CN108094420B - Preparation method of modified konjac glucomannan loaded copper sustained release agent and application of modified konjac glucomannan loaded copper sustained release agent in water bloom control - Google Patents
Preparation method of modified konjac glucomannan loaded copper sustained release agent and application of modified konjac glucomannan loaded copper sustained release agent in water bloom control Download PDFInfo
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Abstract
The invention takes the konjac flour as the raw material to prepare the copper-loaded modified konjac glucomannan, takes blue algae, green algae, diatom, dinoflagellate and the like as the indoor experimental algae species, and the result shows that the modified konjac glucomannan loaded copper has obvious inhibition effect on the growth of different algae and has the characteristic of slow release and control of the growth of the algae. The copper-carrying slow release agent has obvious control effect on blue algae, green algae, diatom and dinoflagellate water blooms in natural water bodies, and field experiments prove that the water blooms can be controlled within 1 to 3 years. Adding Cu in the water body with the adding amount of the copper-carrying modified konjac glucomannan of 0.5-1.0 g/L2+Lower than the standard limit value in sanitary Standard for Drinking Water and the Cu in class III Water quality in quality Standard for surface Water Environment2+And (4) content. The slow-release algaecide has the advantages of high efficiency and high speed of copper sulfate, avoids the defect of overhigh local copper sulfate concentration caused by directly adding copper sulfate in the slow-release capacity, has the properties of being natural, non-toxic and biodegradable, and is natural, safe, efficient and wide in application prospect.
Description
Technical Field
The invention provides a copper-loaded modified konjac glucomannan sustained release agent and application thereof in controlling water bloom outbreak.
Background
With the rapid development of industrial and agricultural production and the enlargement of urban scale, a large amount of industrial wastewater, domestic sewage and farmland surface runoff are discharged into lake water, and the eutrophication of lakes is aggravated. In the eutrophication process of lakes, the massive propagation of algae (especially blue algae) is often caused to form water blooms. The formation of the cyanobacterial bloom leads to the reduction of the water transparency, the reduction of dissolved oxygen and the increase of suspended matters and COD on the one hand; on the other hand, a large amount of secondary metabolites such as toxin, off-flavor compound and the like are generated and secreted. These secondary metabolites not only affect the quality of drinking water and aquatic products, but also poison aquatic and some terrestrial animals, and may even harm human health.
The current removal of algae mainly includes physical, biological and chemical methods. The physical methods include mechanical fishing, clay flocculation, water aeration, ultrasonic methods, shading technologies and the like, but the methods can only be limited to small water bodies or local water bodies of large water bodies. The biological method mainly comprises the steps of controlling algae by fishes, removing algae by microbial technology and inhibiting algae by phytochemical sensing, controls or inhibits algal bloom by utilizing the food chain intake principle of an ecological system and the facies generation and restriction relation of organisms so as to achieve the purpose of controlling the occurrence of the algal bloom, is a green algae removing method, but has the defects of high technical difficulty and management difficulty, slow effect and large investment. The chemical method for removing algae mainly comprises a copper sulfate method, a chlorine dioxide method, a potassium permanganate method and ozone.
Chemical methods are used more often as emergency algae removal methods at present. Compared with other algaecides, the copper ions can effectively inhibit the growth of algae and influence the permeability of a plasma membrane. The copper ion has effective and stable algae killing effect, low cost and low toxicity to human health, and the characteristics make the copper compound become the first choice algicide for controlling the growth of algae in the United states, Australia and the like. At present, the most widely used chemical algae removal method is to directly put copper sulfate into water, but the local copper sulfate concentration is easily overhigh, so that other aquatic organisms in the water are damaged, and the long-term putting can cause secondary pollution to the water. In addition, copper ions formed after copper sulfate enters the water body can be quickly converted into copper carbonate (CuCO) with low solubility3,Kap=1.4×10-10) And copper hydroxide (Cu (OH)2,Kap=2.2×10-20) But precipitates, reducing the efficiency of the algaecide. The literature reports that almost all copper ions are deposited into the sediment within two days when copper sulphate solution is put into the fish pond.
Therefore, when the copper sulfate is used for removing algae, the purpose of controlling the slow release of copper ions can be achieved through the copper-carrying slow release agent so as to control the adding amount of the copper sulfate. Removing red tide algae by yiping river and the like by a method of slowly releasing copper ions by using a soluble glass carrier; the cuprum-carried algicide prepared by the plum-Hongliang et al by using chitosan as a carrier has good effect. Konjak is a pure natural environment-friendly material, has the characteristics of no toxicity and biodegradability, and has wide application prospects in various fields.
Disclosure of Invention
The invention aims to provide a copper-loaded modified konjac glucomannan sustained release agent and application thereof in water bloom treatment.
(1) Drying fresh konjak, crushing, sieving, purifying by using methanol or ethanol, drying, adding distilled water to prepare a konjak glucomannan solution, adding soybean oil and acrylic ester, and stirring in a constant-temperature water bath kettle at 50-85 ℃;
(2) dissolving a catalyst, an emulsifier and absolute ethyl alcohol in distilled water, adding the mixed solution into the solution obtained in the step (1), emulsifying and stirring at 40-80 ℃ for 100-200min, stirring at room temperature for 3-5 h, performing suction filtration, repeatedly washing with distilled water until the filtrate is neutral, and collecting the product, namely the modified konjac glucomannan;
(3) placing the modified konjac glucomannan in a container, adding a copper-containing substance into the container, stirring at room temperature for 2-4 h (the stirring speed is 300-.
5-2000 mg/m of prepared copper-loaded modified konjac glucomannan sustained release agent3And the fertilizer is put into small reservoirs, ponds and small lakes in 3 months. The copper-loaded modified konjac glucomannan slow release agent can float on the water surface, slowly release copper ions, and achieve the purpose of controlling the growth of algae within 1-3 years.
The catalyst is one or two of sodium carbonate, triethylamine, ammonia water, sodium hydroxide and the like, and the addition amount is 1-3%. The emulsifier comprises one or two of saponin, soybean phospholipid, polyacrylamide and the like, and the addition amount is 3-8%. The copper-containing substance includes copper reagents such as copper aminophenylporphyrin, N-substituted azacrown ether, copper dihydroxysuccinate, copper 8-hydroxyquinoline, and copper yeast. The water bloom comprises water blooms with blue algae, green algae, dinoflagellate, diatom and the like as dominant species.
By adopting the technical scheme of the invention, the method has the following advantages:
1. the modified konjac glucomannan loaded with the copper compound has good slow release capability.
2. In experimental experiments, blue algae, green algae, dinoflagellate and diatom are taken as experimental objects respectively, and the copper-loaded slow release agent is found to have an obvious inhibition effect on the growth of phytoplankton. The field experiment proves that the water bloom can be controlled within 1-3 years.
3. Cu for optimum treatment effect2+The concentration of Cu is lower than that of Cu in the national standard of drinking water2+The content (less than 1.0 mg/L).
4. The slow-release algaecide has the advantages of high efficiency and high speed of copper sulfate, avoids the defect of overhigh local copper sulfate concentration caused by directly adding copper sulfate in the slow-release capacity, has the properties of being natural, non-toxic and biodegradable, and is natural, safe, efficient and wide in application prospect.
Drawings
Fig. 1 is a scanning electron microscope image of konjac glucomannan in the first example, wherein a is an electron microscope image at 500 magnifications, and B is an electron microscope image at 1000 magnifications.
Fig. 2 is a scanning electron microscope image of the copper-loaded modified konjac glucomannan in the first example, wherein a is an electron microscope image at 500 magnifications, and B is an electron microscope image at 1000 magnifications.
FIG. 3 is the infrared spectra of konjac glucomannan before and after modification in example one.
FIG. 4 shows the change of chlorophyll-a content of the Cyclotella minitans added with different amounts of sustained-release agents in example two.
FIG. 5 is a graph showing the release of copper ions from various amounts of copper-loaded release agents in the solution for treating growth of Cyclotella tenera according to example two.
FIG. 6 is the copper ion releasing ability of the natural water body added with different amounts of sustained release agents in the fourth example.
FIG. 7 is the concentration change of chlorophyll a added in different amounts to the natural water body in the fourth example.
Detailed Description
Example 1
Drying fresh rhizoma Amorphophalli, pulverizing, sieving, purifying with ethanol, and drying; weighing 1.0 g of purified konjac glucomannan, adding into a 250 mL beaker, adding distilled water to prepare 100g of 1% glucomannan solution, and adding 200g of soybean oil and 30g of acrylic ester. Stirring in a constant temperature water bath kettle, and controlling the temperature to be 75 ℃. 12g of triethylamine, 5g of sapogenin and 30g of absolute ethyl alcohol are dissolved in 30mL of distilled water. Adding the mixed solution into the above solution, emulsifying and stirring for 120 min. Stirring for 4 h at room temperature, filtering, washing with distilled water repeatedly until the filtrate is neutral, and collecting the product. 200g of the modified konjac glucomannan is placed in a 500 mL beaker, and 108g of 8-hydroxyquinoline copper is weighed and added into the beaker. Stirring strongly for 3h at room temperature, filtering, washing repeatedly with distilled water, and collecting the product, namely the modified konjac glucomannan hydrogel loaded with copper ions. Adding 5g copper-loaded modified konjac glucomannan into 5L water solution containing Scenedesmus obliquus and Chlorella (chlorophyll a content is 6.6 mg/L), wherein Scenedesmus obliquus and Chlorella die within 3 days, Scenedesmus obliquus and Chlorella do not grow any more within 60 days, and Cu is added2+The concentration is lower than the national standard of drinking water.
Fig. 1 is a scanning electron microscope image of konjac glucomannan in the first example, wherein a is an electron microscope image at 500 magnifications, and B is an electron microscope image at 1000 magnifications.
Fig. 2 is a scanning electron microscope image of the copper-loaded modified konjac glucomannan in the first example, wherein a is an electron microscope image at 500 magnifications, and B is an electron microscope image at 1000 magnifications.
The results in FIG. 1 show that the KGM surface layer is uniformly and tightly arranged. Because the hydrogen bond interaction between KGM molecules leads the KGM molecules to form an ordered molecular structure, an adsorption layer with a large specific surface area is difficult to form on the KGM surface. FIG. 2 shows that the modification of the modified KGM by crosslinking increases the formation of surface pores and wrinkles, which increases the surface adsorption capacity, as can be seen from the SEM image of the modified KGM. Due to the heterogeneity of the esterification reaction and the generated hydrophobic groups, molecular chains of the konjac glucomannan can not be orderly arranged, so that the surface of the modified konjac glucomannan has heterogeneous porous shapes and overlapped layers, and the surface area and the surface adsorption capacity of the konjac glucomannan are increased.
FIG. 3 is an exampleAn infrared spectrogram of konjac glucomannan before and after modification in the first step. The infrared spectrum of KGM shows that the infrared spectrum is 1007 cm-1-1170 cm-1The peak between the two peaks belongs to the symmetric stretching vibration absorption peak and the asymmetric stretching vibration peak of C-O and-C-O-C-in glucoside on the konjac glucomannan main chain, and the peak is 1634 cm-1Stretching vibration of the C-O bond belonging to the hydroxyl group. 874 cm-1And 807 cm-1Peak of (b) belongs toβA D glycosidic bond configuration absorption peak and a pyranoid ring respiration absorption peak. The infrared spectrum of the modified KGM shows that the modified KGM has the main chain structure of the macromolecule of the konjac glucomannan. But at 1746 cm-1A strong ester carbonyl stretching vibration absorption peak appears, which indicates that the reaction between KGM and fatty acid occurs. At 3009 cm-1And 2854 cm-1An absorption peak of the carboxylic acid appeared, indicating that esterification had occurred.
Example 2
Drying fresh rhizoma Amorphophalli, pulverizing, sieving, purifying with methanol or ethanol, and drying; weighing 2.0 g of purified konjac glucomannan, adding the konjac glucomannan into a 250 mL beaker, adding distilled water to prepare a 3% glucomannan solution, and adding 300g of soybean oil and 30g of acrylic ester into the beaker. Stirring in a constant temperature water bath kettle, and controlling the temperature to be 85 ℃. 10g of sodium hydroxide, 10g of polyacrylamide and 50g of absolute ethanol were dissolved in 50mL of distilled water. Adding the mixed solution into the above solution, emulsifying and stirring for 120 min. Stirring for 4 h at room temperature, filtering, washing with distilled water repeatedly until the filtrate is neutral, and collecting the product modified konjac glucomannan. 200g of the modified konjac glucomannan is placed in a 500 mL beaker, and 205 g of aminophenylporphyrin copper is weighed and added into the beaker. Stirring strongly for 3h at room temperature, filtering, washing repeatedly with distilled water, and collecting the product, namely the modified konjac glucomannan hydrogel loaded with copper ions. 3.2g of copper-loaded modified konjac glucomannan were added to 5 l of aqueous solution containing Cyclotella (biomass 5.31X 10)8 cell/L), the biomass of the Cyclotella tenella gradually decreases within 1 day of the beginning, and the biomass of the 7 th day is 5.67 multiplied by 103 cell/L) and no rebound growth of Cyclotella within ninety days, and Cu2+The concentration is lower than the national standard of drinking water.
FIG. 4 shows the change of chlorophyll-a content of the Cyclotella minitans added with different amounts of sustained-release agents in example two.
As can be seen from FIG. 4, the algae control efficiency is not greatly changed with the increase of the content of the copper-loaded sustained release agent, so the optimal adding amount is 0.5 g/L. The effective component of the copper-carrying modified konjac glucomannan for removing algae is Cu2+. The toxicity of copper to algae is caused by that copper has strong affinity to sulfur-containing groups on the surface of the cell wall of algae, interferes with the normal metabolism and biochemical reaction process of algae, destroys intracellular substances such as chloroplast and the like, and thus has an inhibiting effect on the growth of the Cyclotella tenera. In the experiment, the color of the chlorella solution added with the copper-loaded sustained release agent is changed from green to light after 24 hours, is changed into yellow green after 48 hours, and is changed into yellow after 72 hours, which indicates that most of the chlorella is killed. Therefore, the copper-loaded modified konjac glucomannan sustained release agent has a good algae control effect.
FIG. 5 is a graph showing the release of copper ions from various amounts of copper-loaded release agents in the solution for treating growth of Cyclotella tenera according to example two.
As can be seen from FIG. 5, Cu is added with the amount of the sustained-release agent2+The amount of the released increases. The growth trend is substantially the same. The release rate is very fast in the first 12d, the release rate is slow after 12d, and the release amount of the slow-release agent at low concentration tends to be stable. The modified konjac glucomannan copper-carrying sustained release agent is shown to have good sustained release capability.
Example 3
Drying fresh rhizoma Amorphophalli, pulverizing, sieving, purifying with methanol or ethanol, and drying; weighing 2.5 g of purified konjac glucomannan, adding the konjac glucomannan into a 250 mL beaker, adding distilled water to prepare a 2.2% glucomannan solution, and adding 250g of soybean oil and 45g of acrylate into the solution. Stirring in a constant temperature water bath kettle, and controlling the temperature to be 85 ℃. 20g of sodium hydroxide, 65g of soybean lecithin and 50g of absolute ethyl alcohol were dissolved in 50mL of distilled water. Adding the mixed solution into the above solution, emulsifying and stirring for 150 min. Stirring for 5 h at room temperature, filtering, washing with distilled water repeatedly until the filtrate is neutral, and collecting the product modified konjac glucomannan. Taking a proper amount of modified konjac glucomannan, placing the modified konjac glucomannan into a 500 mL beaker, weighing 170g of dihydroxy copper succinate, and adding the weighed dihydroxy copper succinate into the beakerIn (1). Stirring strongly for 3h at room temperature, filtering, washing repeatedly with distilled water, and collecting the product, namely the modified konjac glucomannan hydrogel loaded with copper ions. 46g of copper-loaded modified konjac glucomannan were added to 150 l of an aqueous solution (biomass 8.06X 10) containing Polydinoflagellate in the enclosure7 cell/L), the biomass of the algae is gradually reduced within seven days (as low as 3.31X 10 of the biomass) from the beginning3 cell/L) and no rebound growth of Dunaliella pseudonana in ninety days, and Cu2+The concentration is lower than the national standard of drinking water.
Example 4
Drying fresh rhizoma Amorphophalli, pulverizing, sieving, purifying with methanol or ethanol, and drying; 3.0 g of purified konjac glucomannan is weighed, added into a 250 mL beaker, and distilled water is added to prepare a 5% glucomannan solution, wherein 250g of soybean oil and 80g of acrylic ester are added. Stirring in a constant-temperature water bath kettle, and controlling the temperature to be 50-85 ℃. 36g of sodium carbonate, 80g of soybean lecithin and 50g of absolute ethyl alcohol were dissolved in 50mL of distilled water. Adding the mixed solution into the above solution, emulsifying and stirring for 150 min. Stirring for 4 h at room temperature, filtering, washing with distilled water repeatedly until the filtrate is neutral, and collecting the product modified konjac glucomannan.
500g of modified konjac glucomannan is placed in a 2000 mL beaker, and 500g of yeast copper is weighed and added into the beaker. Stirring strongly for 3h at room temperature, filtering, washing repeatedly with distilled water, and collecting the product, namely the modified konjac glucomannan hydrogel loaded with copper ions. Adding 1300g of copper-loaded modified konjac glucomannan into 130 m2In a small water pool (the sediment thickness is 20cm, the water depth is 80-120 cm), microcystis aeruginosa and anabaena hycina are dominant species in the water body, the initial biomass is 1.94 multiplied by 108cell/L), Cu within 12 months2+The concentration is lower than the national standard of drinking water, and the biomass is maintained at 6.68 multiplied by 106 cell/L -2.51×103cell/L, blue algae does not grow back.
FIG. 6 is the release capacity of different amounts of sustained release agents to copper ions added to the natural water body in the fourth embodiment
Adding water samples and mud samples of 0, 0.5 mg/L, 1.0 mg/L, 1.5 mg/L slow release copper and copper sulfate into the natural water body, wherein the maximum release amount of copper ions at 7 d is respectively 0, 0.252 mg/L, 0.308 mg/L, 0.420 mg/L, 0.238 mg/L and 0.700 mg/L, which indicates that in the natural water body, part of the copper ions enter algal cells to inhibit growth and reproduction of algae, and are partially precipitated by other organisms and organic matters in the natural water body. The modified konjac glucomannan copper-carrying sustained release agent has a good sustained release effect on copper ions, and the concentration of the released copper ions is lower than the highest concentration of copper in national drinking water by 1 mg/L.
FIG. 7 is the concentration change of different amounts of sustained release agent chlorophyll a added to the natural water body in the fourth embodiment
The result of figure 7 shows that in a natural water body, the modified konjac glucomannan copper-carrying slow release agent has an ideal algae control effect within 24 hours, the concentration of chlorophyll a is almost zero after 24 hours, and the low-concentration copper ions have a promoting effect on the growth of algae after 7 days.
Claims (6)
1. A preparation method of a copper-loaded modified konjac glucomannan sustained release agent is characterized by comprising the following steps:
(1) drying fresh konjak, crushing, sieving, purifying by using methanol or ethanol, drying, adding distilled water to prepare a konjak glucomannan solution, adding soybean oil and acrylic ester, and stirring in a constant-temperature water bath kettle at 50-85 ℃;
(2) dissolving a catalyst, an emulsifier, isopropanol or ethanol in distilled water, adding the mixed solution into the solution obtained in the step (1), emulsifying and stirring for 100-80 ℃ for 200min, stirring at room temperature for 3-5 h, then performing suction filtration, repeatedly washing with distilled water until the filtrate is neutral, and collecting a product, namely the modified konjac glucomannan, wherein the catalyst is sodium carbonate, triethylamine, ammonia water or sodium hydroxide; the emulsifier comprises sapogenin, soybean phospholipid or polyacrylamide; the catalyst is 1-3% of the fresh konjak and the emulsifier is 3-8% of the fresh konjak;
(3) placing the modified konjac glucomannan into a container, adding a copper-containing substance into the container, stirring the copper-containing substance at room temperature for 2-4 h, carrying out suction filtration, repeatedly washing with distilled water, and collecting a product, namely the modified konjac glucomannan hydrogel loaded with copper ions.
2. The preparation method of the copper-loaded modified konjac glucomannan sustained release agent according to claim 1, wherein in the step (1), the mass concentration of the konjac glucomannan solution in the mixed solution is 1-3%.
3. The preparation method of the copper-loaded modified konjac glucomannan sustained release agent as claimed in claim 1, wherein the stirring speed in the step (3) is 300-2000 rpm/min.
4. Use of the copper-loaded modified konjac glucomannan sustained release agent prepared according to any one of claims 1-3 for controlling bloom outbreaks.
5. The use of claim 4, wherein said bloom outbreaks comprise bloom outbreaks triggered by cyanobacteria, green algae, dinoflagellates and diatoms as dominant species.
6. The use as claimed in claim 4, wherein the copper-loaded modified konjac glucomannan sustained release formulation is administered in an amount of 5-2000 mg/m to reservoirs, ponds and lakes where water bloom occurs3。
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