KR102609853B1 - Water treatment agent using green algae agglomeration flotation and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a water treatment agent, and more specifically, to a water treatment agent and a method for producing the same, which enable significantly improved green algae reduction properties even with a small amount of use.

Description

Water treatment agent using green algae agglomeration flotation and method for manufacturing the same}

The present invention relates to a water treatment agent, and more specifically, to a water treatment agent and a method for producing the same, which enable significantly improved green algae reduction properties even with a small amount of use.

Green or red tide occurs when organic substances, nitrogen, or phosphorus are excessively supplied to natural water systems such as reservoirs, lakes, rivers, dams, etc., and artificial water systems such as golf course ponds, resulting in large-scale proliferation of phytoplankton or algae. This means that when green algae occurs, the reservoir or lake turns yellow-green.

Green or red tide mostly occurs in late spring, summer, and early fall when temperatures are high, and occurs mostly in areas where water flow is weak or stagnant. Diatoms mainly occur in spring, flagellated or green algae occur in early summer, and blue-green algae mainly occur in late summer and fall. When algae multiply in each water system and their population exceeds a certain range, serious problems arise in the ecosystem of the water system.

In particular, when green algae occurs, the color of the water system changes to green, and the transparency of the water is significantly reduced, damaging the surrounding landscape. The supply of oxygen in the water is cut off, causing the death of aquatic life, and the death of the green algae that has grown. The resulting debris deposits and decays at the bottom, generating toxic substances and foul odors, deteriorating water quality and the surrounding environment.

In addition, when green algae proliferate in large quantities in water systems used for drinking water, etc., not only is it difficult to purify the water due to toxins generated from the green algae, but there are also problems such as a significant increase in purification costs.

Much effort has been made to eliminate the problematic green algae as mentioned above. Among them, there is a method of spraying red clay into reservoirs or lakes where green algae has occurred to remove or reduce nutrients and grown green algae in the water through the adsorption and cohesion of the red clay. This method takes a lot of time and money, and requires only the appropriate amount of red clay. It is also difficult to obtain.

Another method is to inject a chemical coagulant into a reservoir or lake where green algae has occurred. However, when the coagulant is sprayed, nutrients and green algae are coagulated and removed by the cohesive force of the coagulant, but it causes secondary pollution of the water system. It will be done.

As another method, chemical technology that kills algae by adding ozone and oxidizing agents, and biological technology that kills algae by living organisms are used.

These green algae reduction technologies are relatively effective in reducing green algae in stagnant water areas such as lakes and swamps, but there are almost no technologies applied to reducing green algae in large-scale rivers or oceans with water flow.

Meanwhile, the above-mentioned background technology is technical information that the inventor possessed for deriving the present invention or acquired in the process of deriving the present invention, and cannot necessarily be said to be known technology disclosed to the general public before filing the application for the present invention. .

Republic of Korea Patent Publication No. 10-2010-0131826

The present invention is intended to solve the above problems, and the purpose of the present invention is to provide a water treatment agent and a manufacturing method thereof that can exhibit significantly improved green algae reduction properties even at a lower usage amount compared to existing coagulants.

The above and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

The above object is a first inorganic coagulant, which is polyaluminum chloride sulfate-ferric; A second inorganic coagulant containing at least one selected from the group consisting of aluminum salts, iron salts, calcium, magnesium, and rare earth metals; and flocculation aids; It can be achieved by a water treatment composition, characterized in that the first inorganic coagulant, the second inorganic coagulant, and the coagulation aid are included in a concentration ratio of 10 ppm: 4 ppm: 2 ppm.

The second inorganic coagulant is characterized in that it contains at least one selected from the group consisting of sodium aluminum silicate, magnesium oxide (Mg0), and magnesium chloride (MgCl ₂ ).

The coagulation aid is characterized in that it is one or more selected from organic components, mineral components, natural components, acids, alkali components, and other components, and the mineral component is selected from bentonite, kaolin, zeolite, elvanite, illite, and germanium. It is characterized by one or more types. The other components include silicon dioxide (SiO ₂ ), titanium dioxide (TiO ₂ ), and at least one selected from the group consisting of sodium bicarbonate (NaHCO ₃ ), sodium alginate, chitosan, activated carbon, and activated silica sand. .

The purpose is to prepare a first inorganic coagulant, which is polyaluminum chloride sulfate-ferric; Preparing a second inorganic coagulant containing at least one selected from the group consisting of aluminum salts, iron salts, calcium, magnesium, and rare earth metals; and preparing a flocculation aid; Including,

The first inorganic coagulant, the second inorganic coagulant, and the coagulant aid can be achieved by a method for producing a water treatment composition, characterized in that they are included in a concentration ratio of 10 ppm: 4 ppm: 2 ppm.

According to the present invention, by mixing a coagulant aid component into an existing coagulant composition, the water treatment effect can be excellent and the amount of sludge generated can be minimized even if the amount of coagulant used is the same or less. Furthermore, the water treatment composition of the present invention can more effectively remove green algae even in large-scale rivers or oceans where water flow exists.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

1 is an actual photograph of a water treatment composition according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are merely presented as examples to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Additionally, unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains, and in case of conflict, this specification including definitions The description will take precedence.

In order to clearly explain the proposed invention in the drawings, parts unrelated to the description have been omitted, and similar reference numerals have been assigned to similar parts throughout the specification. And, when it is said that a part "includes" a certain component, this means that it does not exclude other components, but may further include other components, unless specifically stated to the contrary. Additionally, “unit” as used in the specification refers to a unit or block that performs a specific function.

Identification codes (first, second, etc.) for each step are used for convenience of explanation. The identification codes do not describe the order of each step, and each step does not clearly state a specific order in context. It may be carried out differently from the order specified above. That is, each step may be performed in the same order as specified, may be performed substantially simultaneously, or may be performed in the opposite order.

One aspect of the present application is a first inorganic coagulant that is polyaluminum chloride sulfate-ferric; A second inorganic coagulant containing at least one selected from the group consisting of aluminum salts, iron salts, calcium, magnesium, and rare earth metals; and flocculation aids; It provides a water treatment composition, characterized in that the first inorganic coagulant, the second inorganic coagulant, and the coagulant aid are included in a concentration ratio of 10 ppm: 4 ppm: 2 ppm.

The type of contaminated water, that is, raw water, for which the water treatment composition is used is not particularly limited, but may be, for example, tap water, sewage, wastewater, lake water, process water, secondary treated water, or tertiary treated water. Furthermore, the water It can also be used in large-scale rivers or oceans with currents.

The water treatment composition may be a coagulant composition that removes solids and soluble compounds from river water, lake water, and secondary treatment sewage water containing contaminants such as solids and soluble compounds.

First, the first inorganic coagulant can be obtained. The first inorganic coagulant may be polyaluminum chloride sulfate-ferric. The first inorganic coagulant maintains iron and aluminum in a physically and chemically stable state, and can easily react with even trace amounts of contaminants to form flocs quickly and large.

The polyaluminum chloride sulfate-ferric (PACS-F) is, for example, 5.0 to 16% by weight, specifically, 8.0 to 16% by weight of aluminum oxide (Al ₂ O ₃ ); 0.01 to 5.0% by weight, specifically 0.03 to 3.0% by weight of iron oxide (Fe ₂ O ₃ ); 0.1 to 5.0% by weight, specifically 0.2 to 4.0% by weight of sulfate ions (SO ₄ ^2- ); and 0.1 to 0.4% by weight of silicon dioxide.

In one embodiment, the manufacturing method of polyaluminum chloride sulfate-ferric (PACS-F) is as follows.

First, aluminum hydroxide (Al(OH) ₃ ), hydrochloric acid (HCl), and ferric chloride (FeCl ₃ ) can be reacted to form polyaluminum ferric chloride. At this time, ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) can be used instead of the ferric chloride.

, 반응 시간은 200분이 바람직하다. The reaction may be a polymerization reaction performed at high temperature using steam while stirring in a sealed state using a high pressure reactor. At this time, the pressure in the high pressure reactor is, for example, 1 to 10 kg/cm ³ , and the temperature is, for example, 140 to 170.

, the reaction time is preferably 200 minutes.

Then, aluminum hydroxide (Al(OH) ₃ ) and sulfuric acid (H ₂ SO ₄ ) can be reacted to form aluminum sulfate.

Next, the polyaluminum iron chloride and aluminum sulfate can be reacted to form a first compound.

의 고온에서 반응시켜, 알루민산 나트륨(sodium aluminate; SA)을 형성할 수 있다. 그런 다음, 알루민산 나트륨, 규산 소다(sodium silicate), 및 물을 반응시켜 제2 화합물을 형성할 수 있다.On the other hand, aluminum hydroxide (Al(OH) ₃ ) and sodium hydroxide (NaOH) are mixed at 100 to 150

By reacting at a high temperature, sodium aluminate (SA) can be formed. Sodium aluminate, sodium silicate, and water can then be reacted to form a second compound.

Thereafter, polyaluminum chloride sulfate-ferric (PACS-F) can be obtained by slowly mixing the first compound and the second compound with stirring.

However, the manufacturing method is not limited to this, and the manufacturing method commonly used in the field can be manufactured by making any number of design changes.

Next, a second inorganic coagulant can be obtained. The second inorganic coagulant may include at least one selected from the group consisting of aluminum salts, iron salts, calcium, magnesium, and rare earth metals.

For example, the aluminum salt system may be one or more selected from the group consisting of sodium aluminum silicate, aluminum polyhydroxide chloride sulfate, aluminum polyhydroxide chloride sulfate silicate, polyaluminum chloride, polyaluminum chloride silicate, and aluminum polysulfate silicate. .

For example, it is preferable to use sodium aluminum silicate as the aluminum salt.

The iron salt system may be one or more selected from the group consisting of iron sulfate, poly iron sulfate, iron chloride, poly iron chloride, and aluminum iron.

The calcium system may be one or more selected from the group consisting of calcium, polyaluminium chloride calcium silicate, and polyaluminium chloride calcium silicate.

The magnesium-based material may be one or more selected from magnesium, magnesium hydroxide, magnesium oxide, magnesium chloride, magnesium sulfate, and magnesium polyaluminum chloride. For example, the magnesium-based material may be magnesium oxide, magnesium chloride, or a combination thereof.

In one embodiment, the second inorganic coagulant may be a mixture of sodium aluminum silicate, magnesium oxide (MgO), and magnesium chloride (MgCl ₂ ).

The aluminum sodium silicate has an excellent effect in improving the turbidity of raw water during water treatment, and combines with algae to form floc and precipitate it, and its effect is superior to existing aluminum-based ingredients.

The magnesium component of the magnesium oxide and magnesium chloride blocks the food chain of green algae by covering phosphorus and nitrogen, which are food for green algae, with a protective film. In addition, even if magnesium combines with other substances dissolved in water to form a new compound, it does not affect the environment, so there is no secondary pollution problem. In particular, magnesium chloride, which does not dissociate, dissolves in water and increases turbidity. does not occur.

As an example, the sodium aluminum silicate, magnesium oxide (Mg0), and magnesium chloride (MgCl ₂ ) are mixed at a weight ratio of 1:0.4-0.5:0.6-0.8, specifically, 1:0.5:0.75. It is desirable to be

The manufacturing method of the second inorganic coagulant according to one embodiment is as follows.

The sodium aluminum silicate is a compound expressed by the general formula Na _n Al _y (SiO ₄ ) _k , for example, aluminum hydroxide (Al(OH) ₃ ), sodium hydroxide (NaOH), and sodium silicate (Na ₂ O ₃ Si). and water (H ₂ O).

Specifically, the aluminum sodium silicate is aluminum hydroxide (Al(OH) ₃ ) with a concentration of aluminum oxide (Al ₂ O ₃ ) of 45 to 55 wt%, and sodium oxide (Na ₂ O) with a concentration of 10 to 40 wt. It can be prepared by mixing silicate with a concentration of 10 to 20 wt% of sodium hydroxide (NaOH) and silicon dioxide (SiO ₂ ) with the remaining amount of water.

More specifically, the sodium aluminum silicate is 0.5 to 40 parts by weight of aluminum oxide (Al ₂ O ₃ ), 1 to 40 parts by weight of sodium oxide (Na ₂ O), 0.1 to 10 parts by weight of silicon dioxide (SiO ₂ ), and 50 parts by weight of water. It may contain from 100 parts by weight.

The magnesium oxide (Mg0) and magnesium chloride (MgCl ₂ ) may be obtained by a manufacturing method commonly used in the field.

The first inorganic coagulant, the second inorganic coagulant, and the coagulation aid are preferably blended at a concentration ratio of 10ppm:4ppm:2ppm.

With the above-mentioned mixing ratio, the water purification effect is improved compared to when each component is used alone, and the most excellent coagulation effect can be achieved even in various types of raw water. In other words, compared to existing coagulants, the coagulation rate in raw water containing a greater variety of algae and organic matter is excellent, and the overall amount of coagulant used can be minimized, thereby ensuring economic feasibility.

Next, a flocculation aid can be obtained.

The coagulation aid may be one or more selected from organic components, mineral components, natural components, acids, alkali components, and other components.

The type of the organic component is not particularly limited, but may be one or more organic polymers selected from the group consisting of polyacrylamide-based, polyamine-based, polyacrylic ester-based, and polyethyleneimine-based organic coagulants.

The mineral component is a material used to adsorb and coagulate foreign substances such as nutrients, heavy metals, and toxic substances, and can also improve water quality by deodorizing and emitting negative ions and far-infrared rays.

The mineral component may be, for example, one or more selected from bentonite, kaolin, zeolite, elvanite, illite, and germanium.

For example, the mineral component may be a mixture of bentonite and kaolin.

The mineral component may be prepared in any one formulation selected from, for example, a solution, an aqueous solution, a liquid, or a suspension.

For example, the mineral component may be pulverized into powder and then heated and stirred with water in a high pressure chamber at a temperature of 150 to 280°C for 2 to 5 hours to prepare a molten liquid. However, the formulation and manufacturing method of the mineral ingredient are not limited thereto.

The natural ingredient may be one or more selected from green tea, ash tree, chestnut tree, pine needle, and rock tree. For example, the natural ingredient may be a mixture of pine needles and pine needles.

Pine needles can suppress green algae using their strong antibacterial effect.

Selaginella tamariscina is a fern plant belonging to the Selaginella family that has a stem shape with fibrous roots intertwined and is an evergreen perennial plant that grows in rocky areas or around cliffs in mountainous areas. In particular, the amentoflavone component in Baeksun is highly effective in killing Microcystis, one of the harmful blue-green algae and the most common blue-green algae that causes green algae.

For example, the natural ingredient may be a liquid ingredient obtained by crushing, pulverizing, and then heating with water at 70 to 80° C. for 1 to 3 hours, for example, 2 hours. However, the formulation of the natural ingredient and its preparation method are not limited thereto.

As the other components, silicon dioxide (SiO ₂ ) and titanium dioxide (TiO ₂ ) may include one or more selected from sodium hydrogen carbonate (NaHCO ₃ ), sodium alginate, chitosan, activated carbon, and activated silica sand.

Sodium alginate is obtained by alkali extraction of the aluminum and calcium salts of polymannuronic acid found in brown algae such as kelp. When it enters water, the carboxyl group dissociates to become an anionic electrolyte and has a viscosity of 100 to 1,000 cp in a 1% aqueous solution. When added to the granulated suspension, it has a sedimentation-promoting effect by causing cross-linking, adsorption, and coagulation due to the polymer.

Titanium dioxide (TiO ₂ ) is a photocatalytic material that has high photoactivity and a strong decomposition function. It decomposes green algae and amplifies the performance of other main ingredients.

Activated carbon, for example, can be used as either vegetable activated carbon (extracted from coconuts) or mineral activated carbon (extracted from coal), and it removes impurities dissolved in water and improves water quality.

For example, the other ingredients may be one or more selected from sodium alginate, titanium dioxide, activated carbon, and combinations thereof.

The formulation and preparation method of the other ingredients are not greatly limited and may follow known techniques commonly used in the field.

In one embodiment, the coagulation aid is a mixture of bentonite, kaolin, pine needles, and rock sand at a weight ratio of 1:0.7-0.9:1-1.2:1.1-1.4, specifically, 1:0.8:1.1:1.3. May include mixtures.

More preferably, the other ingredients may be included in an amount of 10 to 30 parts by weight, for example, 20 parts by weight, based on 100 parts by weight of the mixture.

The first inorganic coagulant, the second inorganic coagulant, and the coagulation aid may be included in a concentration ratio of 10ppm:4ppm:2ppm.

In other words, when the first inorganic coagulant, the second inorganic coagulant, and the coagulant aid are used together, the water purification effect, that is, turbidity and turbidity removal efficiency, is superior to when used alone. In addition, the composition and mixing ratio described above may be the optimal combination characteristic that allows the composition to exhibit the best coagulation effect for each type of raw water. As a result, the amount of coagulant used can be minimized due to excellent cohesiveness in raw water containing a variety of algae and organic matter, resulting in excellent economic efficiency.

In addition, the flocculation aid having the above-mentioned combination and mixing ratio minimizes the risk of secondary environmental pollution, quickly penetrates the cell membrane of green algae, kills them, and blocks phosphorus and nitrogen, which are food for green algae, thereby eradicating green algae and causing secondary damage. It can reduce the frequency of creation. In addition, the air bubbles created when the algae's cell membrane bursts float the adsorbed nutrients and other foreign substances to the surface, making them easy to remove, and also remove pollutants out of the water, which has the effect of fundamentally removing algae and foreign substances rather than temporarily. there is.

The water treatment composition may be prepared in a liquid formulation such as, for example, a solution, aqueous solution, or suspension. 1 is an actual photograph of a water treatment composition according to an embodiment of the present invention.

Referring to Figure 1, it shows that the water treatment composition was prepared in solution form.

However, the formulation of the water treatment agent composition is not limited to this, and can be used in the form of a water treatment agent product by making any number of design changes according to known techniques commonly used in the field. In addition, depending on the type of final product manufactured, known additive components may be further included.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through specific examples and comparative examples. However, these examples are for illustrating the present invention in more detail, and the scope of the present invention is not limited to these examples.

<Examples 1 to 7>

Water treatment compositions containing 10 ppm of aluminum iron polychloride sulfate as a first inorganic coagulant, 4 ppm of a second inorganic coagulant, and 2 ppm of a coagulation aid were prepared. The specific preparation method and content were in accordance with the above description and commonly used known techniques. Specific ingredients contained in each composition of Examples 1 to 7 are shown in Table 1 below.

Ingredients Ingredient name
(Each component
(based on 100 parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 secondary inorganic coagulant aluminum sodium silicate ○ - - ○ ○ ○ ○ Magnesium Oxide ○ ○ ○ ○ ○ ○ ○ Magnesium chloride ○ ○ ○ - ○ ○ ○ aluminum sulfate - ○ - - - - - Polyaluminum chloride calcium silicate - - ○ - - - - agglomeration
supplements bentonite ○ ○ ○ ○ - ○ ○ kaolin ○ ○ ○ ○ - ○ ○ pine needles ○ ○ ○ ○ ○ - ○ rock hand ○ ○ ○ ○ ○ - ○ sodium alginate ○ ○ ○ ○ ○ ○ - titanium dioxide ○ ○ ○ ○ ○ ○ - activated carbon - - - - - - zeolite - - - - ○ - - elvan stone - - - - ○ - - chestnut - - - - - ○ - ash tree - - - - - ○ - green tea - - - - - ○ -

<Comparative Example 1>

We prepared a water treatment composition consisting of only 16 ppm of our company's polyaluminium iron sulfate (PAC-F).

<Comparative Example 2>

We prepared a water treatment composition consisting of only 18ppm of our company's polyaluminium iron sulfate (PAC-F).

<Comparative Example 3>

We prepared a water treatment composition consisting of only 20ppm of our company's polyaluminium iron sulfate (PAC-F).

<Comparative Example 4>

Except for the details described below, a water treatment composition was prepared in the same manner as in Example 1 described above.

A water treatment agent composition was prepared without containing the second inorganic coagulant, including 14 ppm of aluminum iron polychloride sulfate as the first inorganic coagulant, and 2 ppm of the coagulation aid.

<Comparative Example 5>

Except for the details described below, a water treatment composition was prepared in the same manner as in Example 1 described above.

A water treatment composition was prepared without containing a coagulant aid and including 10 ppm of aluminum iron polychloride sulfate as the first inorganic coagulant and 6 ppm as the second inorganic coagulant.

<Experimental example: Turbidity measurement>

After obtaining a sample of contaminated water (SS (Suspended soild) 11 mg/L) collected from area A, the compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were usually added at the above-mentioned dosage (ppm). After performing the water purification process using the method, turbidity and turbidity removal efficiency were measured. The method for measuring turbidity and turbidity removal efficiency was based on the Water Pollution Process Test Standard (Ministry of Environment Notification No. 2016-65).

At this time, except for the composition and input amount of each composition, conditions such as stirring and precipitation time were all performed the same. The results are shown in Tables 2 and 3 below.

contaminated water Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Turbidity (NTU) 54 0.785 1.088 2.075 2.312 0.928 1.265 1.377 Turbidity removal efficiency (%) - 98.9 97.7 93.6 94.1 98.1 97.3 96.9

contaminated water Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Turbidity (NTU) 54 3.043 2.984 2.817 2.512 2.484 Turbidity removal efficiency (%) - 87.6 89.5 91.7 92.2 92.7

Referring to Tables 2 and 3, the Examples showed superior turbidity removal efficiency compared to the Comparative Examples. In particular, in Comparative Examples 1 to 3 in which aluminum iron polychloride sulfate was used alone, it was confirmed that the turbidity removal efficiency was low even though the total amount of composition added was the same or greater than the Examples. This shows that, as in the examples, when the first inorganic coagulant, the second inorganic coagulant, and the coagulant aid are used together, a better turbidity removal effect is achieved even at a lower usage amount. Among them, it was confirmed that the composition of Example 1 showed the most excellent effect in removing turbidity.

In this specification, only a few examples of various embodiments performed by the present inventors are described, but the technical idea of the present invention is not limited or limited thereto, and of course, it can be modified and implemented in various ways by those skilled in the art.

Claims (5)

The first inorganic coagulant is polyaluminum chloride sulfate-ferric;
a second inorganic coagulant comprising a mixture of sodium aluminum silicate, magnesium oxide (Mg0) and magnesium chloride (MgCl ₂ ); and
flocculation aid; Including,
The coagulation aid includes a mixture of bentonite, kaolin, pine needles, and rock sand,
The bentonite and kaolin are each pulverized into powder, and then heated and stirred with water in a high pressure chamber at a temperature of 150 to 280°C for 2 to 5 hours to produce a melted liquid,
The pine needles and rock needles are liquid ingredients obtained by crushing and powdering each, and then heating them with water at 70 to 80°C for 1 to 3 hours,
A water treatment composition, characterized in that the first inorganic coagulant, the second inorganic coagulant, and the coagulant aid are contained in a concentration ratio of 10ppm:4ppm:2ppm. delete delete delete delete