Deodorants made of conventional chemicals are not only harmful to the human body, but also harmful to the human body in the process of deodorization. The fragrance or naphthalene, which is used to remove odors, causes chemical reactions with ammonia, that is, chemical reaction with NH3, and does not decompose and remove odors by changing the molecular structure of ammonia. Is more indirect than the odor to be decomposed and removed, and thus the user is only an indirect deodorizing function to prevent the user from the odor caused by ammonia.

These deodorants emit a stronger odor than conventional odors, so that the user cannot distinguish odors by the strong scent of chemicals, so that the user feels the illusion that the odor is removed. It just causes the effect.

Conventional patents for water treatment agents using natural products include sea tide removal for charcoal and ocher (Korean Patent Publication No. 2004-0014103), ocher-carp fiber composites for the removal of green algae or red tide and methods for their preparation (Korean Patent No. 0819460), acidic clay Composition for combating green algae (Korea Patent No. 0711900), Phosphorus remover composition for removing phosphorus using aluminum sulfate and water treatment method (Korea Patent No. 1216181) Deodorant composition using natural materials (Korea Patent Publication No. 2011-0080454) And the like, but green algae, red tide and / or odor removal efficiency were not high.

Accordingly, the present inventors have made efforts to solve the above problems, as a result, seawater, ocher, white clay, shellfish powder, marine soil, caustic soda, charcoal powder, aluminum sulfate and sun salt to prepare a water treatment agent, using the green algae It was confirmed that red tide and / or odor were effectively removed, and the present invention was completed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a water treatment agent for treating wastewater and green algae and / or odor removal and a water treatment method using the same.

In order to achieve the above object, the present invention (a) 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, 0.01 to 10 parts by weight of ocher powder, 0.01 to 10 parts by weight of clay powder, 0.01 to 10 parts by weight of clam shell powder, 100 parts by weight of a precipitate (produced 1-1) and 50 to 1000 parts by weight of supernatant thereof (produced 1-2) obtained by stirring 0.01 to 10 parts by weight of marine soil, followed by precipitation for 0.5 to 24 hours; (b) 10 to 500 parts by weight of supernatant obtained by stirring 100 parts by weight of seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then 0.5 to 24 hours of precipitation; And (c) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate, and then Provided is a green algae and / or odor removal water treatment agent comprising 50 to 200 parts by weight of a precipitate (produced by 3-1) and 25 to 2000 parts by weight of supernatant thereof (produced by 3-2).

The present invention also includes (a) green algae contaminated water, red algae contaminated water, mixed contaminated water of green algae and red algae, or 1 L of contaminated odor causing substances, 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, and 0.01 to 10 parts by weight of ocher powder. 0.01 to 10 parts by weight of clay powder, 0.01 to 10 parts by weight of shellfish powder, 0.01 to 10 parts by weight of marine soil, and then precipitated for 0.5 to 24 hours, 0.1 to 5 g of a precipitate (prepared 1-1), and Adding 0.1 to 50 ml of the supernatant (1-2) and stirring for 0.1 to 24 hours to aggregate green algae, red tide, or odor causing substances; And (b) 0.1 to 100 parts by weight of (i) seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then precipitated for 0.5 to 24 hours in (a). 50 ml and (ii) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate Next, green algae comprising the step of adding 0.1 to 5 g of precipitate (prepared by 3-1) and 0.1 to 50 ml of the supernatant (prepared by 3-2), stirring for 0.1 to 24 hours and then precipitating, obtained by precipitating 0.5 to 24 hours, Provides a water treatment method for removing red tide or odor.

According to the present invention, by adsorbing and decomposing the microorganism causing the green algae can exhibit the effect of improving pollution in a short time, by using environmentally friendly natural minerals, no harmful substances are produced or secondary pollution problems. In addition, it uses natural mineral materials that can be infinitely extracted at low cost in nature, does not require large-scale manufacturing facilities, and is easy to use, so it is useful for the treatment of effluent water and red tide and / or odor removal.

Figure 1 shows before and after the treatment of the water treatment agent according to the present invention in the green algae contaminants.
Figure 2 shows before and after the treatment of the water treatment agent according to the present invention in red tide contaminants.

The present invention in one aspect (a) 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, 0.01 to 10 parts by weight of ocher powder, 0.01 to 10 parts by weight of clay powder, 0.01 to 10 parts by weight of shellfish powder, 0.01 to 10 parts by weight of marine soil 100 parts by weight of a precipitate (formulated from 1-1) and 50 to 1000 parts by weight of supernatant thereof (formed from 1-2) obtained by stirring 10 parts by weight and then precipitating 0.5 to 24 hours; (b) 10 to 500 parts by weight of supernatant obtained by stirring 100 parts by weight of seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then 0.5 to 24 hours of precipitation; And (c) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate, and then The present invention relates to 50 to 200 parts by weight of a precipitate (produced by 3-1) and 25 to 2000 parts by weight of supernatant thereof (produced by 3-2), and / or a water treatment agent for removing odor.

The main component of seawater is sodium chloride (NaCl), and the quality and quantity of impurities are different depending on the places of collection and manufacturing methods. Pure is 38.4% Na, 60.6% Cl, and common impurities are KCl, MgCl2, MgSO4, NaSO4, CaSO4 and insolubles.

Seawater has the effects of anti-oxidation, osmotic action, enzyme stop action, protein lysis action, protein coagulation action, cell softening action, detoxification action, antiseptic action, and bactericidal action.

Solar salt is a kind of salt that is the main component of the seawater, and contains almost all of the minerals in the seawater, and calcium, potassium, magnesium, and iron are present as the main minerals. In particular, domestic natural salt is produced in the tidal flat, its manufacturing method is unique in the world, and contains a large amount of minerals compared to foreign natural salt. In other words, rock salts and refined salts consumed by most people around the world have a sodium chloride content of more than 99%, while minerals such as K, Ca, or Mg are hardly present. Natural salts, especially Korean-made tidal flat salts, contain 85% sodium chloride. On the other hand, it is reported to contain a large amount of mineral components such as K, Ca or Mg.

Salt has a bactericidal, disinfecting, antiseptic and deodorizing effect, of which the bactericidal or bacterial growth inhibitory effect is due to the osmotic action of the salt. Brine takes the form of sodium hypochlorite (NaOCl) by the electrolysis reaction, and chlorine hypochlorite, as is widely known, is used for water purification plants, sterilizers for sewage treatment plants, cooling water boilers for general chemical plants, desalination process water and cooling water for power plants. It is a colorless transparent liquid with a strong chlorine odor that is used as a treatment, drinking water treatment, plants and vegetables, meat processing, off-pool laundry and papermaking, household bleach.

In the first or third agent of the present invention, the concentration of the sun salt is preferably used in an amount of 0.1 to 30 parts by weight, and more preferably in the range of 1 to 20 parts by weight. If less than 0.1 parts by weight of the green algae relief effect is not effective, if more than 30 parts by weight is not effective because the difference in effect is not greater than when used in 10%.

Loess is a material that can be easily obtained anywhere, has no harm to living organisms, and has been proved to be harmless in the dissolution test under the Japanese Marine Pollution Prevention Act, and the role of natural circulation and natural purification is particularly high. It has the property of adsorbing and agglomerating, which can be used as a material for removing red tide.

However, if the raw raw loess which is not refined and processed is applied to the sea as it is, the loess and impurities are settled as it is, so there is no time for adsorption and aggregation of red tide organisms. Because of dumping, there is a problem that can cause secondary environmental pollution of the seabed.

In the case of ocher powder, rather than rapidly settling in the seawater, it is widely dispersed in the seawater, causing sufficient collision with the red tide, thereby forming adsorption and aggregates and settling. Since the formation layer is about 3 ~ 5m deep to form red tide bands, spraying by various particle size distribution of ocher powder is possible to adsorb and remove red tide organisms according to the particle level as ocher particles settle at sea level. Appropriate amount spraying can effectively control the tide control.

The physical forces of ocher particles in seawater are settling and diffusion. As the size of the ocher particles increases, the settling velocity of the particles increases geometrically and the diffusion velocity of the particles decreases geometrically. Here, the sedimentation speed is the speed at which the particles sink in the vertical direction by gravity, and the diffusion speed is the speed at which the particles spread out in the horizontal and vertical directions by colliding with the water molecules.

The physicochemical forces of the ocher particles themselves in seawater are attractive and repulsive forces. Seawater is a high concentration of electrolyte solution and ocher particles show very thin electrical double layer in such seawater, so there is little repulsive force between mutually approaching ocher particles. Only the attraction force acts to easily form flocculation.

In the present invention, the adsorption principle of the ocher powder is widely dispersed in seawater, causing sufficient collision with the red tide organisms, and the red tide organisms by the attractive force between the colloid particles of the ocher powder are adsorbed to the pore layer and the surface layer of the ocher powder by high temperature drying. As the molecules are adsorbed, they settle naturally to remove red tide.

In addition, aluminum oxide, the main component of ocher, has the property of adsorbing, and when ocher is dissolved in seawater, aluminum ions are eluted to adsorb and aggregate red tide microorganisms, and the average pH of seawater is 7.4 or more, but ocher is dissolved in seawater. When the pH of seawater is reduced to around 7.0, it has the property of acidifying seawater.

In the first and third agents of the present invention, the content of the ocher powder is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. When the content of ocher powder is less than 0.01 part by weight, the adsorption coagulation efficiency or deodorization efficiency of the green algae is decreased, and when it is mixed in excess of 10 parts by weight, the mixing amount of other components is relatively decreased, thereby reducing the control efficiency of the green algae. have.

Clay is a clay composed of extremely fine powder mainly composed of clay mineral montmorillonite. It is similar to bentonite to the extent that it is thought to be produced by surface weathering of bentonite. The adsorptive catalyst is strong, but it does not swell very much even if it contains water, and its activity is slightly high. There are white, yellow, and blue, which are usually pale yellow. The composition is about 70% of silicon dioxide, and aluminum oxide, iron oxide, magnesium oxide, and the like, and the ignition loss (burn loss) is reduced. The pH of the suspension is 5-6. It is used in bleaching agents, desiccants, adsorbents, ceramics, hard water softeners, pharmaceuticals, pesticides and extenders of powdered soaps, bleaches of old newspapers, catalysts in organic chemical reactions, conversion of sugars, sugaring agents of starches, raw materials of lakes and the like.

In the first and third agents of the present invention, the content of the clay powder is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. If the content of white clay powder is less than 0.01, the adsorption agglomeration efficiency or deodorization efficiency of the green algae is lowered, and if the content exceeds 10 parts by weight, the acid is strongly present, which may harm the environment.

Shell shell powder is incinerated all shells such as oysters, clams, mussels, and pearl mussels produced in the sea at 600 ~ 700 ℃ in shell powder processing plant, and is a roughly crushed crushed powder of 2mm or less. The name of farmland fertilizer) was mixed, and the components of clam shell powder (shell fossil powder) were 51.6% of calcium (CaO), 3.54% of silicon (SiO2), 0.31% of goto (MgO), 0.16% of iron (Fe), and phosphoric acid. (P2O5) 0.03%, potassium (K2 O) 0.04%, organic matter 5.65%, etc. Quicklime or hydrated lime is strong alkalinity around pH10.0, which is effective in improving the polluting environment, but 2 weeks after spraying In order to make up for the shortcomings that the water quality and the low soil alkaline remain insignificant and gradually change to non-decomposable substances such as calcium carbonate (CaCO3), the clamshell powder is mixed with a roughness powder of 2 mm or less particles and then gradually dissolved for a long time after spraying. By letting go And long-lasting maintenance of an alkaline environment is used to supply materials to the mineral component to contribute to nophi productivity.

In the present invention, the content of the clam shell powder is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. If the content of the clam shell powder is less than 0.01, the adsorption and flocculation efficiency of the green algae is lowered, and if it exceeds 10 parts by weight, the difference in effect is not greater than when using 10 parts by weight is not efficient.

Charcoal is made of porous, deodorizing effect, absorbs various viruses and bacteria, has excellent sterilizing power, absorbs various heavy metals, does not oxidize after thousands of years, has a negative charge, and is highly regarded as a safe natural preservative.

In addition, charcoal cleanses contaminated water, enhances the activity of sea microorganisms, prevents decay when settled in various pollutants and water, and becomes a food for meat as it becomes manure.

The physical properties of charcoal vary depending on the species and the state of carbonization. The carbon structure of charcoal is composed of graphite-like microcrystalline and amorphous parts surrounding it. The size of the microcrystalline is larger the higher the carbonization. As crystals develop, their electrical conductivity increases and their electrical resistance decreases. There is a direct relationship between the amount of residual undissolved matter and the electrical resistance. The calorific value is 7000 ~ 8000kcal and the specific gravity is 1.4 ~ 1.9. Volume weights average 0.65 to 0.70. Hardness depends on species, water content, carbonization temperature and refining operation. Among the black coals, the oak and oak trees are hard, the pine charcoal made of conifers, the coals are soft, and the white coal is very hard. Charcoal is porous and adsorptive, especially white charcoal. The ignition point is 440 ~ 482 ℃ for white coal and 330 ~ 390 ℃ for black coal.

The carbon content of charcoal is about 95% of charcoal, about 89% of charcoal, and about 80% of charcoal.The maximum temperature of charcoal is over 1000 ℃ of charcoal, 450 ~ 750 ℃ of charcoal, 400 ~ 450 ℃ of charcoal, and high carbonization temperature. The higher the carbon content, the lower the oxygen and hydrogen contents. Ash in charcoal is 3wt% or less, and because it contains less sulfur, phosphorus, etc., it is an excellent carbon source for various purposes.

In the present invention, the charcoal is characterized in that any one selected from the group consisting of pine charcoal, true wood charcoal and palm charcoal.

In 2nd agent and 3rd agent of this invention, it is preferable that it is 0.01-10 weight part, and, as for content of charcoal, it is more preferable that it is 0.1-5 weight part. When the content of charcoal is less than 0.01, the adsorption agglomeration efficiency or deodorization efficiency of the green algae falls, and when it is more than 10 parts by weight, it is not preferable economically.

Aluminum sulfate, also called alumina sulfate, is used as a flocculant in water treatment agents. There are solid and liquid types, and recently, liquids that are easy to handle are mainly used.

Liquid aluminum sulfate is inexpensive and exhibits effective coagulation for most of the solutes. However, liquid aluminum sulfate has high concentrations of aluminum oxide at low water temperature, so crystals may clog due to precipitation of crystals. Therefore, the concentration of liquid aluminum sulfate should be used with caution, and the treatment effect can be enhanced by using a low temperature or high concentration coagulation aid.

In the present invention, the content of aluminum sulfate is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. If the amount of aluminum sulfate is less than 0.01, the adsorption agglomeration efficiency or deodorization efficiency of the green algae decreases, and if it exceeds 10 parts by weight, the pH may decrease rapidly and the water quality may change rapidly.

Caustic soda (NaOH) is used as alkali agent together with sodium sulfite (Na2SO3) or ammonia (NH3), etc.Alkali aqueous solution (caustic soda solution, sodium sulfite solution or ammonia solution) absorbs hydrogen sulfide, mercaptans and sulfur dioxide in the gas The odorous substance is neutralized by an alkali absorption method, and as a by-product, Na ₂ SO ₃ , Na ₂ SO ₄ , sulfur, sulfuric acid, and the like are generated.

Caustic soda removes hydrogen sulfide in the form of sodium sulfide and mercaptans and sulfur dioxide in the form of sodium sulfite. When caustic soda is supplied, a reaction in which hydrogen sulfide is removed in the form of sodium sulfide is carried out first, followed by a reaction in which mercaptans or sulfur dioxide is removed in the form of sodium sulfite.

In the present invention, the content of caustic soda is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. When the content of caustic soda is less than 0.01 parts by weight, the adsorption agglomeration efficiency or deodorization efficiency of the green algae is lowered, and when it is more than 10 parts by weight, the useful substances in the stream may be easily lost and may not be used as nutrients.

Marine soils (soil soils) contain abundant minerals (inorganic or inorganic salts), and minerals are oxygen (O) and carbon, which constitute the human body and are the major constituents of organic matter among the elements necessary for physiological activities such as growth and maintenance of the human body. Calcium, potassium, sodium, magnesium, phosphorus, sulfur, chlorine, iron, copper, iodine, manganese, baltic and zinc, etc., except for (C), hydrogen (H) and nitrogen (N), are collectively referred to.

Major components of marine soil include Na ⁺ , Mg ^{2 +} , Ca ^{2 +} , K ⁺ , and recently, it has been reported that marine soil contains a large amount of active ingredients such as Ge, Se and Li. By absorbing pollutants, it has a function of water purification and prevention of eutrophication.

In the present invention, the content of the marine soil is preferably used in 0.01 to 10 parts by weight, more preferably used in 0.05 to 5 parts by weight. If the content of marine soil is less than 0.01 parts by weight, the adsorption agglomeration efficiency or deodorization efficiency of the green algae organisms is lowered, and when the mixture is mixed in excess of 10 parts by weight, the amount of other components is relatively reduced, which reduces the control efficiency of the green algae organisms. .

In the present invention, (a) 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, 0.01 to 10 parts by weight of ocher powder, 0.01 to 10 parts by weight of clay powder, 0.01 to 10 parts by weight of clam shell powder, 0.01 to 10 parts of marine soil When making 100 weight part of precipitates (the 1-1 agent) obtained by stirring a weight part and then precipitate for 0.5 to 24 hours, it is preferable that the supernatant (1-2 agent) is 50-1000 weight part, and it is 100-500 weight More preferably denial. When the amount of the 1-2 agent is less than 50 parts by weight, the adsorption agglomeration efficiency or deodorization efficiency of the green algae is lowered, and when it is more than 1000 parts by weight, the difference in effect is not greater than that when 1000 parts by weight is used.

When the 1-1 agent is 100 parts by weight, (b) supernatant water obtained by stirring 100 parts by weight of seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then precipitation for 0.5 to 24 hours. ) Is preferably 10 to 500 parts by weight, more preferably 100 to 200 parts by weight. When the content of the second agent is less than 10 parts by weight, the adsorption agglomeration efficiency or deodorization efficiency of the green algae is lowered, and when the content is greater than 500 parts by weight, the difference in effect is not greater than that when 500 parts by weight is used.

The above 1-2 agent "supernatant" is (a) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-10 parts by weight of clam shell powder, Mean supernatant except for precipitate (1-1) obtained by stirring 0.01 to 10 parts by weight of marine soil and then precipitation for 0.5 to 24 hours.

In the present invention, when the 1-1 agent is 100 parts by weight, (c) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, charcoal powder 50-200 parts by weight of precipitate (form 3-1) and its supernatant (form 3-2) obtained by stirring 0.01-50 parts by weight and 0.01-10 parts by weight of aluminum sulfate, followed by precipitation for 0.5-24 hours. It is preferable that it is weight part, The said 3-1 agent is 80-120 weight part, It is more preferable that 3-1 agent is 50-1000 weight part. When the content of the 3-1 agent is less than 50 parts by weight or the content of the 3-2 agent is less than 25 parts by weight, the adsorption agglomeration efficiency or deodorization efficiency of the green algae is lowered, and the content of the 3-1 agent is 200 parts by weight. If the content is greater than 2 parts by weight or more than 2000 parts by weight, the difference in effect is not as large as it is not exceeded, which is not efficient.

The 3-2 agent "supernatant" (c) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and sulfuric acid Mean supernatant except for precipitate (3-1) obtained by stirring 0.01 to 10 parts by weight of aluminum and then precipitation for 0.5 to 24 hours.

In another aspect, the present invention (a) green algae contaminated water, red algae contaminated water, mixed contaminated water of green algae and red tide, or 1 L of contaminant-causing substances contaminated water 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, 0.01 to 0.5 ocher powder 10 parts by weight, 0.01 to 10 parts by weight of clay powder, 0.01 to 10 parts by weight of shellfish powder, 0.01 to 10 parts by weight of marine soil, followed by precipitation for 0.5 to 24 hours. Adding 5 g and 0.1 to 50 ml of supernatant thereof (1-2) and stirring for 0.1 to 24 hours to aggregate green algae, red tide, or odor causing substances; And (b) 0.1 to 100 parts by weight of (i) seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then precipitated for 0.5 to 24 hours in (a). 50 ml and (ii) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate Next, green algae comprising the step of adding 0.1 to 5 g of precipitate (prepared by 3-1) and 0.1 to 50 ml of the supernatant (prepared by 3-2), stirring for 0.1 to 24 hours and then precipitating, obtained by precipitating 0.5 to 24 hours, The present invention relates to a water treatment method for removing red tide or odor.

In one embodiment of the present invention, using a seawater, ocher, white clay, shellfish powder, marine soil, caustic soda, charcoal powder, aluminum sulfate and sun salt to prepare a sediment or liquid water treatment agent to be treated with green tide contaminated water and stirred When it was made, it was confirmed that agglomeration and sedimentation occurred and exhibited more than 95% of rust control or odor removal effect.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

< Manufacturing example  1> Green tide  And / or odor removal Water treatment agent  Produce

Seawater, loess, white clay, clam shell powder, marine soil, caustic soda, charcoal powder, aluminum sulfate and sun salt were used to prepare a water treatment agent for removing green algae and / or odors.

10 g of natural salt, 3 g of ocher powder, 3 g of white clay powder, and 2 g of clam shell powder and 3 g of marine soil were added to 1 L of purified water, followed by stirring, followed by precipitation for about 1 hour to precipitate a precipitate (1-1) and its supernatant (1-2). Respectively). The precipitate was obtained by passing through 500mash.

2 g of pine charcoal powder and 10 ml of liquid caustic soda were put together in 1 L of seawater, followed by stirring for 1 hour to obtain supernatant water (second agent) except for a precipitate.

10 g of natural salt, 3 g of white clay powder, 3 g of ocher powder, 2 g of charcoal powder and 2 ml of liquid aluminium sulfate were added to 1 L of purified water, followed by stirring for 1 hour. The precipitate (3-1 agent) and its supernatant (3-2) Respectively). The precipitate was obtained by passing through 500mash.

< Manufacturing example  2> Green tide  And / or odor removal Water treatment agent  Produce

30 g of sun-dried salt, 10 g of ocher powder, 10 g of white clay powder, and 5 g of clam shell powder and 10 g of marine soil were added to 1 L of purified water, followed by stirring for about 1 hour to precipitate and precipitate (1-1) and its supernatant (1-2). Respectively). The precipitate was obtained by passing through 500mash.

5 g of pine charcoal powder and 30 ml of liquid caustic soda were put together in 1 L of seawater, followed by stirring for 1 hour to obtain supernatant water (second agent) except for a precipitate.

30 g of natural salt, 10 g of white clay powder, 10 g of ocher powder, 5 g of charcoal powder and 5 ml of liquid aluminium sulfate were added to 1 L of purified water, followed by stirring for 1 hour. The precipitate (3-1) and its supernatant (3-2) Respectively). The precipitate was obtained by passing through 500mash.

< Manufacturing example  3> Green tide  And / or odor removal Water treatment agent  Produce

Seawater, loess, white clay, clam shell powder, marine soil, caustic soda, charcoal powder, aluminum sulfate and sun salt were used to prepare a water treatment agent for removing green algae and / or odors.

80 g of natural salt, 30 g of ocher powder, 30 g of white clay powder, and 15 g of clam shell powder and 30 g of marine soil were added to 1 L of purified water, followed by stirring, followed by precipitation for about 1 hour to precipitate a precipitate (1-1) and its supernatant (1-2). Respectively). The precipitate was obtained by passing through 500mash.

15 g of pine charcoal powder and 80 ml of liquid caustic soda were put together in 1 L of sea water, followed by stirring for 1 hour to obtain supernatant water (second agent) except for a precipitate.

80 g of natural salt, 30 g of white clay powder and 30 g of ocher powder, 15 g of charcoal powder and 15 ml of liquid aluminium sulfate were added together to 1 L of purified water, followed by stirring for about 1 hour. The precipitate (3-1) and its supernatant (3-2) Respectively). The precipitate was obtained by passing through 500mash.

Example  One : Green tide  Check for relief

Using the green algae and / or odor removal water treatment agents obtained in Preparation Example 2, the green algae relief effect was to be examined. 5 g of 1-1 and 5 ml of 1-2 obtained in Preparation Example 2 were placed in 1 L of green tide contaminated water and stirred slowly, and it was confirmed that strong aggregation occurred between the precipitate and the green tide bioparticles.

To the flocculant, 10 ml of the 2nd agent obtained in Preparation Example 2, 5 g of the 3-1, and 5 ml of the 3-2 agent were added and stirred, and the rich aggregate was gradually precipitated. After about 2 hours, 95% or more precipitated and melted. It was confirmed that the red tide relief effect (Fig. 1, Fig. 2).

Using the water treatment agents obtained in Preparation Examples 1 and 3, it was confirmed that similar green algae relief effects were obtained even when the algae algae relief effect was tested in the same manner.

Example  2: Confirm the effect of removing odor

In order to confirm the odor removal effect of the water treatment agents obtained in Preparation Examples 1 to 3, NH ₃ deodorization test was carried out by treating the water treatment agent obtained in Preparation Examples 1 to 3 to 1 L of the water sample collected in the Ganwol lake of Seosan City, Chungnam. Deodorization effect experiment was performed according to the test regulations of KICM-FIR-1085: 2006, the deodorization rate was calculated by the measured reduction rate of NH ₃ .

In the same manner as in Example 1, 5 g of 1-1 agent and 5 ml of 1-2 obtained in Preparation Examples 1 to 3 were added to 1 L of contaminated water, followed by stirring, and then 10 ml of 2 agents obtained in Preparation Examples 1 to 3, respectively. And 5 g of 3-1 and 5 ml of 3-2 were added and stirred, and the deodorization rate was analyzed.

As a result, after 2 hours of treatment with the water treatment agent according to the present invention showed a deodorizing effect of 95% or more, it was confirmed that it has a deodorizing function (Table 4).

NH ₃ deodorization test result Time (min) Blank Concentration (ppm) Sample concentration (ppm) Deodorization rate (%) Production Example 1 Production Example 2 Production Example 3 Production Example 1 Production Example 2 Production Example 3 0 200 200 200 200 0.0 0.0 0.0 30 197 31 28 22 84.5 86 89 60 193 26 23 15 87 88.5 92.5 90 191 15 11 8 92.5 94.5 96 120 186 10 7 3 95 96.5 98.5

 While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (4)

Water treatment agents for removing algae, red algae or odors, including:
(a) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-10 parts by weight of clam shell powder, 0.01-10 parts by weight of marine soil, and then 100 parts by weight of a precipitate (formulated from 1-1) and 50 to 1000 parts by weight of supernatant thereof (formed from 1-2) obtained by precipitation for 0.5 to 24 hours;
(b) 10 to 500 parts by weight of supernatant obtained by stirring 100 parts by weight of seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, and then 0.5 to 24 hours of precipitation; And
(c) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate, followed by 0.5 50-200 parts by weight of a precipitate (form 3-1) obtained by precipitation for ˜24 hours and 25 to 2000 parts by weight of supernatant thereof (form 3-3).
The water treatment agent for removing green algae, red tide or odor according to claim 1, wherein the precipitates of steps (a) and (c) are passed through a mash of 300 to 600 mesh.
The method of claim 1, wherein the char of step (b) and (c) is any one selected from the group consisting of pine charcoal, oak charcoal and coconut charcoal, algae, red tide or odor removing water treatment agent.
Water treatment to remove green algae, red algae or odors, including the following steps:
(a) 100 parts by weight of purified water, 0.1 to 30 parts by weight of natural salt, 0.01 to 10 parts by weight of ocher powder, 0.01 to 10 parts by weight of clay powder, 0.01 g of green algae contaminated water, red algae contaminated water, mixed contaminated water of green algae and red algae or odor-causing substances contaminated water 0.1 to 5 g of precipitate (1-1) obtained by stirring -10 parts by weight, 0.01 to 10 parts by weight of shellfish powder, and 0.01 to 10 parts by weight of marine soil, followed by precipitation for 0.5 to 24 hours. 2) adding 0.1 to 50 ml and stirring for 0.1 to 24 hours to agglomerate green algae, red tide, or odor causing substances; And
(b) 0.1 to 50 ml of supernatant (secondary) obtained by stirring (i) 100 parts by weight of (i) seawater, 0.01 to 50 parts by weight of charcoal powder and 0.01 to 30 parts by weight of caustic soda, followed by precipitation for 0.5 to 24 hours. And (ii) 100 parts by weight of purified water, 0.1-30 parts by weight of natural salt, 0.01-10 parts by weight of ocher powder, 0.01-10 parts by weight of clay powder, 0.01-50 parts by weight of charcoal powder and 0.01-10 parts by weight of aluminum sulfate. 0.1-5 g of a precipitate (produced by 3-1) and 0.1-50 ml of its supernatant (produced by 3-2) were added by stirring for 0.5-24 hours, stirred for 0.1-24 hours, and then precipitated.

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