Composition comprising sericite or zirconium silicate for removing harmful blue-green algae and adsorption cloth

Abstract

The present invention relates to a composition for removing harmful blue-green algae, and an adsorption cloth. The adsorption cloth for removing harmful blue-green algae according to the present invention is for controlling the growth of harmful blue-green algae in water, and comprises: a composition containing sericite and / or zirconium silicate for removing harmful blue-green algae; and an adsorbent, having the harmful blue-green algae removing composition dispersed and accommodated therein, for adsorbing harmful blue-green algae.

Description

Algae removal composition and adsorbent containing sericite or zirconium silicate

[0001] The present invention relates to environmental technology, and more particularly, to a green algae removal composition and an adsorbent for suppressing and removing the growth of green algae occurring in rivers, lakes, etc.

[0002]

[0003] The overgrowth of harmful blue-green algae, also known as "blue-green algae," is a growing problem. In Korea, blue-green algae blooms are particularly prevalent in the Nakdong River basin during the summer, and even after the dam identified as the cause was opened, the phenomenon persists. Beyond the Nakdong River, blue-green algae blooms are reported annually in both natural and man-made water systems, such as agricultural reservoirs and artificial lake parks.

[0004] In addition, the frequency and severity of green algae are worsening due to continued global warming and eutrophication of water systems caused by large amounts of nutrients flowing in from point or non-point sources of pollution.

[0005] The most common harmful cyanobacteria that causes green algae blooms is Microcystis sp., and can release microcystins, a toxic substance, into water systems. Microcystins are known to be neurotoxic and hepatotoxic and can cause fatal diseases in humans and animals, including acute liver hemorrhage and liver cancer. They can enter the human body through ingestion, inhalation, or skin contact. The problem can be even more serious in plants grown in water systems where green algae blooms have occurred, as microcystins can accumulate there.

[0006] Various physical, chemical, and biological techniques have been developed to control and remove harmful blue-green algae, but their practical application is limited. Physical techniques include underwater aeration, fixed-use removal methods such as algae barriers, ultrasonic-induced cavitation, and ultraviolet radiation. However, these techniques are uneconomical in terms of equipment and operation, and generate large amounts of biomass and byproducts, causing secondary pollution of aquatic ecosystems.

[0007] Chemical techniques used to control green algae include hydrogen peroxide, ozone, and hydroxyl radicals. However, when chemical methods are applied, the harmful blue-green algae that die underwater can increase the concentration of toxic substances in the water, posing a significant threat to the health of the aquatic ecosystem. In other words, the dead green algae aggregate and sediment underwater, and then settle to the bottom of the water system. As they naturally decompose, they release nutrients (especially phosphorus) and toxic substances.

[0008] Among various treatment methods, the green algae control technology using yellow soil, which is known as a relatively eco-friendly control method, has problems such as ecosystem disruption due to yellow soil particles blocking sunlight, and accumulation of algal toxic substances due to harmful blue-green algae that are aggregated and settled in yellow soil.

[0009]

[0010] The present invention is intended to solve the above-mentioned problems, and its purpose is to provide a composition for removing blue-green algae (blue-green algae) and an adsorbent cloth for removing blue-green algae that can not only suppress the growth of blue-green algae but also completely remove blue-green algae from a water system by adsorbing the blue-green algae.

[0011] Meanwhile, other unspecified purposes of the present invention will be additionally considered within a range that can be easily inferred from the detailed description and effects thereof below.

[0012]

[0013] To solve the problem described above, the following solutions are proposed.

[0014] The composition for removing blue-green algae according to the present invention for achieving the above purpose is characterized by containing sericite for controlling the growth of harmful blue-green algae in water.

[0015] In addition, the adsorbent for removing blue-green algae according to the present invention for achieving the above purpose is characterized by comprising: a blue-green algae removing composition including sericite for controlling the growth of harmful blue-green algae in water; and an adsorbent in which the blue-green algae removing composition is dispersed and received, and which adsorbs blue-green algae.

[0016] Meanwhile, the green algae removal composition according to the present invention for achieving the above purpose is characterized by containing zirconium silicate (ZrSiO4) for controlling the growth of harmful blue-green algae in water.

[0017] In addition, the adsorbent for removing blue-green algae according to the present invention for achieving the above purpose is characterized by comprising: a blue-green algae removing composition containing zirconium silicate (ZrSiO4) for controlling the growth of harmful blue-green algae in water; and an adsorbent in which the blue-green algae removing composition is dispersed and received, and which adsorbs blue-green algae.

[0018] In one example of the present invention, the adsorbent is CMC (Carboxymethyl cellulose), and can be manufactured by cross-linking sericite to the CMC.

[0019] In one example of the present invention, the adsorbent is polyacrilonitrile (PAN), and can be manufactured by mixing the PAN and the sericite and / or zirconium silicate and electrospinning them.

[0020] In one example of the present invention, the green algae removing composition including sericite may be mixed in a weight ratio of 30 to 70% and the adsorbent may be mixed in a weight ratio of 30 to 70%.

[0021] In one example of the present invention, the green algae removing composition including zirconium silicate may be mixed in a weight ratio of 30 to 70% and the adsorbent may be mixed in a weight ratio of 30 to 70%.

[0022]

[0023] It was confirmed that by using the green algae removal composition and adsorbent cloth according to the present invention, the growth of harmful blue-green algae in water can be effectively controlled and dead blue-green algae can be adsorbed and removed.

[0024] The present invention has the advantage of being able to remove green algae while minimizing the impact on the water system by using a mineral-based green algae removal composition.

[0025] In addition, the present invention has the advantage of not causing secondary pollution due to green algae treatment by adsorbing and recovering dead blue-green algae, thereby preventing them from being deposited on the water surface.

[0026] Meanwhile, even if the effect is not explicitly mentioned herein, it is added that the effect and its provisional effect described in the following specification expected by the technical features of the present invention are treated as described in the specification of the present invention.

[0027]

[0028] Figure 1 is a graph showing the change in the concentration of chlorophyll a over time in the culture solution to which each experimental mineral was added.

[0029] Figure 2 is a graph showing the change in concentration of total chlorophyll a over time in the culture solution to which each experimental mineral was added.

[0030] Figure 3 is a graph showing the change in photosynthetic amount over time in the culture solution into which each experimental mineral was added.

[0031] Figure 4 is a photograph taken after immersing a filter containing minerals in the center of a plate inoculated with a culture medium and harmful blue-green algae and culturing it for a sufficient period of time.

[0032] Figure 5 is a photograph taken immediately after an adsorbent for removing green algae was added to a culture medium containing harmful blue-green algae, and Figure 6 is a photograph taken one day later.

[0033] ※ It is to be noted that the attached drawings are provided for reference only to help understand the technical concept of the present invention, and the scope of the rights of the present invention is not limited thereby.

[0034]

[0035] In describing the present invention, if it is judged that the detailed description of related known functions that are obvious to those skilled in the art and may unnecessarily obscure the gist of the present invention, will be omitted.

[0036] The present invention relates to a composition for controlling / removing the growth of harmful blue-green algae called green algae, and an adsorbent cloth for removing dead or inactive blue-green algae from water by adsorbing them.

[0037] As explained in the background section, existing green algae removal technologies require significant facility investment, making them uneconomical. Furthermore, after death, blue-green algae persist in the water, releasing secondary pollutants such as toxins, which can negatively impact aquatic ecosystems. The most widely used method, loess, also presents challenges, such as the difficulty of removing dead blue-green algae from the water column, and the potential for sunlight blockage when applied.

[0038] The purpose of the present invention is to provide a composition for removing green algae that suppresses the growth of harmful blue-green algae and induces its death by using natural minerals, which are environmentally friendly materials, and an adsorbent cloth that can adsorb dead blue-green algae and remove them from water.

[0039] Hereinafter, with reference to the attached drawings, a green algae removal composition and an adsorbent cloth according to an example of the present invention will be described in more detail.

[0040] A green algae removal composition according to an example of the present invention contains a mineral as a main ingredient.

[0041] In particular, the composition according to the present example has as its main component sericite (sericite), which is a mica mineral, or zirconium silicate (ZrSiO4). Sericite or zirconium silicate may be used alone, or zirconium silicate and sericite may be mixed and used. It may also be mixed and used with other minerals. As other minerals, one or more of fluorite, diatomite, and bauxite may be mixed and used. For example, the composition for removing green algae may be mixed and used in a ratio of 60 to 75 wt% of sericite, 20 to 30 wt% of zirconium silicate, and one or two or more of fluorite, diatomite, and bauxite in a combination ratio of 5 to 15 wt%. Alternatively, the green algae removal composition may be mixed in a ratio of 40 to 60 wt% of sericite and 40 to 60 wt% of zirconium silicate.

[0042] In this example, sericite is used alone or in a blend of at least 80% by weight. As will be described later, sericite is more effective than other minerals in removing green algae. Alternatively, zirconium silicate can be used alone or in a blend of at least 80% by weight. While less effective than sericite, zirconium silicate is equally effective.

[0043] The research team of the present invention was researching an eco-friendly algae removal agent that could overcome the limitations of existing algae removal compositions and minimize the impact on aquatic ecosystems. While researching this material, they discovered the possibility that minerals could effectively control the growth of algae. They investigated the properties of various minerals and conducted experiments on minerals known to have antibacterial effects. As a result, they confirmed that sericite or zirconium silicate was the most effective in inhibiting and removing the growth of algae, and they intend to utilize it as an algae removal composition.

[0044] An experiment was conducted to compare the algae control effects of sericite, the most important ingredient in the algae-removing composition according to this example, and other minerals. The experimental results are presented below.

[0045]

[0046] 1. Experiment on the effect of powder-type minerals on controlling green algae growth

[0047] For the experiment, the reactor, air line, and BG11 medium (microalgae growth medium) solution were sterilized in an autoclave at 121°C for 15 minutes. The optical density of pre-cultured Microcystis aeruginosa was measured to calculate the inoculation ratio for the desired initial algal concentration (approximately OD 0.3). The minerals prepared as follows were each added to the reactor at a concentration of 2 g / L.

[0048] Experimental minerals: Bauxite, Fluorite, Sericite, Zir-silicate, Diatomite

[0049] Control: No minerals added

[0050] After inoculating green algae M. aeruginosa cells into each culture medium, air was injected at 250 mL / min in an incubator at 28°C, and sampling was performed once a day for 10 days to measure chlorophyll a concentration, total chlorophyll concentration, and photosynthetic amount.

[0051]

[0052] The experimental results are shown in [Table 1] below and the graphs in Figures 1 and 2.

[0053]

[0054] [Table 1] Measurement of chlorophyll concentration and total chlorophyll concentration

[0055]

[0056] Referring to the above [Table 1] and the graphs in Figures 1 and 2, the concentration of chlorophyll was lower in all cases where minerals were added compared to the control without minerals. The effect of minerals on controlling green algae was confirmed. In particular, in the culture solution containing sericite, zirconium silicate, and fluorite minerals, the concentration of chlorophyll a and total chlorophyll was measured to be 0.6, which is 40% lower than the control, showing that the above minerals are very effective in controlling the growth of harmful blue-green algae.

[0057] Figure 3 is a graph showing the change in photosynthetic activity over time in the culture medium containing each experimental mineral. Referring to the graph in Figure 3, sericite showed the lowest photosynthetic activity in the analysis, followed by zirconium silicate. A low photosynthetic activity indicates that the green algae in the culture medium are dead or have reduced activity.

[0058] Considering the above experimental results comprehensively, it can be seen that sericite is the most effective in controlling the harmful blue-green algae Microcystis aeruginosa.

[0059]

[0060] 2. Disk Experiment

[0061] 3.3% agarose solution and 2X BG11 medium were sterilized at 121℃ for 15 minutes, respectively, to prepare. When the sterilized solution reached approximately 60-70℃, the two solutions were mixed and Microcystis aeruginosa that had been pre-cultured at approximately 50℃ was mixed together. After the solution had solidified, it was poured onto a plate, dried, and the filter with the minerals on it was turned over and placed on top. Two types of minerals were used, Sericite and Zr-silicate. After the minerals were added, the culture was incubated in a 28℃ incubator for a sufficient period of time.

[0062] The experimental results can be seen in the photo in Fig. 4.

[0063] Figure 4 is a photograph taken after immersing a filter containing minerals in the center of a disk inoculated with a culture medium and harmful blue-green algae and culturing it for a sufficient period of time.

[0064] Referring to the photo in Figure 4, Microcystis aeruginosa strains grow on solid media, revealing a yellowish-green hue. However, the area surrounding the mineral-containing filter is not light green, but rather transparent, resembling a halo. This indicates that Microcystis aeruginosa strains are inhibited and growth is suppressed near sericite and zirconium silicate.

[0065] Meanwhile, the algae removal composition described so far can be used alone, but it is preferable to manufacture it in the form of an adsorbent, as in the present invention. As described in the prior art, if algae is not removed from the water after dying in the water, it can deposit on the bottom and decompose, releasing toxic substances and causing eutrophication. Therefore, the present invention provides an adsorbent capable of removing dead or deactivated algae.

[0066] The adsorbent for removing green algae according to the present invention is manufactured by dispersing the above-described green algae removing composition in an adsorbent.

[0067] Carboxymethyl cellulose (CMC) or polyacrilonitrile (PAN) can be used as an adsorbent.

[0068] A method for manufacturing an adsorbent by dispersing a green algae removal composition in CMC is as follows.

[0069] First, CMC-Na (Mw: 250,000) polymer is dissolved in distilled water to prepare a 1.5 to 2.5 wt% CMC solution.

[0070] Then, the green algae removal composition is mixed in a 1.5 to 2.5 wt% CMC solution at a weight ratio of 15 to 25 wt% and stirred. The mixture is placed in a petri dish and frozen for 24 hours.

[0071] After freeze-drying the frozen sample, the freeze-dried sample is cross-linked in a 0.1 M FeCl3 solution, resulting in cross-linking of the CMC and the green algae removal composition, thereby producing an adsorbent. Finally, the sample is washed at least three times with distilled water to remove unreacted substances.

[0072] A method for manufacturing an adsorbent by dispersing an algae removal composition in PAN is as follows.

[0073] Dissolve PAN polymer in DMF or DMSO solvent at a weight ratio of 5 to 15% to prepare a 5 to 15 wt% PAN solution. Then, mix the green algae removing composition in a weight ratio of 5 to 15% with the 5 to 15 wt% PAN solution and stir. An adsorbent fabric can be manufactured by electrospinning under the conditions of a spinning voltage of 20 kV, a syringe pump flow rate of 0.9 mL / hr, a needle height of 15 cm (TCD), and a needle size of 21 G.

[0074]

[0075] 3. Absorbent pad experiment

[0076] An algae removal experiment was conducted using the adsorbent fabric manufactured by the above method. An adsorbent fabric cross-linked with an algae removal composition to CMC and an adsorbent fabric nano-electrospun by mixing the algae removal composition with a PAN polymer material were prepared, respectively. Each adsorbent fabric experimental group is as follows. In each algae removal composition, the particle size of sericite is in the range of 0.5 to 50 μm, and the particle size of zirconium silicate is in the range of 0.1 to 10 μm. If the particle size is less than this range, there is a problem because it is not evenly distributed within the CMC or PAN, and if the particle size exceeds this range, the surface area that the algae removal composition can contact with the algae is reduced, making it ineffective in removing the algae.

[0077]

[0078] [Table 2] Composition ratio of experimental groups of CMC-based adsorbents

[0079]

[0080] [Table 3] Composition ratio of experimental groups of PAN-based adsorbents

[0081] And the reactor, air line, and BG11 solution were prepared by sterilization in an autoclave at 121℃ for 15 minutes. The optical density of the pre-cultured Microcystis aeruginosa was measured to calculate the inoculation ratio for the desired initial green algae (harmful blue-green algae) concentration (initial concentration: OD approximately 0.3). Each experimental group absorbent cloth was added to the green algae inoculated in the BG11 medium, and air was injected at 250 mL / min in an incubator at 28℃. The optical density was measured immediately after the addition of the green algae and 24 hours later for comparison.

[0082] Figure 5 is a photograph taken immediately after an adsorbent for removing green algae was added to a culture medium containing harmful blue-green algae, and Figure 6 is a photograph taken one day later.

[0083] As shown in the photo of Fig. 5, the culture medium appears green in all experimental groups. However, as shown in the photo of Fig. 6, one day after the introduction of the adsorbent for green algae removal, the color of CMC+Sericite, PAN+Sericite, and PAN+Zr-silicate has noticeably lightened. This shows that the harmful blue-green algae has been adsorbed on the adsorbent for green algae removal. From the above experimental results, it can be seen that the form in which sericite is dispersed in the PAN adsorbent showed the best effect in controlling green algae. In the experimental groups containing only CMC and only PAN, which did not contain the green algae removal composition, the color was slightly lighter than the original, but it was still green. In other words, it can be confirmed that the CMC and PAN adsorbents alone are not effective in controlling green algae, and that the presence of the green algae removal composition is effective in controlling and removing green algae growth. However, in the case of CMC+Zr-silicate, this phenomenon is believed to have occurred because the CMC was dissolved in the culture medium.

[0084] It is believed that the green algae adsorbed on the adsorbent can be reused as energy raw materials after desorption.

[0085] As described above, it was confirmed that by using the green algae removal composition and adsorbent cloth according to the present invention, the growth of harmful blue-green algae in water can be effectively controlled and dead blue-green algae can be adsorbed and removed.

[0086] The present invention has the advantage of being able to remove green algae while minimizing the impact on the water system by using a mineral-based green algae removal composition.

[0087] In addition, the present invention has the advantage of not causing secondary pollution due to green algae treatment by adsorbing and recovering dead blue-green algae, thereby preventing them from being deposited on the water surface.

[0088] The scope of protection of the present invention is not limited to the description and expression of the embodiments explicitly described above. Furthermore, it should be noted that the scope of protection of the present invention may not be limited by obvious modifications or substitutions within the technical field to which the present invention pertains.

Claims

1. A composition for removing blue-green algae, characterized in that it contains sericite, for controlling the growth of harmful blue-green algae in water.

2. A composition for removing blue-green algae, containing sericite, for controlling the growth of harmful blue-green algae in water; and An adsorbent for removing blue-green algae, characterized in that the above-mentioned blue-green algae removing composition is dispersed and received, and an adsorbent for absorbing blue-green algae is provided.

3. A composition for removing blue-green algae, characterized in that it contains zirconium silicate (ZrSiO4) for controlling the growth of harmful blue-green algae in water.

4. A composition for removing blue-green algae, comprising zirconium silicate (ZrSiO4), for controlling the growth of harmful blue-green algae in water; and An adsorbent for removing blue-green algae, characterized in that the above-mentioned blue-green algae removing composition is dispersed and received, and an adsorbent for absorbing blue-green algae is provided.

5. In paragraph 2 or paragraph 4, The above adsorbent is CMC (Carboxymethyl cellulose), An adsorbent for removing green algae, characterized in that sericite or zirconium silicate is cross-linked to the above CMC.

6. In paragraph 2 or paragraph 4, The above adsorbent is PAN (polyacrilonitrile), An adsorbent for removing green algae, characterized in that it is manufactured by mixing the above PAN and the above sericite or zirconium silicate and electrospinning them.

7. In paragraph 2 or paragraph 4, An adsorbent for removing green algae, characterized in that the above green algae removing composition is mixed in a weight ratio of 30 to 70% and an adsorbent is mixed in a weight ratio of 30 to 70%.

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