KR20180119726A - Water clarifying agent for removing water-bloom and red tide - Google Patents

Abstract

The present invention relates to a water purification agent for increasing the efficiency of removing green algae and red tide. The water purification agent comprises: a tourmaline; a titania photocatalyst; a light dolomite coagulant; an alkaline earth metal peroxide; a red clay carrier; vermiculite; sepiolite; perlite; and bentonite.

Description

{WATER CLARIFYING AGENT FOR REMOVING WATER-BLOOM AND RED TIDE}

The present invention relates to a method for improving greenhouse and red tide removing efficiency and improving water quality of four major rivers; Improving water quality in lakes, fresh water, and reservoirs; The present invention relates to a water purification agent comprising a mixture of a tourmaline, a titania photocatalyst, a light dolomite flocculant, an alkaline earth metal peroxide, an alumite carrier, vermiculite, aephrodite, perlite, and kaolin to enable various applications such as improvement of water quality of a golf course and the like.

Eutrophication can be classified into natural eutrophication and artificial eutrophication. Natural eutrophication is a part of natural phenomenon, which is slow in its progress but is also purifying and extinguishing itself due to low load of nutrients.

However, anthropogenic eutrophication occurs in a very short time due to the excessive nutrient loading and accumulation in excess of the purification capacity of nature, resulting in excessive increase of phytoplankton and the occurrence of algae.

When green algae occurs, water displays unpleasant taste and color, obstructs filter paper in water treatment process, and causes deterioration of water quality, wastewater flow, swamping of water system and marsh in addition to increase of drug cost. And eventually destroys the ecosystem.

Damage to cyanobacteria, which is the main cause of the algae phenomenon, also seriously damages the underwater microorganisms, fishes, flora and fauna, livestock, as well as people who use water, which form the normal ecosystem.

The red tide phenomenon is caused by a large number of marine algae breeding and discoloration of seawater, lack of dissolved oxygen and change of benthos, seriously affecting the survival of seafood, causing abnormalities of ecosystem, It is a phenomenon that affects.

When red tide occurs, dissolved oxygen in the water is deficient and aquatic organisms are poisoned by poisonous substances such as toxins produced by suffocation or red tide organisms or secondary hydrogen sulfide, methane gas, and ammonia. Particularly, some species of algae and green algae have toxicity to kill fish and shellfish.

Korean Patent Publication No. 2001-0092003 (published on October 24, 2001)

It is an object of the present invention to provide a water purifying agent comprising a tourmaline, a titania photocatalyst, a light dolomite flocculant, an alkaline earth metal peroxide, an alumite carrier, vermiculite, .

In order to achieve the above object,

The present invention relates to a composition comprising 5-45 wt% tourmaline;

Titania photocatalyst 1 ~ 10 wt%;

5 ~ 20wt% of light dolomite coagulant;

1 to 10 wt% alkaline earth metal peroxide;

1 to 15 wt% of an alumite carrier;

Vermiculite 0.5 to 10 wt%;

Sepiolite 0.5 ~ 10 wt%;

Perlite 0.5 ~ 10wt%;

And a mixture of 0.5 to 10 wt% of Bentonite; and a water purifying agent excellent in red tide removing function.

The water purifying agent according to the present invention is composed of components excellent in purification of water quality, removal of green tide, and removal of red tide, thereby exhibiting a green tide and red tide removal efficiency of 90% or more and a transparency of 10% or more even before using the water quality purifying agent.

Further, the water purifying agent according to the present invention can improve the water quality of the four major rivers; Improving water quality in lakes, fresh water, and reservoirs; Improvement of water quality such as golf course, and so on.

As described above,

According to the present invention, the water purifying agent for green tide and red tide removal comprises

Tourmaline 5 ~ 45wt%;

Titania photocatalyst 1 ~ 10 wt%;

5 ~ 20wt% of light dolomite coagulant;

1 to 10 wt% alkaline earth metal peroxide;

1 to 15 wt% of an alumite carrier;

Vermiculite 0.5 to 10 wt%;

Sepiolite 0.5 ~ 10 wt%;

Perlite 0.5 ~ 10wt%;

And 0.5 to 10 wt% of kaolin (Bentonite).

Hereinafter, a detailed description of the above-described technical configuration will be given.

The tourmaline is a borosilicate having hexagonal columnar crystals and is natural minerals belonging to a closely packed system. The chemical composition is complex borosilicate of aluminum, magnesium, alkali metal and aluminum, and the cleavage is not clear, and the cut is not flat or shell-like. Electricity is generated by friction, and when heated, both ends are positively charged, and this name is attached. The crystal itself has the characteristic of generating electricity and has a nickname of tourmaline and permanent electrical characteristics.

Tourmaline in the tourmaline is a polar crystal with permanent electrical properties, and tourmaline crystals continue to generate weak currents, so when water (H ₂ O) touches the crystal, it electrolyses water instantaneously. Tourmaline also works with moisture in the air to cause electrolysis. The electrolysis at this time is due to the physical action, and is constant and safe, so it changes into the water with vitality.

Tourmaline crystals continue to generate weak currents, so when water comes in contact with crystals, it electrolyses water instantaneously. Tourmaline also acts on water contained in the air to cause electrolysis. At this time, the electrolysis is changed into energetic water.

A tourmaline stone or powder is instantaneously discharged to moisture when it is exposed to moisture. At this time, water is electrolyzed and water molecule (H ₂ O) is separated into hydrogen ion (H ⁺ ) and hydroxide ion (OH ^- ). The separated hydrogen ions (H ⁺ ) are attracted to the negative electrode and are neutralized by being combined with electrons emitted therefrom, and become hydrogen gas (H ₂ ) and evaporate. In addition, the hydroxide ion (OH ^- ) binds to surrounding water molecules and becomes a surfactant called hydroxyl (H ₃ O ₂ ) anion.

H ₂ O (water) ---> H ⁺ (hydrogen ion) + OH ^- (hydroxide ion) (1)

Hydrogen ions combine with undecomposed water and become hydronium ions.

H ⁺ (hydrogen ion) + H ₂ O (water) ---> H ₃ O ^- (Hydronium Ion) (2)

The hydroxide ions are combined with the undecomposed water to form a hydroxyl ion having a surfactant effect.

OH ^- (hydroxyl ions) + H ₂ O ^{_{(water) ---> H 3 O 2 -}} (Hydroxyl Ion) (3)

Since tourmaline sequentially generates hydroxyl ions by discharging, the generation and disappearance of hydroxyl occur in the water, and as a result, anions are continuously generated.

When the tourmaline is used in an amount less than 5 wt%, the water purification function through the above-described method is deteriorated. When it exceeds 45 wt%, the optimal combination with other components can not be achieved, Therefore, the amount of the tourmaline is preferably limited within a range of 5 to 45 wt% with respect to the total weight of the water purification agent.

Titania (titania, TiO ₂₎ is the most widely used photocatalyst. A catalyst is a substance that participates in a chemical reaction and accelerates the reaction rate. Catalyst is a substance that participates in a chemical reaction and accelerates the reaction speed by making a small new reaction path of activation energy. Photocatalyst, one of these catalytic reactions, is a substance that causes a catalytic reaction when it receives light. Therefore, the photocatalyst is not a catalyst of light but a catalyst that acts only when light touches it. The photocatalyst absorbs light and becomes a state of high energy and transfers the energy to the reactant to cause a chemical reaction. Titanium oxide is the ninth largest element in the Earth's sphere.

The characteristics of TiO ₂ can be divided into physical properties and chemical properties. The physical properties are electrical conductivity which is considerably small at room temperature and is an insulator, but exhibits conductivity of semiconductor by irradiation with high temperature of 500 ° C. or near ultraviolet light, , The largest hiding power and coloring power as white pigments are larger than those of the other pigments by one power or more. Its chemical properties are not soluble in sulfuric acid, alkali salts, acids, water, organic solvents, etc., and do not react with sulfur trioxide, chlorine gas, etc., and are chemically stable so as not to deteriorate even by heating at about 800 ° C. On the surface, Ti ⁴⁺ attracts water in the air to form a hydroxyl group. The hydroxyl group (OH) formed on the Ti ⁴⁺ shows basicity, and H formed between Ti shows acidity. The amount of water physically adsorbed on these hydrogen and hydroxyl groups and the kind of hydroxyl groups vary depending on the heat treatment of titanium dioxide and the kind of reactant, and nourishes catalysis and photocatalytic action.

In the present invention, a photocatalyst powder prepared by adding 1 mol% to 10 mol% of Ag ₂ O to the photocatalyst TiO ₂ by ultrasound is used.

When the amount of the titania photocatalyst used is less than 1 wt%, the efficiency of red tide removal is not large. When the amount of the titania photocatalyst is more than 10 wt%, the amount of the titania photocatalyst is 1 to 10 wt% It is preferable to limit it to the range.

The lightweight dolomite flocculant is filled with distilled water at a rotation rate of 100 to 120 rpm for 1 to 3 hours to fill the granular dolomite with a size of 20 to 30 vol% . ≪ / RTI >

Limestone resources including dolomite are classified as major nonmetallic carbonate mineral resources produced in Korea. Quality of dolomite to be produced domestically is CaO 30 ~ 31%, which substantially matches the theoretical maximum value of the chemical components, represents a MgO 2 ~ 22% even extremely small content of SiO _2. In Korea, dolomite ores used in steelmaking process are used to extend the lifetime of refractories or CaO 30% and MgO 20% or more.

The chemical composition of dolomite is represented by CaMg (CO ₃ ) ₂ and is a complex salt complex of calcium carbonate (CaCO ₃ ) and magnesium carbonate (MgCO ₃ ). It is a mineral with intermediate crystalline structure between calcite and magnesite. Dolomite is to be formed is Mg ²⁺ ions in a Ca atom is completely replaced in theory, 54.35% CaCO ₃ and MgCO ₃ or MgO is 45.65% 21.9%, CaO is 30.4%, CO ₂ is composed of 47.7%.

When the amount of the lightweight dolomite coagulant is less than 5 wt%, the efficiency of removing green algae may be lowered. When the amount of the coagulant is greater than 20 wt%, the increase in the removal efficiency of green algae is insignificant. Is preferably limited to a range of 5 to 20 wt%.

The alkali-earth metal peroxides (AMP) are used for bleaching and disinfecting Ca and Mg peroxide such as grain and seed storage, wound medicine materials and the like. It is not so toxic, it has little odor and taste. It is a colorless powder which precipitates when sodium peroxide is reacted with a concentrated aqueous solution of magnesium sulfate in the presence of hydrogen peroxide.

CaO ₂ is versatile, safe and easy to handle compared to other solid inorganic peroxides. There are mainly two ways to produce CaO ₂ .

1. Calcium Oxide Method - Calcium oxide is dissolved in water and hydrogen peroxide and ammonia water are added while stirring. The mixture is cooled at -3 ~ 2 ℃, centrifuged and dried at 150 ~ 200 ℃ to obtain calcium peroxide.

2. Calcium hydroxide method - Calcium hydroxide, ammonia chloride and water are mixed and adjusted to 0 ~ 5 ℃. After adding hydrogen peroxide with stirring, centrifuge and dry dehydrate to obtain calcium peroxide.

Oxygen generated by AMP injection can increase the concentration of dissolved oxygen in the water and provides favorable conditions for promoting the growth or survival of general aerobic microorganisms or fish using oxygen as an electron acceptor.

In the present invention, CaO ₂ (calcium peroxide) having a purity of 70 to 75% and MgO ₂ (magnesium peroxide) having a purity of 25 to 30% are mixed in an amount of 1: 1 by weight as an alkaline earth metal peroxide. When the amount of the alkaline earth metal peroxide is less than 1 wt%, the effect of increasing the dissolved oxygen concentration in the water is insignificant. When the amount of the alkaline earth metal peroxide is more than 10 wt%, the amount of the alkaline earth metal peroxide is not sufficient It is preferable to limit the amount of the cleaning agent to a range of 1 to 10 wt% with respect to the total weight of the cleaning agent.

The yellow mortar carrier is obtained by sieving loess powder at 100 to 200 mesh, 72 to 85 wt% of loess dried at 100 to 120 DEG C for 20 to 30 hours in a dryer,

15 to 28 wt% of a CuSO ₄ .5H ₂ O solution were mixed to form an ocher carrier,

The green clay is naturally dried for 1 to 3 days and then calcined in an electric furnace at 800 to 1,000 ° C for 1 to 3 hours.

The properties of the loess are determined by the type of clay minerals contained in the loess. The types of clay minerals constituting the loess are determined by the geological environment, the hydrological environment, the topography and the climate in which the loess is formed. Many of the spaces have a multi-layered structure with a large honeycomb structure, such as kaolinite, halloysite, ilite, vermiculite, and chlorite. Most of the far infrared rays are absorbed and stored in the sponge-like holes. Stimulates the molecular activity of an object.

Copper sulfate is used to remove algae present in the water and is the most commonly used salt additive. Copper sulfate is inexpensive and is effective in algae control even in small amounts, and is harmless to human shafts and is easy to store and handle. It is known that the copper component in copper sulfate inhibits the photosynthesis of algae, suppressing the growth of algae, and exhibiting a killing effect.

Copper sulfate differs from algae according to algae effect, especially Microcystis sp. Anabaena sp., Asterionella sp. Closterium sp. Has excellent killing effect.

When the amount of the yellow soil carrier is less than 1 wt%, the effect of algae is insignificant. When the amount of the yellow soil carrier is more than 15 wt%, the increase in the algae effect is insignificant. %. ≪ / RTI >

Vermiculite is a silica-based mineral that exists in nature as mica. Vermiculite is mostly used as an expanded state, and is known as an environmentally friendly material that is lightweight, nonflammable and excellent insulation and is also used as an absorbent.

The vermiculite is a functional mica which is a modification product of phlogopite and biotite. Its structural formula is M _x (Mg · Fe) ₆ (Si _8-x Al) O ₂₀ (OH) ₄ · yH ₂ O, Phase clay minerals. Where x is 1 to 1.4, y is 8, and M is the exchangeable cation (Mg ²⁺ , Ca ^2+, etc.).

The vermiculite used in the present invention is one having photosynthetic bacteria fixed to pores and having a function of purifying water by photosynthetic bacteria.

When the amount of the vermiculite is less than 0.5 wt%, the function of purifying water by the photosynthetic bacteria is inferior. When the amount of the vermiculite is more than 10 wt%, the increase of the water purification function is insignificant. To be in a range of 0.5 to 10 wt.

The sepiolite is a 2: 1 layered magnesium silicate mineral having a fibrous form of sepiolite. The structural difference with other layered silicate minerals is that the ribbon structure is formed by continuing to form the ribbon structure of the channel structure, that is, eight octahedrons, and then the octahedron is disconnected as the oxygen direction of the tetrahedron is reversed will be. Unlike other clay minerals due to the rectangular voids formed between these ribbons, the particles stay connected without being swollen when put into water, so that they remain resistant.

Due to such characteristics, it has commercially useful properties such as high adsorptivity, catalytic property, flowability, dry solidification and sinterability. It is widely used commercially as a sedimentation agent or floatant for cigarette filters, removal of spilled oil, pet rugs, tank cleaning, potting composites, non-flowing paint, liquid cleaners, adhesives, printing inks, .

When the amount of the seawall is less than 0.5 wt%, the adsorbing ability of the pollutant is insufficient and the contribution to the purification of the water is insignificant. When the amount exceeds 10 wt%, the use of sepiolite is not significant. Is preferably limited to a range of 0.5 to 10 wt% based on the total weight of the water purification agent. At this time, the granular size of sepiolite is 0.1 ~ 71.9 ㎛.

Perlite is a naturally occurring term in siliceous volcanic rocks. Another striking feature of other glass and perlite rocks is that they expand 20 to 40 times the volume of mineral gypsum when they are heated to soften the ondol. This expansion is caused by the presence of water in the perlite of perlite. When heated rapidly above 870 ℃, the ore becomes swollen like popcorn. Due to the bubbles generated at this time, it is known as a material having excellent heat insulating properties and light weight characteristics.

When the use amount of the perlite is less than 0.5 wt%, the amount contributing to improvement of the water quality is insignificant. When the amount of the perlite is more than 10 wt%, there is no significant change in improvement of the water quality improvement, It is preferably limited to a range of 0.5 to 10 wt% with respect to the total weight of the cleaning agent.

The kaolin (Bentonite) is called kaolin, kaolin, and kaolin. Its main ingredient is kaolinite and halloysite. Feldspars such as feldspar, feldspar, soda feldspar, and feldspathic rock in rocks are produced by chemical decomposition by carbonic acid or water, and a thick layer of several meters thick is formed on rocks of usually protruding soil.

The resulting kaolin is a silicate-based clay mineral that forms an interlayer structure and is used in many fields such as ceramics, papermaking, organic compounds, medicines, cosmetics, and deodorization.

The kaolin is a porous kaolin, and H ₂ O ₂ is absorbed into the kaolin surface and expands the pores by corroding the surface of the pores.

Specifically, a 5% H ₂ O ₂ aqueous solution is prepared, mixed with kaolin at a ratio of 1: 1, and reacted for 24 hours. A 5% aqueous solution of H ₂ O ₂ for 24 hours will corrode the surface of the kaolin and cause pore expansion and pore formation. After completion of the reaction, the kaolin is filtered from a 5% aqueous solution of H ₂ O _2, washed and dried.

The kaolin has a cyanobacteria removal efficiency. When the amount of the kaolin is less than 0.5 wt%, it is difficult to expect such an effect. When the amount of the kaolin exceeds 10 wt%, the degree of change in the cyanobacteria removal efficiency is insignificant, ) Is preferably limited within a range of 0.5 to 10 wt% with respect to the total weight of the water purification agent. At this time, the particle size of the kaolin (Bentonite) is 0.12 ~ 52.3 탆.

Table 1 below shows examples of formulation of the water purifying agent for removing green tide and red tide according to the present invention.

Formulation of water purification agent (unit wt%) ingredient Example 1 Example 2 Example 3 Example 4 Example 5 tourmaline
(Tourmaline)
40
37
34
34
33 Titania
Photocatalyst
7
10
10
10
10 Light
Dolomite coagulant
15
16
17
19
20 Alkaline earth metal peroxide
5
6
7
8
10 ocher
carrier
10
11
12
13
15 Vermiculite
(Vermiculite)
5
5
5
4
3 meerschaum
(Sepiolite)
6
5
5
4
3 Perlite
(Perlite)
6
5
5
4
3 china clay
(Bentonite)
6
5
5
4
3

A test for measuring the green tide and red tide purification efficiency of the water purifying agent was performed as follows.

5 liters of each of green tide and red tide fungus and 2 liters of medium were mixed to maintain the ecological condition of the fungus to the maximum, and then 10 g / L of the water purifying agent of Examples 1 to 5 was administered. The control (Comparative Example 1) irradiated only ultraviolet light. The measurement results after 60 minutes are shown in Tables 2 and 3 below.

Measurement of greenhouse purification efficiency Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 96.14% 97.54% 97.65% 98.10% 98.25% 9.52%

Red Tide Purification Efficiency Measurement Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 90.52% 95.45% 97.96% 97.98% 99.35% 11.12%

The water purifying agent for removing green tide and red tide according to the present invention is excellent in the effect of removing green tide and red tide. Therefore, it has a great effect of replacing natural materials with chemicals used for removing green tide and red tide which are conventionally used. ; Improving water quality in lakes, fresh water, and reservoirs; And water quality improvement such as golf course, etc., and it is possible to provide water quality improvement effect, which is highly likely to be used in industry.

Claims (5)

Tourmaline 5 ~ 45wt%;
Titania photocatalyst 1 ~ 10 wt%;
5 ~ 20wt% of light dolomite coagulant;
1 to 10 wt% alkaline earth metal peroxide;
1 to 15 wt% of an alumite carrier;
Vermiculite 0.5 to 10 wt%;
Sepiolite 0.5 ~ 10 wt%;
Perlite 0.5 ~ 10wt%;
And 0.5 to 10 wt% of kaolin (Bentonite); and a water purifying agent having an excellent green algae / red tide removing function.
The method according to claim 1,
The titania photocatalyst is a photocatalyst powder prepared by adding 1 mol% to 10 mol% of Ag ₂ O to the photocatalyst TiO ₂ by ultrasonic chemical method.
The method according to claim 1,
The dolomite flocculant is filled with distilled water at a rate of 100 ~ 120 rpm for 1 ~ 3 hours to fill the granular dolomite of 20 ~ 30 vol% Which is characterized in that it is uniformly produced.
The method according to claim 1,
Alkali-earth metal peroxides are prepared by mixing CaO ₂ (calcium peroxide) having a purity of 70 to 75% and MgO ₂ (magnesium peroxide) having a purity of 25 to 30% in a 1: 1 weight ratio. · Water purification agent with excellent red tide removal function.
The method according to claim 1,
The yellow mortar is obtained by sieving the loess powder at 100 ~ 200 mesh, 72 ~ 85wt% of the loess dried at 100 ~ 120 ℃ for 20 ~ 30h in the dryer,
15 to 28 wt% of a CuSO ₄ .5H ₂ O solution were mixed to form an ocher carrier,
Wherein the greenhouse carrier is naturally dried for 1 to 3 days and then fired in an electric furnace at 800 to 1,000 ° C for 1 to 3 hours.