KR101176365B1 - Kit and method for removing green or red tides - Google Patents

Abstract

The present invention relates to a green alga or red algae removal kit and a method of removing algae or red algae using the same, wherein the green alga or red algae removal kit according to the present invention is one or more substances selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH) First additive and aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], A second additive comprising an aqueous solution of at least one substance selected from the group consisting of ferrous chloride (FeCl ₂ ), and ferric chloride (FeCl ₃ ), the second additive being comprised separately from the first additive It features. Green algae or red algae removal kit according to the present invention is composed of the first and second additives in the liquid form of the component, it is easy to spray uniformly in the green water or the water generated red tide, the aggregation reaction and precipitation quickly It is possible to remove the green algae or red tide in a short time. In addition, since photosynthetic activity of the precipitated green algae or red tide organisms can be maintained for a long time, oxygen is continuously supplied to the water body to maintain the dissolved oxygen amount in the water body at a level suitable for marine life to survive.

Green algae, red tide, flocculation, precipitation, photosynthetic activity, saturated aqueous solution

Description

Green algae or red algae removal kit and a method of removing green algae or red algae using the same {Kit and method for removing green or red tides}

The present invention relates to a green algae or red tide removal kit and a method of removing green algae or red tide using the same, and more specifically, it can effectively remove the green algae or red algae by causing two stages of agglomeration reactions, and easily put into green water or a red tide generated water body. The present invention relates to a green alga or red tide removing kit, and a method of removing green alga or red tide using the same.

Green algae refers to a phenomenon in which the green algae, which are phytoplanktons, increase greatly in the streams of eutrophiced lakes or low-velocity streams, turning the water to green. When the surface of the lake is covered with green algae, the sun is blocked by water and no additional This reduces the amount of dissolved oxygen in the water. This causes fish and aquatic life to die and stink, destroying the ecosystems of the waters and creating many social, economic and environmental problems. Once the nutrients have been removed from the water, they will remain in the aquatic ecosystem, so the green algae will be repeated. To prevent the algae, the algae must be absorbed or removed.

On the other hand, red tide is a phenomenon in which the plankton multiplies in a huge number and changes the color of the sea, rivers, canals, lakes, etc. Generally, red tide is called red tide in the sense of red water because the water often changes red. The color depends on the color of the plankton causing. The most common phytoplankton that causes red tide is phytoplankton such as diatoms and dinoflagellates. Sometimes happens. The biggest cause of red tide is the eutrophication of water, as in South Korea, when there is too much organic nutrients in the water. In addition, it is known that red tide occurs when the water temperature rises due to the change in temperature, when the microorganisms grow more vigorously or when the sea water is not mixed well due to the less wind. In particular, it is known that red tide appears more frequently due to an increase in water temperature caused by global environmental changes such as El Nino.

  When the green algae or red tide occurs, the concentration of oxygen dissolved in the water is lowered, so the fish and shellfish that breathe using oxygen in the water suffocate and die a lot. In addition, plankton is sometimes physically suffocated by the gills of fish, and algae, which are toxic among algae or red tide, cause death due to this toxicity.

In order to remove green algae or red tide, ocher spreading is generally used. The ocher spreading method is a method of spreading ocher in green algae or red tide-producing waters to make green algae or red tide organisms and ocher coagulate and then settle in water. Incidentally, it is known that the cells of green algae and red tide organisms are destroyed by aluminum in loess. However, the ocher spreading method has only a temporary effect, the problem of re-emergence of precipitated green algae or red tide organisms, the turbidity of the water due to the large amount of ocher spreading causes the fish to die, and the slime formed of the ocher particles is formed. As the soil becomes acidified, it can cause a variety of secondary environmental pollution, including problems with marine life causing physiological disorders or death.

The present invention is to solve the conventional problems, one object of the present invention is easy to uniformly spray, remove the green algae or red tide by rapidly agglomeration and precipitation of the green algae or red algae organisms in the water green or red tide is generated. The present invention provides a green algae or red tide removal kit capable of maintaining the amount of dissolved oxygen at a constant level by continuously supplying oxygen to the water body by maintaining photosynthetic activity of the precipitated green algae or red algae organisms for a long time. It is also an object of the present invention to agglomerate and precipitate green algae or red algae organisms in the water bodies in which the green algae or red algae are generated, as well as green algae or red algae which can be removed by precipitating phosphorus or nitrogen components known as nutrient sources of green algae or red algae organisms. To provide a removal kit.

Another object of the present invention is to provide a method for effectively removing green alga or red tide using a green alga or red alga removal kit.

In order to achieve the object of the present invention, the present invention is a first additive and aluminum sulfate [Al ₂ (SO ₄ ) consisting of an aqueous solution of at least one substance selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH). ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], ferrous chloride (FeCl ₂ ), and ferric chloride (FeCl ₃₎ It provides a green algae or red tide removal kit, characterized in that it comprises a second additive consisting of an aqueous solution of one or more substances selected from the group consisting of), wherein the second additive is configured separately from the first additive. The first additive is more preferably made of a saturated aqueous solution of sodium hydroxide (NaOH), and the second additive is more preferably made of a saturated aqueous solution of aluminum sulfate [Al ₂ (SO ₄ ) ₃ ).

In order to achieve the other object of the present invention, the present invention is to add a first additive consisting of an aqueous solution of at least one substance selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH) to the green water or the red water generated water First agglomerating; And aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], chloride after completion of the first aggregation. Incorporating a second additive comprising an aqueous solution of at least one substance selected from the group consisting of ferrous iron (FeCl ₂ ) and ferric chloride (FeCl ₃ ) to the water body to agglomerate and precipitate the primary aggregate secondarily; It provides a green alga or red tide removal method comprising a. Here, the green water or the red water generated water is characterized in that the pH is adjusted to the range of 9 to 11 by the addition of the first additive, and the pH is 6.5 to 8.5 after the end of the secondary flocculation and precipitation. .

Green algae or red algae removal kit according to the present invention is composed of the first and second additives in the liquid form of the component, it is easy to spray uniformly in the green water or the water generated red tide, the aggregation reaction and precipitation quickly It is possible to remove the green algae or red tide in a short time. In addition, the photosynthetic activity of the precipitated green algae or red algae can be maintained for a long time, thereby continuously supplying oxygen to the water body to maintain the amount of dissolved oxygen in the water at a level suitable for marine life. In addition, by precipitating and removing phosphorus or nitrogen components known as nutrients of green algae or red algae, it prevents excessive growth of green algae or red algae.

One aspect of the present invention relates to a green algae or a red tide removal kit, and more particularly, it is possible to effectively remove the green algae or red algae by causing two stages of agglomeration reactions, and the green algae or red algae which can be easily added to the water bodies in which the green algae or red tide are generated. A red tide removal kit.

The green alga or red tide removal kit according to the present invention includes a first additive for agglutinating green algae or red algae organisms suspended in a water body and a second additive for secondly aggregating and precipitating green algae or red algae organisms aggregated first. Hereinafter, a green alga or red tide removing kit according to the present invention will be described by dividing into a first additive and a second additive.

First additive

The first additive consists of an aqueous solution of one or more substances selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH). Since the first additive is formed in an aqueous solution, it may be uniformly sprayed on the water body. In addition, the water body is the main phase is liquid because water occupies the main volume, and the first additive added is also liquid, so that the first additive added in a short time to change the chemical state in the water body, and quickly Primary agglomeration FIG. 1 is a photograph showing the result when primary agglomerates by adding a first additive to a water body in which a predetermined green algae organism is suspended. As shown in FIG. 1, green algae or red algae organisms suspended in a water body by primary aggregation are mostly agglomerated and converted into aggregates having a large volume. It is not large enough to cause it to form a dense shape and still exist in the water body.

The first additive includes alkali metal, in particular sodium hydroxide (NaOH) or potassium hydroxide (KOH) as an active ingredient. Sodium hydroxide and potassium hydroxide have high solubility at room temperature, and thus can be prepared in an aqueous phase having a high concentration. [Solubility of sodium hydroxide in water: 111 g / 100 ml (20 ° C.), solubility of potassium hydroxide in water: 110 g / 100 ml (25 ° C.)]. The concentration of sodium hydroxide (NaOH) or potassium hydroxide (KOH) in the first additive is not particularly limited, but considering the aggregation rate and economic efficiency, since the concentration is preferably high, the first additive is composed of a saturated aqueous solution. More preferably, it consists of a saturated aqueous solution of sodium hydroxide (NaOH).

Second additive

The second additive is aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], ferrous chloride (FeCl ₂ ), and ferric chloride (FeCl ₃ ), an aqueous solution of one or more materials selected from the group consisting of. Common green algae or red algae removers take the form of a composition of uniformly mixed materials effective for flocculation or sedimentation. Particularly in the green algae or red algae removal kits according to the present invention, the second additive is constituted separately from the first additive, and the first additive After the primary aggregation is terminated by the addition to the water body serves to induce secondary aggregation and precipitation of the aggregate.

Since the second additive is composed of an aqueous solution like the first additive, it can be uniformly sprayed on the water body. In addition, the water body is the main phase is liquid because water occupies the main volume, and the sprayed second additive is also a liquid phase, so the sprayed second additive changes the chemical state in the water body within a short time, and the first agglomerated green algae or red tide. Rapidly secondary coagulation of organisms to enhance aggregation and settle. FIG. 2 is a photograph showing the result of secondary aggregation and precipitation by adding a second additive to a water body after completion of primary aggregation of FIG. 1. As shown in FIG. 2, the aggregates, which are converted into agglomerates having a large volume by the first agglomeration but are still suspended in the water body, are more strongly aggregated by the second additive and have an increased specific gravity, thereby making precipitation more advantageous. . At the same time, aluminum hydroxide [Al (OH) ₃ ], iron hydroxide [Fe (OH) ₂ , or Fe (OH) ₃ ], which are insoluble and high in specific gravity, formed by the reaction of the aluminum ions or iron ions of the second additive with the hydroxyl groups in the water body. The back acts synergistically to allow rapid precipitation. In addition, the aluminum ions or iron ions of the second additive can react with the phosphorus component in the water body to form a phosphate which is insoluble in water and has a high specific gravity, and the formed phosphate precipitates effectively, thereby removing the phosphorus component. In addition, the formed phosphate induces precipitation of suspended primary aggregates in the precipitation process.

The second additive is aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], ferrous chloride (FeCl ₂ ) or ferric chloride (FeCl ₃ ) as an active ingredient, aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), sulfuric acid Ferric iron [Fe ₂ (SO ₄ ) ₃ ], ferrous chloride (FeCl ₂ ), or ferric chloride (FeCl ₃ ) can be prepared in aqueous phase with high concentration because of its high solubility at room temperature. [Solubility of aluminum sulfate in water: 36.4 g / 100 ml (20 ° C.), solubility of aluminum chloride in water: 45.8 g / 100 ml (20 ° C.), solubility of ferrous sulfate in water: 25.6 g / 100 ml, solubility in ferrous chloride in water: 68.5 g / 100 ml (20 ° C.), solubility in ferric chloride in water: 92 g / 100 ml (20 ° C.)]. In the second additive, aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], ferrous chloride Although the concentration of (FeCl ₂ ) or ferric chloride (FeCl ₃ ) is not particularly limited, the second additive is composed of a saturated aqueous solution because the concentration is preferably high in consideration of the rate of aggregation strengthening, precipitation rate, and economic efficiency. In particular, in consideration of the influence on the water environment and the like, and more preferably, a saturated aqueous solution of aluminum sulfate [Al ₂ (SO ₄ ) ₃ ) is preferable.

Another aspect of the present invention relates to a method of removing the green algae or red tide using the green algae or red tide removal kit according to the present invention, the green algae or red algae removal method of the present invention is sodium hydroxide (NaOH) and potassium hydroxide (KOH) First agglomerating the first additive comprising an aqueous solution of at least one substance selected from the group consisting of green algae or red tide and agglomerating the water firstly; And aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], chloride after completion of the first aggregation. Incorporating a second additive comprising an aqueous solution of at least one substance selected from the group consisting of ferrous iron (FeCl ₂ ) and ferric chloride (FeCl ₃ ) to the water body to agglomerate and precipitate the primary aggregate secondarily; It includes.

In general, the green algae or the red algae that occur in the water can be acidified due to the production of nitrogen oxides or phosphates and a decrease in dissolved oxygen, generally 6-7 has a pH. The green alga or red tide in which the green tide according to the present invention is generated is preferably adjusted to a pH of 9 to 11 by the addition of a first additive. In the pH range, the first aggregation and its rate show the maximum value, and the aggregation strengthening effect or the precipitation effect of the second additive shows the maximum value. In addition, it is preferable that the green water or red tide generated according to the present invention has a pH in the range of 6.5 to 8.5, which is the primary water standard after the completion of the secondary aggregation and precipitation.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for clearly describing the present invention, and do not limit the protection scope of the present invention.

<Examples>

1. Remove algae or red tide Kit  Manufacture of components

Example 1.

A first additive was prepared by dissolving 110 g of sodium hydroxide in 100 ml of water at about 20 ° C., and 35 g of aluminum sulfate was dissolved in 100 ml of water at about 20 ° C. to prepare a second additive.

Comparative Example 1

110 g of sodium hydroxide and 35 g of aluminum sulfate were added to 200 ml of water at about 20 ° C., and stirred to prepare a green alga or red algae remover. In the prepared green alga or red tide remover, white aluminum hydroxide produced by the reaction of aluminum ions and a hydroxyl group was precipitated.

2. Measure the algae removal ability

(1) Algae removal experiment

Experimental Example 1

100 mL of the first additive prepared in Example 1 was added to 100 l of the water sample (raw water) in which the green algae collected from Shinjeongho, Asan-si, were aggregated firstly. After the completion of the primary aggregation, 100 mL of the second additive prepared in Example 1 was added to induce secondary aggregation and precipitation.

Experimental Example 2.

100 mL of the first additive prepared in Example 1 was added to 100 L of the water sample (raw water) in which the green algae collected from Dangjin-Great Great Lake were aggregated. After the completion of the primary aggregation, 100 mL of the second additive prepared in Example 1 was added to induce secondary aggregation and precipitation.

Comparative Experimental Example 1.

200 mL of the green algae or red algae remover prepared in Comparative Example 1 was added to disperse the precipitated aluminum hydroxide in 100 l of the water sample (raw water) in which green algae were collected from Sinjeongho, Asan-si, to induce aggregation and precipitation.

Comparative Experimental Example 2.

200 g of fine loess powder was added to 100 l of the water sample (raw water) in which green algae were collected from Sinjeongho in Asan-si to induce aggregation and precipitation.

(2) Observation result of flocculation time and aggregation time

In the algae removal experiment, the aggregation and precipitation of the algae organisms and the end time were observed, and the results are shown in Table 1.

division Flocculation and precipitation Coagulation and sedimentation end time Experimental Example 1 Aggregation and precipitation of green algae End of first aggregation: about 10 seconds
End of 2nd flocculation and settling: about 5 minutes Experimental Example 2 Aggregation and precipitation of green algae End of first aggregation: about 10 seconds
End of 2nd flocculation and settling: about 5 minutes Comparative Experimental Example 1 Precipitation of aluminum hydroxide is mainly performed, and aggregation and precipitation of green algae rarely occurs. - Comparative Experimental Example 2 Aggregation and precipitation of green algae About 24 hours

As shown in Table 1, when the green algae removal kit according to the present invention was used, the agglomeration and precipitation of the green algae organisms occurred quickly, but when the ocher was used, the agglomeration and precipitation proceeded very slowly, and the green algae remover prepared in Comparative Example 1 Almost no aggregation of green algae occurred when used.

(3) Changes in photosynthetic activity of aggregated and precipitated green algae

The water bodies including the green algae organisms flocculated and precipitated by Experimental Example 1 and Comparative Experiment 2 were stored at about 5 ° C. for 6 months, and then the flocculated and precipitated green algae organisms were taken out, placed in uncontaminated fresh water, and irradiated with natural light. The amount of oxygen generated by natural light irradiation was measured using an oxygen sensor to investigate photosynthetic activity of green algae. It has been shown that the green algae organisms aggregated and precipitated by the algae removal kit according to the present invention are still photosynthetic while the green algae organisms aggregated and precipitated by ocher are not photosynthetic.

(3) Changes in biological and chemical properties of raw water by flocculation and precipitation

After leaving the waterbody including the green algae organisms aggregated and precipitated by Experimental Example 1 and Experimental Day for one day, clear water existing in the upper part of the waterbody was collected, and biological and chemical properties were measured.

Table 2 shows the results of the biological, chemical properties of the raw water according to Experimental Example 1, Table 3 shows the results of the biological, chemical properties of the raw water according to Experimental Example 2.

Biological and chemical properties How to measure enemy Experimental Example 1 pH Electrode method 7.0 8.5 BOD (ppm) Winkler-Sodium Azide Method 2.0 0.7 COD (ppm) Potassium Permanganate Method 8.0 4.0 SS (mg / l) Glass fiber excitation method 5.0 4.4 DO (ppm) Winkler-Sodium Azide Method 8.4 8.3 NO ₃ ^- (ppm) Absorbance method 0.763 Not detected PO ₄ ^- (ppm) Absorbance method 0.060 0.031

Biological and chemical properties How to measure enemy Experimental Example 2 pH Electrode method - 7.3 BOD (ppm) Winkler-Sodium Azide Method - COD (ppm) Potassium Permanganate Method 8.0 5.0 SS (mg / l) Glass fiber excitation method 22.0 1.4 DO (ppm) Winkler-Sodium Azide Method 2.0 8.1 NO ₃ ^- (ppm) Absorbance method 1.880 0.476 PO ₄ ^- (ppm) Absorbance method 0.100 Not detected

Description of the key items in Table 2 or Table 3

BOD: biological oxygen demand, COD: chemical oxygen demand, DO: dissolved oxygen

SS: Suspended Solids are solid materials containing organic matter and organic matter suspended in water that are not dissolved in water having a particle diameter of 2 mm or less, and are not filtered when the sample is filtered using a filter paper having a void of 0.1%. Part.

When treating the water-containing green algae using the green algae removal kit according to the present invention, as shown in Tables 2 to 3, the biological oxygen demand, chemical oxygen demand, suspended solids, nitric acid content, phosphoric acid content of the raw water are significantly reduced and It has been shown to significantly increase the amount of dissolved oxygen. In addition, it can be seen that most biological and chemical properties were converted from the fourth grade to the fifth grade to the first grade based on the river water quality criteria table of Table 4.

Water quality BOD or COC (ppm) DO (ppm) NO ₃ ^- (ppm) PO ₄ ^- (ppm) pH Grade 1 1 or less 7.5 or more 0.2 or less 0.01 or less 6.5 ~ 8.5 Grade 2 3 or less 5 or more 0.4 or less 0.03 or less 6.5 ~ 8.5 Grade 3 6 or less 5 or more 0.6 or less 0.05 or less 6.5 ~ 8.5 Grade 4 8 or less 2 or more 1.0 or less 0.10 or less 6.0-8.5 Grade 5 below 10 2 or more 1.5 or less 0.15 or less 6.0-8.5

Figure 1 is a photograph showing the result of the first flocculation by adding the first additive to the water suspended in a predetermined green algae organism, Figure 2 is a second additive in the water after the first flocculation of FIG. It is a photograph showing the result of the addition and the secondary aggregation and precipitation.

Claims (10)

delete delete delete delete First agglomerating the first additive comprising an aqueous solution of at least one substance selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH) to a green algae or a red tide; And After completion of primary aggregation, aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], and chloride 1 Incorporating a second additive comprising an aqueous solution of at least one substance selected from the group consisting of iron (FeCl ₂ ) and ferric chloride (FeCl ₃ ) into the water body to agglomerate and precipitate the primary aggregate secondarily; Green algae or red tide removal method comprising. The method according to claim 5, wherein the first additive comprises a saturated aqueous solution of at least one substance selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH). The method of claim 6, wherein the second additive is aluminum sulfate [Al ₂ (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), ferrous sulfate (FeSO ₄ ), ferric sulfate [Fe ₂ (SO ₄ ) ₃ ], ferric chloride (FeCl ₂ ), and ferric chloride (FeCl ₃ ) A green algae or red tide removing method characterized in that consisting of a saturated aqueous solution of one or more substances selected from the group consisting of. According to claim 7, wherein the first additive is made of a saturated aqueous solution of sodium hydroxide (NaOH), the second additive is a green algae, characterized in that made of a saturated aqueous solution of aluminum sulfate [Al ₂ (SO ₄ ) ₃ ) How to get rid of red tide. 10. The method according to any one of claims 5 to 9, wherein the green water or red tide in which the green tide is generated is adjusted to a pH of 9 to 11 by the addition of a first additive. 10. The method according to claim 9, wherein the green algae or the red tide in which the green algae are generated have a pH of 6.5 to 8.5 after the second agglomeration and precipitation.

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