Algaecide and preparation method thereof
By combining nano-sized copper molybdate particles with a dispersant, a nano-copper molybdate algaecide was prepared, which solved the drawbacks of traditional algaecides and achieved efficient, safe, and environmentally friendly algae removal and algae toxin degradation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-14
- Publication Date
- 2026-04-10
Smart Images
Figure CN121823754A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of algaecide technology, and in particular to an algaecide and its preparation method. Background Technology
[0002] With the rapid development of industry and agriculture, the problem of eutrophication of water bodies has become increasingly prominent. The phenomenon of algal blooms caused by the massive proliferation of algae occurs frequently, which not only disrupts the ecological balance of water bodies, but may also release algal toxins that endanger human health and water ecological safety. Therefore, the research and development of highly efficient algaecides has become an important issue in the field of water environment management.
[0003] Currently, common chemical algaecides on the market, such as chlorinated compounds, copper sulfate, and quaternary ammonium salts, while able to quickly inhibit algae growth to some extent, all have significant drawbacks. For example, chlorinated compounds easily produce harmful byproducts, posing potential toxicity to aquatic organisms and humans; copper sulfate contains copper ions, and concentrations exceeding a certain threshold can harm fish and mollusks; long-term use of quaternary ammonium salt algaecides can easily lead to algae resistance. These chemical agents have a short duration of action, requiring continuous application and causing sustained environmental impacts. Biological algaecides, including microbial inhibitors and algal viruses, while having a smaller environmental impact, face problems such as high cost and slow onset of action, making them unsuitable for emergency control of algal blooms. Furthermore, regardless of whether chemical or biological algae control methods are used, algal toxins released after algal death can still threaten the aquatic body and surrounding ecosystem, further exacerbating ecological risks.
[0004] Copper ions are the active ingredient in copper sulfate, a commonly used algaecide. Copper-based molybdates also contain copper. However, ordinary copper molybdate and basic copper molybdate are poorly soluble, with extremely low solubility in aqueous solutions, and are difficult to disperse uniformly to achieve effective algae-killing concentrations, limiting their direct application in water algae control. On the other hand, copper molybdate possesses excellent photocatalytic activity, which can promote the degradation of organic pollutants (including algal toxins) in water bodies, thus purifying them. If nano-copper-based molybdates can be prepared and their stable dispersion achieved, not only can highly efficient algae killing be achieved, but their photocatalytic advantages can also be fully utilized for algal bloom control. However, no related research has been reported yet.
[0005] Therefore, it is urgent to develop an algaecide that can quickly kill algae, inhibit their growth in the long term, reduce the harm of algal toxins, and be environmentally friendly without affecting human life or the survival of plants and animals. Summary of the Invention
[0006] To address the above problems, this invention provides an algaecide and its preparation method. The technical solution provided by this invention is as follows: This invention provides an algaecide, the components of which include nano-sized copper molybdate particles and a dispersant, wherein... The nanoscale copper molybdate particles include one or more of nanoscale copper molybdate and nanoscale copper hydroxymolybdate.
[0007] Further, the dispersant is selected from one or more of sodium hexametaphosphate, polyacrylamide with a molecular weight of 10-30 million, polyethylene glycol, Tween 60, Span 40 or Span 80.
[0008] Further, the mass ratio of the nanoscale copper molybdate particles and the dispersant is 1:3-1:5.
[0009] The application also provides a preparation method of the alga removing agent, and the method comprises: dissolving the dispersant in water to obtain a dispersant solution; adding the nanoscale copper molybdate particles into the dispersant solution and mixing uniformly to obtain the alga removing agent.
[0010] Further, the mass fraction of the dispersant in the dispersant solution is 0.1%-1%.
[0011] Further, the preparation method of the nanoscale copper molybdate comprises: mixing butanol, cyclohexane and a polymer uniformly to obtain an oil phase; dividing the oil phase into a first oil phase and a second oil phase; adding a molybdate solution into the first oil phase and mixing uniformly to obtain a first microemulsion; adding a copper nitrate or copper chloride solution into the second oil phase and mixing uniformly to obtain a second microemulsion; adding the first microemulsion into the second microemulsion under stirring to perform a reaction to obtain a nanoscale copper molybdate precursor; performing heat treatment on the nanoscale copper molybdate precursor to obtain the nanoscale copper molybdate.
[0012] Further, the preparation method of the nanoscale copper molybdate comprises: mixing butanol, cyclohexane and a polymer uniformly to obtain an oil phase; dividing the oil phase into a first oil phase and a second oil phase; adding an amine molybdate solution into the first oil phase and mixing uniformly to obtain a first microemulsion; adding a copper nitrate or copper chloride solution into the second oil phase and mixing uniformly to obtain a second microemulsion; adding the first microemulsion into the second microemulsion under stirring to perform a reaction to obtain a nanoscale copper molybdate precursor; adding the nanoscale copper molybdate precursor and water into a reaction kettle to perform a hydrothermal reaction to obtain a hydrothermal reaction product; The hydrothermal reaction product is washed and dried to obtain a dried solid; The dried solid is placed in a muffle furnace for a predetermined time to obtain a nanoscale copper molybdate, which is nanometer copper molybdate.
[0013] Further, the preparation method of the nanometer copper molybdate includes: The butanol, cyclohexane and polymer are uniformly mixed to obtain an oil phase; The oil phase is evenly divided into a first oil phase and a second oil phase; The sodium molybdate or ammonium molybdate solution is added to the first oil phase and uniformly mixed to obtain a first microemulsion; The copper nitrate or copper chloride solution is added to the second oil phase and uniformly mixed to obtain a second microemulsion; The first microemulsion is added dropwise to the second microemulsion under stirring to react and obtain a nanoscale copper molybdate precursor; The nanoscale copper molybdate precursor and water are added to a reaction kettle to perform a hydrothermal reaction to obtain a nanoscale copper molybdate, which is nanometer copper molybdate.
[0014] Further, the mass ratio of butanol, cyclohexane and polymer is (2-10):(5-20):(1-3). The polymer includes one or more of fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether or polyoxyethylene nonyl phenol ether.
[0015] Further, the nanoscale copper molybdate precursor is obtained by adding the first microemulsion dropwise to the second microemulsion under stirring to react, and includes: Under stirring, the first microemulsion is added dropwise to the second microemulsion, and after the dropwise addition is completed, the stirring is continued for 30-60 min to obtain a first mixed solution. The organic solvent is added to the first mixed solution, and the second mixed solution is obtained after standing for 24 h-48 h; the organic solvent is a mixture of acetone and anhydrous ethanol.
[0016] The second mixed solution is subjected to solid-liquid separation to obtain the nanoscale copper molybdate precursor.
[0017] The technical effects and advantages of the present application are: The application adopts a microemulsion hydrothermal method to prepare nano copper molybdate and nano alkaline copper molybdate, and uses a non-toxic and effective dispersant to stably disperse the same in water, and develops a new type of nano copper molybdate algaecide with high efficiency and low secondary pollution, which can more safely and efficiently remove algae, can continuously inhibit algal blooms, has a wider pH application range, will not cause local copper ion concentration to be too high, is environmentally friendly, can photocatalytically remove other organic pollutants such as algal toxins, further controls water pollution, and has a good application prospect.
[0018] The nano copper molybdate prepared in the application can be stably dispersed in the algaecide.
[0019] 1. The new type of nano copper molybdate algaecide does not produce toxic by-products when removing algae.
[0020] 2. The main active ingredient of the new type of nano copper molybdate algaecide is a hardly soluble substance, which will not release a large amount of copper ions in a short time to cause secondary pollution to the water body.
[0021] 3. Under complex water quality conditions such as different pH values, temperatures and turbidities, the new type of nano copper molybdate algaecide can maintain good dispersibility and algaecidal activity, and has a wide application range.
[0022] 4. The new type of nano copper molybdate algaecide has a slow-release effect, can maintain a safe and effective copper ion concentration for removing algae in the water body all the time, and can efficiently remove algae while inhibiting the growth of algae for a long time.
[0023] 5. The new type of nano copper molybdate algaecide has high photocatalytic activity and can effectively remove other organic pollutants such as algal toxins, and better improve the water quality of the water body.
[0024] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or can be learned by practice of the present application. The objects and other advantages of the present application will be realized and attained by the structures particularly pointed out in the description and the appended drawings. BRIEF DESCRIPTION OF DRAWINGS
[0025] Figure 1a is a water sample chart provided by the application after culturing Microcystis aeruginosa; Figure 1b is a water sample chart provided by the application after adding the algaecide for treatment; Figure 2 is the algaecidal effect of the new type of algaecide provided by the application in Example 6 Figure 3 is the catalytic algal toxin MC-LR removal effect provided by the application in Example 6; Figure 4 is the algaecidal effective component Cu 2+ concentration-time chart provided by the application in Example 7. DETAILED DESCRIPTION
[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.
[0027] To solve the problems in the prior art, the present application discloses an algae-removing agent, and components of the algae-removing agent include nanoscale copper-based molybdate particles and a dispersant, which work together to achieve efficient algae removal. The nanoscale copper-based molybdate particles include one or more of nanoscale copper molybdate and nanoscale alkaline copper molybdate. As the core algae-removing component, the nanoscale copper-based molybdate particles have a much larger specific surface area and surface energy than ordinary non-nanoscale copper-based molybdate, and have higher surface activity. The nanoscale copper-based molybdate particles can slowly release copper ions to interfere with the normal physiological functions of algal cells. The dispersant can change the surface tension of the nanoscale particles, promote the dispersion of the particles, and enable the copper-based molybdate particles to stably exist in the water body for a long time, thereby ensuring their high algae-removing activity. In terms of connection, the nanoscale copper-based molybdate particles are the core algae-removing component, and the dispersant enables the nanoscale copper-based molybdate particles to stably disperse in the system by changing the surface charge and surface tension of the colloids, thereby jointly forming a new nanoscale copper molybdate algae-removing agent system.
[0028] In a specific embodiment of the present application, the dispersant is selected from one or more of sodium hexametaphosphate, polyacrylamide with a molecular weight of 10-30 million, polyethylene glycol, Tween 60, Span 40, or Span 80.
[0029] In a specific embodiment of the present application, the mass ratio of the nanoscale copper-based molybdate particles to the dispersant is 1:3-1:5.
[0030] The present application also provides a preparation method of the algae-removing agent, which comprises the following steps: The dispersant is dissolved in water to obtain a dispersant solution, and the mass fraction of the dispersant in the dispersant solution is 0.1%-1%.
[0031] The nanoscale copper-based molybdate particles are added to the dispersant solution, mixed uniformly, and an algae-removing agent is obtained.
[0032] In a specific embodiment of the present application, the preparation method of the nanoscale copper-based molybdate comprises the following steps: Step 1: butanol, cyclohexane and polymer are mixed uniformly to obtain an oil phase; the mass ratio of butanol, cyclohexane and polymer is (2-10):(5-20):(1-3); preferably, the mass ratio of butanol, cyclohexane and polymer is 2:5:1 or 3:5:1 or 6:10:3 or 10:20:3.
[0033] The polymer includes one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether or polyoxyethylene nonylphenol ether.
[0034] Step 2: the oil phase is equally divided into a first oil phase and a second oil phase; Step 3: a molybdate solution is added to the first oil phase and mixed uniformly to obtain a first microemulsion; Step 4: a copper nitrate or copper chloride solution is added to the second oil phase and mixed uniformly to obtain a second microemulsion; Step 5: the first microemulsion is added dropwise to the second microemulsion under stirring to react, to obtain a nanoscale copper molybdate precursor; specifically, the first microemulsion is added dropwise to the second microemulsion under stirring, after the dropwise addition is completed, the first mixed solution is obtained after stirring for 30-60 min; An organic solvent is added to the first mixed solution, and the solution is left to stand for 24-48 h to obtain a second mixed solution; the organic solvent is a mixture of acetone and anhydrous ethanol; the volume ratio of acetone to anhydrous ethanol is 3:4-1:1, and preferably, the volume ratio of acetone to anhydrous ethanol is 20:15.
[0035] Step 6: the nanoscale copper molybdate precursor is subjected to heat treatment to obtain a nanoscale copper molybdate.
[0036] In one specific embodiment of the present application, the preparation method of the nanoscale copper molybdate comprises: Step 1: butanol, cyclohexane and polymer are mixed uniformly to obtain an oil phase; the mass ratio of butanol, cyclohexane and polymer is (2-10):(5-20):(1-3); preferably, the mass ratio of butanol, cyclohexane and polymer is 2:5:1 or 3:5:1 or 6:10:3 or 10:20:3.
[0037] The polymer includes one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether or polyoxyethylene nonylphenol ether.
[0038] Step 2: the oil phase is equally divided into a first oil phase and a second oil phase; Step 3: an amine molybdate solution is added to the first oil phase and mixed uniformly to obtain a first microemulsion; Step 4: a copper nitrate or copper chloride solution is added to the second oil phase and mixed uniformly to obtain a second microemulsion; Step 5': under the condition of stirring, the first microemulsion is added dropwise into the second microemulsion to react, so as to obtain the nanoscale copper molybdate precursor; specifically, under the condition of stirring, the first microemulsion is added dropwise into the second microemulsion, after the dropwise addition is completed, the stirring is continued for 30-60 min, and then a first mixed solution is obtained; An organic solvent is added into the first mixed solution, and the solution is left to stand for 24-48 h, so as to obtain a second mixed solution; the organic solvent is a mixture of acetone and anhydrous ethanol; the volume ratio of the acetone to the anhydrous ethanol is 3:4-1:1, and preferably, the volume ratio of the acetone to the anhydrous ethanol is 20:15.
[0039] Step 6': the nanoscale copper molybdate precursor and water are added into a reaction kettle to perform a hydrothermal reaction, so as to obtain a hydrothermal reaction product; Step 7': the hydrothermal reaction product is washed and dried, so as to obtain a dried solid; Step 8': the dried solid is placed into a muffle furnace, and the reaction is performed at 400-600 ℃ for 1-3 h, so as to obtain the nanoscale copper molybdate, and the nanoscale copper molybdate is nanometer copper molybdate.
[0040] In one specific embodiment of the present application, the preparation method of the nanometer copper hydroxymolybdate comprises: Step 1": the butanol, the cyclohexane and the polymer are uniformly mixed to obtain an oil phase; The mass ratio of the butanol, the cyclohexane and the polymer is (2-10):(5-20):(1-3); preferably, the mass ratio of the butanol, the cyclohexane and the polymer is 2:5:1 or 3:5:1 or 6:10:3 or 10:20:3.
[0041] The polymer comprises one or more of a fatty alcohol polyoxyethylene ether, an alkylphenol polyoxyethylene ether or a polyoxyethylene nonylphenyl ether.
[0042] Step 2": the oil phase is equally divided into a first oil phase and a second oil phase; Step 3": a sodium molybdate or ammonium molybdate solution is added into the first oil phase and uniformly mixed, so as to obtain a first microemulsion; Step 4": a copper nitrate or copper chloride solution is added into the second oil phase and uniformly mixed, so as to obtain a second microemulsion; Step 5": under the condition of stirring, the first microemulsion is added dropwise into the second microemulsion to react, so as to obtain the nanoscale copper molybdate precursor; specifically, under the condition of stirring, the first microemulsion is added dropwise into the second microemulsion, after the dropwise addition is completed, the stirring is continued for 30-60 min, and then a first mixed solution is obtained; The first mixed solution is added with an organic solvent, and is left to stand for 24-48 hours to obtain a second mixed solution; the organic solvent is a mixture of acetone and anhydrous ethanol. The volume ratio of acetone to anhydrous ethanol is 3:4-1:1, preferably, the volume ratio of acetone to anhydrous ethanol is 20:15.
[0043] Step 6'': the second mixed solution is subjected to solid-liquid separation to obtain the nanoscale copper molybdate precursor.
[0044] Step 7'': the nanoscale copper molybdate precursor and water are added to a reaction kettle for hydrothermal reaction to obtain the nanoscale copper molybdate, which is nanometer basic copper molybdate.
[0045] For example, the nanometer copper molybdate is prepared by selecting ammonium molybdate as the molybdenum source and copper nitrate as the copper source, the nanometer basic copper molybdate is prepared by selecting sodium molybdate as the molybdenum source and copper nitrate, and the dispersing agent is selected from sodium hexametaphosphate, polyacrylamide with a molecular weight of 100-300 million, polyethylene glycol, Tween 60, Span 40 and Span 80.
[0046] For example, the nanometer copper molybdate is synthesized as follows: 30-50 mL of butanol and 50-100 mL of cyclohexane are weighed into a beaker, 10-15 g of AEO (fatty alcohol polyoxyethylene ether) or APEO (alkyl phenol polyoxyethylene ether) or OP (polyoxyethylene nonyl phenol ether) is added, the solution is stirred under ultrasonic at room temperature until it is clear and transparent, then the stirring is stopped, and one portion of the oil phase is prepared under the same conditions for standby; dried ammonium molybdate and copper nitrate are weighed and dissolved in deionized water respectively, and stirred at room temperature until completely dissolved to obtain 10 mL of 0.1 mol / L ammonium molybdate solution and 10 mL of 0.1 mol / L copper nitrate solution, then the two solutions are added to two portions of the oil phase respectively, and stirred at room temperature for 10-20 min until the solution is uniform and not stratified, to prepare two kinds of microemulsions containing ammonium molybdate and copper nitrate; the microemulsion containing ammonium molybdate is slowly added to the microemulsion containing copper nitrate under magnetic stirring, and the stirring is continued for 30-60 min, then the magnet is removed, 20 mL of acetone and 15 mL of anhydrous ethanol are added, and left to stand for 24-48 h; the mixture is filtered, the precipitate is collected and transferred to a reaction kettle, and an appropriate amount of deionized water is added, and reacted at 180-220℃ for 10-14 h, then the product is collected after natural cooling to room temperature, washed and dried, and then the dried solid is placed in a muffle furnace and reacted at 400-600℃ for 1-3 h, and then cooled to room temperature to obtain the nanometer copper molybdate product.
[0047] Example of synthesis of nano-copper-molybdate: Take 30-50 mL of butanol and 50-100 mL of cyclohexane as a mixture in a beaker, add 10-15 g of OP to it, stir under ultrasonic for 20 min until the solution is clear and transparent, repeat the preparation of one as the oil phase under the same conditions; weigh the dry sodium molybdate and copper nitrate, respectively dissolved in deionized water, stirred at room temperature until completely dissolved, to obtain 10 mL of 0.1 mol / L sodium molybdate solution and 10 mL of 0.1 mol / L copper nitrate solution, then add the two solutions to the two oil phases respectively, stir at room temperature for 10 min until the solution is uniform and not layered, to prepare two kinds of microemulsion containing sodium molybdate and copper nitrate; slowly drop the microemulsion containing sodium molybdate into the microemulsion containing copper nitrate under the condition of magnetic stirring and continue to stir for 30-60 min, after the stirring is completed, the magnet is taken out, 20 mL of acetone and 15 mL of anhydrous ethanol are added in turn, and it is placed for 24-48 h, and the precipitate is separated by centrifuge to obtain the precipitate, which is washed with acetone, anhydrous ethanol and deionized water for two to three times and placed in a 60°C oven to dry, and the dried solid is moved to a 50 mL reaction kettle, 10 mL of water is added, and it is reacted at 160-200°C for 8-24 h, after the hydrothermal reaction is completed, the solid is taken out, and the washing and drying operations are repeated to obtain the product.
[0048] Note: The preparation process of nano-copper-molybdate is more complex, and the cost is higher than that of nano-copper-molybdate, but its effect of photocatalytic decomposition of algal toxins is better than that of nano-copper-molybdate, so the two can be mixed for use in actual preparation of algae removal agent.
[0049] The copper sulfate algae removal agent has the risk of secondary pollution, and the effect lasts for a short time, so it needs to be added frequently to maintain the effect; while the new nano-copper-molybdate algae removal agent can remain stable and dispersed in the water body for a long time, its components are environmentally friendly, and molybdate copper is a difficult-soluble substance that can slowly release copper ions, which will not cause the local copper ion concentration to be too high, so the copper ion concentration can always be kept within a safe and effective range, which can not only efficiently remove algae, but also continuously inhibit algal blooms, and can also photocatalytically remove other organic pollutants such as algal toxins, further controlling water pollution.
[0050] Particle size and performance: Traditional copper sulfate algae removal agents mostly use micrometer-sized particles (conventional particle size 5-50 μm), and the specific surface area is usually less than 10 m² / g, resulting in a lack of active sites and an inability to fully trigger the reaction, so the algae removal efficiency is low; while the new nano-copper-molybdate algae removal agent uses nanometer-sized particles (particle size controlled at 50-200 nm), the specific surface area is greatly increased to 80-120 m² / g, and the number of active sites is increased by 10-15 times compared with traditional products, which can penetrate the polysaccharide layer of algal cell walls and directly react with key structures inside the cells, significantly enhancing the reaction activity and greatly improving the algae removal capacity.
[0051] Surface treatment and dispersibility: traditional copper sulfate algae-removing agent lacks effective dispersion and stabilization system, the surface of particles is easy to agglomerate through van der Waals force and hydrogen bond in water body due to charge and polarity effect, which leads to that algae in the upper layer of water body cannot contact the agent, and the algae-removing effect is unstable; the new type of algae-removing agent can reduce the agglomeration force of particles through the action of dispersant surface modification layer, and can prevent agglomeration through charge repulsion effect, so that it can maintain stable dispersion state for a long time, and effectively ensure the persistence of algae-removing effect.
[0052] The technical solutions of the present application will be further described below in combination with specific embodiments.
[0053] Example 1 Synthesis of nano copper molybdate: weigh 30 mL of butanol and 50 mL of cyclohexane into a beaker, add 15 g of AEO (fatty alcohol polyoxyethylene ether) or APEO (alkyl phenol polyoxyethylene ether) or OP (polyoxyethylene nonyl phenol ether), stop stirring after ultrasonic stirring at room temperature until the solution is clear and transparent, repeat the preparation under the same conditions to prepare one portion as oil phase for standby; weigh dry ammonium molybdate and copper nitrate, respectively dissolved in deionized water, and stirred at room temperature until completely dissolved, to obtain 10 mL of 0.1 mol / L ammonium molybdate solution and 10 mL of 0.1 mol / L copper nitrate solution, then add the two solutions to two portions of oil phase respectively, and stir at room temperature for 15 min until the solution is uniform and not stratified, to prepare two kinds of microemulsions containing ammonium molybdate and copper nitrate; slowly drop the microemulsion containing ammonium molybdate into the microemulsion containing copper nitrate under the condition of magnetic stirring and continue to stir for 30 min, then remove the magnet, add 20 mL of acetone and 15 mL of anhydrous ethanol, and stand for 24 h; filter the mixed solution, collect the precipitate and transfer it to a reaction kettle, add appropriate amount of deionized water, and react at 180-220℃ for 12 h, then naturally cool to room temperature, collect the product, wash and dry, then put the dried solid into a muffle furnace and react at 500℃ for 2 h, and cool to room temperature to obtain nano copper molybdate product.
[0054] Example 2 Nano-copper-molybdate synthesis: Take 50 mL of butanol, 100 mL of cyclohexane as mixed in a beaker, 10 g of OP is added to it, and it is stirred under ultrasonic for 20 min until the solution is clear and transparent. Repeat the preparation of a portion as the oil phase under the same conditions; weigh the dried sodium molybdate and copper nitrate, respectively, and dissolve in deionized water, and stir at room temperature until completely dissolved, to obtain 10 mL of 0.1 mol / L sodium molybdate solution and 10 mL of 0.1 mol / L copper nitrate solution, then add the two solutions to the two oil phases respectively, and stir at room temperature for 10 min until the solution is uniform and not layered, to prepare two kinds of microemulsion containing sodium molybdate and copper nitrate; slowly drop the microemulsion containing sodium molybdate into the microemulsion containing copper nitrate under the condition of magnetic stirring and continue to stir for 30 min, after the stirring is completed, the magnet is taken out, 20 mL of acetone and 15 mL of anhydrous ethanol are added in turn, and it is placed for 24 h, and the precipitate is separated by centrifuge to obtain the precipitate, which is washed with acetone, anhydrous ethanol and deionized water for two to three times and placed in a 60°C oven to dry, and the dried solid is moved to a 50 mL reaction kettle, 10 mL of water is added, and it is reacted at 200°C for 8 h, after the hydrothermal reaction is completed, the solid is taken out, and the washing and drying operation is repeated to obtain nano-copper-molybdate.
[0055] Note: The preparation process of nano-copper-molybdate is more complex, and the cost is higher than that of nano-copper-molybdate, but its photocatalytic decomposition of algal toxin effect is better than that of nano-copper-molybdate, so in the actual preparation of algae-removing agent, the two can be mixed for use.
[0056] Example 3 Algae-removing agent preparation: Dissolve 1 g of nano-copper-molybdate in 15 mL of water (1 wt%), and add 0.3 g of nano-copper-molybdate particles after stirring uniformly, and ultrasonic for 10 min to make it fully dissolved, to obtain the finished product of the algae-removing agent.
[0057] Algal liquid: Take 50 mL of initial algal liquid in the culture medium, add culture solution for dilution, so that the final diluted algal liquid absorbance reaches 0.4, at this time the concentration of Microcystis aeruginosa is about 10 10 cell / L. Prepare 100 mL of the above experimental algal liquid.
[0058] Algae-removing effect test: Take 3 mL of algae-removing agent and add it to 100 mL of algal liquid, and slightly shake, and perform algae removal under the condition of 25°C white light irradiation. Every 24 h, detect the content of algae in the algal liquid, and the concentration of chlorophyll and the concentration of algal toxin. Finally, after 192 h, the algae removal rate reaches 99%, the chlorophyll decomposition rate reaches 85%; the algal toxin degradation rate reaches more than 60% within 1 h, and more than 80% after 5 h.
[0059] Example 4 Algae-removing agent preparation: Dissolve polyethylene glycol in 10 mL water (0.5 wt%), and ultrasonic for 15 min to make it fully dissolved. Then add 0.5 g nano basic copper molybdate, and ultrasonic for 15 min to obtain the finished product of copper algae-removal agent.
[0060] Algae solution: Take 50 mL of initial algae solution in the culture medium, and dilute it with the culture solution to make the final diluted algae solution have an absorbance of 0.4. At this time, the concentration of Microcystis aeruginosa is about 10 10 cells / L. Prepare 100 mL of the above experimental algae solution.
[0061] Algae-removal effect test: Take 3-5 mL of nano basic copper molybdate algae-removal agent and add it to 100 mL of algae solution, and slightly shake. Perform algae removal under the condition of white light irradiation at 25°C. Every 24 h, detect the content of algae, the concentration of chlorophyll, and the concentration of algae toxin in the algae solution. Finally, after 192 h, the algae removal rate reaches 99%, the chlorophyll decomposition rate reaches 80%; the algae toxin degradation rate reaches more than 40% within 1 h, and more than 60% after 5 h.
[0062] Example 5 Preparation of algae-removal agent: Dissolve polyethylene glycol and polyacrylamide in 5 mL water (1 wt% polyethylene glycol, 0.5 wt% polyacrylamide with a molecular weight of 10 million), and ultrasonic for 15 min to make it fully dissolved to obtain a dispersant solution. Then add 0.3 g of nano basic copper molybdate and 0.2 g of nano copper molybdate to the dispersant solution, and ultrasonic for 15 min to obtain the finished product of algae-removal agent.
[0063] Algae solution: Take 50 mL of initial algae solution in the culture medium, and dilute it with the culture solution to make the final diluted algae solution have an absorbance of 0.4. At this time, the concentration of Microcystis aeruginosa is about 10 10 cells / L. Prepare 100 mL of the above experimental algae solution.
[0064] Algae-removal effect test: Take 3-5 mL of nano basic copper molybdate algae-removal agent and add it to 100 mL of algae solution, and slightly shake. Perform algae removal under the condition of white light irradiation at 25°C. Every 24 h, detect the content of algae, the concentration of chlorophyll, and the concentration of algae toxin in the algae solution. Finally, after 192 h, the algae removal rate reaches 99%; the chlorophyll decomposition rate reaches 87%; the algae toxin degradation rate reaches more than 60% within 1 h, and more than 80% after 5 h.
[0065] Example 6 Cultivate Microcystis aeruginosa to a certain concentration, and dilute it to an absorbance of 0.4 (concentration of about 10 10At this point, *Microcystis aeruginosa* reaches the logarithmic growth phase concentration in the culture medium, and a *Microcystis aeruginosa* solution (e.g., cell / L) is obtained. Figure 1a (As shown). Preparation for algae removal was carried out. The *Microcystis aeruginosa* solution was divided into four equal parts: A, B, C, and D. Group A was prepared by adding 5 mL of culture medium solution; Group B was prepared by adding 5 mL of a dispersant solution containing 1 wt% polyethylene glycol and 0.5 wt% polyacrylamide with a molecular weight of 10 million; Group C was prepared by adding 5 mL of a nano-copper molybdate solution containing 0.3 g of basic copper molybdate and 0.2 g of nano-copper molybdate; and Group D was prepared by adding 5 mL of the algaecide prepared in Example 5. The final volume of each of the four algae removal systems was 105 mL. Algal biomass, chlorophyll content, and copper ion concentration were measured periodically.
[0066] After the algae removal cycle is completed, the color of the algae solution becomes significantly lighter (e.g., Figure 1b Macroscopic analysis confirmed the effectiveness of the novel copper molybdate algaecide. Quantitative analysis showed that this algaecide exhibited excellent growth inhibition effects on algae. After 144 hours of treatment, its algal cell removal rate approached 100% (e.g., ...). Figure 2 The effect is similar to that of copper sulfate, but the concentration of copper ions in the system is much lower than the Class II surface water quality standard. Meanwhile, the new formulation also shows a significant advantage in the removal of algal toxins.
[0067] like Figure 3 As shown, the algaecide in group D exhibits significant photocatalytic removal of the algal toxin MC-LR, achieving a degradation rate of over 60% within 1 hour and over 80% after 5 hours. This indicates that the algaecide prepared in this invention demonstrates superior photocatalytic removal of the algal toxin MC-LR compared to copper molybdate nanoparticles alone, with the removal efficiency continuously increasing over time.
[0068] Example 7 Group 1 was configured to contain 105 mL of Microcystis aeruginosa solution and 0.016 g of copper sulfate; Group 2 contained 105 mL of culture medium and 0.016 g of copper sulfate; Group 3 contained 105 mL of Microcystis aeruginosa solution and 0.03 g of nano-copper molybdate; Group 4 contained 105 mL of culture medium and 0.03 g of nano-copper molybdate; Group 5 contained 100 mL of Microcystis aeruginosa solution and 5 mL of the algaecide prepared in Example 5; Group 6 contained 100 mL of culture medium and 5 mL of the algaecide prepared in Example 5. The Microcystis aeruginosa solution was the Microcystis aeruginosa solution prepared in Example 6.
[0069] like Figure 4 As shown, the concentration of copper sulfate changes significantly before and after algae removal. When copper sulfate of the same initial molar concentration is added to water, the Cu... 2+The concentration is far more than that of the nanometer copper molybdate to pollute the water body; and after contacting with the algae, the concentration is rapidly reduced to a lower level together with the algae and cannot be recovered, and the ability of removing the algae is lost. The copper molybdate in the new nanometer copper molybdate algae-removing agent can be dispersed in the water body for a long time at a higher concentration compared with the simple insoluble substance after being dispersed, and the Cu 2+ The concentration is far lower than that of the medium + copper sulfate group (comparing the black hollow square line, the red hollow circle line and the blue hollow triangle line). The Cu 2+ pollution of the heavy metal is maintained at the same time, and the efficient ability of removing the algae is maintained. The nanometer copper molybdate can release the Cu 2+ at a slow speed when removing the algae (comparing the blue solid triangle line and the blue hollow triangle line), and then the concentration is reduced, and finally the concentration is recovered to the initial level. That is, the Cu 2+ is released at a slow speed when removing the algae, and then the Cu 2+ is recovered after the removal of the algae is completed. The working principle is that, by virtue of the nanometer size advantage, the highly dispersed nanometer copper molybdate particles can easily approach and adhere to the surface of the algae cells. The copper ions on the surface of the nanometer particles are released, the copper ions penetrate the cell membrane of the algae, combine with the biological macromolecules such as proteins and enzymes in the cells, destroy the activity of the enzymes, interfere with the key physiological processes such as cell respiration and photosynthesis, the molybdate ions destroy the ion balance and material transportation system of the algae cells, affect the osmotic pressure regulation of the cells, and cause the physiological function of the cells to be disordered. With the continuous destruction of the physiological function of the cells, the algae cells gradually lose the activity, die and lyse, and finally the purpose of removing the algae is achieved. The nanometer copper molybdate can also have a high efficient photocatalytic effect to remove other organic pollutants in the water such as the algal toxins.
[0070] The algae-removing agent has the following advantages: High efficiency and fast speed: the new nanometer copper molybdate algae-removing agent can quickly control the outbreak of the algae and timely improve the water quality by virtue of the high specific surface area and the strong activity.
[0071] The dosage is saved: due to the efficient algae-removing performance, the use amount of the new nanometer copper molybdate algae-removing agent is less when achieving the same algae-removing effect, the use cost is greatly reduced, and the overall load of the chemical agents to the water body is reduced.
[0072] Environment-friendly: the nanometer copper molybdate in the new algae-removing agent is stable in dispersion, the residues of the algae-removing agent in the water body are reduced, the influence on the non-target organisms is effectively reduced compared with the traditional algae-removing agent, the photocatalytic activity can effectively remove other organic pollutants such as the algal toxins, and the water quality of the water body is better improved.
[0073] Strong adaptability: under the complex water quality conditions of different pH value, temperature, turbidity, etc., the new type of nano copper molybdate algae-removing agent can maintain good dispersibility and algae-removing activity, has wide application range, and can be applied to algae treatment in lakes, reservoirs, landscape water bodies, industrial circulating water and various scenes, and has stronger environmental adaptability and practicality.
[0074] Finally, it should be noted that: the above only for the preferred embodiments of the present application, and not for limiting the present application, although the foregoing embodiments of the present application are described in detail, for those skilled in the art, it still can be modified, or part of the technical features of the equivalent replacement, within the spirit and principles of the present application, any modification, equivalent replacement, improvement, etc., should be included in the scope of protection of the present application.
Claims
1. An algaecide, characterized in that, The algaecide comprises nano-sized copper molybdate particles and a dispersant, wherein, The nanoscale copper-based molybdate particles include one or more of nano-copper molybdate and nano-basic copper molybdate.
2. The algaecide according to claim 1, characterized in that, The dispersant is selected from one or more of sodium hexametaphosphate, polyacrylamide with a molecular weight of 10 million to 30 million, polyethylene glycol, Tween 60, Span 40 or Span 80.
3. The algaecide according to claim 1, characterized in that, The mass ratio of the nano-sized copper molybdate particles to the dispersant is 1:3 to 1:
5.
4. The method for preparing the algaecide according to any one of claims 1-3, characterized in that, The method includes: Dissolve the dispersant in water to obtain a dispersant solution; Nanoscale copper molybdate particles are added to a dispersant solution and mixed evenly to obtain an algaecide.
5. The method for preparing the algaecide according to claim 4, characterized in that, The mass fraction of the dispersant in the dispersant solution is 0.1%~1%.
6. The method for preparing the algaecide according to claim 4, characterized in that, The preparation method of the nanoscale copper-based molybdate includes: After mixing butanol, cyclohexane, and the polymer evenly, an oil phase is obtained. The oil phase is divided into a first oil phase and a second oil phase; A molybdate solution was added to the first oil phase and mixed thoroughly to obtain a first microemulsion. Add copper nitrate or copper chloride solution to the second oil phase and mix well to obtain the second microemulsion; Under stirring, the first microemulsion is added dropwise to the second microemulsion to react and obtain a nanoscale copper molybdate precursor; The nanoscale copper-based molybdate precursor was heat-treated to obtain nanoscale copper-based molybdate.
7. The method for preparing the algaecide according to claim 6, characterized in that, The method for preparing the nano-copper molybdate includes: After mixing butanol, cyclohexane, and the polymer evenly, an oil phase is obtained. The oil phase is divided into a first oil phase and a second oil phase; Add an ammonium molybdate solution to the first oil phase and mix thoroughly to obtain a first microemulsion; Add copper nitrate solution to the second oil phase and mix well to obtain the second microemulsion; Under stirring, the first microemulsion is added dropwise to the second microemulsion to react and obtain a nanoscale copper molybdate precursor; The nanoscale copper molybdate precursor was added to a reactor with water to carry out a hydrothermal reaction to obtain the hydrothermal reaction product. The hydrothermal reaction products were washed and dried to obtain a dried solid. The dried solid is placed in a muffle furnace and reacted for a predetermined time to obtain nano-sized copper molybdate, wherein the nano-sized copper molybdate is nano-copper molybdate.
8. The method for preparing the algaecide according to claim 6, characterized in that, The preparation method of nano-basic copper molybdate includes: After mixing butanol, cyclohexane, and the polymer evenly, an oil phase is obtained. The oil phase is divided into a first oil phase and a second oil phase; Add sodium molybdate or ammonium molybdate solution to the first oil phase and mix well to obtain the first microemulsion; Add copper nitrate or copper chloride solution to the second oil phase and mix thoroughly to obtain the second microemulsion; Under stirring, the first microemulsion is added dropwise to the second microemulsion to react and obtain a nanoscale copper molybdate precursor; The nanoscale copper-based molybdate precursor is added to a reaction vessel with water for hydrothermal reaction to obtain nanoscale copper-based molybdate, wherein the nanoscale copper-based molybdate is nanoscale basic copper molybdate.
9. The method for preparing the algaecide according to any one of claims 6-7, characterized in that, The mass ratio of butanol, cyclohexane, and polymer is (2-10):(5-20):(1-3); The polymer includes one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or polyoxyethylene nonylphenol ether.
10. The method for preparing the algaecide according to claim 6, characterized in that, Under stirring, the first microemulsion is dropwise added to the second microemulsion to react and obtain a nanoscale copper-based molybdate precursor, comprising: Under stirring, the first microemulsion is added dropwise to the second microemulsion. After the addition is complete, stirring is continued for 30-60 minutes to obtain the first mixed solution. An organic solvent was added to the first mixed solution and allowed to stand for 24-48 hours to obtain the second mixed solution; the organic solvent was a mixture of acetone and anhydrous ethanol. The second mixed solution was subjected to solid-liquid separation to obtain a nanoscale copper-based molybdate precursor.