CN110282744B - Floating ball for water ecological restoration - Google Patents
Floating ball for water ecological restoration Download PDFInfo
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- CN110282744B CN110282744B CN201910476082.XA CN201910476082A CN110282744B CN 110282744 B CN110282744 B CN 110282744B CN 201910476082 A CN201910476082 A CN 201910476082A CN 110282744 B CN110282744 B CN 110282744B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/025—Biological purification using sources of oxygen other than air, oxygen or ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a floating ball for water ecological restoration, which relates to the technical field of ecological restoration and comprises a shell and wing plates integrally formed on the outer surface of the shell, wherein the shell is of a hollow spherical structure, a plurality of through holes are formed in the bottom of the shell, a partition plate is arranged in the shell, a through hole is formed in the middle of the partition plate, a limiting pipe is integrally formed in the partition plate at a position corresponding to the through hole, the limiting pipe is communicated with the through hole, a water body purification matrix is filled below the partition plate in the shell and comprises the following raw materials: the biological active microsphere is a core-shell structure which takes tricalcium phosphate as a core and is externally coated with a plurality of polylactic acid/calcium peroxide layers. The floating ball for water ecological restoration has larger buoyancy and better lodging resistance, can excite the activity of beneficial microorganisms in the polluted water body, and has better treatment effect on the polluted water body.
Description
Technical Field
The invention relates to the technical field of ecological restoration, in particular to a floating ball for water ecological restoration.
Background
With the rapid development of society, human activities are more and more, and a lot of river channels are polluted more and more seriously, so that the restoration is urgently needed. In the riverway water ecological restoration treatment, the ecological floating bed technology is a common biological restoration technology, the floating bed is placed in a water area to be treated, plants planted on the floating bed are used for carrying out in-situ restoration on the water body to purify the water quality, the plants absorb and absorb pollutants in the water body, particularly nutrient salts such as nitrogen, phosphorus and the like, through the metabolism in the growth process of the plants, so that the self growth and development are realized, the aim of improving the water quality is fulfilled, the root systems of the plants can provide places with large surface areas for the attachment of microorganisms in the water, the water quality is synchronously purified, and therefore, the ecological floating bed technology is widely applied to the field of water ecological restoration due to the excellent characteristics of the ecological floating bed technology.
However, in the practical application process, most aquatic plants can only absorb and utilize inorganic ions in polluted water, and the purification of organic pollutants still needs to depend on the elimination effect of beneficial microorganisms; the anaerobic decomposition of organic matters in the water body can cause the water body to smell, a large amount of oxygen is consumed in the anaerobic decomposition process of the organic matters to cause the water body to be anoxic, anaerobic microorganisms are propagated in a large amount and decomposed to generate ammonia gas, hydrogen sulfide and the like to escape from the water surface, the water body anoxic inhibits the growth and the propagation of beneficial microorganisms and aquatic plants, the aerobic action of the microorganisms is greatly weakened, the vicious circle is caused, the water body restoration effect by the aquatic plants is poor, the restoration period is long, and therefore the research of the in-situ purification treatment of the polluted water body by the microorganisms is necessary while the water body restoration is carried out by the aquatic plants.
Disclosure of Invention
In view of the above problems, the present invention aims to design and provide a floating ball for water ecological restoration, which has a large buoyancy and a good lodging resistance, can excite the activity of beneficial microorganisms in a polluted water body, and has a good treatment effect on the polluted water body.
The invention solves the technical problems by the following technical means:
the utility model provides a floater for water ecological restoration, includes the shell to and integrated into one piece at the pterygoid lamina of shell surface, the shell is hollow globular structure, the bottom of shell is provided with a plurality of through-holes, be provided with the division board in the shell, the through hole has been seted up to the intermediate position of division board, there is spacing pipe in the position integrated into one piece that the through hole corresponds on the division board, spacing pipe and through hole are linked together, it has water purification matrix to fill in the below of division board in the casing, water purification matrix includes following raw materials: the biological active microsphere is a core-shell structure which takes tricalcium phosphate as a core and is externally coated with a plurality of polylactic acid/calcium peroxide layers.
The floating ball for ecological restoration has a hollow ball structure and larger buoyancy, the floating ball is filled with the water purification substrate, on one hand, the water purification substrate is filled at the bottom of the floating ball, the lodging resistance of the floating ball is increased, and a certain fixing and supporting effect can be provided for the root system of the aquatic plant, on the other hand, the earthworm excrement and the modified kaolin in the water purification substrate provide nutrition for the aquatic plant, wherein the coconut shell powder, the alum and the active carbon can assist in the purification effect of the polluted water body and increase the purification effect, and the bioactive microspheres, the coconut shell powder and the active carbon can stimulate the activity of beneficial microorganisms originally existing in the polluted water body and provide carbon sources and nutrient substances for the propagation of the beneficial microorganisms, thereby increasing the decomposition capacity and the treatment effect of the beneficial microorganisms on organic substances and increasing the treatment effect of the polluted water body, the time for restoring the water body is shortened to a certain extent.
Further, the pterygoid lamina includes integrated into one piece's horizontal plate and vertical board, be provided with two joints on the vertical board and detain and two joint grooves, the joint is detained, the joint groove is in turn even arranges on vertical board, the joint is detained and joint groove phase-match.
Through the structure setting of pterygoid lamina, can increase the area of contact of floater and water, increase its buoyancy that receives, improve and prevent the lodging performance, buckle through the joint simultaneously and the design in joint groove, can link together between a plurality of floaters, increased stability promptly, be favorable to the recovery in later stage again.
Furthermore, the inner diameter of the limiting pipe is of a gradually-changing structure which is reduced from large to small towards the direction far away from the isolation plate, the limiting pipe comprises a plurality of mutually-independent limiting pieces, and two adjacent limiting pieces are in contact with each other.
The structural design of spacing pipe accords with the biological stem portion from bottom to top characteristic that reduces gradually, can play certain supporting role to aquatic plant, and the design of the spacing piece of mutual independence can satisfy the growth demand of plant simultaneously, also can not play the effect of fastening up to the plant in the later stage of growing.
Further, the tricalcium phosphate core is coated with a first polylactic acid/calcium peroxide layer, a second polylactic acid/calcium peroxide layer and a third polylactic acid/calcium peroxide layer from inside to outside in sequence, the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer are all in porous structures, the pore size of the first polylactic acid/calcium peroxide layer is smaller than that of the second polylactic acid/calcium peroxide layer, the pore size of the second polylactic acid/calcium peroxide layer is smaller than that of the third polylactic acid/calcium peroxide layer, and the pores of the third polylactic acid/calcium peroxide layer are filled with humic acid solution.
The structure is arranged, at the initial stage of use, humic acid solution filled in the pores of the third polylactic acid/calcium peroxide layer is separated out, so that the activity of catalase and polyphenol oxidase in water plants can be enhanced, the division and growth of tissue cells at the tips of plant root systems can be stimulated, the survivability of aquatic plants can be improved, meanwhile, the activity of beneficial microorganisms in the water can be stimulated, and the propagation and growth of beneficial microorganisms can be promoted.
Meanwhile, calcium peroxide can be decomposed in water to generate oxygen to supplement oxygen for polluted water and further promote the growth of beneficial microorganisms and aquatic plants, but the existing time is relatively short and the oxygen supply cannot be continuously carried out, so that the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer are structurally arranged, the calcium peroxide is wrapped by the polylactic acid as the polylactic acid is a biodegradable material, and the calcium peroxide is decomposed to generate oxygen only after the polylactic acid is decomposed and then is decomposed, so that the aim of continuously and permanently supplementing the oxygen in the water is fulfilled, in addition, the porous structures of the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer increase the attachment points of the microorganisms on one hand, the structure can promote the beneficial microorganisms to reproduce and generate micelles, and on the other hand, the structure can increase the degradation speed of the high polymer material to a certain extent and balance the amount of oxygen generated by the decomposition of calcium peroxide, and the speed is neither too fast nor too slow.
Furthermore, the tricalcium phosphate is prepared by taking lotus leaf stems as templates through a water phase coprecipitation method, and has a natural porous structure of the lotus leaf stems.
The natural lotus leaf rods are distributed with a large number of holes and have large specific surface area, the tricalcium phosphate prepared by adopting the natural lotus leaf rods as the template also has a porous structure and good adsorption performance, and when the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer coated on the outer surface of the tricalcium phosphate are decomposed, the tricalcium phosphate can also adsorb heavy metal ions and the like in a water body, so that the treatment effect is further enhanced.
Further, the first polylactic acid/calcium peroxide layer has a porosity of 80 to 85%, the second polylactic acid/calcium peroxide layer has a porosity of 75 to 80%, and the third polylactic acid/calcium peroxide layer has a porosity of 70 to 75%.
Further, the preparation method of the bioactive microsphere comprises the following steps:
preparing tricalcium phosphate: soaking the pretreated lotus leaf rods in a calcium hydroxide solution, dropwise adding a urea phosphate solution, stirring, heating to 70-90 ℃ for reaction for 30-70min, stopping the reaction when the pH value is detected to be 8-9, cooling to room temperature, centrifuging, placing the separated solid matter in a tubular furnace, heating to 70-80 ℃ at the speed of 1-3 ℃/min, drying for 0.5-1h, heating to 400-5 ℃/min, keeping the temperature for 1-2h, heating to 900-1000 ℃ at the speed of 2-5 ℃/min, calcining for 0.5-1h, cooling with the furnace, taking out, grinding, and sieving with a 100-mesh sieve to obtain tricalcium phosphate with a porous structure;
preparation of gelatin grafted polylactic acid: cleaning polylactic acid with 50 wt% ethanol solution, drying, soaking in 0.02g/ml hexanediamine/isopropanol mixed solution, reacting at 37 ℃ for 10min, taking out, cleaning with deionized water, drying, soaking in 1 wt% glutaraldehyde solution, reacting at 30 ℃ for 1h, cleaning with deionized water, drying, soaking in 2 wt% gelatin aqueous solution for 6h, cleaning with warm water, and drying to obtain gelatin grafted polylactic acid;
coating of the first polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate and calcium carbonate particles with the particle size of 60-75nm, stirring and reacting at 50 deg.C for 30-40min, taking out to obtain tricalcium phosphate microsphere coated with gelatin grafted polylactic acid/calcium carbonate layer, washing with deionized water, and dispersed in an excessive hexamethylenediamine tetraacetic acid solution with the concentration of 0.1mol/L after being dried, oscillating in vortex oscillator for 12h to remove calcium carbonate particles, washing with anhydrous ethanol, drying, adding into 0.5% glutaraldehyde solution, adding nanometer calcium peroxide, stirring and dispersing under ultrasonic condition, reacting under ultraviolet irradiation for 10-12h, taking out after reaction, washing, drying, carrying out low-temperature plasma treatment to obtain tricalcium phosphate microspheres coated with a first polylactic acid/calcium peroxide layer;
coating of the second polylactic acid/calcium peroxide layer: repeating the coating step of the first polylactic acid/calcium peroxide layer, wherein the added tricalcium phosphate is changed into tricalcium phosphate microspheres coated with the first polylactic acid/calcium peroxide layer on the surface, and the particle size of calcium carbonate particles is 120-135 nm;
coating of the third polylactic acid/calcium peroxide layer: the coating step of the first polylactic acid/calcium peroxide layer was repeated except that the resultant product was prepared by changing the added tricalcium phosphate to the coating step of the second polylactic acid/calcium peroxide layer, and the particle size of the calcium carbonate particles was 185-200 nm.
Further, argon is adopted as working gas for low-temperature plasma treatment in the steps of coating the first polylactic acid/calcium peroxide layer and coating the second polylactic acid/calcium peroxide layer, the power is 60-80W, the pressure is 6-8Pa, and the treatment time is 80-100s, oxygen is adopted as working gas for low-temperature plasma treatment in the step of coating the third polylactic acid/calcium peroxide layer, the power is 80-100W, the pressure is 10-15Pa, and the treatment time is 80-100 s.
Grafting the polylactic acid by gelatin, increasing the hydrophilicity and wettability of the polylactic acid, and simultaneously, during subsequent calcium peroxide compounding, performing self-crosslinking on double bonds in the gelatin under the illumination condition, so as to coat the nano calcium peroxide, so that the nano calcium peroxide is better compounded with a polylactic acid matrix, in addition, after the coating of the first polylactic acid/calcium peroxide layer and the second polylactic acid/calcium peroxide layer is completed, argon is adopted as working gas to perform low-temperature plasma treatment, in the treatment process, the argon plasma bombards the surfaces of the first polylactic acid/calcium peroxide layer and the second polylactic acid/calcium peroxide layer, so that the surfaces of the polylactic acid/calcium peroxide layer and the second polylactic acid/calcium peroxide layer become rough, the binding property is better in the subsequent coating process, and after the coating of the third polylactic acid/calcium peroxide layer is completed, oxygen plasma is adopted for treatment, high-oxidizing hydroxyl groups are introduced to the outer surface of the third polylactic acid/calcium peroxide layer, so that the hydrophilic performance of the bioactive microspheres is improved, the bioactive microspheres can be better contacted with a water body in water, and the treatment performance of the bioactive microspheres on polluted water bodies is improved.
Further, the pretreatment of the lotus leaf stems is as follows: taking natural lotus leaves, cleaning the lotus leaves with clear water, cutting into sections, drying, treating with 5 wt% ammonia water solution for 5-6h, taking out, washing with deionized water to be neutral, drying, and placing in a plasma reactor for plasma reaction for 5-10 min.
The invention has the beneficial effects that:
1. the floating ball for ecological restoration has larger buoyancy, the water body purification substrate is filled in the floating ball, the lodging resistance of the floating ball is increased, and a certain fixing and supporting effect is provided for the root system of the aquatic plant.
2. The bioactive microspheres adopt biodegradable materials as raw materials, are green and environment-friendly, and the calcium peroxide can continuously provide oxygen for the polluted water body, so that the growth of aquatic plants and beneficial microorganisms is further promoted, a virtuous cycle is formed, and the treatment effect of the polluted water body is improved.
Drawings
FIG. 1 is a schematic cross-sectional view of a floating ball for water ecological restoration according to the present invention;
FIG. 2 is a top view of a float for use in water ecology restoration according to the present invention;
the device comprises a shell 1, a wing plate 2, a horizontal plate 21, a vertical plate 22, a clamping buckle 23, a clamping groove 24, a through hole 3, an isolation plate 4, a through hole 41, a limiting pipe 5 and a limiting sheet 51.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
the invention relates to a floating ball for water ecological restoration, which comprises a shell 1 and a wing plate 2 integrally formed on the outer surface of the shell 1, wherein the wing plate 2 comprises a horizontal plate 21 and a vertical plate 22 which are integrally formed, the vertical plate 22 is provided with two clamping buckles 23 and two clamping grooves 24, the clamping buckles 23 and the clamping grooves 24 are alternately and uniformly arranged on the vertical plate 22, the clamping buckles 23 are matched with the clamping grooves 24, through the structural arrangement of the wing plate 2, the contact area between the floating ball and a water body can be increased, the buoyancy borne by the floating ball is increased, the lodging resistance performance is improved, meanwhile, through the design of the clamping buckles 23 and the clamping grooves 24, a plurality of floating balls can be connected together, namely, the stability is increased, the later recovery is facilitated, the shell 1 is of a hollow spherical structure, the borne buoyancy is larger, the lodging resistance performance is better, the bottom of the shell 1 is provided with a plurality of through holes 3, the root system of aquatic plants can conveniently stretch out, be provided with division board 4 in the shell 1, division board 4 and shell 1's inner wall is through the structure looks fixed connection of common joint, through hole 41 has been seted up to division board 4's intermediate position, there is spacing pipe 5 in the position integrated into one piece that through hole 41 corresponds on division board 4, spacing pipe 5 and through hole 41 are linked together, spacing pipe 5's internal diameter size is the gradual change structure by diminishing greatly towards the direction of keeping away from division board 4, the stem portion that accords with biology is by the characteristic that up reduces gradually down, can play certain supporting role to aquatic plant, spacing pipe 5 includes polylith mutually independent spacing piece 51, contact between two adjacent spacing pieces 51 and separate, the growth demand of plant can be satisfied in mutually independent spacing piece 51's design, also can not play the effect of confinement to the plant in growth later stage.
Wherein, the water body purification substrate is filled in the shell below the isolation plate 4, and the water body purification substrate comprises the following raw materials: bioactive microspheres, kaolin, coconut shell powder, earthworm excrement, sodium polyacrylate, alum and active carbon.
The bioactive microsphere is a core-shell structure which takes tricalcium phosphate as a core and is externally coated with a plurality of polylactic acid/calcium peroxide layers, specifically, the tricalcium phosphate takes lotus leaf stems as a template, and the tricalcium phosphate prepared by a water phase coprecipitation method has a natural porous structure of the lotus leaf stems; the calcium phosphate core is coated with a first polylactic acid/calcium peroxide layer, a second polylactic acid/calcium peroxide layer and a third polylactic acid/calcium peroxide layer from inside to outside in sequence, the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer are all in porous structures, the pore size of the first polylactic acid/calcium peroxide layer is smaller than that of the second polylactic acid/calcium peroxide layer, the pore size of the second polylactic acid/calcium peroxide layer is smaller than that of the third polylactic acid/calcium peroxide layer, and the pores of the third polylactic acid/calcium peroxide layer are filled with humic acid solution.
EXAMPLE preparation of bioactive microspheres 1
Pretreatment: taking natural lotus leaves, cleaning the lotus leaves with clear water, cutting into sections, drying, treating with 5 wt% of ammonia water solution for 5-6h, preferably 5h, taking out, washing with deionized water to be neutral, drying, placing in a plasma reactor, taking mixed gas of ammonia gas and nitrogen gas mixed according to the volume ratio of 1:1 as working gas, and carrying out plasma reaction for 5-10min, preferably 8min, under the conditions that the pressure is 5Pa and the power is 85W.
Preparing tricalcium phosphate: soaking the pretreated lotus leaves in a calcium hydroxide solution, dropwise adding a urea phosphate solution according to the molar ratio of 2:3 of urea phosphate to calcium hydroxide, stirring, heating to 70 ℃ for reaction for 70min, stopping the reaction when the pH value is detected to be 8-9, cooling to room temperature, centrifuging, placing the separated solid matter in a tubular furnace, heating to 80 ℃ at the speed of 2 ℃/min, drying for 0.5h, heating to 400 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, heating to 1000 ℃ at the speed of 3 ℃/min, calcining for 0.5h, cooling with the furnace, taking out, grinding, and sieving with a 100-mesh sieve to obtain the tricalcium phosphate with the porous structure.
Preparation of gelatin grafted polylactic acid: washing polylactic acid with 50 wt% ethanol solution, drying, soaking in 0.02g/ml hexanediamine/isopropanol mixed solution, reacting at 37 ℃ for 10min, taking out, washing with deionized water, drying, soaking in 1 wt% glutaraldehyde solution, reacting at 30 ℃ for 1h, washing with deionized water, drying, soaking in 2 wt% gelatin aqueous solution for 6h, washing with warm water, and drying to obtain gelatin grafted polylactic acid.
Coating of the first polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate and calcium carbonate particles with the particle size of 60nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting at 50 ℃ for 40min, fishing out to obtain tricalcium phosphate microspheres coated with a gelatin grafted polylactic acid/calcium carbonate layer, washing the tricalcium phosphate microspheres clean with deionized water, drying at 30 ℃, dispersing the tricalcium phosphate microspheres in an excessive hexamethylenediamine tetraacetic acid solution with the concentration of 0.1mol/L, placing the solution in a vortex oscillator for oscillation for 12h, removing calcium carbonate particles, washing with anhydrous ethanol, drying, placing the solution in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide by mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 11h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing with acetone, drying, and carrying out low-temperature plasma treatment for 90s under the conditions of argon as working gas, the power of 80W and the pressure of 6Pa to obtain the tricalcium phosphate microsphere with the surface coated with the first polylactic acid/calcium peroxide layer.
Coating of the second polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 135nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting for 40min at 50 ℃, fishing out and washing with deionized water, drying at 30 ℃, dispersing in excessive hexamethylenediamine tetra-acetic acid solution with the concentration of 0.1mol/L, placing in a vortex oscillator for oscillation for 12h, washing calcium carbonate particles with anhydrous ethanol, drying, placing in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide with the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 11h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing with acetone, drying, and carrying out low-temperature plasma treatment for 90s under the conditions of argon as working gas, power of 80W and pressure of 6Pa to obtain the tricalcium phosphate microsphere with the surface coated with the second polylactic acid/calcium peroxide layer and the first polylactic acid/calcium peroxide layer.
Coating of the third polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a second polylactic acid/calcium peroxide layer and a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 190nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, wherein the addition amount of the calcium carbonate particles is 1/12 of the mass of tricalcium phosphate, stirring and reacting for 40min at 50 ℃, fishing out and washing with deionized water, drying at 30 ℃, dispersing in excessive 0.1mol/L hexanediamine tetraethoxysilane solution, oscillating for 12h in a vortex oscillator, removing calcium carbonate particles, washing with anhydrous ethanol, drying, then placing in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide of the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 11h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing and drying by acetone, and carrying out low-temperature plasma treatment for 80s under the conditions of oxygen serving as working gas, the power being 90W and the pressure being 15Pa to obtain the bioactive microsphere.
EXAMPLE two preparation of bioactive microspheres 2
The pretreatment was the same as in example one.
Preparing tricalcium phosphate: soaking the pretreated lotus leaves in a calcium hydroxide solution, dropwise adding a urea phosphate solution according to the molar ratio of 2:3 of urea phosphate to calcium hydroxide, stirring, heating to 90 ℃ for reaction for 30min, stopping the reaction when the pH value is detected to be 8-9, cooling to room temperature, centrifuging, placing the separated solid matter in a tubular furnace, heating to 70 ℃ at the speed of 3 ℃/min, drying for 1h, heating to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, heating to 900 ℃ at the speed of 5 ℃/min, calcining for 0.5h, cooling with the furnace, taking out, grinding, and sieving with a 100-mesh sieve to obtain the tricalcium phosphate with the porous structure.
The preparation of the gelatin grafted polylactic acid was the same as in example one.
Coating of the first polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate and calcium carbonate particles with the particle size of 75nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting at 50 ℃ for 35min, fishing out to obtain tricalcium phosphate microspheres coated with a gelatin grafted polylactic acid/calcium carbonate layer, washing the tricalcium phosphate microspheres clean by deionized water, drying at 30 ℃, dispersing the tricalcium phosphate microspheres in an excessive hexamethylenediamine tetraacetic acid solution with the concentration of 0.1mol/L, placing the solution in a vortex oscillator for oscillation for 12h, removing calcium carbonate particles, washing by anhydrous ethanol, drying, placing the solution in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide by mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 10 hours under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing and drying by using acetone, and carrying out low-temperature plasma treatment for 80s under the conditions of argon as working gas, the power of 60W and the pressure of 7Pa to obtain the tricalcium phosphate microsphere with the surface coated with the first polylactic acid/calcium peroxide layer.
Coating of the second polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 120nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting at 50 ℃ for 35min, fishing out, washing with deionized water, drying at 30 ℃, dispersing in excessive hexamethylenediamine tetra-acetic acid solution with the concentration of 0.1mol/L, placing in a vortex oscillator for oscillation for 12h, washing calcium carbonate particles with anhydrous ethanol, drying, placing in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide with the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 10 hours under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing with acetone, drying, and carrying out low-temperature plasma treatment for 80s under the conditions of argon as working gas, power of 60W and pressure of 7Pa to obtain the tricalcium phosphate microsphere with the surface coated with the second polylactic acid/calcium peroxide layer and the first polylactic acid/calcium peroxide layer.
Coating of the third polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a second polylactic acid/calcium peroxide layer and a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 200nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, wherein the addition amount of the calcium carbonate particles is 1/12 based on the mass of tricalcium phosphate, stirring and reacting for 35min at 50 ℃, fishing out and washing with deionized water, drying at 30 ℃, dispersing in an excessive hexamethylenediamine tetra-acetic acid solution with the concentration of 0.1mol/L, oscillating for 12h in a vortex oscillator, removing calcium carbonate particles, washing with anhydrous ethanol, drying, then placing in a 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide based on the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 10h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing and drying by acetone, and carrying out low-temperature plasma treatment for 90s under the conditions of the power of 90W and the pressure of 10Pa by taking oxygen as working gas to obtain the bioactive microsphere.
EXAMPLE three preparation of bioactive microspheres 3
The pretreatment was the same as in example one.
Preparing tricalcium phosphate: soaking the pretreated lotus leaves in a calcium hydroxide solution, dropwise adding a urea phosphate solution according to the molar ratio of 2:3 of urea phosphate to calcium hydroxide, stirring, heating to 80 ℃ for reaction for 50min, stopping the reaction when the pH value is detected to be 8-9, cooling to room temperature, centrifuging, placing the separated solid matter in a tubular furnace, heating to 75 ℃ at the speed of 1 ℃/min, drying for 1h, heating to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 1.5h, heating to 950 ℃ at the speed of 2 ℃/min, calcining for 1h, cooling with the furnace, taking out, grinding, and sieving with a 100-mesh sieve to obtain the tricalcium phosphate with the porous structure.
The preparation of the gelatin grafted polylactic acid was the same as in example one.
Coating of the first polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate and calcium carbonate particles with the particle size of 70nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting at 50 ℃ for 30min, fishing out to obtain tricalcium phosphate microspheres coated with a gelatin grafted polylactic acid/calcium carbonate layer, washing the tricalcium phosphate microspheres clean with deionized water, drying at 30 ℃, dispersing the tricalcium phosphate microspheres in an excessive hexamethylenediamine tetraacetic acid solution with the concentration of 0.1mol/L, placing the solution in a vortex oscillator for oscillation for 12h, removing calcium carbonate particles, washing with anhydrous ethanol, drying, placing the solution in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide by mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 12h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing and drying by using acetone, carrying out low-temperature plasma treatment for 100s under the conditions of argon serving as working gas, power of 70W and pressure of 8Pa to obtain the tricalcium phosphate microsphere with the surface coated with the first polylactic acid/calcium peroxide layer.
Coating of the second polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 125nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, stirring and reacting for 30min at 50 ℃, fishing out and washing with deionized water, drying at 30 ℃, dispersing in excessive hexamethylenediamine tetra-acetic acid solution with the concentration of 0.1mol/L, placing in a vortex oscillator for oscillation for 12h, washing calcium carbonate particles with anhydrous ethanol, drying, placing in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide with the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 12h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing with acetone, drying, and carrying out low-temperature plasma treatment for 100s under the conditions of argon as working gas, power of 70W and pressure of 8Pa to obtain the tricalcium phosphate microsphere with the surface coated with the second polylactic acid/calcium peroxide layer and the first polylactic acid/calcium peroxide layer.
Coating of the third polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate microspheres coated with a second polylactic acid/calcium peroxide layer and a first polylactic acid/calcium peroxide layer and calcium carbonate particles with the particle size of 185nm into the gelatin grafted polylactic acid solution according to the solid-to-liquid ratio of 30g/L, wherein the addition amount of the calcium carbonate particles is 1/12 of the mass of tricalcium phosphate, stirring and reacting for 30min at 50 ℃, fishing out and washing with deionized water, drying at 30 ℃, dispersing in excessive hexamethylenediamine tetra-acetic acid solution with the concentration of 0.1mol/L, oscillating for 12h in a vortex oscillator, removing calcium carbonate particles, washing with anhydrous ethanol, drying, then placing in 0.5% glutaraldehyde solution, adding 0.5 times of nanometer calcium peroxide of the mass of tricalcium phosphate, stirring and dispersing under the ultrasonic conditions of 20KHz frequency and 120W power, reacting for 12h under the condition of 275nm ultraviolet irradiation, taking out after the reaction is finished, washing and drying by acetone, and carrying out low-temperature plasma treatment for 100s under the conditions of oxygen serving as working gas, the power of 80W and the pressure of 12Pa to obtain the bioactive microsphere.
Example preparation of four Water purification media
When the bioactive microspheres are needed to be used, the bioactive microspheres are used for absorbing humic acid solution, namely preparation and use are carried out, the specific method is that potassium fulvate is dissolved in deionized water solution to prepare 1g/L solution, the bioactive microspheres are dispersed in the solution according to the solid-to-liquid ratio of 25g/L, and the bioactive microspheres loaded with the humic acid solution are obtained through stirring and absorption for 1 h.
Putting the bioactive microspheres loaded with humic acid solution, kaolin, coconut shell powder, earthworm feces, sodium polyacrylate, alum and active carbon into a stirrer, and uniformly stirring and mixing at the speed of 100r/min to obtain the water body purification matrix, wherein the mass ratio of the bioactive microspheres, the kaolin, the coconut shell powder, the earthworm feces, the sodium polyacrylate, the alum and the active carbon is 3:4:1:2:0.1:0.5: 0.5.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (8)
1. The utility model provides a floater for water ecological restoration, its characterized in that includes the shell to and integrated into one piece at the pterygoid lamina of shell surface, the shell is hollow globular structure, the bottom of shell is provided with a plurality of through-holes, be provided with the division board in the shell, the through hole has been seted up to the intermediate position of division board, there is spacing pipe in the position integrated into one piece that the through hole corresponds on the division board, spacing pipe and through hole are linked together, it has water purification matrix to fill in the below of division board in the casing, water purification matrix includes following raw materials: the biological active microsphere is a core-shell structure which takes tricalcium phosphate as a core and is externally coated with a plurality of polylactic acid/calcium peroxide layers;
the preparation method of the bioactive microsphere comprises the following steps:
preparing tricalcium phosphate: soaking the pretreated lotus leaf rods in a calcium hydroxide solution, dropwise adding a urea phosphate solution, stirring, heating to 70-90 ℃ for reaction for 30-70min, stopping the reaction when the pH value is detected to be 8-9, cooling to room temperature, centrifuging, placing the separated solid matter in a tubular furnace, heating to 70-80 ℃ at the speed of 1-3 ℃/min, drying for 0.5-1h, heating to 400-5 ℃/min, keeping the temperature for 1-2h, heating to 900-1000 ℃ at the speed of 2-5 ℃/min, calcining for 0.5-1h, cooling with the furnace, taking out, grinding, and sieving with a 100-mesh sieve to obtain tricalcium phosphate with a porous structure;
preparation of gelatin grafted polylactic acid: cleaning polylactic acid with 50 wt% ethanol solution, drying, soaking in 0.02g/ml hexanediamine/isopropanol mixed solution, reacting at 37 ℃ for 10min, taking out, cleaning with deionized water, drying, soaking in 1 wt% glutaraldehyde solution, reacting at 30 ℃ for 1h, cleaning with deionized water, drying, soaking in 2 wt% gelatin aqueous solution for 6h, cleaning with warm water, and drying to obtain gelatin grafted polylactic acid;
coating of the first polylactic acid/calcium peroxide layer: dissolving the prepared gelatin grafted polylactic acid in acetonitrile solution, adding tricalcium phosphate and calcium carbonate particles with the particle size of 60-75nm, stirring and reacting at 50 deg.C for 30-40min, taking out to obtain tricalcium phosphate microsphere coated with gelatin grafted polylactic acid/calcium carbonate layer, washing with deionized water, and dispersed in an excessive hexamethylenediamine tetraacetic acid solution with the concentration of 0.1mol/L after being dried, placing in a vortex oscillator, oscillating for 12h to remove calcium carbonate particles, washing with anhydrous ethanol, drying, placing in 0.5 wt% glutaraldehyde solution, adding nanometer calcium peroxide, stirring and dispersing under ultrasonic condition, reacting under ultraviolet irradiation for 10-12h, taking out after reaction, washing, drying, carrying out low-temperature plasma treatment to obtain tricalcium phosphate microspheres coated with a first polylactic acid/calcium peroxide layer;
coating of the second polylactic acid/calcium peroxide layer: repeating the coating step of the first polylactic acid/calcium peroxide layer, wherein the added tricalcium phosphate is changed into tricalcium phosphate microspheres coated with the first polylactic acid/calcium peroxide layer on the surface, and the particle size of calcium carbonate particles is 120-135 nm;
coating of the third polylactic acid/calcium peroxide layer: the coating step of the first polylactic acid/calcium peroxide layer was repeated except that the resultant product was prepared by changing the added tricalcium phosphate to the coating step of the second polylactic acid/calcium peroxide layer, and the particle size of the calcium carbonate particles was 185-200 nm.
2. The floating ball for water ecological restoration according to claim 1, wherein the wing plate comprises a horizontal plate and a vertical plate which are integrally formed, the vertical plate is provided with two clamping buckles and two clamping grooves, the clamping buckles and the clamping grooves are alternately and uniformly arranged on the vertical plate, and the clamping buckles and the clamping grooves are matched.
3. The floating ball for water ecological restoration according to claim 2, wherein the inner diameter of the limiting pipe gradually decreases in a direction away from the partition plate, the limiting pipe comprises a plurality of mutually independent limiting pieces, and two adjacent limiting pieces are in contact with each other.
4. The floating ball for aquatic ecology restoration according to claim 1, wherein the tricalcium phosphate core is coated with a first polylactic acid/calcium peroxide layer, a second polylactic acid/calcium peroxide layer and a third polylactic acid/calcium peroxide layer from inside to outside in sequence, the first polylactic acid/calcium peroxide layer, the second polylactic acid/calcium peroxide layer and the third polylactic acid/calcium peroxide layer are all in a porous structure, the pore size of the first polylactic acid/calcium peroxide layer is smaller than that of the second polylactic acid/calcium peroxide layer, the pore size of the second polylactic acid/calcium peroxide layer is smaller than that of the third polylactic acid/calcium peroxide layer, and the pores of the third polylactic acid/calcium peroxide layer are filled with humic acid solution.
5. The floating ball for aquatic ecology restoration according to claim 4, wherein the tricalcium phosphate is prepared by taking lotus leaf stems as templates and performing water phase coprecipitation to obtain tricalcium phosphate with natural porous structure of lotus leaf stems.
6. The floating ball for water ecological restoration according to claim 4, wherein the first polylactic acid/calcium peroxide layer has a porosity of 80 to 85%, the second polylactic acid/calcium peroxide layer has a porosity of 75 to 80%, and the third polylactic acid/calcium peroxide layer has a porosity of 70 to 75%.
7. The floating ball for water ecological restoration according to claim 6, wherein the low temperature plasma treatment in the first polylactic acid/calcium peroxide coating step and the second polylactic acid/calcium peroxide coating step uses argon gas as working gas, the power is 60-80W, the pressure is 6-8Pa, and the treatment time is 80-100s, and the low temperature plasma treatment in the third polylactic acid/calcium peroxide coating step uses oxygen gas as working gas, the power is 80-100W, the pressure is 10-15Pa, and the treatment time is 80-100 s.
8. The floating ball for water ecological restoration according to claim 7, wherein the pretreatment of the lotus leaf stem is as follows: taking natural lotus leaves, cleaning the lotus leaves with clear water, cutting into sections, drying, treating with 5 wt% ammonia water solution for 5-6h, taking out, washing with deionized water to be neutral, drying, and placing in a plasma reactor for plasma reaction for 5-10 min.
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| CN111333139B (en) * | 2020-03-16 | 2020-12-01 | 深圳集智云创科技开发有限公司 | Efficient treatment trailing type restoration floating ball for water environment pollution |
| CN111252910B (en) * | 2020-03-24 | 2020-11-06 | 河南省商丘生态环境监测中心 | Industrial water purifying agent and water purifying device thereof |
| CN111994989A (en) * | 2020-08-04 | 2020-11-27 | 李金岩 | Novel marine environment restoration ball |
| CN112551671B (en) * | 2021-01-04 | 2021-09-10 | 江苏亚太水务集团股份有限公司 | Sewage treatment device with breathing type suspension balls and treatment method |
| CN113575404B (en) * | 2021-08-17 | 2022-06-21 | 中国科学院生态环境研究中心 | Integrated wind wave-proof ecological floating ball for water ecological restoration |
| CN114212897A (en) * | 2021-12-14 | 2022-03-22 | 湖北省水利水电规划勘测设计院 | Lake water environment prediction early warning equipment |
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