Water purifying agent for aquaculture and preparation method thereof

Abstract

The invention relates to the technical field of water quality purification treatment, in particular to a water quality purifying agent for aquaculture and a preparation method. The water quality purifying agent is prepared from potassium peroxymonosulfate composite salt, citric acid, humic acid, sodium carbonate, magnesium carbonate, sodium hexametaphosphate, probiotics, polyethylene glycol, anhydrous sodium sulphate, a composite plant cell additive, plant active ingredients and water. According to the water quality purifying agent disclosed by the invention, various effective components are scientifically compounded, so that the water quality purifying effect of the water quality purifying agent is more outstanding, and the compound plant cell additive is specially added, so that the metal trapping agent is limited and fixed in pores, and gelated plant active cells are wrapped; the water quality purifying agent has the advantages that secondary pollution to a water body after metal ions are adsorbed and chelated is avoided, and damage to plant active cells caused by microorganisms and phosphate is also avoided, so that the water quality purifying agent is more stable, the efficacy time is prolonged, and good economic benefits are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of water purification treatment, and specifically provides a water quality purifying agent for aquaculture and a preparation method thereof. Background Art

[0002] China is a major country in aquaculture. However, with the development of the aquaculture industry, people have ignored the decline in the water quality of the aquaculture water, which has led to the death or reduction of aquaculture production. Part of the reason for the death or reduction of aquaculture production is the excessive feeding of bait by people, as well as the unreasonable discharge of some eutrophic substances such as phosphorus that are prone to cause water blooms and red tides. In addition, there are also heavy metals, etc. Although there have been great breakthroughs in the physical aspect of aquaculture water treatment in recent years, there are still great deficiencies in chemical agents. At present, in China's water treatment, coagulants such as potassium ferrate, polyaluminum chloride, polyferric sulfate, non-ionic polyacrylamide, and cationic polyacrylamide are still being used. In addition, there are also oxidants and adsorbents such as activated carbon, bromochlorohydantoin, zeolite powder, and diatomite, and oxygen increasing agents such as sodium percarbonate and potassium persulfate. Although these chemical agents have good treatment effects, they have limitations and pertinence: coagulants can only coagulate and have a long action cycle, flocculants can only flocculate, oxidants have little effect when the amount is small and cause phytotoxicity when the amount is large, adsorbents have no phytotoxicity, but a large amount is used, and oxygen increasing agents can only increase oxygen.

[0003] For example, Chinese Patent CN107673481B discloses a water quality purifying agent for aquaculture water and a preparation method thereof. By culturing photosynthetic bacteria, denitrifying bacteria, and bacillus in a culture medium containing porous SiC ceramic particles, a water quality purifying agent for aquaculture water is prepared by enriching microorganisms on the porous SiC ceramic particles. Although this water quality purifying agent for aquaculture water has good effects on water quality purification and disease prevention in aquaculture water, since the microorganisms are enriched on the porous structure of silicon carbide ceramic particles, the enrichment stability is poor. In water, under the action of water flow, the enriched microorganisms are easily detached from the ceramic particles, resulting in the loss of microorganisms with water, thus affecting the water purification effect. Moreover, this water quality purifying agent can only degrade nitrite, ammonia nitrogen, active phosphorus, etc. in the water, and cannot remove heavy metals in the water. Therefore, the improvement effect on the water is general and cannot meet the needs of modern aquaculture. Summary of the Invention

[0004] Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a water quality purifying agent for aquaculture and a preparation method thereof.

[0005] To achieve the above purpose, the present invention provides the following technical solutions: An aquaculture water quality purifier, the water quality purifier comprising the following components in parts by weight: 15-25 parts of potassium monopersulfate compound salt, 5-8 parts of citric acid, 1-5 parts of humic acid, 2-6 parts of sodium carbonate, 0.1-0.5 parts of magnesium carbonate, 1-3 parts of sodium hexametaphosphate, 1-5 parts of probiotics, 0.03-0.08 parts of polyethylene glycol, 5-10 parts of sodium sulfate, 10-16 parts of a composite plant cell additive, 0.2-0.7 parts of plant active ingredients, and 20-30 parts of water; The plant active ingredients are composed of aloe polysaccharide and saponin in a mass ratio of 1:(1.0-1.6); The preparation method of the composite plant cell additive is as follows: S1 Embed nanorod materials on the surface of porous carbon particles to obtain a composite nanomaterial, and then use the vacuum impregnation method to infiltrate a metal scavenger into the composite nanomaterial to obtain a metal scavenger material; S2 Use a hollow porous carbon microsphere as a matrix, and through a hydrothermal reaction, deposit nanowires on the matrix to obtain a composite porous carbon. Then, using the metal scavenger material as the core and the composite porous carbon as the shell, by means of mechanical stirring, the composite porous carbon is covered on the surface of the metal scavenger material to obtain a composite carrier material; S3 Immobilize plant algal cells on the composite carrier material and rinse with distilled water by oscillation to obtain the composite plant cell additive.

[0006] As a further preferred method of the present invention, in S1 above, the specific operation steps are as follows: According to the mass ratio of the metal scavenger to the composite nanomaterial of 1:(10-18), first place the composite nanomaterial in a vacuum impregnation tank, evacuate to 50-100 Pa, and maintain for 10-20 min. Then add the metal scavenger to deionized water, fully stir and inject it into the vacuum impregnation tank, evacuate to 10-60 Pa and maintain for 20-30 min. After the treatment is completed, slowly release the pressure to normal pressure, and after centrifugal separation, the metal scavenger material can be obtained; Among them, the metal scavenger is selected from at least one of polyaluminum chloride, polyacrylamide, and dithiocarbamic acid.

[0007] As a further preferred method of the present invention, in S2 above, the specific operation steps are as follows: According to the mass ratio of the composite porous carbon to the metal scavenger material being 1:(2 - 3), first disperse the metal scavenger material in deionized water and stir it at a rotation speed of 800 - 1000 r / min for 1 - 2 h. By the intercalation of the nanorod materials, the metal scavenger materials are agglomerated and connected together to form aggregates. Then add the composite porous carbon and continue to stir for 1 - 2 h. After the treatment is completed, perform centrifugal separation. At this time, through secondary stirring, the nanowires deposited on the composite porous carbon will wind around the nanorods of the aggregates, causing the composite porous carbon to cover the surface of the aggregates, thereby forming a composite carrier material with the metal scavenger material as the core and the composite porous carbon as the shell.

[0008] As a further preferred method of the present invention, in the above S3, the specific operation steps are as follows: 1) According to the weight parts, uniformly mix 4 - 7 parts of Chlorella pyrenoidosa cells, 6 - 10 parts of Anabaena cells, 6 - 10 parts of a 2% calcium alginate solution, and 10 - 18 parts of the composite carrier material to obtain a mixture; 2) At a position 20 - 25 cm above the liquid surface of the pre-cooled 0.1 - 0.2 mol / L calcium chloride solution, drop the mixture into the calcium chloride solution, gel it at 4 - 5 °C for 8 - 10 h, take out the particles and put them into a shaker with filter holes at the bottom, and rinse with distilled water for 20 - 30 min under the oscillation of 300 - 500 r / min to obtain the composite plant cell additive; Among them, the preparation of Chlorella pyrenoidosa: According to the weight parts, inoculate 5 - 10 parts of Chlorella pyrenoidosa seeds into an Erlenmeyer flask containing 15 - 30 parts of SE medium, culture it at a temperature of 24 °C, with 10 - 13 h of light, 10 - 13 h of no light, and a light intensity of 1900 lx. Centrifuge the Chlorella pyrenoidosa in the logarithmic phase at 3800 - 4000 r / min for 14 - 16 min, discard the supernatant to obtain Chlorella pyrenoidosa cells, and the process is aseptic operation; Under this condition, the growth rate of Chlorella pyrenoidosa cells is the fastest, the obtained Chlorella pyrenoidosa cells have a high yield, high activity, and strong absorption capacity for ammonia nitrogen in water; The preparation of Anabaena: According to the weight parts, inoculate 8 - 12 parts of Anabaena seeds into an Erlenmeyer flask containing 15 - 25 parts of SE medium, culture it at a temperature of 24 °C, with 12 - 15 h of light, 12 - 15 h of no light, and a light intensity of 2300 lx. Centrifuge the Anabaena in the logarithmic phase at 3800 - 4000 r / min for 14 - 16 min, discard the supernatant to obtain Anabaena cells, and the process is aseptic operation; Under this condition, the growth rate of Anabaena cells is the fastest, the obtained Anabaena cells have a high yield, high activity, and strong absorption capacity for nitrates and nitrites in water.

[0009] As a further preferred embodiment of the present invention, the preparation method of the composite nanomaterial is as follows: 1) Add titanium dioxide nanopowder to an aqueous sodium hydroxide solution, stir well, transfer to a reaction kettle, react at 150 - 160 °C for 45 - 50 h, cool to room temperature, filter by suction, wash repeatedly with dilute hydrochloric acid and deionized water, and dry to obtain nanorod materials; 2) Disperse porous carbon particles in deionized water to obtain a dispersion, then add nanorod materials, mechanically stir at a speed of 800 - 1000 r / min for 1 - 2 h, and then ultrasonically treat at 500 - 800 W for 1 - 2 h. After the treatment is completed, centrifuge the product and dry to obtain the composite nanomaterial.

[0010] As a further preferred embodiment of the present invention, the ratio of the titanium dioxide nanopowder to the aqueous sodium hydroxide solution is (1.5 - 3.0) g : (100 - 200) mL; The aqueous sodium hydroxide solution has a concentration of 12 - 13 mol / L; The ratio of the porous carbon particles, deionized water, and nanorod materials is (3 - 8) g : (500 - 700) mL : (0.5 - 1.0) g.

[0011] As a further preferred embodiment of the present invention, the preparation method of the porous carbon particles is as follows: 1) Dissolve cobalt chloride in deionized water, then add polyacrylic acid type cation exchange resin, place in an oil bath at 80 - 85 °C and stir to evaporate to dryness, then place in an oven at 80 - 90 °C to completely dry, put into a ball milling tank, and grind at a speed of 300 - 500 r / min for 2 - 5 h to obtain a sieved product for standby; 2) Add calcium hydroxide to deionized water, stir well, add the sieved product, place in an oil bath at 80 - 85 °C and stir to evaporate to dryness, then place in an oven at 80 - 90 °C to completely dry. Weigh potassium hydroxide and dissolve it in absolute ethanol, stir until completely dissolved, add the above sample, place in an oil bath at 80 - 85 °C and stir to evaporate to dryness, then place in an oven at 80 - 90 °C to completely dry; 3) Put the dried product into a porcelain boat, place it in a tubular furnace filled with an argon atmosphere, heat from room temperature to 800 - 830 °C at a rate of 2 - 3 °C / min, and keep warm for 2 - 3 h. After the treatment is completed, take out the product from the tubular furnace, wash with acid and filter by suction, wash until neutral and then dry, and obtain three - dimensional structured porous carbon particles after ultrafine pulverization and grinding.

[0012] As a further preferred embodiment of the present invention, the mass ratio of the cobalt chloride to the polyacrylic acid type cation exchange resin is (1 - 2) : (10 - 20); The ratio of calcium hydroxide, deionized water, sieved product, potassium hydroxide, and absolute ethanol is (6 - 10) g : (12 - 20) mL : (3 - 5) g : (3 - 5) g : (6 - 10) mL.

[0013] As a further preferred embodiment of the present invention, the composite porous carbon is prepared as follows: 1) Add sucrose to deionized water, stir until homogeneous, then add stannic chloride and sodium dodecyl sulfate thereto respectively, and stir well. Then transfer the solution to a high-pressure hydrothermal reactor and react at 190 - 195 °C for 24 - 30 h. After the reaction is completed, wash repeatedly with deionized water and ethanol alternately, and dry at 80 - 85 °C for 6 - 10 h to obtain composite microspheres; 2) Take the composite microspheres, mix them with hydrochloric acid solution, stir evenly, then transfer the mixture to a high-pressure hydrothermal reactor and react at 190 - 195 °C for 24 - 30 h. After the reaction is completed, wait for it to cool to room temperature, wash with deionized water until the filtrate is neutral, collect the filter cake and dry at 80 - 85 °C for 6 - 10 h to obtain hollow porous carbon microspheres; 3) Measure oleic acid and absolute ethanol, stir and mix them well to obtain an oleic acid - ethanol mixture. Then add a sodium hydroxide solution with a concentration of 50 - 70 g / L, a calcium chloride solution with a concentration of 17 - 20 g / L, and a sodium dihydrogen phosphate solution with a concentration of 23 - 28 g / L to the oleic acid - ethanol mixture in sequence, with a dropping rate of 30 - 40 drops / min. Stir for 10 - 30 min after each solution is added dropwise to obtain a reaction solution; 4) According to a solid - liquid ratio of 1 : (30 - 50) g / mL, add the hollow porous carbon microspheres to the reaction solution, stir well, transfer to a reaction kettle, and react at 180 - 185 °C for 20 - 25 h under ultrasonic action of 200 - 300 W. After the reaction is completed, centrifuge and separate the product, and then dry it to obtain the composite porous carbon.

[0014] As a further preferred embodiment of the present invention, the ratio of sucrose, deionized water, stannic chloride, and sodium dodecyl sulfate is (8.5 - 15.0) g : (50 - 120) mL : (8.7 - 14.6) g : (0.4 - 1.2) g; The ratio of the composite microspheres to the hydrochloric acid solution is (2 - 5) g : (60 - 150) mL; The hydrochloric acid solution has a concentration of 7 - 10 wt%; The volume ratio of oleic acid, absolute ethanol, sodium hydroxide solution, calcium chloride solution, and sodium dihydrogen phosphate solution is (8 - 12) : (9 - 15) : (10 - 20) : (10 - 20) : (10 - 20).

[0015] A preparation method of a water quality purifying agent for aquaculture, specifically including the following steps: S1 By weight, take potassium monopersulfate compound salt, add citric acid and humic acid under stirring, and mix evenly to obtain mixture A; S2 Add sodium carbonate, magnesium carbonate, sodium sulfate, and a composite plant cell additive to mixture A, stir evenly, then add sodium hexametaphosphate and polyethylene glycol, and continue to stir evenly to obtain mixture B; S3 First dissolve probiotics in water at 35 - 45 °C, add plant active ingredients under stirring, mix evenly, and then add them to mixture B, stir well to obtain the water quality purifying agent.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: In the present invention, an intermediate is obtained by an ion exchange reaction between polyacrylic acid type cation exchange resin and cobalt chloride. The transition metal cobalt ions therein can play a catalytic role, enabling the subsequent resin to obtain a higher degree of graphitization during the carbonization process. Then, potassium hydroxide and calcium hydroxide are added to the intermediate as chemical activation pore-forming agents, and after heat treatment, three-dimensional porous carbon particles are obtained. They have a high porosity and a large specific surface area. As a framework matrix, they can buffer the collision impact force under mechanical stirring and ultrasonic action, maintaining the integrity of the structure. Then, using titanium dioxide nanopowder as the raw material, nanorod materials are synthesized, and through mechanical stirring and ultrasonic treatment, the nanorod materials can be embedded into the pores of the porous carbon particles, thereby forming a convex "burr" - like structure on the surface of the porous carbon particles. The convex "burr" - like structures can be connected together by inter - embedding with each other subsequently, enabling the porous carbon particles to form aggregated aggregates. In the way of vacuum impregnation, a metal scavenger is infiltrated into the synthesized composite nanomaterial to generate a metal scavenger material. Through the way of vacuum pumping, it can promote the infiltration of the metal scavenger deep into the pores of the composite nanomaterial. During the subsequent water purification process, under the capillary action of the porous carbon particles, heavy metal ions in the water body will migrate into it and undergo a chelation precipitation reaction with the metal scavenger, generating large - granular chelation precipitates insoluble in water. And due to the action of mechanical stirring and ultrasonic treatment, it will increase the depth of embedding of the nanorod materials into the pores of the porous carbon particles. Thus, the part of the nanorod materials that penetrates into the pores of the porous carbon particles will have a certain blocking effect on the movement of the large - granular chelation precipitates. Under the restriction of the nanorod materials, the chelation precipitates are not easily detached from the pores, thereby avoiding the secondary pollution of the water body after the metal ions are adsorbed and chelated.

[0017] Secondly, in order to provide a good carrier material for the immobilization of plant algal cells, in the present invention, sucrose is used as a carbon source, and hollow porous carbon microspheres are synthesized by hydrothermal reaction. Taking the hollow porous carbon microspheres as the matrix material, the nanowires generated by the hydrothermal reaction are deposited on the matrix. And because the matrix has a porous structure, one end of the deposited nanowires will be embedded into the pores, thus forming a firm structure with the hollow porous carbon microspheres to generate composite porous carbon. Then, by means of mechanical stirring, the metal scavenger material is dispersed in deionized water. Through high-speed stirring, the metal scavenger materials are connected together by the intercalation of the "burr"-shaped structures protruding from the surface, forming an aggregated aggregate. Then, the composite porous carbon is added. Through high-speed stirring, the nanowires deposited on the composite porous carbon will wind around the nanorods of the aggregate, making the composite porous carbon cover the surface of the aggregate, thus forming a composite carrier material with the metal scavenger material as the core and the composite porous carbon as the shell. By combining the two, the migration path of the chelated precipitate in the core is increased and its migration time is prolonged, so that the chelated precipitate is more difficult to break away. Then, the plant active cells composed of Chlorella pyrenoidosa cells and Anabaena cells are subjected to gelation treatment and immobilized in the composite carrier material, thus obtaining a composite plant cell additive. And because a large number of nanowires are present on the surface of the composite carrier material, it can wrap the gelated plant active cells. On the one hand, it improves the firmness of the attachment of the plant active cells, and at the same time can play a protective role, isolating the direct contact between the plant active cells and microorganisms and phosphates, and avoiding the damage of microorganisms and phosphates to the plant active cells. Finally, by rinsing with distilled water under oscillating conditions, the plant active cells that are not firmly attached to the composite carrier material can be washed away, thus exposing the pores on the composite carrier material, providing an unobstructed pore channel for the migration of heavy metals during the water purification process.

[0018] In the water purifying agent of the present invention, through the scientific compounding of various active ingredients, the physical treatment and chemical treatment purification act synergistically, making its water purification effect more prominent. And the specially added composite plant cell additive, by confining the metal scavenger inside the pores and wrapping the gelated plant active cells, makes it difficult for metal ions to break away from the pores after chelation precipitation, avoiding the secondary pollution of the water body caused by metal ions after being adsorbed and chelated. At the same time, it also avoids the damage of microorganisms and phosphates to the plant active cells, thus making the water purifying agent more stable, prolonging the efficacy time, and having good economic benefits. Detailed implementation mode

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] In the embodiments of the present invention, the preparation of Chlorella pyrenoidosa: By weight, 5 parts of Chlorella pyrenoidosa seeds are inoculated into an Erlenmeyer flask containing 15 parts of SE medium, and cultured at a temperature of 24 °C, with 10 h of light, 10 h of no light, and a light intensity of 1900 lx. The Chlorella pyrenoidosa in the logarithmic phase is centrifuged at 4000 r / min for 15 min, and the supernatant is discarded to obtain Chlorella pyrenoidosa cells. The process is aseptic operation. The preparation of Anabaena: By weight, 10 parts of Anabaena seeds are inoculated into an Erlenmeyer flask containing 20 parts of SE medium, and cultured at a temperature of 24 °C, with 15 h of light, 15 h of no light, and a light intensity of 2300 lx. The Anabaena in the logarithmic phase is centrifuged at 4000 r / min for 14 min, and the supernatant is discarded to obtain Anabaena cells. The process is aseptic operation.

[0021] The plant active ingredient is composed of aloe polysaccharide and saponin in a mass ratio of 1:1.2.

[0022] Example 1 An aquaculture water quality purifier, which contains the following components by weight: 15 parts of potassium monopersulfate compound salt, 5 parts of citric acid, 1 part of humic acid, 2 parts of sodium carbonate, 0.1 part of magnesium carbonate, 1 part of sodium hexametaphosphate, 1 part of probiotic, 0.03 part of polyethylene glycol, 5 parts of sodium sulfate, 10 parts of compound plant cell additive, 0.2 part of plant active ingredient, and 20 parts of water; The preparation method of the water quality purifier specifically includes the following steps: S1 By weight, take the potassium monopersulfate compound salt, add citric acid and humic acid under stirring, and mix evenly to obtain mixture A; S2 Add sodium carbonate, magnesium carbonate, sodium sulfate, and the compound plant cell additive to mixture A, stir evenly, then add sodium hexametaphosphate and polyethylene glycol, and continue to stir evenly to obtain mixture B; S3 First dissolve the probiotic in water at 35 °C, add the plant active ingredient under stirring, mix evenly, and then add it to mixture B, and stir evenly to obtain the water quality purifier.

[0023] Among them, the preparation method of the compound plant cell additive is as follows: S1 According to the mass ratio of the metal scavenger to the composite nanomaterial being 1:10, first place the composite nanomaterial in a vacuum impregnation tank, evacuate to 50 Pa and maintain for 10 min. Then add the metal scavenger to deionized water, fully stir and inject it into the vacuum impregnation tank, evacuate to 10 Pa and maintain for 20 min. After the treatment is completed, slowly release the pressure to atmospheric pressure, and after centrifugal separation, the metal scavenger material can be obtained; Among them, the metal scavenger selects polyaluminum chloride; Among them, for the composite nanomaterial, its preparation method is as follows: 1) Dissolve 1 g of cobalt chloride in deionized water, then add 10 g of polyacrylic acid type cation exchange resin, place it in an 80 °C oil bath and stir to dry, then place it in an 80 °C oven to completely dry, load it into a ball mill tank, and grind at a rotation speed of 300 r / min for 2 h to obtain a sieved product for standby; 2) Add 6 g of calcium hydroxide to 12 mL of deionized water, stir evenly, then add 3 g of the sieved product, place it in an 80 °C oil bath and stir to dry, then place it in an 80 °C oven to completely dry. Then weigh 3 g of potassium hydroxide and dissolve it in 6 mL of absolute ethanol, stir until completely dissolved, add the above sample, place it in an 80 °C oil bath and stir to dry, then place it in an 80 °C oven to completely dry; 3) Place the dried product in a porcelain boat, place it in a tubular furnace filled with an argon atmosphere, heat from room temperature to 800 °C at a rate of 2 °C / min, and keep it warm for 2 h. After the treatment is completed, take out the product from the tubular furnace, perform acid washing and then suction filtration, wash until neutral and then dry, and obtain three-dimensional porous carbon particles after ultrafine pulverization and grinding; 4) Add 1.5 g of titanium dioxide nanopowder to 100 mL of sodium hydroxide aqueous solution with a concentration of 12 mol / L, fully stir evenly and transfer it to a reaction kettle, react at 150 °C for 45 h, cool to room temperature and then perform suction filtration, repeatedly wash with dilute hydrochloric acid and deionized water, and obtain nanorod materials after drying; 5) Disperse 3 g of porous carbon particles in 500 mL of deionized water to obtain a dispersion liquid, then add 0.5 g of nanorod materials, mechanically stir at a rotation speed of 800 r / min for 1 h, and then perform ultrasonic treatment at 500 W for 1 h. After the treatment is completed, centrifuge the product and dry it to obtain the composite nanomaterial; S2 According to the mass ratio of the composite porous carbon to the metal scavenger material being 1:2, first disperse the metal scavenger material in deionized water and stir at a rotation speed of 800 r / min for 1 h, then add the composite porous carbon and continue to stir for 1 h. After the treatment is completed, perform centrifugal separation to obtain the composite carrier material; Among them, for the composite porous carbon, its preparation method is as follows: 1) Add 8.5 g of sucrose to 50 mL of deionized water. After stirring until homogeneous, add 8.7 g of tin tetrachloride and 0.4 g of sodium dodecyl sulfate thereto, and stir well. Then transfer the solution to a high-pressure hydrothermal reactor and react at 190 °C for 24 h. After the reaction is completed, wash repeatedly with deionized water and ethanol, and dry at 80 °C for 6 h to obtain composite microspheres; 2) Take 2 g of the composite microspheres, mix them with 60 mL of a hydrochloric acid solution with a concentration of 7 wt%, stir evenly, transfer the mixture to a high-pressure hydrothermal reactor, and react at 190 °C for 24 h. After the reaction is completed, wait for it to cool to room temperature, wash with deionized water until the filtrate is neutral, collect the filter cake and dry at 80 °C for 6 h to obtain hollow porous carbon microspheres; 3) Measure 8 mL of oleic acid and 9 mL of absolute ethanol, stir and mix well to obtain an oleic acid-ethanol mixture. Then sequentially add 10 mL of a sodium hydroxide solution with a concentration of 50 g / L, 10 mL of a calcium chloride solution with a concentration of 17 g / L, and 10 mL of a sodium dihydrogen phosphate solution with a concentration of 23 g / L to the oleic acid-ethanol mixture at a dropping rate of 30 drops / min. Stir for 10 min after each solution is added dropwise to obtain a reaction solution; 4) According to a solid-liquid ratio of 1:30 g / mL, add the hollow porous carbon microspheres to the reaction solution, stir well, transfer to a reaction kettle, and react at 180 °C for 20 h under the action of 200 W ultrasonic waves. After the reaction is completed, centrifuge and separate the product, and dry it to obtain the composite porous carbon; S3 According to parts by weight, uniformly mix 4 parts of Chlorella pyrenoidosa cells, 6 parts of Anabaena cells, 6 parts of a 2% calcium alginate solution, and 10 parts of the composite carrier material to obtain a mixture. Then, at a position 20 cm above the liquid surface of the pre-cooled 0.1 mol / L calcium chloride solution, drop the mixture into the calcium chloride solution, gel at 4 °C for 8 h, take out the particles and put them into a shaker with filter holes at the bottom, and rinse with distilled water for 20 min under oscillation at 300 r / min to obtain the composite plant cell additive.

[0024] Example 2 An aquaculture water quality purifier, which contains the following components by weight: 20 parts of potassium monopersulfate compound salt, 7 parts of citric acid, 3 parts of humic acid, 5 parts of sodium carbonate, 0.3 parts of magnesium carbonate, 2 parts of sodium hexametaphosphate, 3 parts of probiotics, 0.05 parts of polyethylene glycol, 7 parts of sodium sulfate, 15 parts of the composite plant cell additive, 0.5 parts of plant active ingredients, and 25 parts of water; The preparation method of the water quality purifier specifically includes the following steps: S1 According to parts by weight, take the potassium monopersulfate compound salt, add citric acid and humic acid under stirring, and mix evenly to obtain mixture A; S2 Add sodium carbonate, magnesium carbonate, Glauber's salt, and a composite plant cell additive to mixture A. After stirring evenly, add sodium hexametaphosphate and polyethylene glycol, and continue to stir evenly to obtain mixture B; S3 First dissolve the probiotic in water at 40 °C. Under stirring, add the plant active ingredients. After mixing evenly, add them to mixture B and stir well to obtain the water purifying agent.

[0025] Among them, the preparation method of the composite plant cell additive is as follows: S1 According to the mass ratio of the metal scavenger to the composite nanomaterial being 1:15, first place the composite nanomaterial in a vacuum impregnation tank, evacuate to 80 Pa, and maintain for 15 min. Then add the metal scavenger to deionized water, stir well and inject it into the vacuum impregnation tank, evacuate to 50 Pa and maintain for 25 min. After the treatment is completed, slowly release the pressure to atmospheric pressure, and after centrifugal separation, the metal scavenger material can be obtained; Among them, the metal scavenger selects polyaluminum chloride; Among them, the preparation method of the composite nanomaterial is as follows: 1) Dissolve 1.5 g of cobalt chloride in deionized water, then add 15 g of polyacrylic acid type cation exchange resin, place it in an oil bath at 83 °C and stir to dry, then place it in an oven at 85 °C to completely dry, put it into a ball mill tank, and grind at a rotation speed of 400 r / min for 3 h to obtain a sieved product for standby; 2) Add 8 g of calcium hydroxide to 15 mL of deionized water, stir evenly and then add 4 g of the sieved product, place it in an oil bath at 83 °C and stir to dry, then place it in an oven at 85 °C to completely dry. Weigh 4 g of potassium hydroxide and dissolve it in 8 mL of absolute ethanol, stir until completely dissolved, add the above sample, place it in an oil bath at 83 °C and stir to dry, then place it in an oven at 85 °C to completely dry; 3) Put the dried product into a porcelain boat, place it in a tube furnace filled with an argon atmosphere, heat from room temperature to 820 °C at a rate of 3 °C / min, and keep it warm for 2.5 h. After the treatment is completed, take out the product from the tube furnace, pickling and then suction filtration, wash until neutral and then dry, and obtain three-dimensional porous carbon particles through ultra-fine pulverization and grinding; 4) Add 2.6 g of titanium dioxide nanopowder to 170 mL of sodium hydroxide aqueous solution with a concentration of 12.5 mol / L, stir well and transfer it to a reaction kettle, react at 155 °C for 47 h, cool to room temperature and then suction filter, wash repeatedly with dilute hydrochloric acid and deionized water, and obtain the nanorod material after drying; 5) Disperse 5 g of porous carbon particles in 600 mL of deionized water to obtain a dispersion liquid, then add 0.8 g of nanorod material, mechanically stir at a rotation speed of 900 r / min for 1.5 h, and then perform ultrasonic treatment at 600 W for 1.5 h. After the treatment is completed, centrifuge the product and dry it to obtain the composite nanomaterial; S2 According to the mass ratio of the composite porous carbon to the metal scavenger material being 1:2.5, first disperse the metal scavenger material in deionized water and stir at a rotation speed of 900 r / min for 1.5 h, then add the composite porous carbon and continue to stir for 1.5 h. After the treatment is completed, perform centrifugal separation to obtain the composite support material; Among them, the preparation method of the composite porous carbon is as follows: 1) Add 12.5 g of sucrose to 86 mL of deionized water, stir until uniform, then add 13.0 g of tin tetrachloride and 0.9 g of sodium dodecyl sulfate thereto and stir well. Then transfer the solution to a high-pressure hydrothermal reaction kettle and react at 192 °C for 28 h. After the reaction is completed, wash repeatedly with deionized water and ethanol alternately and dry at 83 °C for 8 h to obtain composite microspheres; 2) Take 3 g of the composite microspheres, mix them with 90 mL of hydrochloric acid solution with a concentration of 8 wt%, stir evenly, transfer the mixture to a high-pressure hydrothermal reaction kettle, and react at 192 °C for 28 h. After the reaction is completed, wait for it to cool to room temperature, wash with deionized water until the filtrate is neutral, collect the filter cake and dry it at 83 °C for 8 h to obtain hollow porous carbon microspheres; 3) Measure 10 mL of oleic acid and 13 mL of absolute ethanol, stir and mix them well to obtain an oleic acid-ethanol mixed solution. Then add 15 mL of sodium hydroxide solution with a concentration of 60 g / L, 15 mL of calcium chloride solution with a concentration of 18 g / L, and 15 mL of sodium dihydrogen phosphate solution with a concentration of 25 g / L to the oleic acid-ethanol mixed solution in sequence. The dropping speed is 35 drops / min, and stir for 20 min after each solution is added dropwise to obtain a reaction solution; 4) According to the solid-liquid ratio of 1:40 g / mL, add the hollow porous carbon microspheres to the reaction solution, stir well, transfer to a reaction kettle, and react at 183 °C for 24 h under the action of 260 W ultrasonic. After the reaction is completed, centrifuge the product and dry it to obtain the composite porous carbon; S3 Mix 5 parts of Chlorella pyrenoidosa cells, 8 parts of Anabaena cells, 8 parts of a 2% calcium alginate solution by weight, and 15 parts of a composite carrier material uniformly to obtain a mixture. Then, at a distance of 25 cm from the surface of a pre-cooled 0.2 mol / L calcium chloride solution, drop the mixture into the calcium chloride solution, gel it at 5 °C for 10 h, take out the particles and place them in a shaker with filter holes at the bottom, and rinse with distilled water for 25 min under oscillation at 400 r / min to obtain the composite plant cell additive.

[0026] Example 3 An aquaculture water quality purifier, which contains the following components by weight: 25 parts of potassium monopersulfate compound salt, 8 parts of citric acid, 5 parts of humic acid, 6 parts of sodium carbonate, 0.5 part of magnesium carbonate, 3 parts of sodium hexametaphosphate, 5 parts of probiotics, 0.08 part of polyethylene glycol, 10 parts of sodium sulfate, 16 parts of composite plant cell additive, 0.7 part of plant active ingredient, and 30 parts of water; The preparation method of the water quality purifier specifically includes the following steps: S1 Take potassium monopersulfate compound salt by weight, add citric acid and humic acid under stirring, and mix evenly to obtain mixture A; S2 Add sodium carbonate, magnesium carbonate, sodium sulfate, and the composite plant cell additive to mixture A, stir evenly, then add sodium hexametaphosphate and polyethylene glycol, and continue to stir evenly to obtain mixture B; S3 First dissolve the probiotics in water at 45 °C, add the plant active ingredient under stirring, mix evenly, and then add it to mixture B, and stir well to obtain the water quality purifier.

[0027] Among them, the preparation method of the composite plant cell additive is as follows: S1 According to the mass ratio of the metal scavenger to the composite nanomaterial of 1:18, first place the composite nanomaterial in a vacuum impregnation tank, evacuate to 100 Pa, and maintain for 20 min. Then add the metal scavenger to deionized water, stir well and inject it into the vacuum impregnation tank, evacuate to 60 Pa and maintain for 30 min. After the treatment is completed, slowly release the pressure to atmospheric pressure, and perform centrifugal separation to obtain the metal scavenger material; Among them, the metal scavenger selects polyaluminum chloride; Among them, the preparation method of the composite nanomaterial is as follows: 1) Dissolve 2 g of cobalt chloride in deionized water, then add 20 g of polyacrylic acid type cation exchange resin, place it in an 85 °C oil bath and stir to dry, then place it in a 90 °C oven to completely dry, put it into a ball mill tank, and grind at a rotation speed of 500 r / min for 5 h to obtain a sieved product for standby; 2) Add 10g of calcium hydroxide to 20mL of deionized water, stir evenly, then add 5g of the sieved product, place in an 85℃ oil bath, stir and evaporate to dryness, then place in a 90℃ oven to completely dry, then weigh 5g of potassium hydroxide and dissolve in 10mL of anhydrous ethanol, stir until completely dissolved, add the above sample, place in an 85℃ oil bath, stir and evaporate to dryness, then place in a 90℃ oven to completely dry; 3) The dried product is placed in a porcelain boat, placed in a tubular furnace filled with argon atmosphere, heated from room temperature to 830°C at a rate of 3°C / min, and kept warm for 3 hours. After the treatment is completed, the product is taken out of the tubular furnace, acid-washed and filtered, washed to neutrality and then dried, and ultrafine ground to obtain porous carbon particles with a three-dimensional structure; 4) Add 3 g of titanium dioxide nanopowder to 200 mL of 13 mol / L sodium hydroxide aqueous solution, stir well and transfer to a reactor, react at 160 ° C for 50 h, cool to room temperature and filter, wash repeatedly with dilute hydrochloric acid and deionized water, and dry to obtain nanorod material; 5) 8 g of porous carbon particles were dispersed in 700 mL of deionized water to obtain a dispersion, and then 1 g of nanorod material was added, and mechanical stirring was performed at a speed of 1000 r / min for 2 h, and then ultrasonic treatment was performed at 800 W for 2 h. After the treatment was completed, the product was centrifuged and dried to obtain a composite nanomaterial; S2: The mass ratio of the composite porous carbon to the metal scavenger material is 1:3. The metal scavenger material is first dispersed in deionized water and stirred at a speed of 1000 r / min for 2 h. The composite porous carbon is then added and stirred for another 2 h. After the treatment, centrifugal separation is performed to obtain a composite carrier material. Among them, the composite porous carbon is prepared by the following method: 1) Add 15g of sucrose to 120mL of deionized water, stir until uniform, then add 14.6g of tin tetrachloride and 1.2g of sodium dodecyl sulfate respectively, stir well, then transfer the solution to a high-pressure hydrothermal reactor, react at 195°C for 30h, after the reaction is completed, wash with deionized water and ethanol alternately, and dry at 85°C for 10h to obtain composite microspheres; 2) Take 5 g of the composite microspheres, mix them with 150 mL of 10 wt% hydrochloric acid solution, stir them evenly, move the mixture into a high-pressure hydrothermal reactor, react at 195 ° C for 30 h, and after the reaction is completed, wait for it to cool to room temperature, and wash it with deionized water until the filtrate is neutral. Collect the filter cake and dry it at 85 ° C for 10 h to obtain hollow porous carbon microspheres; 3) 12 mL of oleic acid and 15 mL of anhydrous ethanol were weighed and mixed thoroughly to obtain an oleic acid-ethanol mixed solution, and then 20 mL of a 70 g / L sodium hydroxide solution, 20 mL of a 20 g / L calcium chloride solution, and 20 mL of a 28 g / L sodium dihydrogen phosphate solution were added to the oleic acid-ethanol mixed solution in sequence at a dropping rate of 40 drops / min. After each solution was added, it was stirred for 30 minutes to obtain a reaction solution; 4) Add hollow porous carbon microspheres to the reaction solution at a solid-liquid ratio of 1:50 g / mL, stir thoroughly, transfer to a reactor, react at 185°C for 25 h under 300 W ultrasound, centrifuge the product after the reaction is complete, and dry to obtain composite porous carbon; S3: According to weight proportions, 7 parts of Chlorella proteoglycans cells, 10 parts of Anabaena cells, 10 parts of 2% calcium alginate solution, and 18 parts of composite carrier materials are uniformly mixed to obtain a mixture, and then the mixture is dripped into a pre-cooled 0.2 mol / L calcium chloride solution at a distance of 25 cm from the liquid surface, and gelled at 5°C for 10 hours. The particles are taken out and placed in a shaking incubator with a filter hole at the bottom, and washed with distilled water for 30 minutes under shaking at 500 r / min to obtain a composite plant cell additive.

[0028] Comparative Example 1: This comparative example is basically the same as Example 1, except that the nanorod material in S1 is omitted in the preparation of the composite plant cell additive.

[0029] Comparative Example 2: This comparative example is basically the same as Example 1, except that the composite nanomaterial in S1 is omitted in the preparation of the composite plant cell additive.

[0030] Comparative Example 3: This comparative example is basically the same as Example 1, except that the nanowires in S2 are omitted in the preparation of the composite plant cell additive.

[0031] Comparative Example 4: This comparative example is basically the same as Example 1, except that, in the preparation of the composite plant cell additive, the composite porous carbon in S2 is omitted.

[0032] Comparative Example 5: This comparative example is basically the same as Example 1, except that, in the preparation of the composite plant cell additive, the oscillation and washing in S3 is omitted.

[0033] Test experiment: It was used in a fish pond in Lingang, Guangdong, with an area of ​​2 mu. The water quality in the pond was too concentrated in spring, and the water color was not good. The ammonia nitrogen, nitrite and heavy metal copper ions in the water reached 1.43 mg·L -1 , 0.59mg·L -1, 0.096 mg·L -1 , the bottom was black and stinky, seriously affecting the growth of fish. On a sunny day, this water quality purifier was used in this aquaculture pond at a dosage of 260 g / mu·meter water depth. After 24 hours of use, the contents of ammonia nitrogen, nitrite, COD, and heavy metal copper ions in the water body were detected, and the results are shown in Table 1.

[0034] Table 1 As can be seen from Table 1, the water quality purifier in the present invention can effectively reduce the concentrations of ammonia nitrogen, nitrite, and heavy metals in the water body, improve the water quality visibility, purify the water quality, and meet the requirements for aquaculture water.

[0035] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A water purifier for aquaculture, characterized in that: The water purifier comprises the following components in parts by weight: 15-25 parts of potassium persulfate complex salt, 5-8 parts of citric acid, 1-5 parts of humic acid, 2-6 parts of sodium carbonate, 0.1-0.5 parts of magnesium carbonate, 1-3 parts of sodium hexametaphosphate, 1-5 parts of probiotics, 0.03-0.08 parts of polyethylene glycol, 5-10 parts of sodium sulfate, 10-16 parts of composite plant cell additives, 0.2-0.7 parts of plant active ingredients, and 20-30 parts of water; The plant active ingredient is composed of aloe polysaccharide and saponin in a mass ratio of 1: (1.0-1.6); The composite plant cell additive is prepared as follows: S1 embeds nanorod materials on the surface of porous carbon particles to obtain composite nanomaterials, and then uses vacuum impregnation to infiltrate metal scavengers into the composite nanomaterials to obtain metal scavenger materials; S2 uses hollow porous carbon microspheres as a matrix, and deposits nanowires on the matrix through a hydrothermal reaction to obtain a composite porous carbon. Then, a metal capture agent material is used as a core and the composite porous carbon is used as a shell. The composite porous carbon is covered on the surface of the metal capture agent material by mechanical stirring to obtain a composite carrier material. S3: immobilize the plant algae cells on the composite carrier material, and then wash them by shaking with distilled water.

2. A water purifier for aquaculture according to claim 1, characterized in that: The metal scavenger is selected from at least one of polyaluminium chloride, polyacrylamide and dithiocarbamic acid; The mass ratio of the metal capture agent and the composite nanomaterial is 1:(10-18); The mass ratio of the composite porous carbon and the metal capture agent material is 1:(2-3).

3. A water purifier for aquaculture according to claim 1, characterized in that: The composite nano material is prepared by the following method: 1) Add titanium dioxide nanopowder to sodium hydroxide aqueous solution, stir well and transfer to a reactor, react at 150-160°C for 45-50h, cool to room temperature and filter, wash repeatedly with dilute hydrochloric acid and deionized water, and dry to obtain nanorod material; 2) The porous carbon particles are dispersed in deionized water to obtain a dispersion, and then the nanorod material is added, and mechanical stirring is performed at a speed of 800-1000r / min for 1-2h, and then ultrasonic treatment is performed at 500-800W for 1-2h. After the treatment is completed, the product is centrifuged and dried to obtain a composite nanomaterial.

4. A water purifier for aquaculture according to claim 3, characterized in that: The ratio of the titanium dioxide nanopowder to the sodium hydroxide aqueous solution is (1.5-3.0) g: (100-200) mL; The sodium hydroxide aqueous solution has a concentration of 12-13 mol / L; The ratio of the porous carbon particles, deionized water and nanorod material is (3-8) g: (500-700) mL: (0.5-1.0) g.

5. The water purifier for aquaculture according to claim 3, characterized in that: The porous carbon particles are prepared by the following method: 1) Dissolve cobalt chloride in deionized water, then add polyacrylic acid type cation exchange resin, place in an 80-85°C oil bath, stir and evaporate to dryness, then place in an 80-90°C oven to completely dry, put into a ball mill, grind at a speed of 300-500r / min for 2-5h to obtain a sieved product for standby use; 2) Add calcium hydroxide to deionized water, stir evenly, then add the sieved product, place in an 80-85℃ oil bath, stir and evaporate to dryness, then place in an 80-90℃ oven to completely dry, then weigh potassium hydroxide and dissolve in anhydrous ethanol, stir until completely dissolved, add the above sample, place in an 80-85℃ oil bath, stir and evaporate to dryness, then place in an 80-90℃ oven to completely dry; 3) The dried product is placed in a porcelain boat, placed in a tubular furnace filled with argon atmosphere, heated from room temperature to 800-830°C at a rate of 2-3°C / min, and kept warm for 2-3 hours. After the treatment is completed, the product is taken out of the tubular furnace, acid-washed and filtered, washed to neutrality and then dried, and ultrafine ground to obtain porous carbon particles with a three-dimensional structure.

6. A water purifier for aquaculture according to claim 5, characterized in that: The mass ratio of the cobalt chloride and the polyacrylic acid type cation exchange resin is (1-2): (10-20); The ratio of calcium hydroxide, deionized water, sieved product, potassium hydroxide and anhydrous ethanol is (6-10) g: (12-20) mL: (3-5) g: (3-5) g: (6-10) mL.

7. The water purifier for aquaculture according to claim 1, characterized in that: The composite porous carbon is prepared by the following method: 1) Add sucrose to deionized water, stir until uniform, then add tin tetrachloride and sodium dodecyl sulfate respectively, stir well, then transfer the solution to a high-pressure hydrothermal reactor, react at 190-195°C for 24-30h, after the reaction is completed, wash with deionized water and ethanol alternately, and dry at 80-85°C for 6-10h to obtain composite microspheres; 2) Take the composite microspheres, mix them with the hydrochloric acid solution, stir them evenly, move the mixture into a high-pressure hydrothermal reactor, react at 190-195°C for 24-30 hours, and after the reaction is completed, cool them to room temperature, wash them with deionized water until the filtrate is neutral, collect the filter cake and dry it at 80-85°C for 6-10 hours to obtain hollow porous carbon microspheres; 3) Measure oleic acid and anhydrous ethanol, stir and mix them thoroughly to obtain an oleic acid-ethanol mixed solution, then add a 50-70 g / L sodium hydroxide solution, a 17-20 g / L calcium chloride solution and a 23-28 g / L sodium dihydrogen phosphate solution to the oleic acid-ethanol mixed solution in sequence at a dripping rate of 30-40 drops / min, and stir for 10-30 minutes after each solution is added to obtain a reaction solution; 4) Add hollow porous carbon microspheres to the reaction solution at a solid-liquid ratio of 1: (30-50) g / mL, stir thoroughly, transfer to a reactor, and react at 180-185°C for 20-25 hours under 200-300W ultrasound. After the reaction is completed, centrifuge the product and dry it to obtain a composite porous carbon.

8. A water purifier for aquaculture according to claim 7, characterized in that: The ratio of sucrose, deionized water, tin tetrachloride and sodium dodecyl sulfate is (8.5-15.0) g: (50-120) mL: (8.7-14.6) g: (0.4-1.2) g; The ratio of the composite microspheres to the hydrochloric acid solution is (2-5) g: (60-150) mL; The hydrochloric acid solution has a concentration of 7-10wt%; The volume ratio of oleic acid, anhydrous ethanol, sodium hydroxide solution, calcium chloride solution and sodium dihydrogen phosphate solution is (8-12): (9-15): (10-20): (10-20): (10-20).

9. The water purifier for aquaculture according to claim 1, characterized in that: The specific operation method of step S3 is as follows: 1) uniformly mixing 4-7 parts of Chlorella pyrenoidosa cells, 6-10 parts of Anabaena cells, 6-10 parts of 2% calcium alginate solution, and 10-18 parts of a composite carrier material by weight to obtain a mixture; 2) Drop the mixture into the pre-cooled 0.1-0.2 mol / L calcium chloride solution at a distance of 20-25 cm from the surface. Gel at 4-5°C for 8-10 hours. Take out the particles and put them into a shaker with filter holes at the bottom. Rinse with distilled water for 20-30 minutes at 300-500 r / min.

10. A method for preparing a water purifier for aquaculture according to claim 1, characterized in that: The specific steps include: S1: taking potassium persulfate composite salt in parts by weight, adding citric acid and humic acid under stirring, and mixing evenly to obtain a mixture A; S2: adding sodium carbonate, magnesium carbonate, sodium sulfate, and a composite plant cell additive to the mixture A, stirring evenly, and then adding sodium hexametaphosphate and polyethylene glycol, and continuing to stir evenly to obtain a mixture B; S3: Dissolve the probiotics in 35-45°C water, add the plant active ingredients while stirring, mix well, add to mixture B, stir well to obtain a water purifier.

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