Medicament for ecologicalized cyanobacteria treatment and preparation method thereof

Abstract

The invention belongs to the field of blue-green algae treatment, and particularly relates to a medicament for ecological blue-green algae treatment and a preparation method thereof. The medicament comprises degradable cellulose tablets, a flocculating agent, a cyclodextrin adsorbent and humic acid, and contains or does not contain a corn soaking solution, the degradable cellulose tablets and other components are mutually independent, and the medicament comprises the following components in parts by mass: 10-20 parts of the flocculating agent, 5-8 parts of the cyclodextrin adsorbent, 3-7 parts of the humic acid and 100-500 parts of the corn soaking solution. The water quality can be effectively improved, and the cost is low.

Description

Technical Field

[0001] The invention belongs to the field of blue algae treatment, and in particular relates to a medicament for ecological blue algae treatment and a preparation method thereof. Background Art

[0002] With the development of aquaculture technology, the per-acre hair yield of fish ponds, shrimp ponds, etc. has gradually increased. With the increase in fish, shrimps, crabs, etc., the amount of feed will also increase accordingly, which will also lead to an increase in excrement, which will lead to an increase in ammonia nitrogen in the water body. At the same time, aquaculture water bodies are usually connected to municipal pipelines, which will discharge pollutants generated by human activities into the water bodies. The pollutants contain a large amount of ammonia nitrogen and phosphorus, which will lead to eutrophication of water bodies and algal blooms.

[0003] Algal bloom is mainly caused by the massive reproduction of cyanobacteria in eutrophic water bodies, forming huge cyanobacterial sewage masses that float in the water body or settle to the bottom of the water. During the decomposition process of cyanobacteria, a large amount of dissolved oxygen in the water body will be consumed, causing serious water pollution, black and smelly water, and producing the special odor of cyanobacterial decay. Cyanobacterial toxins can also poison or even kill various mammals, fish, shrimps, and birds, causing great economic losses to animal husbandry and aquaculture. What's more serious is that it can affect human health in many ways, so it needs to be controlled in a timely manner.

[0004] At present, the commonly used methods for controlling blue-green algae include physical methods, chemical methods, water exchange method for algae removal, biological treatment methods, etc. The chemical method achieves the purpose of algae removal by adding potassium permanganate, copper sulfate, etc. to the water body to destroy the structure of blue-green algae. However, the effect of chemical reagents is short-lived, which will not only bring new pollution to the water body, but also affect the normal growth of aquatic animals; the physical method is to form a colloidal suspension in the water through artificial salvage or adding flocculants such as aluminum chloride and bentonite to the water body, which will form a loose solid after adsorbing the blue-green algae and sink to the bottom of the water to form bottom mud, releasing dissolved oxygen to improve the water quality. However, the cost of using only flocculants such as aluminum chloride and bentonite is high and the purification time is long; the water exchange method needs to further treat the polluted water after replacing the water in the water body. It does not substantially improve the water quality of the water body and only treats the symptoms but not the root cause. Summary of the invention

[0005] In order to improve the deficiencies of the prior art, the present invention provides an agent for ecological blue algae control and a preparation method and application thereof. The agent can effectively improve water quality and has low cost.

[0006] In a first aspect, the present invention provides an agent for ecological cyanobacteria control, comprising a degradable cellulose sheet, a flocculant, a cyclodextrin adsorbent, humic acid, and containing or not containing corn steep liquor. The degradable cellulose sheet is independent of other ingredients. In parts by mass, the agent comprises 10 to 20 parts of flocculant, 5 to 8 parts of cyclodextrin adsorbent, 3 to 7 parts of humic acid and 100 to 500 parts of corn steep liquor.

[0007] According to an embodiment of the present invention, the flocculant includes one or more of a high molecular polymer and clay.

[0008] According to an embodiment of the present invention, the high molecular polymer includes a synthetic high molecular polymer and / or a natural high molecular polymer.

[0009] According to an embodiment of the present invention, the synthetic high molecular polymer is at least one selected from polyacrylamide, acrylate and the like.

[0010] According to an embodiment of the present invention, the natural high molecular polymer may be one or more of chitosan and its derivatives, chitin and its derivatives, carboxymethyl starch and other modified starches, carboxymethyl cellulose and other cellulose derivatives, guar gum and its derivatives, xanthan gum and its derivatives, and alginic acid and its derivatives.

[0011] According to an embodiment of the present invention, the high molecular polymer is a mixture of polyacrylamide and chitosan.

[0012] According to an embodiment of the present invention, the cyanobacteria is Microcystis.

[0013] According to an embodiment of the present invention, the degradable cellulose sheet is selected from the straw or leaves of wheat, rice, corn, potato, rape, cotton, sugarcane, etc., preferably leaves, such as 0.5-1 cm long and 0.1-1 cm wide sheet straw or leaves. In use, the amount of the degradable cellulose sheet is adjusted according to the area of ​​use, and the water surface needs to be completely covered. The degradable cellulose sheet can be dispersed on the water surface, blocking the sunlight on the water surface, quickly reducing the photosynthesis of cyanobacteria, and the degradable cellulose sheet floats on the water surface. After use, it can be collected and reused, and can also be further used to prepare humic acid, etc.

[0014] According to an embodiment of the present invention, in order to increase the dispersion speed of the degradable cellulose sheet in water, the degradable cellulose sheet may be first immersed in a cyclodextrin solution with a concentration of 0.1 to 0.5 mol / L to form a hydrophobic surface.

[0015] According to an embodiment of the present invention, the preparation method of corn soaking liquid includes the following steps: washing corn and soaking it in water for 1 to 2 hours, taking the supernatant after separation, and concentrating it 5 to 10 times to obtain corn soaking liquid, wherein the pH value of the corn soaking liquid is 4.5 to 6, and it has strong acidity, and the main component providing acidity is phytic acid, which can adjust the pH value of the water body and release a large amount of P under the action of cyanobacteria to reduce the N / P ratio in the water body.

[0016] According to an embodiment of the present invention, the clay can be one or more of talc, kaolin, light shale, clay, attapulgite, silica mud, illite, ferromagnetic clay, mica, clinoptilolite, montmorillonite, light aggregate pumice, white mud, zeolite, sepiolite, pumice, foot-rubbing stone, volcanic slag, diatomaceous earth, porcelain clay and general soil, preferably a mixture of diatomaceous earth and kaolin, wherein the mass ratio of diatomaceous earth to kaolin is 1:(1-5).

[0017] According to an embodiment of the present invention, the cyclodextrin adsorbent is one or more of hydroxypropyl-β-cyclodextrin, mono-(6-oxy-ethylenediaminetetraacetyl)-cyclodextrin, and β-cyclodextrin.

[0018] In a second aspect, the present invention also provides a method for preparing the above-mentioned agent for ecological blue algae control, comprising the following steps:

[0019] The flocculant, cyclodextrin adsorbent and humic acid are mixed, and the degradable cellulose sheets and corn soaking liquid are placed separately.

[0020] According to an embodiment of the present invention, the mixing is performed at normal temperature and pressure.

[0021] Beneficial Effects

[0022] 1) The inventors unexpectedly discovered that by adding corn steep liquor to the water body, the pH value of the water body can be lowered, thereby inhibiting the growth of Microcystis. At the same time, Microcystis can absorb phytic acid in the corn steep liquor and utilize the P therein. Under this condition, the N / P ratio in the water body can be effectively improved, and the N / P ratio can be adjusted to a range of 1:15 to 1:25, which is not suitable for the growth of Microcystis, thereby controlling the growth of Microcystis and inhibiting algal blooms.

[0023] 2) The present invention uses biodegradable cellulose sheets as shading materials. The cellulose sheets are first soaked in a cyclodextrin solution to increase their hydrophobicity so that the biodegradable cellulose sheets are evenly dispersed on the water surface, completely covering the water surface and isolating direct sunlight, thereby inhibiting the photosynthesis of Microcystis and effectively controlling water blooms.

[0024] 3) The present invention uses a flocculant, a cyclodextrin adsorbent and humic acid in combination. The flocculant and humus can quickly adsorb and cross-link with the polypeptides and sugar macromolecules secreted by Microcystis to form floccules. The cyclodextrin adsorbent can adsorb ions such as Fe and Cu in the water body that stimulate the growth of Microcystis, which can not only inhibit the growth of Microcystis, but also improve the environment of the water body from the root and avoid the recurrence of algal blooms. DETAILED DESCRIPTION

[0025] The following will further describe the medicament of the present invention and its preparation method in conjunction with specific examples. It should be understood that the following examples are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0026] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0027] In the following experiments, the concentration was selected as 10 8 cell / mL of Microcystis solution, the volume of the Microcystis solution is 500mL, stored in a beaker, the solution is dark green.

[0028] The OD value of the Microcystis solution was measured using a spectrophotometer.

[0029] Cationic polyacrylamide has a molecular weight of 8 million to 12 million and was purchased from Zhongbei Chemical; chitosan (carboxymethyl chitosan), kaolin, zeolite, β-cyclodextrin, humic acid (nitrohumic acid), carboxymethyl cellulose, and carboxymethyl starch were purchased from Wuhan Jiyesheng Chemical Co., Ltd.; mono-(6-oxy-ethylenediaminetetraacetyl)-cyclodextrin was purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd., and corn soaking liquid was prepared by ourselves.

[0030] Example

[0031] A pharmaceutical agent for ecological blue algae control, comprising the components described in Table 1.

[0032] Table 1 Pharmaceutical ingredients

[0033]

[0034] Note: The degradable cellulose sheets used in Examples 1-4 and Comparative Example 1 are corn leaves that have been soaked in a cyclodextrin solution with a concentration of 0.5 mol / L and dried to form a hydrophobic surface. The degradable cellulose sheets used in Example 5 and Comparative Example 2 are corn leaves that have not been soaked.

[0035] Test Case

[0036] According to the components in Table 1, to each Microcystis solution (initial OD680 was about 1.45, and 3 comparative examples were set for each component), corn soaking liquid was first added to the Microcystis solution, and then flocculant, cyclodextrin adsorbent and humic acid were added. After stirring for 2 minutes, the degradable cellulose sheets were dispersed on the surface of the solution and observed under simulated sunlight irradiation.

[0037] Among them, the soaked corn leaves quickly dispersed and completely covered the surface of the solution, while the unsoaked corn leaves were stacked in large quantities and did not completely cover the surface of the solution.

[0038] Table 2 Treatment effects of different embodiments and comparative examples

[0039]

[0040]

[0041] As can be seen from Table 2, in this embodiment, the pH value is adjusted by adding corn soaking liquid to the Microcystis solution, and then a flocculant, a cyclodextrin adsorbent and humic acid are added, and finally the hydrophobic corn leaves are used to cover the water surface to clean the Microcystis. The method can quickly (within 30 minutes) remove the Microcystis and make the water clear.

[0042] Furthermore, sodium nitrate and sodium hydrogen phosphate were added to the cleaned solution to make an N / P ratio of 7 / 1, the temperature was adjusted to 30°C, pH = 9, and the water body was observed under light. Among them, in Comparative Example 2, cyanobacteria visible to the naked eye appeared after 10 hours of light exposure; in Comparative Example 3, cyanobacteria visible to the naked eye appeared after 6.5 hours of light exposure. No cyanobacteria visible to the naked eye appeared in other comparative examples and embodiments, indicating that after the scheme of the present invention treats the water body, the recurrence of cyanobacteria in the water body can be effectively avoided.

[0043] The above examples are used to illustrate the specific implementation of the present invention. However, the protection scope of the present invention is not limited to the above exemplary implementation. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A pharmaceutical agent for ecological blue algae control, characterized in that: The invention comprises a degradable cellulose sheet, a flocculant, a cyclodextrin adsorbent, humic acid, and may or may not contain corn steep liquor. The degradable cellulose sheet is independent of other ingredients. In parts by mass, the agent comprises 10 to 20 parts of flocculant, 5 to 8 parts of cyclodextrin adsorbent, 3 to 7 parts of humic acid and 100 to 500 parts of corn steep liquor.

2. The agent for ecological blue algae control according to claim 1, characterized in that: The flocculant includes one or more of a high molecular polymer and clay; Preferably, the high molecular polymer includes a synthetic high molecular polymer and / or a natural high molecular polymer; Preferably, the synthetic high molecular polymer is selected from at least one of polyacrylamide, acrylate and the like.

3. The agent for ecological blue algae control according to claim 2, characterized in that: The natural high molecular polymer can be one or more of chitosan and its derivatives, chitin and its derivatives, carboxymethyl starch and other modified starches, carboxymethyl cellulose and other cellulose derivatives, guar gum and its derivatives, xanthan gum and its derivatives, and alginic acid and its derivatives.

4. The agent for ecological blue algae control according to claim 1, characterized in that: The cyanobacteria is Microcystis.

5. The agent for ecological blue algae control according to any one of claims 1 to 4, characterized in that: The degradable cellulose sheet is selected from the straw or leaves of wheat, rice, corn, potato, rape, cotton, sugarcane, etc., preferably leaves, such as sheet-shaped straw or leaves with a length of 0.5 to 1 cm and a width of 0.1 to 1 cm.

6. The agent for ecological blue algae control according to claim 5, characterized in that: The surface of the degradable cellulose sheet has a hydrophobic layer.

7. The agent for ecological blue algae control according to any one of claims 1 to 4, characterized in that: The preparation method of the corn soaking liquid comprises the following steps: washing corn and soaking it in water for 1 to 2 hours, separating and taking the supernatant, and concentrating it 5 to 10 times to obtain the corn soaking liquid, wherein the pH value of the corn soaking liquid is 4.5 to 6.

8. The agent for ecological blue algae control according to any one of claims 1 to 4, characterized in that: The clay can be one or more of talc, kaolin, light shale, clay, attapulgite, silica mud, illite, ferromagnetic clay, mica, clinoptilolite, montmorillonite, light aggregate pumice, white mud, zeolite, sepiolite, pumice, foot-rubbing stone, volcanic slag, diatomaceous earth, porcelain clay and general soil, preferably a mixture of diatomaceous earth and kaolin, wherein the mass ratio of diatomaceous earth to kaolin is 1:(1-5).

9. The agent for ecological blue algae control according to any one of claims 1 to 4, characterized in that: The cyclodextrin adsorbent is one or more of hydroxypropyl-β-cyclodextrin, mono-(6-oxy-ethylenediaminetetraacetyl)-cyclodextrin and β-cyclodextrin.

10. A method for preparing the agent for ecological blue algae control according to any one of claims 1 to 9, characterized in that: The steps include: The flocculant, cyclodextrin adsorbent and humic acid are mixed, and the degradable cellulose sheets and corn soaking liquid are placed separately.

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